EML Prosedur Manual

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Information and Instructions
Volume I Introduction and Preface
G - General Section
1 - Quality Assurance
2 - Sampling
3 - Radiation Measurements
Table of Contents
3.1 - Overview
3.2 - Ionization Chambers
3.3 - Field Gamma-Ray Spectrometry
3.4 - Remote Gamma-Ray Spectrometry Stations
3.5 - Thermoluminescence Dosimetry
3.6 - Bonner-Sphere Neutron Spectrometry
4 - Analytical Chemistry
Table of Contents
4.1 - Overview
4.2 - Atmospheric Tracer Technology
4.3 - Inorganics
4.4 - Organics
4.5 - Radiochemical
4.5.1 - Scope
4.5.2 - Radiometrology
4.5.3 - Quality Control and Detection Limits
4.5.4 - Radiochemical Analysis Procedures
Americium
Iron
Tritium
Lead
Polonium
Plutonium
Radium *
Radon
Strontium *
Technetium
Thorium
Uranium *
Yttrium
4.5.5 - Generic Procedures *
4.5.6 - Sequential Analyses
5 - Radionuclide Data
6 - Special Facilities
Table of Contents
6.1 - Overview
6.2 - Radon Gas and Radon/Thoron Progeny Facilities for Testing and Research
6.3 - Scanning Electron Microscope Facility
7 - Specifications
Volume II (procedures not currently performed at EML)
2 - Sampling
4 - Analytical Chemistry *
* Contains EPA Approved Procedures

EML: Publications: HASL-300
HASL-300
EML Procedures Manual, 28th Edition
Since 1957, the EML Procedures Manual, HASL-300, has served as a significant resource for scientists throughout the
world who collect samples, perform field measurements or analyze samples. The Manual includes sections on Quality
Assurance, Sampling Techniques, Radiation Measurements, Analytical Chemistry Procedures, Radionuclide Data,
EML Special Facilities, and Specifications for Equipment and Supplies. The 28th edition, released in February 1997 is
available on-line in Adobe Acrobat PDF format. If you do not have the Adobe Acrobat reader, you can download it
free.
The Procedures Manual is no longer being updated.
Please note that the special facilities in Section 6 no longer exist.
Please send questions regarding the Procedures Manual to: NUSTL.webmaster@hq.dhs.gov
Links to sections and subsections inside the chapters:
For chapters 3, 4, and 6 you can either use the links on the left side of the screen or click on the table of contents
and use the section and subsection links in it.
For chapters 1, 2, 5, 7, and volume 2; click on the chapter link on the left side, then page to the table of contents
and use the section and subsection links in it.
http://www.nbl.doe.gov/htm/EML_Legacy_Website/ProcMan/support/Info.htm[4/12/2012 3:43:30 PM]

EML: Publications: HASL-300: Introduction
EML Procedures Manual
Welcome to the on-line version of EML's Procedure Manual. The on-line version differs in presentation but not in
content from the printed version. Each section is a file in PDF format.
HASL-300
THE PROCEDURES MANUAL OF THE ENVIRONMENTAL

MEASUREMENTS LABORATORY
Volume I, 28th Edition
February, 1997
Mitchell D. Erickson, Director
Nancy A. Chieco, Editor
U.S. Department of Homeland Security

201 Varick St. 5th Floor
New York, NY 10014-4811
This report supersedes: HASL-300, 27th edition issued 1990, revised 1992; 26th edition issued 1983; 25th edition
issued 1982; supplement 8 issued 1981; supplement 7 issued 1979; supplement 6 issued 1978; supplement 5 issued
1977; supplement 4 issued 1976; supplement 3 issued 1972 (revised 1975); NYO-4700 issued 1957 (revised 1960,
1962); supplements 1 and 2 issued 1963.
DISCLAIMER
"This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of
their employees, makes any warrenty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus,
product or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name,
trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof.
The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof."
Preface
This 28th edition supersedes all previous versions. The Manual was originally issued in 1957 as a U.S. Atomic Energy
Commission Report (NYO-4700). In 1972, substantive changes were made and the designation became HASL-300
(Health and Safety Laboratory). When the Laboratory's name was changed in 1977 to the Environmental
Measurements Laboratory (EML), the Manual was retitled to the EML Procedures Manual (supplement 6, issued
1978). In subsequent years, parts of HASL-300 were updated as necessary.
Volume I of this edition covers existing technology and procedures currently in use at EML. Some older procedures
have been updated and new procedures have been added. Procedures no longer in use at EML, but still valid and used
at other laboratories, appear in Volume II.
The Manual includes contributions from most of the EML scientific staff. We welcome any questions, corrections or
information you may have concerning this publication. Points of contact are listed in the text. Additional information is
available on EML's web site (www.eml.st.dhs.gov). The special contributions of Sylvia Kendall for desktop publishing
support and of Jenny May-Maiello for graphic design are also acknowledged.
http://www.nbl.doe.gov/htm/EML_Legacy_Website/ProcMan/support/Intro.htm[4/12/2012 3:43:39 PM]

General, Vol. I Rev. 0
HASL-300, 28th Edition February 1997
GENERAL
U.S. Department of Energy

201 Varick Street, 5th Floor
New York, NY 10014-4811
Environmental Measurements Laboratory

U.S. Department of Energy G-i
TABLE OF CONTENTS
Page
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-1
Units and Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-2
The Chemical Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-7
Greek Alphabet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-8
Chemical Conventions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-9
Concentration of Common Acids and Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . G-10
Indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-11
Julian Date Calendar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-12

U.S. Department of Energy G-ii
INTRODUCTION
Volume I of this Manual contains the procedures that are currently used by the
Environmental Measurements Laboratory (EML). Volume II contains procedures
currently not used at EML, but that are still valid and used at other laboratories. In any
manual of this kind, it is necessary to set up certain conventions. Contained in this
section are the units, abbreviations, and reagent and procedural conventions that are used
in the various written methods.

U.S. Department of Energy G-1
UNITS AND ABBREVIATIONS
PREFIXES FOR UNITS IN THE INTERNATIONAL SYSTEM
__________________________________________________________________
exa E 1018 deci d 10-1

peta P 1015 centi c 10-2
12
tera T 10 milli m 10-3
giga G 109 micro : 10-6
6
mega M 10 nano n 10-9
kilo k 103 pico p 10-12
2
hecto h 10 femto f 10-15
deka da 101 atto a 10-18
__________________________________________________________________
BASE UNITS OF THE INTERNATIONAL SYSTEM
________________________________________________________
Quantity Name of unit Symbol

________________________________________________________
length meter m
mass kilogram kg
time second s
electric current ampere A
temperature kelvin K
luminous intensity candela cd
amount of substance mole mol
________________________________________________________

UNITS OF LENGTH
_______________________________________________________________________________________
Units cm m km inch foot mile

_______________________________________________________________________________________
1 cm = 1. 0.01 1x10-5 0.39370 0.032808 6.2137x10-6

1m = 100. 1. 0.001 39.3701 3.280840 6.2137x10-4
1 km = 1x105 1000. 1. 3.937x104 3.281x103 0.62137
-5
1 in = 2.54 0.0254 2.54x10 1. 0.083333 1.5783x10-5
1 ft = 30.48 0.3048 3.05x10-4 12. 1. 1.8939x10-4
1 mile = 1.609x105 1.609x103 1.609344 6.336x104 5280. 1.
_______________________________________________________________________________________
UNITS OF AREA
_____________________________________________________________________________________
Units cm2 m2 ha km2 foot2 mile2

_____________________________________________________________________________________
1 cm2 = 1. 1x10-4 1x10-8 1x10-10 1.08x10-3 3.861x10-11

1 m2 = 1x104 1. 1x10-4 1x10-6 10.76391 3.8610x10-7
8 4 5
1 ha = 1x10 1x10 1. 0.01 1.076x10 3.8610x10-3
2 10 6 7
1 km = 1x10 1x10 100. 1. 1.076x10 0.3861022
2 -6 -8
1 ft = 929.0304 0.0929030 9.29x10 9.29x10 1. 3.5870x10-8
2 10 6 7
1 mile = 2.59x10 2.59x10 258.9988 2.589988 2.788x10 1.
_____________________________________________________________________________________
UNITS OF VOLUME
_____________________________________________________________________________________
liter
Units cm3 (L) m3 inch3 foot3 quart
_____________________________________________________________________________________
1 cm3 = 1. 1x10-3 1x10-6 0.0610237 3.53x10-5 1.0567x10-3

-3
1L = 1000. 1. 1x10 61.02374 0.0353147 1.056688
3 6 4
1m = 1x10 1000. 1. 6.102x10 35.31467 1056.688
1 in3 = 16.38706 0.0163871 1.64x10-5 1. 5.79x10-4 0.01731602
1 ft3 = 2.832x104 28.31685 0.0283168 1728. 1. 2.992208
-4
1 qt = 946.353 0.946353 9.46x10 57.75 0.0342014 1.
_____________________________________________________________________________________

UNITS OF MASS
_______________________________________________________________________________________
ton oz lb ton
Units g kg (metric) (avdp) (avdp) (avdp)
_______________________________________________________________________________________
1g = 1. 1x10-3 1x10-6 0.0352740 2.20x10-3 1.1023x10-6

1 kg = 1000. 1. 1x10-3 35.27396 2.204623 1.1023x10-3
1 metric
ton = 1x106 1000. 1. 3.527x104 2204.623 1.102311
-5
1 oz = 28.34952 0.0283495 2.84x10 1. 0.0625 3.125x10-5
1 lb = 453.5924 0.4535924 4.54x10-4 16. 1. 5.x10-4
1 ton
(avdp) = 9.072x105 907.1847 0.9071847 3.2x104 2000. 1.
_______________________________________________________________________________________
UNITS OF DENSITY
______________________________________________________________________________________
Units g cm-3 g L-1 kg m-3 oz in-3 lb ft-3 lb gal-1

_______________________________________________________________________________________
1 g cm-3 = 1. 1000 1000 0.5780365 62.42795 8.345403

1 g L-1 = 1x10-3 1. 1.0 5.780x10-4 0.06242795 8.345x10-3
1 kg m-3 = 1x10-3 1.0 1. 5.780x10-4 0.06242795 8.345x10-3
-3
1 oz in = 1.729994 1729.994 1729.994 1. 108. 14.4375
-3 -3
1 lb ft = 0.0160185 16.01847 16.01847 9.259x10 1. 0.1336806
1 lb gal-1 = 0.1198264 119.8264 119.8264 0.069264 7.480519 1.
_______________________________________________________________________________________
UNITS OF PRESSURE
_______________________________________________________________________________________
mm Hg
Units Pascal dyn cm-2 bar atm (torr) in Hg
_______________________________________________________________________________________
1 Pascal = 1. 10 1x10-5 9.869x10-6 7.501x10-3 2.953x10-4

1 dyn cm-2 = 0.1 1. 1x10-6 9.869x10-7 7.501x10-4 2.953x10-5
5 6
1 bar = 1x10 1x10 1. 0.9869233 750.0617 29.52999
5 6
1 atm = 1.013x10 1.013x10 1.013250 1. 760. 29.92126
1 mm Hg = 133.3224 1333.224 1.333x10-3 1.316x10-3 1. 0.039370
1 in Hg = 3386.388 3.386x104 0.0338639 0.03342105 25.4 1.
_______________________________________________________________________________________
UNITS OF ENERGY

______________________________________________________________________________________
International
Units Joule calIT BtuIT kWh hp hr L-atm
______________________________________________________________________________________
1 int J = 1. 0.2388853 9.48x10-4 2.78x10-7 3.73x10-7 9.871x10-3

-3 -6 -6
1 calIT = 4.186109 1. 3.97x10 1.16x10 1.56x10 0.0413205
-4 -4
1 BtuIT = 1054.882 251.9958 1. 2.93x10 3.93x10 10.41259
1 kWh = 3.599x106 8.598x105 3412.142 1. 1.341022 3.5529x104
1 hp h = 2.684x106 6.412x105 2544.33 0.7456998 1. 2.6494x104
-5 -5
1 L-atm = 101.3083 24.20106 0.0960376 2.81x10 3.77x10 1.
_____________________________________________________________________________________
UNITS OF RADIOACTIVITY
______________________________________________________________
becquerel disint./minute Curie picoCurie

Units (Bq) (dpm) (Ci) (pCi)
______________________________________________________________
1 Bq = 1. 60. 2.70x10-11 27.

-13
1 dpm = 0.01667 1. 4.5x10 0.450
1 Ci = 3.7x1010 2.22x1012 1. 1.0x1012
1 pCi = 0.037 2.22 1.0x10-12 1.
______________________________________________________________
UNITS OF RADIATION EXPOSURE
___________________________________________
roentgen coulombs/kilogram
Units (R) (C kg-1)
___________________________________________
1R = 1 2.58x10-4
1 C kg-1 = 3876 1
___________________________________________
UNITS OF ABSORBED DOSE
___________________________________________________

gray joule/kilogram
Units (Gy) (J kg-1) rad
___________________________________________________
1 Gy = 1 1 100
-1
1 J kg = 1 1 100
1 rad = 0.01 0.01 1
___________________________________________________
UNITS OF RADIATION DOSE EQUIVALENT
_____________________________________________________________________
joule/kilogram roentgen equivalent

-1
Sievert (J kg ) man (rem)
_____________________________________________________________________
1 Sievert = 1. 1.0 100.

1 J kg-1 = 1.0 1. 100.
1 rem = 0.01 0.01 1.
______________________________________________________________________

THE CHEMICAL ELEMENTS
_________________________________________________________________________________________________
Atomic Atomic
____________________ __________________
Element Symbol Number Weight Element Symbol Number Weight
_________________________________________________________________________________________________
Actinium Ac 89 227.028 Mendelevium Md 101 (258.)
Aluminum Al 13 26.9815 Mercury Hg 80 200.59
Americium Am 95 (243.) Molybdenum Mo 42 95.94
Antimony Sb 51 121.75 Neodymium Nd 60 144.24
Argon Ar 18 39.948 Neon Ne 10 20.179
Arsenic As 33 74.9216 Neptunium Np 93 237.048
Astatine At 85 (210.) Nickel Ni 28 58.69
Barium Ba 56 137.33 Niobium Nb 41 92.9064
Berkelium Bk 97 (247.) Nitrogen N 7 14.0067
Beryllium Be 4 9.01218 Nobelium No 102 (259.)
Bismuth Bi 83 208.980 Osmium Os 76 190.2
Boron B 5 10.81 Oxygen O 8 15.9994
Bromine Br 35 79.904 Palladium Pd 46 106.42
Cadmium Cd 48 112.41 Phosphorus P 15 30.9738
Calcium Ca 20 40.08 Platinum Pt 78 195.08
Californium Cf 98 (251.) Plutonium Pu 94 (244.)
Carbon C 6 12.011 Polonium Po 84 (209.)
Cerium Ce 58 140.12 Potassium K 19 39.0938
Cesium Cs 55 132.905 Praseodymium Pr 591 40.908
Chlorine Cl 17 35.453 Promethium Pm 61 (145.)
Chromium Cr 24 51.996 Protactinium Pa 91 231.036
Cobalt Co 27 58.9332 Radium Ra 88 226.025
Copper Cu 29 63.546 Radon Rn 86 (222.)
Curium Cm 96 (247.) Rhenium Re 75 186.207
Dysprosium Dy 66 162.50 Rhodium Rh 45 102.906
Einsteinium Es 99 (252.) Rubidium Rb 37 85.4678
Erbium Er 68 167.26 Ruthenium Ru 44 101.07
Europium Eu 63 151.96 Samarium Sm 62 150.36
Fermium Fm 100 (257.) Scandium Sc 21 44.9559
Fluorine F 9 18.9984 Selenium Se 34 78.96
Francium Fr 87 (223.) Silicon Si 14 28.0855
Gadolinium Gd 64 157.25 Silver Ag 47 107.868
Gallium Ga 31 69.72 Sodium Na 11 22.9898
Germanium Ge 32 72.59 Strontium Sr 38 87.62
Gold Au 79 196.967 Sulfur S 16 32.06
Hafnium Hf 72 178.49 Tantalum Ta 73 180.948
Helium He 2 4.00260 Technetium Tc 43 (98.)
Holmium Ho 67 164.930 Tellurium Te 52 127.60
Hydrogen H 1 1.00794 Terbium Tb 65 158.925
Indium In 49 114.82 Thallium Tl 81 204.383
Iodine I 53 126.905 Thulium Tm 69 168.934
Iridium Ir 77 192.22 Thorium Th 90 232.038
Iron Fe 26 55.847 Tin Sn 50 118.71
Krypton Kr 36 83.80 Titanium Ti 22 47.88
Lanthanum La 57 138.906 Tungsten W 74 183.85
Lawrencium Lr 103 (260.) Uranium U 92 238.029
" Lw " " Vanadium V 23 50.9415
Lead Pb 82 207.2 Xenon Xe 54 131.29
Lithium Li 3 6.941 Ytterbium Yb 70 173.04
Lutetium Lu 71 174.967 Yttrium Y 39 88.9059
Magnesium Mg 12 24.305 Zinc Zn 30 65.39
Manganese Mn 25 54.9380 Zirconium Zr 40 91.224
_________________________________________________________________________________________________
GREEK ALPHABET

________________________________________________________________________________
!," Alpha H,0 Eta N,< Nu T,J Tau

B,ß Beta 1,2 Theta O,P Xi Y,L Upsilon
',( Gamma I,4 Iota O,o Omicron M,N Phi
),* Delta K,6 Kappa A,B Pi X,P Chi
E,, Epsilon 7,8 Lamba P,D Rho Q,R Psi
Z,. Zeta M,: Mu E,F Sigma S,T Omega
________________________________________________________________________________

CHEMICAL CONVENTIONS
1. The commercial concentrated acids and ammonium hydroxide are indicated by the
chemical symbol only.
2. "Water" or "H2O" refers to distilled water or deionized water. Special requirements are
noted in the procedures.
3. Diluted acids are usually given as parts of acid to be added to parts of water. Thus 1:9
means one part of concentrated acid plus 9 parts of water by volume. In a few
procedures, normality (N) or molarity (M) values are given.
4. All concentrations or dilutions are approximate, unless stated as exact or that preparation
or dilution in a volumetric flask is required.
5. Carrier concentrations are given in the reagent list for each procedure. In the
procedures, all additions of carrier are made by volume with a pipet. Carrier solutions
must be standardized if recovery values are to be determined gravimetrically.
6. Approximate tracer concentrations are given in the reagent list for each procedure. The
addition of tracer is usually made by weight, and the tracer "standardization" is made
with each batch of samples.
7. The conventions used for pH determination are that wide-range pH papers may be used
for obtaining the pH indicated unless measurements with narrow range paper or a pH
meter are specifically mentioned.
8. It is considered that good analytical and laboratory safety practices will be followed in
all work: that the apparatus is clean, that all transfers are quantitative and that all
precipitates are washed carefully. Where qualifications appear, they indicate that extra
care is required.

CONCENTRATIONS OF COMMON ACIDS AND BASES
________________________________________________________________
Specific
Name and Formula Gravity Percent Molarity Normality
________________________________________________________________
Hydrofluoric acid, HF 1.17 48 28 28
Hydrochloric acid, HCl 1.18 37 12 12
Perchloric acid, HClO4 1.5-1.6 60 10 10
Nitric acid, HNO3 1.42 70 16 16
Nitric acid, HNO3 1.49 90 21 21

fuming
Sulfuric acid, H2SO4 1.84 96 18 36
Phosphoric acid, H3PO4 1.70 85 15 45
Acetic acid, HC2H3O2 1.05 99.5 17 17

glacial
Ammonium hydroxide, 0.90 27 (NH3) 14 14

NH4OH
________________________________________________________________

INDICATORS
Acid-Base Indicators
_________________________________________________________________________________
Indicator Type Acidic Color Basic Color pH Range

_________________________________________________________________________________
Bromocresol Green Acid Yellow Blue 3.8-5.4

Bromthymol Blue Acid Yellow Blue 6.0-7.6
Cresol Purple Acid Yellow Purple 7.4-9.0

Phenolphthalein Acid Colorless Red-Violet 8.5-10.0
Thymol Blue Acid Red Yellow 1.2-2.8

Thymolphthalein Acid Colorless Blue 9.3-10.5
Methyl Orange Base Red Yellow 3.1-4.4

Methyl Red Base Red Yellow 4.2-6.2
Tropeoline OO Base Red Yellow 1.3-3.0

_________________________________________________________________________________
Reduction Indicators
_________________________________________________________________
_
Color of Color of
Indicator Reduced Form Oxidized Form
_________________________________________________________________
_
Orthophenanthroline Ferrous Red Pale Blue

Diphenylamine Sulfonate Colorless Violet
Starch-Iodine-Iodide Colorless Blue

Indigo Sulfonates Colorless Blue
_________________________________________________________________
_

JULIAN DATE CALENDAR (for leap years only)
Day Jan Feb Mar Apr May June July Aug Sep Oct Nov Dec Day
1 001 032 061 092 122 153 183 214 245 275 306 336 1
2 002 033 062 093 123 154 184 215 246 276 307 337 2
3 003 034 063 094 124 155 185 216 247 277 308 338 3
4 004 035 064 095 125 156 186 217 248 278 309 339 4
5 005 036 065 096 126 157 187 218 249 279 310 340 5
6 006 037 066 097 127 158 188 219 250 280 311 341 6
7 007 038 067 098 128 159 189 220 251 281 312 342 7
8 008 039 068 099 129 160 190 221 252 282 313 343 8
9 009 040 069 100 130 161 191 222 253 283 314 344 9
10 010 041 070 101 131 162 192 223 254 284 315 345 10
11 011 042 071 102 132 163 193 224 255 285 316 346 11
12 012 043 072 103 133 164 194 225 256 286 317 347 12
13 013 044 073 104 134 165 195 226 257 287 318 348 13
14 014 045 074 105 135 166 196 227 258 288 319 349 14
15 015 046 075 106 136 167 197 228 259 289 320 350 15
16 016 047 076 107 137 168 198 229 260 290 321 351 16
17 017 048 077 108 138 169 199 230 261 291 322 352 17
18 018 049 078 109 139 170 200 231 262 292 323 353 18
19 019 050 079 110 140 171 201 232 263 293 324 354 19
20 020 051 080 111 141 172 202 233 264 294 325 355 20
21 021 052 081 112 142 173 203 234 265 295 326 356 21
22 022 053 082 113 143 174 204 235 266 296 327 357 22
23 023 054 083 114 144 175 205 236 267 297 328 358 23
24 024 055 084 115 145 176 206 237 268 298 329 359 24
25 025 056 085 116 146 177 207 238 269 299 330 360 25
26 026 057 086 117 147 178 208 239 270 300 331 361 26
27 027 058 087 118 148 179 209 240 271 301 332 362 27
28 028 059 088 119 149 180 210 241 272 302 333 363 28
29 029 060 089 120 150 181 211 242 273 303 334 364 29
30 030 090 121 151 182 212 243 274 304 335 365 30
31 031 091 152 213 244 305 366 31

JULIAN DATE CALENDAR (perpetual)

Day Jan Feb Mar Apr May June July Aug Sep Oct Nov Dec Day
1 001 032 060 091 121 152 182 213 244 274 305 335 1
2 002 033 061 092 122 153 183 214 245 275 306 336 2
3 003 034 062 093 123 154 184 215 246 276 307 337 3
4 004 035 063 094 124 155 185 216 247 277 308 338 4
5 005 036 064 095 125 156 186 217 248 278 309 339 5
6 006 037 065 096 126 157 187 218 249 279 310 340 6
7 007 038 066 097 127 158 188 219 250 280 311 341 7
8 008 039 067 098 128 159 189 220 251 281 312 342 8
9 009 040 068 099 129 160 190 221 252 282 313 343 9
10 010 041 069 100 130 161 191 222 253 283 314 344 10
11 011 042 070 101 131 162 192 223 254 284 315 345 11
12 012 043 071 102 132 163 193 224 255 285 316 346 12
13 013 044 072 103 133 164 194 225 256 286 317 347 13
14 014 045 073 104 134 165 195 226 257 287 318 348 14
15 015 046 074 105 135 166 196 227 258 288 319 349 15
16 016 047 075 106 136 167 197 228 259 289 320 350 16
17 017 048 076 107 137 168 198 229 260 290 321 351 17
18 018 049 077 108 138 169 199 230 261 291 322 352 18
19 019 050 078 109 139 170 200 231 262 292 323 353 19
20 020 051 079 110 140 171 201 232 263 293 324 354 20
21 021 052 080 111 141 172 202 233 264 294 325 355 21
22 022 053 081 112 142 173 203 234 265 295 326 356 22
23 023 054 082 113 143 174 204 235 266 296 327 357 23
24 024 055 083 114 144 175 205 236 267 297 328 358 24
25 025 056 084 115 145 176 206 237 268 298 329 359 25
26 026 057 085 116 146 177 207 238 269 299 330 360 26
27 027 058 086 117 147 178 208 239 270 300 331 361 27
28 028 059 087 118 148 179 209 240 271 301 332 362 28
29 029 088 119 149 180 210 241 272 302 333 363 29
30 030 089 120 150 181 211 242 273 303 334 364 30
31 031 090 151 212 243 304 365 31

Section 1, Vol. I Rev. 0
48$/,7<$6685$1&(
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U.S. Department of Energy 1-i
HASL-300, 28th Editiion February 1997
Page
4XDOLW\$VVXUDQFH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1
1.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1
1.2 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-2
1.3 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-2
1.4 Staff Qualifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-3
1.5 Staff Responsibilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-3
1.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-3

1.5.2 Responsibilities of Field Workers and Laboratory
Workers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-4
1.5.3 Responsibilities of First Line Supervisors . . . . . . . . . . . . . . . . . . . . 1-4
1.5.4 Responsibilities of Individual Project Leaders . . . . . . . . . . . . . . . . 1-5
1.5.5 Responsibilities of Division Directors and Program
Coordinators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-6
1.5.6 Responsibilities of the QA Officer . . . . . . . . . . . . . . . . . . . . . . . . . . 1-7
1.6 Field Measurements and Sampling . . . . . . . . . . . . . . . . . . . . . . 1-8
1.6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-8

1.6.2 Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-8
1.6.3 Preparation and Storage of Samples . . . . . . . . . . . . . . . . . . . . . . . . . 1-10
1.6.4 Coding and Record Keeping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-11
1.7 Chemical and Radiochemical Analyses . . . . . . . . . . . . . . . . . 1-12
1.7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-12

U.S. Department of Energy 1 - ii
HASL-300, 28th Editiion February 1997
Page
1.7.2 Approved Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-12
1.7.3 QC Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-13
1.8 Instrumental Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-14
1.8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-14

1.8.2 Instruments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-15
1.8.3 Calibrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-15
1.8.4 Background Evaluations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-15
1.8.5 Checks of the Stability of the Instrument . . . . . . . . . . . . . . . . . . . . 1-17
1.9 Data Reduction, Storage, and Reporting . . . . . . . . . . . . . . . 1-17
1.9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-17

1.9.2 Field and Laboratory Records . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-17
1.9.3 Data Reduction and Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-18
1.9.4 Data Reporting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-19
1.10 Materials and Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-22
1.10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-22

1.10.2 Standards and Reference Materials Library . . . . . . . . . . . . . . . . . 1-22
1.10.3 Data Validation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-22
1.10.4 Intralaboratory Comparisons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-23
1.10.5 Interlaboratory Comparisons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-23
1.11 Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-25

U.S. Department of Energy 1 - iii
48$/,7<$6685$1&(
1.1 OVERVIEW
The Management of the Environmental Measurements Laboratory (EML) is fully

committed to the maintenance of an effective quality assurance (QA) program in order
that all work carried out by EML will be of high quality. The EML Institutional Quality
Assurance Program Plan (EM-6-2) describes the QA procedures used at the Laboratory.
Guidelines for the design of the EML Institutional Quality Assurance Program Plan are
provided for by: DOE Order 5700.6C, "Quality Assurance;" DOE-ER-STD-6001-92,
"DOE Standard: Implementation Guide for Quality Assurance Programs for Basic and
Applied Research;" and Chicago Operations Office Order CH 5700.6C, "Quality
Assurance." The EML QA program has been designed to conform to those guidelines.
The management system of the QA program at EML includes the entire staff, from
the Laboratory Director, through the Deputy Director and the Division Directors to the
project leaders and first line supervisors, and finally to the scientist or engineer in the
laboratory or in the field. The QA Officer oversees the functioning of the Institutional
QA Program (see Section 1.5).
An important aspect of the EML QA program is the written documentation of QA and

quality control (QC) procedures that are used in the performance of research projects. A
Project QA Plan is prepared for each project that is contained in a field work proposal,
describing or referencing the procedures used during the project and the quality of results
from these procedures that is required for the successful performance of the project.
Twice each year, the Division Director or Program Coordinator who oversees a project
submits to the EML QA Officer a brief evaluation of the current level of quality of
performance on that project. The QA Officer selects a few of these projects and makes a
detailed examination of the evidence of quality that was used to evaluate them. The
documentation of the quality of the work is described in this section, and in subsequent
sections of this Manual. Under normal circumstances, all research reports contain a
section in which the QA procedures used and the results obtained are discussed. When
they believe that it will be beneficial, Division Directors may require the submission of

U.S. Department of Energy 1-1
special QA reports for specific projects within their divisions. QA reports can be used
during assessments of a project by the Division Director or by the QA Officer to assure
that QA requirements are being met. For a QA program to be effective, corrective action
must always be taken when substandard results are detected, and subsequent follow-up
audits must be made to verify that any problems have been solved. The Division
Directors oversee the planning, performance, and documentation of any needed remedial
actions required as the result of an audit.
The most important requirement for the success of the QA program is the
commitment in the Laboratory that our goal is to always perform high quality work. This
requires both a degree of dedication of the staff and an absolute honesty in data
preparation.
1.2 SCOPE
The policies, procedures, guidelines, and implementation practices at EML with

regard to its QA program are presented in this section. Also, outlined are the
responsibilities of EML personnel to ensure the quality of the data at all phases of the
project from planning to the reporting of the data.
1.3 DEFINITIONS
Three definitions related to QA practices are given below. A more complete list may
be found in Section 1.11.
QA involves all those planned and systematic actions necessary to provide adequate
confidence that a facility, structure, system, or component will perform satisfactorily and
safely in service.
QC, which is included within QA, comprises all those actions necessary to control
and verify the features and characteristics of a material, process, product, or service to
specified requirements.

Audit/Appraisal is a planned and documented activity performed in accordance with

procedures to determine, by examination and evaluation of objective evidence, the
adequacy of and extent to which applicable elements of the QA program have been
developed, documented, and effectively implemented in accordance with specified
requirements.
1.4 STAFF QUALIFICATIONS
The first step in establishing a QA program is the securing of personnel who are
competent to perform the technical procedures, and training them so that they are
thoroughly familiar with the instruments and procedures that they will use. This is as
important as are written QC procedures and record keeping. Technical personnel should
understand the nature of the physical and chemical properties that affect the measurement
procedures that they perform, so that they may recognize and interpret any deviations
from the expected behavior. When technical personnel are to perform a procedure in
which they are not experienced, they are first trained, then tested in order to demonstrate
that they can perform the procedure with an acceptable level of uncertainty.
1.5 STAFF RESPONSIBILITIES
1.5.1 INTRODUCTION
All individuals and all levels of management at EML have responsibilities within the
QA program. Although the Laboratory Director has overall supervision of and responsi-
bility for the program, and the QA Officer oversees its functioning, the Deputy Director,
Division Directors, first line supervisors, project leaders, field workers and laboratory
workers are responsible for the quality of the work that is performed under their control.
The specific responsibilities that are described below are applicable in most instances.
However, each research project has its own individual characteristics, and Division
Directors may reassign specific responsibilities within particular projects to attain the
most efficient organization.

1.5.2 RESPONSIBILITIES OF FIELD WORKERS

AND LABORATORY WORKERS
The field workers and laboratory workers are responsible for the quality of their
performance of assigned tasks. They must be thoroughly familiar with the QA aspects of
the procedures that they follow. For the most part, these procedures are described in later
sections of this Manual. All personnel must carefully adhere to those procedures, must
report to their supervisors any problems that caused deviation from these procedures or
results from standard procedures or expected results, and must undertake to correct
identified problems. They are responsible for the prevention of the loss of quality during
handling of the equipment and materials that they use in their work, and for the routine
maintenance, calibration and the general care of their equipment. They maintain records
of instrument calibrations and of the results of the QC procedures that they perform.
1.5.3 RESPONSIBILITIES OF FIRST LINE SUPERVISORS
First line supervisors ensure that the personnel under their supervision are aware of,
and fulfill their responsibilities for the QA aspects of the tasks that they perform. They
ensure that only authorized personnel perform the research operations, that proper care is
taken of equipment and materials to avoid loss of quality, and that approved sampling and
measurement procedures (most of which are described in Sections 2, 3, and 4) are used.
First line supervisors are responsible for the specification and supervision of appropriate
QA procedures to be performed by the personnel under their supervision, and they
periodically review the procedures that are in use to ensure their adequacy for
determining the quality of the results that will be obtained from current and future
operations. They see that logbooks and other records, such as calibrations and the results
of QC procedures, are maintained properly, that appropriate information is recorded, and
that any changes that are made in documents that give instructions or describe procedures
are reviewed and approved. They test the validity of measurement data that they report,
and ensure that corrective actions are taken when problems arise, and that follow-up
verification is obtained of the success of those actions.
First line supervisors ensure that measuring and test equipment and materials are
traceable to national standards or to equivalent calibration standards, and that they are

cared for properly by those who are using them. They implement documented QA
procedures to ensure that the quality of items and services procured to accomplish tasks
under their supervision meets appropriate QA criteria, and they ensure that documents
needed to verify the quality of these items and services are retained in a recoverable form.
They design and implement documented QA procedures to cover the calibration and
continuing operation of such equipment and the confirmation of the suitability of such
supplies. They ensure that defective equipment is not used until it has been repaired, and
that records are kept of the repair of equipment.
1.5.4 RESPONSIBILITIES OF INDIVIDUAL PROJECT LEADERS
Project leaders must participate in the preparation of the Project QA Plan, in which
are specified the level of quality required for each phase of their research projects, and the
QC methods to be used to ensure that the required levels of quality are attained. They
must continually evaluate the specified levels of uncertainty and the levels that are
actually being attained, and they must maintain retrievable records that furnish evidence
that shows whether the quality of data produced by their project conforms to the
requirements of the project. Project leaders ensure that the field measurements, sample
collection and handling, laboratory analysis, data analysis and reporting of results are
performed properly to prevent the loss of the quality of the data. They must be actively
involved in monitoring the quality of all aspects of the work that is being done on their
projects, and they review and approve documents and changes in documents that describe
the QA requirements of work done on these projects. They must seek to obtain corrective
actions if these are needed, and must initiate and provide follow-up verification of any
such corrective actions.
When equipment, supplies or services are purchased for use on their projects, project
leaders must design and implement documented QA procedures to cover the calibration
and operation of the equipment and the confirmation of the suitability of the supplies or
services. Project leaders are responsible for determining that documents needed to verify
the quality of such equipment, supplies or services are retained in a recoverable form.
They must also continually monitor the quality of equipment, supplies and services that
are actually in use on their projects. When contractors are hired to perform some aspects

of a research project, the project leader must see that the contract documents include
specifications of the quality of the work that must be done by the contractor, and must
design and implement a documented QA program to cover the contractor's performance

under the contract.
Project leaders have the overall responsibility for the quality of the final products
from their projects, and especially for the quality of the data and interpretations published
under their projects. They ensure that measurement data that they have received are
validated and that inaccurate information is corrected before the research results are
submitted for publication. They are responsible for the proper care and protection of
measurement data that they have received. Project leaders normally prepare the progress
reports and the final publications of project accomplishments and they must verify the
accuracy of the published data, and must include a QA section within these reports. The
project leader is responsible for the timely submission of QA reports if these are required
for the project. The frequency and content of these reports are to be specified by the
appropriate Division Director. Normally such reports should list the data from QC
measurements, and should include a discussion of the adequacy of the QC results in light
of the project requirements. This discussion should include a review of corrective
measures taken and of the results obtained for any problems discussed in the previous
report, and it should describe any corrective measures that are being taken for current
problems. The project leader must see that retrievable records that furnish evidence of
the quality of the work done on the project are specified, prepared and maintained, and
must be sure that any and all documentation required for possible QA audits is available.
1.5.5 RESPONSIBILITIES OF DIVISION DIRECTORS AND

PROGRAM COORDINATORS
Division Directors and Program Coordinators provide ongoing supervision of QA for

work within their divisions and programs. They develop specific QA objectives,
involving documented procedures, for the laboratory worker and field worker,
communicate these objectives to the workers, and then ensure that these documented
operating procedures and protocols are followed, and that the desired quality of work is
maintained. They periodically review the QA procedures that are in use to ensure their

adequacy for determining the quality of the results that will be obtained from current and
future operations. Division Directors and Program Coordinators must approve any
changes in documents that detail procedures that are used within their divisions. They
also review the procedures used to select items and services procured for their divisions
and programs, and they ensure that QA requirements for these items and services are
being met and are properly documented.
The Division Directors and Program Coordinators have the ultimate responsibility for
the quality of the products delivered by each of the projects within their divisions and
programs, and must be actively involved in ensuring that the required quality of work is
achieved in all aspects of these projects. They must be active in the review, criticism, and
correction of the work of persons who are working on their projects. Twice a year,
Division Directors and Program Coordinators supply the EML QA Officer with brief
written evaluations of each project for which they are responsible. Division Directors and
Program Coordinators must ensure that any QA reports that they require for a project are
submitted on time and are complete. They oversee the procedures used in the peer review
of reports originating in their division, and they ensure that these procedures are rigorous
enough to detect and eliminate faulty data and interpretations. They ensure that all
research reports undergo peer review within EML before publication in EML reports or
submission to scientific journals. They encourage project leaders to submit reports of
their research to peer-reviewed scientific journals whenever this is feasible. Division
Directors and Program Coordinators perform QA reviews of projects under their
supervision semiannually, and ensure that any needed corrective actions are taken.
1.5.6 RESPONSIBILITIES OF THE QA OFFICER
The EML QA Officer keeps informed about and investigates any problems that arise
in the quality of the work that is performed at the Laboratory, and keeps the Laboratory
Director informed. Twice a year the QA Officer receives brief evaluations from the
Division Directors and Program Coordinators of the quality of work that is being
performed on the projects that are under their supervision. The QA Officer selects a few
of these projects for more detailed investigation, choosing some at random, others based
upon their importance to the Laboratory, and others because of their quality history. The
QA Officer maintains written records of the semiannual evaluations submitted by the

Division Directors and Program Coordinators and of any subsequent investigations, as

well as of any other QA appraisals or investigations performed at the Laboratory. The
QA Officer also ensures that the EML Institutional Quality Assurance Program Plan is
kept current.
1.6 FIELD MEASUREMENTS AND SAMPLING
1.6.1 INTRODUCTION
Some measurements of environmental parameters, such as the intensity and compo-

sition of environmental radiation, are performed in the field, while others, such as the
concentration of specific radionuclides in samples of soil or vegetation, are performed in
the laboratory on samples that were collected in the field. In either situation the proce-
dures used in the field work must be performed correctly if the measurements are to
produce valid results. There are many potential pitfalls involved in this initial step, and
precautions must be taken to avoid them to ensure the validity of the final data. Before
sampling is begun, all project personnel should be informed of the procedures to be used,
so that it is certain that the material and the amount of material to be sampled or the
property to be measured are appropriate at all phases of the project.
1.6.2 TECHNIQUES
A field measurement or a collected sample must be representative of the parameter or

material that is to be analyzed. However, obtaining a representative measurement or
sample of environmental parameters or materials is often not straightforward. Most
environmental parameters and materials vary with location and time. For example,
cosmic-ray intensities vary with time, and various organs of plants and animals differ in
their contents of organic and inorganic constituents. Soil typically contains particles of
various sizes, and the chemical composition and surface reactivity of these particles often
vary as a function of particle size. Water bodies, such as lakes and the ocean, are
commonly stratified, with variations in physical and chemical compositions from one
layer to another, and usually have a surface film in which many reactive chemical
constituents are strongly concentrated. The atmosphere also is stratified, and air parcels

differ from place to place in their concentrations of trace gases and suspended particles.
Thus, even at a single site, the composition of air will vary with time, and especially as
the wind shifts. The intensity of radiation from radionuclides within the soil varies from
location to location. When possible, statistical tests should be applied to determine the
number of observations or samples that are needed to achieve the required level of
uncertainty.
Before measurements of environmental radiation are begun, the appropriateness of the

measurement location must be ascertained. If radiation from the soil is to be measured,
the representativeness of the soil at the measurement location must be checked. It must
be verified that there are no objects in the vicinity of the radiation detector that can affect
the readings that the detector gives.
If samples are to be collected, before sampling is begun the researcher must define
clearly the material that is to be sampled to be certain that the sample will be represen-
tative of that material. If vegetation is to be sampled, will the sample include the roots of
the plant, and if so, must all soil that is clinging to the roots be meticulously removed? If
a sample of the atmospheric aerosol that is representative of air over a large region is to
be collected, does wind direction matter, at what height above ground is the sample to be
taken, and is there danger that nearby structures or activities will affect the composition
of the sample? The sample should be representative of the complete material, but it must
not be contaminated by extraneous materials. The sampling process itself can affect the
validity of the sample. Thus, a rain gauge may distort the flow of winds in its vicinity and
cause less rain to fall into its opening than would fall onto the same area of open soil. A
water sampler lowered into a lake may carry water from a near surface layer into a lower
layer that is being sampled. Therefore, the details of sampling and of sample handling
must be considered carefully before sampling is performed in order that the entire
research effort not be jeopardized by the careless omission of some needed safeguard.
Because the intensity of environmental radiation and the composition and physical
characteristics of environmental materials often vary with location over short distances,
and may vary significantly with time, it is usually advisable to do replicate measurements
or sampling. The analysis of the data from such measurements or samples can provide a
measure of the random error of the entire operation. When a material that is being
sampled is clearly heterogeneous, as are many soils and biological materials, replicate

samples should be taken. When the intensity of radiation or the composition of the
material is expected to change significantly with time, it is usually advisable to take a
series of measurements or samples over the period of interest. This replicate or serial
measurement or sampling can yield a more useful picture of the characteristics of interest
than would data for a single measurement or sample. The measurement or sampling
interval and frequency are often dictated by the research objectives of the project. If
portions of samples are to be retained in storage, this should be considered in planning
how much material is to be collected, and the treatment it is to receive.
1.6.3 PREPARATION AND STORAGE OF SAMPLES
Many types of measurements of environmental materials, such as vegetation, water,

and atmospheric particles, require that a sample of the material be collected and returned
to the laboratory for analysis. These samples may require some form of pretreatment
before they can be analyzed. For example, vegetation samples may be dried or ashed, and
water samples may be filtered. Where possible, groups of samples that are expected to
contain high concentrations of an analyte are processed independently from those with
low concentrations to minimize the possibility of cross contamination. Pretreatment
normally alters the physical state of the sample, and also sometimes alters its chemical
state. In planning the pretreatment, the researcher considers the nature of the
measurement that is to be made and the state that the sample must be in to undergo that
measurement. The possibility should also be considered that the results obtained from the
sample might lead to a desire to reanalyze it for the same property, or to analyze it for
some other property. Hence, it will often be desirable to collect more sample than will be
processed, and to process more sample than will be used in the analysis (if the analytical
process is such as to consume the sample).
Another consideration in planning and in carrying out the pretreatment of samples is

the reference state of the samples that will be used in reporting the results of the
measurements. For example, samples of vegetation, of soil or of sediment are usually
weighed before being analyzed, and the results are reported with reference to unit weight
and/or the unit area from which the samples were collected. Normally these types of
samples are weighed directly after collection (wet weight), dried and weighed again (dry
weight) before they are analyzed. Under this protocol, the researcher must ensure that all
samples are dried to the same extent to report results per unit dry weight. But this

U.S. Department of Energy 1 - 10
restriction is lifted if results are reported per unit weight or per unit area of sample
collection.
Decisions concerning the pretreatment process to be used can be complicated if the

process is such that it may alter the property of the sample that is to be measured. For
example, if a volatile component, such as iodine, is to be measured in vegetation, the
pretreatment of the vegetation sample must not be such as to volatilize that component.
Project leaders are responsible for their own samples until the project is complete.
Upon completion of a project, any portions of samples that are to be saved should be
entered into and stored in an archival system.
1.6.4 CODING AND RECORD KEEPING
At the time of sample collection or of field measurement, samples and resulting

data sets are normally given code numbers that serve to identify them during subsequent
analytical, calculation and data reporting stages. Sometimes a coding system separate
from that used for field measurements or sample collection is used for the analysis stage,
either for the convenience of the analysts or to aid in ensuring the "blindness" of the QC
samples or measurements. A number of factors enter into the designing of these codes.
There is always an advantage in keeping the codes as simple as possible to minimize the
probability that errors will be made in transferring data. However, the code should be
distinctive enough to distinguish each set of samples and data from other, unrelated
samples and data that pass through the laboratory. Care must be taken to mark samples
and field data clearly to minimize the possibility of misreading of labels and notes.
Especially during the sampling or field measurement phase, it is often desirable to use
codes that contain information on the site and/or time of sampling or measurement, or
upon the nature of the sample or measurement.
In designing protocols for recording field measurements or sampling and subsequent

analytical data, the researcher must consider whether the recorded data will be sufficiently
complete for the possible future uses that may be made of the final analytical results.
Normally, much more detailed information is available during the field measurement or
sampling and analytical phases than is expected to be of importance for the interpretation

of the results, and only the information that appears to be immediately useful is recorded.
At times, as the final data have been studied, it has become evident that some of the
unrecorded information might have been useful in interpreting those results. To avoid the
possible loss of useful information, the researcher should make a habit of keeping
detailed field and laboratory notes, either in a bound notebook or another recoverable
medium. Researchers should think through as many possibilities as they can based on
their experience before designing the systems and codes of data recording.
1.7 CHEMICAL AND RADIOCHEMICAL ANALYSES
1.7.1 INTRODUCTION
The EML QA program for chemical and radiochemical analyses has long been well-
defined and carefully followed. QC measures are an integral part of each analytical
procedure, and quantitative estimates of analytical uncertainties are made and reported
routinely.
1.7.2 APPROVED PROCEDURES
There are often several chemical or radiochemical techniques that may be used to
accomplish a particular analysis. In most instances, past experience at EML or amongst
the scientific community generally has shown that one of these techniques is to be
preferred to the others, at least for a particular type of sample and with the concentration
of the constituent of interest falling within a specific range. In these instances, the
particular analytical procedure to be used is specified in Section 4 of this Manual. The
details of these procedures are documented in those sections, and they are updated
periodically. At times it may be necessary for the analyst to modify a procedure when
working with a particular set of samples. Such modifications must be noted so that the
exact procedures that were used can be identified if questions arise at a later time. In
order to have a written record of all pertinent information relating to the analysis of all
samples, analysts should record their daily progress or results in a laboratory notebook or
other recoverable medium.

1.7.3 QC SAMPLES
Whenever possible, the project leader, as part of the external QC program, should
submit QC samples to the analyst along with routine samples in such a way that the
analyst does not know which of the samples are the QC samples. These external QC
samples, which usually include duplicate and blank samples, should test sample
collection and preparation as well as sample analysis whenever this is possible. In
addition, analysts are expected to run internal QC samples that will indicate to them
whether the analytical procedures are in control. Both the external and internal QC
samples should be prepared in such a way as to duplicate the chemical matrix of the
routine samples, insofar as this is practical. The QC samples that are routinely used
consist of five basic types: blank samples, replicate samples, reference materials, control
samples and "spiked" samples. Special definitions of these terms related to QA are
defined in the Appendix.
Blank samples are analyzed to give a measure of any contamination of the sample that
is occurring during the course of the collection, preparation or analysis. The analyst
commonly introduces blank samples into the sample stream. Often these are "reagent
blanks" that are prepared by starting with deionized water or with an empty sample
container and going through all of the normal procedures involved in the analysis; i.e.,
adding all of the reagents at the proper points. Whenever possible, the matrix of blank
samples should be the same as that of the samples being analyzed. The data for the
routine samples are usually corrected by subtracting from their measured values the value
of the blank. It must be remembered, however, that blank measurements of only the
analytical processes cannot be used to evaluate contamination that occurs during the
collection and preparation of the sample.
Replicate samples are obtained sometimes by repeating the collection as well as the
analysis of samples, but often only replicate aliquots of the same laboratory sample are
analyzed. Repeated sampling of a heterogeneous solid environmental material, such as
soil, may not yield truly replicate samples. If such materials are taken into solution before
being measured, replicate subsamples of the solution are often analyzed. Commonly,
individual samples are measured more than once, and for nondestructive techniques, such

as gamma-ray spectroscopy on whole samples, replicate measurements may involve

exactly the same sample, renumbered and resubmitted for analysis.
The third type of QC sample, the reference material or standard reference material, is
used primarily to calibrate the measurement method or apparatus.
The concentration of the control sample, or check standard, has an overall analytical
uncertainty that is known well enough for this control sample to be used in place of a
standard reference material to insure that the measurement method is in control. Such
control samples should have the same matrix and the same range of concentrations as do
the routine samples when this is possible.
Spiked samples, the fifth type of QC sample, are prepared by adding a known amount
of the constituent of interest to blank samples or to samples that have already been
analyzed, to provide samples with known concentrations. They may be used to estimate
chemical yields of analytical processes. Where the presence of other constituents in a
sample may be affecting the response of an instrument to the constituent of interest,
multiple spiking may be done. In this process, a series of samples are spiked by the
addition of increasing amounts of the constituent of interest. The measured values are
inspected to determine whether the instrument yielded a linear response to the increasing
concentrations, and whether the rate of increase of the response was that expected from
the differences in concentration between samples.
1.8 INSTRUMENTAL ANALYSES
1.8.1 INTRODUCTION
Virtually all measurements performed at EML require the use of an electronic instru-
ment to provide quantitative data. This is true of measurements of radiation, of radio-
active materials and of non-nuclear measurements. Thus, it is of crucial importance to
the quality of the work done at EML that all analysts be thoroughly familiar with the
proper procedures to be followed in calibrating, operating and caring for the instruments

that they must use. Usually this requires that the analyst understand at least the general
scientific principles that are the basis of the measurement.
1.8.2 INSTRUMENTS
To maximize the quality of the research data produced at EML, every effort is made
to keep abreast of the state of the art in instrumentation used in environmental research
and, where it is financially possible, to obtain the best available instruments. To keep
instruments performing efficiently, a schedule of preventive maintenance is followed
where appropriate. A record of instrument performance is maintained, and any modifi-
cations made in the instruments, whether permanently or for a particular project, are
documented. Any such modifications in any instrument must conform to the safety
standards and practices that are specified in the EML Safety Manual.
1.8.3 CALIBRATIONS
Provisions have been made for the periodic, quantitative assessment of the
performance of most instruments used by EML. For many instruments, calibration
standards are available. These standards are measured to obtain a curve that relates the
intensity of the signal from the instrument to the concentration of the substance or the
intensity of the property being measured. In other instances, this calibration consists of a
one point check using a single standard reference instrument, source, material or sample.
For the quality of the measurements to be optimized, the analyst must use the appropriate
standards, calibration procedures and frequency of calibration, and must keep a record of
the traceability of the standardization.
1.8.4 BACKGROUND EVALUATIONS
Commonly, instruments will provide a background signal that may be the result of
minor fluctuations in an electrical field. Also, phenomena or materials that produce
effects that are similar to the effects produced by the parameter or substance of interest

may occur in the environment of the detector and may produce a signal from the detector.
It is then necessary to measure this background signal so that the data from routine
measurements may be corrected for its presence. Even when the signal from the
measured parameter or samples is high relative to the background and the background
correction is small, the background signal should be measured regularly to be sure that it
has not changed and that the instrument has not become defective or contaminated. The
analyst must be sure that the procedures that are in use to measure background are
adequate in nature and are performed with the needed frequency. A record must be kept
of the measured backgrounds and this record should be analyzed statistically so that data
may be properly corrected, and also so that variations resulting from instrument problems
or from contamination can be detected and eliminated.

1.8.5 CHECKS OF THE STABILITY OF THE INSTRUMENT
The analyst must always be on guard against any instability of the instruments that are
being used to produce analytical data. All electronic components are subject to variations
because of changes in environmental factors, such as temperature and humidity, and to
degradation over time, and even new equipment may contain weak components. The
records of instrument calibrations and of background measurements, including control
charts, are the main data base used to judge the stability of an instrument. The occasional
remeasurement of a set of samples that showed a range of instrumental response may be
useful in providing another check on the performance of an instrument.
1.9 DATA REDUCTION, STORAGE, AND REPORTING
1.9.1 INTRODUCTION
The quality of the data reported by EML depends not only upon the care with
which sampling and analysis are performed, but also upon the care with which
calculations of the resulting data are performed, and upon the manner in which the data
are presented in reports. A key aspect of a QA program is maintaining records that
document every step of the process that leads to the data that ultimately are reported.
1.9.2 FIELD AND LABORATORY RECORDS
A measurement is useful if it is representative of the environmental material or

parameter that is under study. The field notes taken during measurement or sampling
normally provide a basis for judging the representativeness of a sample or a field
measurement. Similarly, the laboratory notes made during the analysis of a sample serve
as a basis for judging the quality of the analysis, indicating whether any problems arose
during the analytical procedures that might have adversely affected their outcome. For
this reason, every effort should be made during field measurement or sampling and during
sample preparation and analysis to record all aspects of the procedure that might
reasonably be expected to affect the outcome of the analysis. As a general rule, every
possibly relevant variable that is amenable to quantification should be recorded, even if

only by a check mark on a form. These records may be needed not only by the person
who is writing them, and not only for the time period during which they are being written,
but in many instances they may be needed by other persons and at some future time. It is
important, therefore, that the notes be both legible and clear in meaning, so that others
who read them will be able to reconstruct the events that are referred to.
It is often convenient to preserve electronically the data records from those

instruments which provide digital electronic output signals. When this is done, great care
must be taken to ensure that blocks of data are thoroughly annotated to identify the time
and location and all other important circumstances concerning the measurements. Often
the best way to do this is to organize blocks of data into files with distinctive file names,
and to keep a logbook with the supporting information for each file. Alternatively, if
electronic editing capabilities are available, comments can be entered into the data file
itself.
1.9.3 DATA REDUCTION AND STORAGE
When a new project is initiated, the project leader and appropriate Division Directors
should discuss the policies to be followed concerning the manner and length of time of
storage of data that will be produced during that project. There are types of data, such as
those related to possible legal actions involving the U.S. Government, that should be
stored indefinitely. When data are stored electronically, backup files must be prepared to
eliminate the possibility that the data may inadvertently be lost. When it begins to
become evident that a medium on which data are stored, such as a particular type of
magnetic disk or tape, is in danger of becoming obsolete, and there is thus a danger that
the data will become irretrievable, the data should be copied to a better medium.
Whenever data are to be transferred or stored, an appropriate control procedure should

be established to minimize the danger that human error will compromise the quality of
the data. Data reduction is normally accomplished electronically using computer
programs, both to avoid the drudgery of repeated "hand" calculations and to avoid
calculation errors. For small numbers of unusual measurements or samples, however,
hand calculations may be more efficient than writing a computer program of limited

applicability. When unfamiliar calculations are performed, whether by hand or by using

computer programs, care must be taken to be sure that the logic built into the calculation
is correct. Calculations are often checked by performing them on data that lead to a
known result.
1.9.4 DATA REPORTING
When data are reported, an estimate of their uncertainty must be given. Contained
below are the guidelines and definitions of the terms that are used at EML for reporting
the errors and uncertainties of data. The meaning of reported uncertainties must be
indicated either by stating exactly what they represent or by describing how they were
calculated, because a simple X ± Y statement may be interpreted in any one of a number
of ways. The statement of uncertainty should include estimates of all significant sources
of error involved, whether these result from the field measurement or sampling phase, the
analysis phase or the data reduction phase, if they will affect the final result within the
number of significant figures reported.
When data are reported, the reporting format must be commensurate with their
expected use. Tables of data allow the full presentation of values and of their estimated
uncertainties. Graphical presentation typically allows better visualization of the data.
With both tabular and graphical presentations, it is important to assume that nothing will
be immediately obvious to the reader, and the column headings or legends must include
all information that is necessary in order to understand the data that are presented.
When data are presented, it is important to report only the appropriate number of
significant figures. Usually the data should be carried to additional figures during
preliminary calculations, and then the final result should be rounded off to the proper
number of significant figures. When the tables are printed by a computer, the format that
is used may result in too many decimal places being reported for some samples. If this
happens, the table should be edited to limit all data to the appropriate number of figures.
One approach to determining the number of significant figures to be reported (Sanderson
et al., 1980 ) first determines the number of significant figures in the uncertainty, and
rounds the reported value to the same decimal place as the uncertainty. In this approach,
it is assumed that the rounded-off standard deviation reported should not differ from the

calculated value of the standard deviation by more than 20%. For example, if the
calculated standard deviation is 0.1635, it should be reported as 0.16, which differs from
the original by only 2%. Rounding off to 0.2 should be avoided because it differs from
the original by over 22%. The value of the measurement is then rounded such that its last
significant figure will be in the same decimal place as that of the error.
When data are presented in memoranda or internal EML reports, it is usually both
possible and desirable to include a complete discussion of the QA data that are pertinent
to the measurements. The information to be presented may include, in addition to the
uncertainties, various statistical tests and indications of analytical sensitivity, such as the
lower limit of detection (LLD), the instrumental detection limit (IDL), the method
detection limit (MDL), the limit of detection (LOD) (Currie, 1988 ), the specificity
(identification), and purity (absence of contaminant). The specificity and purity may be
estimated from the resolution of a signal or from the goodness of fit to known quantities,
such as energy, wavelength or rate of radioactive decay. Reporting the results for QC
samples, replicates and blank samples also provides important information about the
quality of data. If a discussion of QA cannot be included in a journal or symposium
publication, normally a separate, supporting QA report should be prepared.
Terms such as "below detection limits" should not be reported in place of the actual
analytical results obtained. Reporting results as "less than" some minimum detectable
level also results in some loss of statistical information, and may lead to erroneous
interpretations. When low activities or concentrations are measured, the actual results
obtained, including any negative values, normally should be reported along with the
associated overall uncertainties and the measures of analytical sensitivity that are
mentioned above. An interpretation of negative values can be included in the text. Waite
et al. (1980) and Gilbert and Kinnison (1981) have discussed techniques that may be
followed in averaging data sets that contain "less than" values.
A number of terms have been used by the scientific community to describe data
quality, but these terms are often given different meanings by different individuals.
The definitions that follow are the preferred usage for the purposes of this document and
have been taken from Croarkin (1985), Taylor (1985, 1987), and Taylor and Oppermann
(1986).

Error - The difference between the true value and the measured value of a quantity or
parameter.
Uncertainty - The range of values within which the true value is estimated to lie. It is a
best estimate of possible inaccuracy due to both random and systematic
errors.
Random Errors - Errors that vary in a nonreproducible way around the limitingmean.
These errors can be treated statistically by use of thelaws of
probability.
Systematic Errors - Errors that are reproducible and tend to bias a result in one
direction. Their causes can be assigned, at least in principle, and
they can have both constant and variable components. Generally,
these errors cannot be treated statistically.
A statement of uncertainty assigns credible limits to the reported value, stating to

what extent that value may differ from its true value. The uncertainty of a measured
value can be defined by a statistically determined confidence interval for the random error
and by an estimate of the bounds for systematic error; they should be stated separately.
When appropriate, they may also be combined into a single range to describe the overall
uncertainty. Since there are a variety of methods suggested in the literature for combining
random and systematic errors, the particular method used must be explicitly stated. One
accepted practice (Croarkin, 1985) is to combine in quadrature, systematic errors that are
known to be independent, to add linearly systematic errors that may not be independent,
and to combine systematic and random errors linearly. The confidence level chosen must
be stated whenever a confidence interval is reported.
Systematic errors which can be determined by calculation or by experiment should be

eliminated by an appropriate correction. Estimating the magnitude of some systematic
errors may require scientific judgement on the part of the experimenter. All significant
sources of error should be identified and reported.

1.10 MATERIALS AND PROCEDURES
1.10.1 INTRODUCTION
Certain materials and procedures must be used during routine analyses for the
successful performance of the EML QA program. These include standard instruments,
reference materials, and standard reference materials that are used to calibrate instruments
or to test the quality of measurements. They also include the QC procedures that are used
during the performance of routine analyses and data validation procedures that are used to
check the reasonableness of data. In addition, whenever it is possible, EML takes part in
intralaboratory comparisons, using more than one operator, instrument or technique, and
in interlaboratory comparisons with other government or private laboratories that are
making comparable measurements.
1.10.2 STANDARDS AND REFERENCE MATERIALS LIBRARY
EML divisions may maintain a library of standard and reference materials that are
needed for calibrating the analytical instruments in that division and for use in the internal
QC program in that division. Where possible, any sample matrix that is routinely
analyzed should be represented among these reference materials. The division staff
maintains records to document the history of acquisition and use of those materials. The
Division Director, or a designated subordinate, is responsible for keeping this library
complete and current.
1.10.3 DATA VALIDATION
For many analytical processes, control charts or other QC records are continually
updated to enable the operator to determine whether these processes are under control.
The operator enters data for blank samples, background measurements and standard or
control samples into the records, and onto the appropriate charts. The records and charts
are reviewed and evaluated to determine whether the process is in control and the data are
acceptable, or if corrective actions must be taken. Chemical yields, rates of

radioactive decay, energy calibrations, and other operating characteristics must be

evaluated routinely and unusual results must be flagged for immediate investigation.
1.10.4 INTRALABORATORY COMPARISONS
Whenever it is possible, attempts are made to verify that no systematic error is

introduced into the results of analytical procedures because of differences in techniques
among analysts, or because of differences in performance between supposedly equivalent
instruments. Analyses of selected samples are repeated using different analysts or
different instruments, and the results are compared to insure that variations are within the
expected range. In addition, where it is possible, measurements are made or samples are
analyzed using more than one technique, to be sure that the technique that is routinely in
use gives results that are consistent with results from other approved techniques.
1.10.5 INTERLABORATORY COMPARISONS
It is a policy at EML to take part in as many interlaboratory comparisons of

measurement and analytical techniques as is practical. The EML staff has taken the
initiative in organizing many such intercomparisons, as for example for
thermoluminescent detectors (TLDs) and radon detectors, and EML has participated in
many intercomparisons sponsored by other government or private laboratories or
organizations, as in the chemical analysis of precipitation. In addition, EML has provided
reference measurements for Department of Energy contractors in the analysis of
radionuclides in environmental samples.
REFERENCES
Croarkin, C.
"Measurement Assurance Programs Part II: Development and Implementation"
National Bureau of Standards Special Publication 676-II, April (1985)

Currie, L. A.
"Detection in Analytical Chemistry"
ACS Symposium Series 361, p. 17 (1988)
Gilbert, R. O. and R. R. Kinnison

"Statistical Methods for Estimating the Mean and Variance from Radionuclide Data
Sets Containing Negative, Unreported or Less-Than Values"
Health Physics, 40, 377-390 (1981)
Sanderson, C. G., L. K. Cohen, A. Goldin, A. N. Jarvis, L. Kanipe, C. Sill,

M. Trautman, and B. Kahn
"Quality Assurance for Environmental Monitoring Programs"
J. E. Watson (Chairman)
in: Upgrading Environmental Radiation Data, Health Physics Society Committee
Report HPSR-1, pp. 5-1 to 5-7, U.S. Environmental Protection Agency Report EPA
520/1-80-012 (1980)
Taylor, J. K.
"Handbook for SRM Users"
National Bureau of Standards Special Publication 260-100, September (1985)
Taylor, J. K.
Quality Assurance of Chemical Measurements
Lewis Publishers, Inc., Chelsea, MI 48118 (1987)
Taylor, J. K. and H. V. Oppermann

"Handbook for the Quality Assurance of Metrological Measurements"
National Bureau of Standards Handbook 145, November (1986)
Waite, D. A., D. H. Denham, J. E. Johnson, D. E. Michels and N. Turnage

"Statistical Methods for Environmental Radiation Data Interpretation"
J. E. Watson (Chairman)
in: Upgrading Environmental Radiation Data
Health Physics Society Committee Report HPSR-1, pp 7-1 to 7-19, U.S.
Environmental Protection Agency Report EPA 520/1-80-012 (1980)

1.11 APPENDIX
DEFINITIONS OF QA TERMS
USED IN THE CHEMICAL LABORATORY
Some terms concerning standards and calibration are defined by Taylor (1985):
A standard is "a substance or material, the properties of which are believed to be

known with sufficient accuracy to permit its use to evaluate the same property of another.
In chemical measurements, it often describes a solution or substance, commonly prepared
by the analyst, to establish a calibration curve or the analytical response function of an
instrument."
A primary standard is "a substance or artifact, the value of which can be accepted
(within specific limits) without question when used to establish the value of the same or
related property of another material."
A check standard is "in physical calibration, an artifact measured periodically, the

results of which typically are plotted on a control chart to evaluate the measurement
process."
Standardization, in analytical chemistry, is "the assignment of a compositional value

to one standard on the basis of another standard."
A standard reference material is "a reference material distributed and certified by the
National Institute of Standards and Technology."
A certified reference material (CRM) is "a reference material one or more of whose
property values are certified by a technically valid procedure, accompanied by or
traceable to a certificate or other documentation which is issued by a certifying body."
A certified value is "the value that appears in a certificate as the best estimate of the
value for a property of a reference material."

A reference material (RM) is "a material or substance one or more properties of which
are sufficiently well established to be used for the calibration of an apparatus, the
assessment of a measurement method, or for the assignment of values to materials."
Traceability is "the ability to trace the source of uncertainty of a measurement or a

measured value."
Calibration is the "comparison of a measurement standard or instrument with another

standard or instrument to report or eliminate by adjustment any variation (deviation) in
the accuracy of the item being compared."
A calibrant is "a substance used to calibrate or to establish the analytical response of a

measurement system."
Intercalibration is "the process, procedures, and activities used to ensure that the
several laboratories engaged in a monitoring program can produce compatible data.
When compatible data outputs are achieved and this situation is maintained, the
laboratories can be said to be intercalibrated."
A standard method is "a method (or procedure) of test developed by a standards-

writing organization, based on consensus opinion or other criteria, and often evaluated for
its reliability by a collaborative testing procedure."
A reference method is "a method which has been specified as capable, by virtue of
recognized accuracy, of providing primary reference data."
Two useful terms defined by the International Institute of Technology (IOLM, 1976) are:
Repeatability of measurements - "The closeness of the agreement between the results

of successive measurements of the same quantity carried out by the same method, by the
same observer, with the same measuring instruments, in the same laboratory, at quite
short intervals of time."

Reproducibility of measurements - "The closeness of the agreement between the

results of measurements of the same quantity, where the individual measurements are
made:
- by different methods, with different measuring instruments,
- by different observers, in different laboratories,
- after intervals of time that are quite long compared with the duration of a
single measurement, and
- under different normal conditions of use of the instruments employed."
"The term reproducibility is also used when some of the factors listed above are different
in the individual measurements; these factors should be specified in detail in each
particular case."
Some additional terms that are of use in discussing QA are defined by Taylor (1985):
A technique is "a physical or chemical principle utilized separately or in combination

with other techniques to determine the composition (analysis) of materials."
A method is "an assemblage of measurement techniques and the order in which they
are used."
A procedure is "a set of systematic instructions for using a method of measurement or

of sampling or of the steps or operations associated with such."
A protocol is "a procedure specified to be used when performing a measurement or

related operation, as a condition to obtain results that could be acceptable to the
specifier."
An analyte is "the specific component measured in a chemical analysis; also called

analate."
A sample is "a portion of a population or lot. It may consist of an individual or

groups of individuals. It may refer to objects, materials, or to measurements, conceivable
as part of a larger group that could have been considered."

An increment is "an individual portion of material collected by a single operation of a

sampling device, from parts of a lot separated in time or space. Increments may be either
tested individually or combined (composited) and tested as a unit."
A composite sample is "a sample composed of two or more increments selected to

represent a population of interest."
A blind sample is "a sample submitted for analysis whose composition is known to
the submitter but unknown to the analyst. A blind sample thus is one way to test
proficiency of a measurement process."1
Double blind refers to "a sample, known by the submitter but submitted to an analyst
in such a way that neither its composition nor its identification as a check sample are
known to the latter."*
A blank is "the measured value obtained when a specified component of a sample is

not present during the measurement. In such a case, the measured value/signal for the
component is believed to be due to artifacts, hence should be deducted from a measured
value to give a net value due to the component contained in a sample. The blank
measurement must be made so that the correction process is valid."2
A split sample is "a replicate portion or subsample of a total sample obtained in such
a manner that it is not believed to differ significantly from other portions of the same
sample."
A duplicate sample is "a second sample randomly selected from a population of

interest (see also split sample) to assist in the evaluation of sample variance."
A replicate is "a counterpart of another, usually referring to an analytical sample or a

measurement. It is the general case for which duplicate is the special case consisting of
two samples or measurements."
1
These definitions of "blind sample" and "double blind" are applicable to certain uses in quality
assurance, but these terms are also commonly used with other, somewhat different meanings.
2
This definition of "blank" is applicable to certain uses in QA, but this term is also
commonly used with other, somewhat different meanings.

A duplicate measurement is "a second measurement made on the same (or identical)
sample of material to assist in the evaluation of measurement variance."
A control sample is "a material of known composition that is analyzed concurrently

with test samples to evaluate a measurement process (see also Check Standard)."
The limiting mean is "the value approached by the average as the number of
measurements, made by a stable measurement process, increases indefinitely."
An outlier is "a value which appears to deviate markedly from that for other members
of the sample in which it occurs."
The coefficient of variation is "the standard deviation divided by the value of the
parameter measured."
The relative standard deviation is "the coefficient of variation, expressed as a

percentage."
Validation is "the process by which a sample, measurement method, or a piece of data

is deemed to be useful for a specific purpose."
A control chart is "a graphical plot of test results with respect to time or sequence of
measurement together with limits within which they are expected to lie when the system
is in a state of statistical control."
The control limits are "the limits shown on a control chart beyond which it is highly
improbable that a point could lie while the system remains in a state of statistical
control."
The warning limits are "the limits shown on a control chart within which most of the
test results are expected to lie (within a 95% probability) while the system is in a state of
statistical control."
The terms error, uncertainty, random errors and systematic errors, all of which
concern data quality, are defined in Section 1.9.4, Data Reporting.

REFERENCES TO DEFINITIONS
International Organization of Legal Metrology

"Vocabulary of Legal Metrology: Fundamental Terms"
Paris, France (1976)
Taylor, J. K.
"Handbook for SRM Users"
National Bureau of Standards Special Publication 260-100, September (1985)

Section 2,
2.1,
Vol.
Vol.
I I Rev. 0
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U.S. Department Laboratory 2-i
Table of Contents, Vol. I Rev. 0
Page
6DPSOLQJ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1-1
2.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1-1
2.2 Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-1
2.2.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-1

2.2.2 Aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-1
2.2.2.1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-1
2.2.2.2
Total Particle Collections . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-3
2.2.2.3
Dichotomous Sampler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-7
2.2.2.4
High Volume Cascade Impactors . . . . . . . . . . . . . . . . . . . . . 2.2-8
2.2.2.5
Moudi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-13
2.2.2.6
Diffusion Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-15
2.2.2.7
Graded Screen Array . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-22
2.2.2.8
Mathematical Analysis of Particle Size Data . . . . . . . . . . . . 2.2-25
2.2.3 Radon and Thoron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-33
2.2.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-33
2.2.3.2 Grab Sampling for Radon . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-34
2.2.3.3 Two-Filter Tube Sampling for Radon and Thoron . . . . . . . 2.2-36
2.2.3.4 Continuous Radon Monitoring . . . . . . . . . . . . . . . . . . . . . . . 2.2-39
2.2.3.5 Integrating Radon Monitors . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-40
2.2.3.6 Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-43
2.2.3.7 220Rn and 222Rn in Soil Gas . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-46
2.2.4 Radon and Thoron Progeny . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-50
2.2.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-50
2.2.4.2 Sampling Train . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-50
2.2.4.3 Alpha Particle Counting System . . . . . . . . . . . . . . . . . . . . . 2.2-52
2.2.4.4 Modified Kusnetz Method . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-53
2.2.4.5 Modified Tsivoglou Method . . . . . . . . . . . . . . . . . . . . . . . . 2.2-55
2.2.4.6 Raabe-Wrenn Least-Squares Method . . . . . . . . . . . . . . . . . . 2.2-58
2.2.5 Atmospheric Tracing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-66

U.S. Department Laboratory 2 - ii
Page
2.2.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2-66
2.2.5.2 The Programmable Atmospheric Tracer Sampler . . . . . . . . 2.2-67
2.2.5.3 Adsorbent Tube Bake-Out Procedure . . . . . . . . . . . . . . . . . 2.2-68
2.2.5.4 Deployment, Sampling, and Retrieval . . . . . . . . . . . . . . . . . 2.2-70
2.3 Atmospheric Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-1
2.3.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-1

2.3.2 Pot Collector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-1
2.3.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-1
2.3.2.2 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-2
2.3.2.3 Deployment, Sampling, and Retrieval . . . . . . . . . . . . . . . . . . 2.3-2
2.3.3 Ion Exchange Fallout Collector . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-3
2.3.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-3
2.3.3.2 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-3
2.3.3.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-4
2.3.3.4 Collector Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-4
2.3.3.5 Site Operator Instructions . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-4
2.3.4 Wet/Dry Deposition Collector . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-6
2.3.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-6
2.3.4.2 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-6
2.3.4.3 Sampling and Deployment . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-7
2.4 Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-1
2.4.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-1

2.4.2 Sampling Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-1
2.4.2.1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-1
2.4.2.2
Deposition Inventories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-2
2.4.2.3
Deposition Increment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-4
2.4.2.4
Operational or Accidental Releases . . . . . . . . . . . . . . . . . . . . 2.4-4
2.4.2.5
Agricultural Availability . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-5
2.4.2.6
Resuspension Availability . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-6
2.4.3 Recommended Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-6

U.S. Department Laboratory 2 - iii
Page
2.4.3.1
Core Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-7
2.4.3.2
Template Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-10
2.4.3.3
Trench Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-11
2.4.3.4
Nonhomogeneous Terrain Method . . . . . . . . . . . . . . . . . . . . 2.4-13
2.4.4 Sample Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-15
2.4.4.1 Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-16
2.4.4.2 Homogenizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-17
2.4.4.3 Rapid Preparation Method . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-17
2.4.4.4 Processing Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-18
2.4.5 Reproducibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-19
2.4.5.1 Representativeness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-19
2.4.5.2 Aliquoting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-20
2.4.5.3 Analytical Accuracy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4-20
2.5 Sediment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-1
2.5.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-1

2.5.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-1
2.5.3 Equipment Design and Application . . . . . . . . . . . . . . . . . . . . . . . 2.5-2
2.5.4 Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-3
2.5.4.1 General Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-3
2.5.4.2 Bathymetric Survey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-4
2.5.4.3 Sediment Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-4
2.5.4.4 Sediment Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-5
2.6 Uranium and Radium in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6-1
2.6.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6-1

2.6.2 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6-1
2.6.3 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6-1
2.7 Food (see Volume II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7-1

U.S. Department Laboratory 2 - iv
Section 2.1, Vol. I Rev. 0
6$03/,1*
2.1 OVERVIEW
The purpose of environmental sampling and analysis is to obtain data that describe a
particular site at a specific point in time from which an evaluation can be made as a basis
for possible action. In this process, the collection of valid samples is the vital first step.
Sampling should be done with the same care as the analysis, and both should be done
with a rigor that is appropriate for the project at hand. In order for the data to be mea-
ningful, sampling must be carried out with a clear purpose and with an understanding of
the problem to be solved and the physical conditions that exist.
At EML, environmental sampling is carried out for purposes such as inventorying a

pollutant at a specific point in time, calculating the pollutant transfer coefficients, and
reconstructing deposition chronologies. Through these long-term studies, experience has
been gained in sampling radioactive fallout, air particulates and gases, and total and rate
of deposition. In this section, we describe the procedures developed by EML for
environmental sampling. The corresponding analytical procedures are presented later in
this Manual.
General guidance on collecting valid samples is given in Section 1.6.2. Unlike

chemical or radiometric analyses, it is not possible to set down step-by-step procedures
for sampling. For example, a variety of samples may be required for the purpose of
establishing relationships between concentrations in different matrices to further the
understanding of dynamic processes. Also, the concentration of a particular pollutant in
an environmental matrix will change with time and location.
Usually, the crucial decisions in planning a sampling program are how many sites
should be sampled and how often they should be sampled. These decisions can only be
made based on a knowledge of the degree of variability due to these two factors (see
Section 1.6.2). Most sampling programs require exploratory sampling so that the varia-
bility with time and location can be assessed in comparison with the required uncertainty.
Experience has shown that statistical approaches based on these exploratory samples

U.S. Department of Energy 2.1 - 1
usually lead to the taking of a smaller number of samples than would have otherwise been
predicted. Another important consideration is that the number of samples must be
consistent with the available analytical facilities.
Many times, the samples received in the laboratory may be representative of the
particular conditions to be evaluated, but are not in the proper physical form for analysis.
The samples may require reduction in size, drying or some form of homogenizing before
subsamples can be taken for analysis. Some general considerations concerning sample
preparation are discussed in Section 1.6.3 of this Manual.
The philosophy at EML is usually to collect a sufficient amount of sample so that

there is not only enough to measure the constituent of interest, but also enough for
reanalysis at a later time (see Section 1.6.3). Storage of samples for later analyses
requires judgment in order to avoid loss of constituents to be measured or to avoid
undesirable decomposition. EML maintains an extensive library of samples associated
with its research programs, in some cases going back over 30 years (Klusek, 1989).
REFERENCE
Klusek, C. S.
"The EML Soil Inventory and Archive"
U.S. Department of Energy Report EML-519 (1989)

Section 2.2, Vol. 1 Rev. 0
2.2 AIR
Contact Person(s) : Alfred Cavallo and Raymond J. Lagomarsino
2.2.1 SCOPE
Described in this section are the equipment and procedures used at EML in sampling
for trace amounts of certain gases, liquids or solids dispersed in air. For gases, this
involves either "whole air" samplers, or samplers which selectively adsorb the gas of
interest. For the liquids and solids (aerosols), the techniques involve separating the
particles from air by means of filtration or impaction.
In situ methods in which the sampling and analysis are one combined operation are
not described as they are not commonly used at EML. Further information can be found
in Air Sampling Instruments for Evaluation of Atmospheric Contaminants, a handbook
published by the American Conference of Government Industrial Hygienists (ACGIH,
1989). This handbook, which is updated every 5 to 6 years, includes descriptions of
practically every commercially available instrument for sampling trace gases and
aerosols. It also has concise theory sections covering basic physics and experimental
design pertinent to air sampling.
The locales for sampling in EML programs range from indoor (residential or
occupational) to outdoor (surface to upper troposphere).
2.2.2 AEROSOLS
2.2.2.1
INTRODUCTION
Many of EML's research programs require that samples be taken of aerosols, defined
as "a system of colloidal particles dispersed in a gas". The suspending gas is normally
indoor or outdoor air. Smoke and mist are common examples of aerosols, but frequently

the particles are so small that the aerosol cannot be detected by eye. Typically,
environmental aerosols contain a broad mixture of chemical species, both liquid and
solid, including some radioactive materials.
The sampling of aerosols involves a number of complications that are not present
when sampling for environmental gases. Therefore, specialized training or experience is
highly desirable for personnel responsible for aerosol sampling. Some universities —
such as New York University (Institute of Environmental Medicine) — conduct annual or
semiannual one-semester courses in aerosol science; inquiries can be made about auditing
such courses. Also, the University of Minnesota offers a 4-day short course each
summer.
Excellent books are now available which consolidate the advances in aerosol science
over the past 25 years. Two of the best are the textbook by Hinds (1982) and the
handbook by the ACGIH (1989), already mentioned.
There are two broad categories of aerosol sampling methods: integral and size-
selective. In the former, the goal is to collect a single sample in which the sizes and types
of collected particles accurately represent those in the air. The integral samplers
commonly used at EML are described in Sections 2.2.2.2 and 2.2.4. Size-selective
samplers are designed to provide information on particle size as well as particle amount.
Sections 2.2.2.3 through 2.2.2.8 describe the size-selective samplers commonly used at
EML.
Among the size-selective samplers, the high volume cascade impactor and the
diffusion battery (when supplemented with the appropriate chemical analysis) produce
sufficient data to generate complete particle size spectra for the chemical species of
interest. Although shortcuts are possible, the proper way to generate these spectra is to
apply a suitable mathematical technique to "unfold" or "deconvolute" the data (see
Section 2.2.2.8).
The modern method of presenting aerosol size spectrum data is the "generalized
histogram" described in Chapter E of ACGIH (1989).

REFERENCES
Hinds, W. C.
"Aerosol Technology: Properties, Behavior and Measurement of Air borne
Particles"
Wiley-Interscience, New York (1982)
Air Sampling Instruments for Evaluation of Atmospheric Contaminants

Hering, S. (Editor)
American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH,
Seventh Edition (1989)
2.2.2.2
TOTAL PARTICLE COLLECTIONS
A. Introduction.
The procedures discussed in this section are limited to the specific requirements of
programs currently conducted at EML and may not be applicable to other studies that
require the total collection of air particles.
Since January 1963, EML has conducted the Surface Air Sampling Program (SASP).
In 1987, the Remote Atmospheric Measurements Program (RAMP) was initiated as an
extension and modification of SASP. The primary objectives of SASP/ RAMP are to
identify and study the temporal and spatial distribution of anthropogenic and natural
radionuclides in the lower troposphere. These objectives are achieved by filtration of
large volumes of air to concentrate the radionuclides in the aerosol prior to sample
analyses. The sampling procedures used in SASP/RAMP would not be appropriate if one
requires particle size analyses or particle specific activity distributions. The filters used in
these programs also will not collect uncharged, unattached radioactive gas molecules.
To sample large volumes of air and obtain total particle collection, it is necessary to
use an appropriate filter material and an air mover. In SASP/RAMP, the air mover must
be capable of continual operation at high flow rates under harsh environmental
conditions. To calculate air concentrations of radionuclides, it is necessary to accurately
determine the total volume of the air which has been sampled.

B. Filter material for total particle collections.
The criteria for filter selection are good collection efficiency for submicron particles
at the range of face velocities used, high particle and mass loading capacity, low-flow
resistance, low cost, high mechanical strength, low-background activity, compress-
ibility, low-ash content, solubility in organic solvents, non-hygroscopicity, temperature
stability, and availability in a variety of sizes and in large quantities. In the selection of a
filter material, a compromise must be made among the above criteria that best satisfies
the sampling requirements. An excellent review of air filter material used to monitor
radioactivity was published by Lockhart et al. (1964). Lippmann (1989a) also provides
information on the selection of filter materials for sampling aerosols by filtration.
Two filter sizes are presently used in SASP/RAMP, a 20.32 cm circle and a
20.32 cm × 25.40 cm rectangle. The polypropylene fiber filter, Dynaweb Grade
DW7301L (see Specification 7.17) is used at all SASP and RAMP sites. The filter is
composed of a 100% polypropylene web that is 100% binderless. Three layers of this
web are collated and sandwiched between two sheets of a protective DuPont Reeme
(100% polyester) scrim. The top scrim is removed prior to sampling at RAMP sites
because after their return to EML for analysis these samples are compressed into pellets
and the scrim hinders compression. At all other sites, the filter can be used during
sampling with both top and bottom scrim in place.
C. Air movers.
A large variety of air movers are commercially available and have been reviewed by
Rubow and Furtado (1989).
Many factors must be considered when selecting an air mover. Such factors as
portability, power requirements, maximum operational flow rate/temperature/pressure,
cost, durability, and maintenance must be considered in the selection of an air mover. It is
also important that the air mover itself is not a source of contamination in any study.
The major factors that were considered in the selection of an air mover for the SASP
sites were durability, low maintenance, and a flow rate of ~ 1 m 3 min -1 [288 oK, 101.3 kPa

(760 mm Hg)] at pressure drops across the filter ranging from ~ 5 kPa to ~ 20 kPa (20-80
in water).
Two air mover systems are currently used in SASP/RAMP. The SASP sites are
equipped with a Roots Blower (see Specification 7.18) connected to a 1 HP electric motor
(see Specifications 7.18) by a fan belt. The RAMP sites are equipped with a Fuji ring
compressor (see Specification 7.18) in which the air mover is directly connected to a 0.5
HP electric motor. The Roots system must be enclosed in a louvered shelter to protect
the pump from direct exposure to precipitation. The Roots system is frequently mounted
on a 1-m high metal stand. The Fuji system is enclosed in a custom manufactured
aluminum container. The Roots system is heavier than the Fuji system and may be more
durable for continual operation in harsh environments. The Roots system exhausts some
oil vapors which may be a contaminant in certain studies. The Roots system is designed
for 20.32 cm round filters, while the Fuji system is designed for 20.32 cm × 25.40 cm
rectangular filters.
D. Flow calibration and sample volume determination.
To calculate the concentrations of radionuclides in the lower troposphere or

concentrations of any air pollutant collected and concentrated by filtration, it is necessary
to accurately determine the total volume of air sampled.
Generally, a parameter of the air mover can be related to flow. If the mean flow
during a collection period can be determined, the total volume of air sampled can be cal-
culated. Accurate flow measurements and the total integrated sample volume of air can
be obtained using a mass flow meter and a totalizer. This direct technique of air flow
measurement becomes impractical at remote field locations due to cost and exposure of
the flow meter to harsh environments. Other procedures for the measurement of air flow
in sampling systems are reviewed by Lippmann (1989b).
We have determined that the best technique to measure flow, at sites equipped with
Roots systems, is to determine an empirical relationship between the Roots blower inlet
pressure and the flow through the upstream filter. An orifice meter was manufactured at
EML to derive this relationship. The orifice meter has been calibrated for flow using
secondary flow measurement devices that are traceable to a primary standard volume

meter. All Roots systems are calibrated using this orifice meter prior to field installation.
Periodic calibrations are conducted at the field sites.
During sampling, the pressure at the Roots blower inlet is measured using a Magne-
helic gauge. The initial and final pressure values are averaged. The average inlet
pressure is then used in the previously described empirical relationship to calculate the
average flow. This average flow is multiplied by the collection interval to obtain the total
volume sampled. The total volume sampled is adjusted to a pressure of 101.3 kPa
(760 mm Hg) and a temperature of 288 oK.
At sites equipped with a Fuji system, the flow is determined using an empirical
relationship between the pressure differential across a fixed orifice located in the blower
exhaust. The initial and final pressure values are used to calculate a mean flow and a
total sample volume as previously described. The relationship between flow and the
pressure differential across the fixed orifice plate and in the Fuji flow system was
determined using a Hastings Laminar flow element traceable to a primary standard
volume meter.
REFERENCES
Lippmann, M.
"Sampling Aerosols by Filtration"
Hering, S. (Technical Editor)
in: Air Sampling Instruments, 7th Edition, American Conference of Governmental
Industrial Hygienists, Cincinnati, Ohio, pp. 305-336 (1989a)
Lippmann, M.
"Calibration of Air Sampling Instruments"
Hering, S. (Technical Editor)
Industrial Hygienists, Cincinnati, Ohio, pp. 73-100 (1989b)

Lockhart, L., R. Patterson and W. Anderson

"Characteristics of Air Filter Media Used for Monitoring Airborne Radioactivity"
Naval Research Laboratory Report NRL-6054, June (1964)
Rubow, K. and V. Furtado

"Air Moves and Samplers"
Hering, S. (Editor)
Industrial Hygienists, Cincinnati, Ohio, pp. 241-274 (1989)
2.2.2.3
DICHOTOMOUS SAMPLER
A Sierra Model 245 automatic dichotomous sampler is used to study the "inhalable"
(<10 µm) particles in ambient air. The original commercial design was developed and
sold by Sierra Instruments Inc., but is now sold by Andersen Instruments, Inc., Sierra
Anderson Division, 4801 Fulton Industrial Blvd., Atlanta, GA 30336.
The dichotomous sampler is capable of separating the particles <10 µm (determined

by the aerosol 10 µm inlet cut-off size) into two fractions. By means of virtual impaction,
the sampled particles are separated into two fractions, the fine fraction, <2.5 µm, and the
coarse fraction between 2.5 and 10 µm. This technique has the added advantage of
eliminating problems associated with particle bounce and re-entrainment that are
sometimes experienced in cascade impactor sampling.
The particles are collected on Teflon membrane filters which are ideal for gravimetric
analyses of the fine, coarse, and inhalable (sum of fine and coarse) fractions, and for
chemical analyses by X-ray fluorescence or other high-resolution chemical techniques.
The experimental procedures used at EML are defined in the instrument manual along
with literature references on the development and application of the sampler for studies of
PM-10 compliance monitoring, source discrimination, fine-particle monitoring, and
visibility monitoring.

2.2.2.4
HIGH VOLUME CASCADE IMPACTORS
A. Introduction.
A description of the Sierra Model 235 multistage cascade impactor, which is used to
measure the particle size distribution of both indoor and outdoor aerosols, is presented
here. The original design was developed and sold by Sierra Instruments, Inc., but now is
sold by Andersen Instruments, Inc., Sierra Anderson Division, 4801 Fulton Industrial
Blvd., Atlanta, GA 30336. A number of articles are available in the literature that deal
with both the theoretical and experimental development of inertial impactors (Marple et
al., 1973, 1974; Marple and Willeke, 1979).
At EML, this impactor is used for research studies and is not commonly used for
long-term sampling projects. The methods described herein are used for 1-5 day
sampling periods, and the units are checked on a daily basis.
B. Operating conditions.
The sampler is capable of sampling at flow rates ranging from 0.56 m 3 min -1 to
1.68 m3 min-1. The flow is regulated by a constant flow controller that automatically
adjusts to any flow rate change caused by loading conditions or motor variances. In the
majority of our outdoor sampling efforts, the unit is operated at a flow rate of 0.85 m 3
min-1 (30 cfm) to prevent overloading and to assure that the flow rate remains constant
during the sampling interval.
Configuration. The unit is housed in a standard high-volume sampling shelter

without a size selective inlet. Under some conditions a 10 µm or 15 µm size-selective
inlet is used. The impaction substrate is slotted Whatman No. 41 filter paper treated with
light mineral oil (Fisher Scientific, 50 Faden Road, Springfield, NJ 07081). The oiled
filter minimizes particle rebound and reentrainment, which has been found during
previous impactor evaluations to bias impactor size distribution measurements toward
smaller sizes (Knuth, 1979a). This method of oil treating the filter is not compatible with
mass determination by weighing methods. All of our analyses are done by chemical or
radiochemical procedures.

General maintenance. The impactor plates are washed with alcohol and the slots are
cleaned using a cotton swab or soft cloth. Care must be taken so that the integrity of the
slot is not altered by using any cleaning material that may damage the slot spacing or
edges in any manner. The plates are dried with compressed air and the slots are visibly
examined to assure that no foreign material remains in the slot. The impactor plates
should be numbered 1-5 in a corresponding corner of the plates, starting with the largest
slotted plate numbered 1 to the smallest plate numbered 5.
Loading procedures. The loading and unloading of the impactor assembly should be
done in a clean environment (clean room or clean bench). The loaded unit can then be
transported to the sampling area and installed on site. In handling the filters, reasonable
care should be taken to minimize contamination of the sample. Filters should be handled
at the extreme corners, and latex gloves or forceps should be used during the following
loading procedures.
1. Soak the total number of filter impaction substrates needed for the number of
impactors being loaded in mineral oil using a Pyrex or comparable dish. Note: A few
extra oiled filters may be required for blank analysis values.
2. After the filters are completely wetted, they are removed from the oil and allowed to
drip until all excess oil has run off.
3. Starting with the slotted base plate, place a mineral oil wetted filter on the plate
assuring that the paper is centered and all slots are open. Using a glass rod, assure
that the paper is in contact with the plate and no air bubbles are present.
4. Carefully place the slotted plate, #5, on top of the filter. Assure that it is flat, and that
it secures the impaction filter #5 beneath it to the base plate. At this time, the filter
paper should be visible through the slots. If not, remove plate #5 and reposition it 180
degrees. Check again.
5. Continue placing filters and plates #4 to #1 as described in Step 4 above.
6. After positioning slotted plate #1, tighten the two screws that secure the five plates
sandwiched to the base plate. At this time, wipe any excess oil from the sides of the

plate assembly. Note: If there is an extreme amount of oil seeping through the edges
of the plates, start over at Step 1 allowing a longer time for the filters to drip dry.
7. The extra wetted filter is carefully folded over on itself once or twice and placed in a
polyethylene bag. Attach an appropriate identification label to the bag.
8. The loaded impactor assembly is taken to the sampling site and placed in position
over an appropriate back-up filter. For our work, a suitable back-up filter is
determined dependent on the analytical procedure to be used. Back-up filters which
have been used for different applications are glass fiber, Microsorban, Microdon, and
Whatman No. 41.
9. Tighten wing nut assemblies on four corners of the base plate to secure impactor
assembly to back-up filter holder.
Sampling procedure.
1. Start unit and adjust the in-line orifice reading to the desired setting. This setting
corresponds to the flow rate determined from a calibration curve of the orifice.
Note: A top loading calibrated orifice can be used to verify flow rate in the field.
2. Record all pertinent flow and time information required. Note: If a number of runs
will be required for the experiment, a data sheet form should be developed and used
for recording data.
3. Whenever possible, the unit should be visibly checked during the sampling period. If
an in-line orifice is being used, the manometer reading can be read and recorded at
any time during the exposure period without interrupting the sampling procedure.
4. At the end of the sampling period, record all data and if possible recheck the flow rate
with the top loading orifice.

Sample recovery.
1. Carefully remove the impactor assembly from above the back-up filter. Immediately
fold the back-up filter over on itself, soiled side in, twice if required, and place in
prelabeled polyethylene bag.
2. Take the impactor assembly to a clean environment and begin the disassembly
procedure by carefully removing the top plate, #1, folding the soiled filter over on
itself, soiled side in, and placing it in a prelabeled envelope or polyethylene bag.
Note: We have found that polyethylene bags are better than glassine envelopes for
storing the oiled filters prior to analysis. A glass rod can be used for creasing the
oiled filter when folding.
3. Place the five oiled impaction filter polyethylene bags into a larger polyethylene bag,
appropriately labelled, along with the back-up filter and the appropriate blank oiled
filter. This is the extra-oiled impaction filter prepared prior to loading the impactor.
Note: Although you can usually determine the stage the oiled filter came from by
visual determination of the width of the deposit on the filter, care should be taken
when removing the filters from the impactor to assure that the filter is correctly
identified when placed in the polyethylene bag.
4. The impactor plates can be placed in an alcohol bath to remove any excess oil from
the plates prior to cleaning for assembly. Compressed air can be used to clean slots if
necessary.
Data analysis. Various methods of describing the particle size distribution of

sampled aerosol have been used through the years for impactor data. In order to use any
one or more of these methods it is necessary to determine the amount of material
collected on each of the impactor stages and back-up filter. At EML, this is usually done
by measuring the radioactivity or by chemical analyses.
Two of the most used methods of describing the distribution derived from impactor
data are histograms and cumulative plots (Knutson and Lioy, 1989). At EML we use a
computer program, UNFOLD.PS, to construct smooth particle size spectra from the

impactor data. To do this, construct an impactor efficiency file from the curves given in
Figure 7 of Knuth (1979b) per the instructions given in UNFOLD.PS, then follow the
steps in Section 2.2.2.8, C6.
REFERENCES
Knuth, R. H.
"Comments on Inertial Impactor Calibration and Use"
in: Aerosol Measurements, University of Florida, Gainesville, pp. 108-116 (1979a)
Knuth, R. H.
"Calibration of a Modified Sierra Model 235 Slotted Cascade Impactor"
USDOE Report EML-360 (1979b)
Knutson, E. O. and P. J. Lioy

"Measurements and Presentation of Aerosol Size Distributions"
Lioy, P. J. and M. J. Y. Lioy (Editors)
in: Air Sampling Instruments for Evaluation of Atmospheric Contaminants
American Conference of Governmental Industrial Hygienists, Cincinnati, OH,
pp. E1-E12, Seventh Edition (1989)
Marple, V. A. and K. Willeke

"Inertial Impactors"
D. A. Lundgren et al. (Editors)
in: Aerosol Measurements
University of Florida, Gainesville, pp. 90-107 (1979)
Marple, V. A., B. Y. H. Liu, and K. T. Whitby

"Fluid Mechanics of the Laminar Flow Aerosol Impactor"
J. Aerosol Sci., 5, 1-16 (1973)
Marple, V. A., B. Y. H. Liu, and K. T. Whitby

"On the Flow Fields of Inertial Impactors"
J. Fluids Eng., 96, 394-400 (1974)

2.2.2.5
MOUDI
A. Introduction.
Procedures are presented for using the micro-orifice uniform deposit impactor
(MOUDI) in determining the particle size distribution of the decay products of radon
and/or thoron gas. The MOUDI covers the size range of 50-5000 nm and complements
the capabilities of the diffusion batteries (Section 2.2.2.6), which cover a range of 5-500
nm. To sample a broader size range, 0.5-5000 nm, the MOUDI may be used in parallel
with the graded screen array, described in Section 2.2.2.7.
The MOUDI consists of two basic assemblies -- the cascade impactor itself, and its
housing. The cascade impactor consists of an air inlet, eight impaction stages, and a
backup filter, which is located in the base of the impactor. Each stage contains a
removable impact plate for the stage above and a nozzle plate for the stage below.
Contained in the housing is a valve for controlling the flow through the impactor, two
pressure gauges to monitor the flow, and a mechanism for rotating the impaction stages.
The table below gives the main characteristics of the MOUDI. Further information
about the MOUDI can be found in Marple (1991).

CHARACTERISTICS OF THE MOUDI

(Manufacturer's data)
No. of Pressure
Stage Cut Size, nm Nozzles Reading
3A 3200 10
4A 1800 20
5A 1000 40 1250 Pa,
upper gauge
6A 560 80
7A 290 900
8A 173 900
B 97 2000
BB 45 2000 45 kPa,
lower gauge
C. Sampling procedure.
Preparation. Assemble the MOUDI for sampling by first inserting a filter in the
backup filter holder at the base of the MOUDI, then by placing clean impaction plates on
each stage starting from bottom to top of the impactor. Coating the plates with silicone
spray (to prevent bounce) is necessary only in dry, dusty conditions. Finally, place the
cover onto the upper stage.
Checking air flow rate. Start the pump and adjust the pressure reading to 1250 Pa
for the upper gauge and 45 kPa for the lower one. If this cannot be accomplished, stop
the pump and disassemble the MOUDI. Reassemble it after checking each stage to see if
the gaskets are properly placed and greased. Then repeat the air flow test. If the pressure
readings are satisfactory, proceed to sampling.
Caution: After testing the air flow rate, always check the backup filter, which is
easily broken by a reverse airflow when the sampling pump is shut off.
Sampling. For radon progeny, the sampling time is usually 5 min, but 10 to

20 min is also used for low radon concentrations. For measurements of thoron progeny, a
sampling period of 10 or more hours might be needed. In this case, use the rotating
feature by turning on the switch at the base of the MOUDI. Use a stopwatch to time the
sampling and keep the watch running to time the interval between sampling and counting.
Alpha counting. After sampling, disassemble the MOUDI starting with the upper
stage and working downward to the base. Transfer the impaction plates into the alpha
counters, being careful to keep them in order. Alpha count the plates simultaneously and
analyze for activity using methods described in Procedure 2.2.4.6.
Generally, 10 alpha counters are needed. To complete sample transfer within

2 min, two experienced operators are needed.
Calculation of particle size. Follow the procedures given in Procedure 2.2.2.8,

Sections C.6 or C.7. Use the calibration curves supplied by the manufacturer.
REFERENCES
Marple, V. A., Rubow, K. L. and Behm, S. M.

"A Microorifice Uniform Deposit Impactor (MOUDI): Description, Calibration, and
Use"
Aerosol Science and Technology, 14, 434-446 (1991)
2.2.2.6
DIFFUSION BATTERIES
A. Introduction.
We describe in this section EML's diffusion batteries (DB), and their use in measuring
aerosol particle size distributions. There are five EML designs covering two main
applications:

No. of Typical
channels flow rate Typical
Type of diffusion battery or stages (L min -1) application
Multichannel disk-type 5 3 Radon progeny

Multistage disk-type 12 4 Aitken particles
Multichannel screen-type 5 25 Radon progeny
Multistage screen-type 11 4 Aitken particles
Multichannel carbon-type 5 283 Radon progeny
The multichannel designs, also called parallel diffusion batteries, are those in which
air is drawn simultaneously through side-by-side samplers. Thus, all aerosol samples
needed to construct the particle size distribution are collected simultaneously. In the
multistage design, also called series, the aerosol samples are collected sequentially. The
term Aitken particles refers to outdoor atmospheric particles with diameters < 0.2 µm.
(However, diffusion batteries can be used for somewhat larger particles, either indoors or
outdoors.) The term radon progeny particles refers to those few particles, typically 1 in
106, which carry short-lived radon progeny atoms. The batteries can also be used for
other species, such as sulfate in airborne particles.
The type most commonly used in recent years is the multichannel screen battery, so
this will be used for illustration in the discussion to follow. Consult Knutson and
Sinclair (1979), Sinclair (1972), Sinclair and Hoopes (1975), and Sinclair et al. (1978) for
further information on the other types.
We also use wire screens for a different but related radon progeny aerosol
measurement (George, 1972).
B. Description of the multichannel screen diffusion battery.
Figure 2.1 shows the main components of the multichannel screen diffusion battery,
and Figure 2.2 shows one of the components in the cross section. The system consists of
five filter-type aerosol sampler units, each preceded by a different number of screens:

Sampler unit: B0 B1 B2 B3 B4
Number of screens: 0 1 5 15 40
(Unit B0 is also called the reference filter.)
The screen used is a standard industrial twill-weave stainless-steel screen with the
following dimensions:
Mesh 250 cm-1

Wire diameter 20 µm
Screen thickness* 50 µm
Solid fraction 0.345
Diameter of flow area 10.16 cm
*
As measured with a machinist's micrometer
C. Sampling procedure.
In normal use, the five samplers are loaded with clean 0.8 µm pore membrane filters
(Type AA, Millipore Corp., Bedford, MA) and air is drawn at 25 L min -1 through each
unit. As the air flows through the screens, particles are selectively removed from the
airstream and deposited on the wires. Particles that escape collection by the screens are
collected on the filters. For radon progeny the preferred sampling period is 5 min, but 10
or 20 min can be used if the concentration is low. For other species, the sampling period
must be adjusted.
After sampling, the filters are removed and analyzed. When analyzing for radon
progeny, any of the three alpha-counting protocols described in Section 2.2.4 can be used.
As described there, it is important that the counting begin no more than 2 min after the
end of sampling. This can be accomplished if two experienced operators are on hand at
the time when the filters are transferred.

D. Calculations.
Recovery of the particle size distribution from the activity measured on the five filters
is possible only with a quantitative knowledge of transport through the screens as a
function of the particle size. We currently use the "CKK" equation (Cheng et al., 1980;
Cheng and Yeh, 1983):
0 = exp [-n · m · ln (10)] (1)
where
0 = the fractional penetration through a stack of n screens
n = number of screens in the stack
m = A0 Pe-2/3 + A1 R2 + A 2 R2/3 Pe1/2
A0 = 1.96, A1 = 3.37, A2 = 1.94
Pe = ufdw/D, the Peclet number
R = dp/dw, the interception parameter
D = kTC/(3 %µdp), the diffusion coefficient
k = 1.38x10-23 J oK-1, Boltzmann's constant
T = temperature in degrees absolute, normally 293 oK
C = 1 + (/dp)[2.514 + 0.800 exp(-0.55 dp/)], the Cunningham slip factor
dp = particle diameter, m
dw = wire diameter, m
= mean free path of air molecules, normally 66 x 10 -9 m

µ = viscosity of air, normally 1.81 x 10-5 Pa sec
uf = air approach velocity, m sec-1.
The values for A0, A1, and A2 apply to the standard (250 mesh cm -1) screen - see
Cheng and Yeh (1983) for other screens. The equation for the Cunningham factor is from
Hinds (1982). In some of our computer programs we use an older equation with slightly
different coefficients.
To analyze data from our diffusion batteries, we use one of the following two
computer codes, which run on IBM-compatible personal computers:
Unfold.Pas - This is a Pascal program that uses the above-described Twomey

algorithm. An alternative algorithm, the expectation-maximization algorithm,
described by Maher and Laird (1985), is also available.
NMSimplx.Pas - This program, also in Pascal, makes use of the Nelder-Mead

downhill simplex method to fit single or dual lognormal distributions to the data.
The logic involved in the first of these is the same as that in ExMaxDB.Pas, described in
Knutson (1989).
REFERENCES
Cheng, Y. S. and H. C. Yeh

"Performance of a Screen-Type Diffusion Battery"
V. A. Marple and B. Y. H Liu (Editors)
in: Aerosols in the Mining and Industrial Environment
Ann Arbor Science Publishers, Ann Arbor MI (1983)
Cheng, Y. S., J. A. Keating, and G. M. Kanapilly

"Theory and Calibration of a Screen-Type Diffusion Battery"
J. Aerosol Sci., 11, 549-556 (1980)

George, A. C.
"Measurement of the Uncombined Fraction of Radon Daughters with Wire Screens"
Health Physics, 23, 390-392 (1972)
Hinds, W. C.
Aerosol Technology
John Wiley, NY (1982)
Knutson, E. O.
"Personal Computer Program for Use in Radon/Thoron Progeny Measurements"
USDOE Report EML-517, March (1989)
Knutson, E. O. and D. Sinclair

"Experience in Sampling Urban Aerosols with the Sinclair Diffusion Battery and Nucleus
Counter"
Proceedings: Advances in Particle Sampling and Measurement, EPA Report No. EPA-
600/7-79-065, pp. 98-120, February (1979)
Sinclair, D.
"A Portable Diffusion Battery - Its Application to Measuring Aerosol Size
Characteristics"
Am. Ind. Hyg. Assoc. J., 33, 729-735 (1972)
Sinclair, D. and G. S. Hoopes

"A Novel Form of Diffusion Battery"
Am. Ind. Hyg. Assoc. J., 36, 39-42 (1975)
Sinclair, D., A. C. George and E. O. Knutson

"Application of Diffusion Batteries to Measurement of Submicron Radioactive Aerosols"
in: Airborne Radioactivity
American Nuclear Society, La Grange Park, IL, Order No. 71001. pp. 103-114 (1978)

Figure 2.1. EML multichannel screen diffusion battery.
Figure 2.2. Cross section of the sampler units of the multichannel screen diffusion battery.

2.2.2.7
GRADED SCREEN ARRAY
A. Introduction.
The graded screen array (GSA, also called the graded screen diffusion battery) is used
for measuring the particle size of radon progeny in the range below 20 nm. The GSA is not
capable of dealing with larger sized aerosol particles, particularly those above 50 nm.
Therefore, the GSA should be used simultaneously with one of the diffusion batteries
shown in Section 2.2.2.6 or with the MOUDI impactor (see Section 2.2.2.5). For example,
the GSA used together with the MOUDI provides size information in the range of 0.5-5000
nm.
It is permissible to use the GSA alone, but only in laboratory studies in which radon
progeny or thoron progeny are sampled from a chamber free of larger aerosol particles.
B. Apparatus required.
1. One set of four circular stainless steel screens, each mounted on a metal ring — the
properties of these screens are:
Screen Mesh, Wire diameter, Screen Solid

label cm cm thickness, cm fraction
60 23.6 0.0187 0.0356 0.360
100 39.4 0.0108 0.0249 0.308
200 78.7 0.0052 0.0135 0.275
635 250 0.0020 0.0050 0.345

Two ring sizes are available: small and large. The dimensions and recommended uses are
shown below.
Size Outside Inside Ring Flow Typical For use at radon

of diameter, diameter, thickness, area, flow rate, concentration,
Ring cm cm cm cm-2 L min-1 Bq m-3
Small 2.67 1.91 0.25 2.86 3 >1000

Large 5.19 3.96 0.38 12.3 10 >200
2. A holder for the size of the screen selected.
3. A supply of Metricel DM-800 filters of the same size as the selected screens, and an
open-faced holder.
4. A pair of rotameter-type flow meters, one for the GSA and one for the open-faced filter,
and a suction pump.
5. Five drawer-type scintillation alpha counters of the type described in

Section 2.2.4,Table 2.4.
6. A personal computer equipped with Keithley-Metrabyte CTM-05 (or equivalent) pulse-

counting hardware and the software program ALPHALOG, as described in Section
2.2.4.6.
7. A stopwatch.
C. Procedure
1. Set up and check out the alpha-counting equipment, as described in Section 2.2.4.3B.
2. Calibrate both flow meters as described in Section 2.2.4.2A.
3. Using the alpha counters, check the background activity of the wire screens (the
background should be no higher than 0.2 counts min-1). This step may be omitted if it is
known that the screens have not been used in the past 24 h.

4. Mount the four screens into the holder so that the air will flow through in the sequence
60-100-200-635; orient the mounting rings so that the flush side faces upstream.
5. Set up the filter for sampling, as described in Section 2.2.4.2B; set up the screen-holder
in the same way.
6. Draw samples simultaneously through the filter and the screens, as described in Section
2.2.4.6.
7. After sampling, transfer the screens and the filter into separate alpha counters, and
perform minute-by-minute counting using ALPHALOG, as described in
Section 2.2.4.6.
8. Use program RWRENN6.EXE to calculate activity concentrations from the above

count data.
9. Use this data to calculate particle size distributions, as described in Section 2.2.2.8.
This method has been used to measure the diffusion coefficient of unattached radon
progeny in filtered room air (George, 1994).
D. Quality Control.
1. For the air sampling and alpha counting steps, follow the quality control procedures
outlined in Section 2.2.4.2A and 2.2.4.3B.
2. Whenever possible, take duplicate or triplicate samples from each experimental

condition.
REFERENCES
George, A. C. and E. O. Knutson

"Particle Size of Unattached Radon Progeny in Filtered Room Air"
Radiation Protection Dosimetry, 56, 119-121 (1994)

2.2.2.8
MATHEMATICAL ANALYSIS OF PARTICLE SIZE DATA
A. Introduction.
This section describes the steps needed to calculate particle size distributions from
samples taken with the MOUDI impactor (Section 2.2.2.5), a diffusion battery
(Section 2.2.2.6), and a graded screen array (Section 2.2.2.7), used individually or in
combination. It can also be used for Sierra impactor data (Section 2.2.2.4).
The mathematical algorithms used in these calculation programs are described by

Maher and Laird (1985), Solomon and Ren (1992), Knutson (1991), and Twomey (1975).
Early versions of some of these programs are given in Knutson (1989). The full set of
updated programs is available on a disk labeled EOKEMLUS.DOE.
B. Equipment and supplies needed.
1. An input data file (on disk) produced by the program RWRENN6.EXE.
2. Copies (on disk) of the files ABC^INP2.EXE, NMSIMPLX.EXE , UNFOLDPS and

EMLMOUDI.EFF.
3. An IBM-compatible personal computer, preferably 386 or better.
C. Procedure.
1. Prepare the computer for this task as follows:
a. From the root directory of the computer's C: drive, make a directory called UTIL
and copy the above .EXE files into the UTIL directory.
b. Include the UTIL directory in the PATH statement.

c. From the root directory, make a directory called (for example) SIZEDATA and
copy the above-mentioned input data file and the EMLMOUDI.EFF file into this
directory.
d. Change to the SIZEDATA directory.
2. Type ABC^INP2; when requested, supply:
- the name of the RWRENN6 output file;

- the number of data points in each data set (that is, the number of alpha counters
that were used to collect the data);
- whether or not the RWRENN6 program was instructed to analyze for thoron as
well as radon progeny;
- answer Y to the question about mapping.
This procedure produces a new file, with name ending in the character ^, that is ready
for use by either NMsimplx or UnfoldPS.
From this point on, the procedure differs according to which sampler or combination of
samples was used.

Program
Sampler to use Option
Diffusion battery NMsimplx Classical RnP
Graded screen array NMsimplx Unimodal
Diffusion battery plus

graded screen array Nmsimplx Bimodal (fixed, common
geometric standard deviation,
GSD)
MOUDI impactor UnfoldPS
MOUDI plus graded

screen array UnfoldPS
Both of these programs require that certain information be entered from the keyboard.
When answering a Y or N question it is not necessary to press ENTER. Other responses
require pressing the ENTER key to signal completion of the response. For many
questions, the proper response will be obvious; these are not discussed in the itemized
procedure below.
3. Diffusion Battery Alone. As indicated above, use NMSIMPLX. Supply data as

indicated below. Type:
- a mask, such as *.??^, for the input data file,

- the number of the input data file, or 0 to try another mask,
- Y in answer to the question about error terms,
- A to select diffusion battery,
- a digit from 1 to 5 to specify which diffusion battery,
- the flow rate in L min-1,
- the uncertainty in the flow rate (normally about 3% of the flow rate itself),
- 5 to select the Classical RnP,
- Y in answer to the question about default starting values,
- 0 in answer to the question about Monte Carlo replications,
- or N, as appropriate, for the default temperature and pressure,
- Y in answer to each question about acceptable data quality.

The progress of the calculation can be viewed on the screen as NMsimplx runs. The
results will also be stored in an ASCII file with an extension .NM5. The program produces
an uncertainty estimate for each of the calculated parameters; this estimate is printed
directly below the value of parameter.
4. Graded Screen Array Alone. Use NMsimplx. Type in the data indicated below.

- B to select graded screen array,
- N in answer to the questions about adding screens and showing rules,
- BCDE X in answer to prompt for GSconfig, 1
- Y in answer to the question about alpha counting,
- the flow rates in L min-1,
- the uncertainty in the flow rate(s) (normally about 3% of the flow rate itself),
- N to the question about inlet losses,
- the flow area of the screens that were used,
- 1 to select unimodal,
- N in answer to the question about default starting values,
- 1 in answer to the request for a starting diameter,
- Y or N, as desired, to the question about switching to diffusion coefficient, (if
no, answer Y or N, as appropriate, to the next question about temperature
and pressure),
The program will run and produce a file as described under Diffusion Battery Alone,
except that the file extension will be .NM1.
1
This is the proper response if: the four screens were stacked into one holder during the sampling, such
that the air flowed through in the sequence B-C-D-E; the filter was in a separate holder; and the data
in the input file are in the sequence B,C,D,E,X Otherwise, answer Y to the question about screen rules,
and use these rules to decide how to answer the GSconfig prompt.

5. Diffusion Battery plus Graded Screen Array. Use NMsimplx. Type in the information
itemized below.

- AB to select the combination of diffusion battery and graded screens, 1
- a digit from 1 to 5 to specify which diffusion battery,
- the diffusion battery flow rate in L min -1,
- the uncertainty in the above flow rate (normally about 3% of the flow rate
itself),
- BCDE X in answer to prompt for GSconfig, 2
- the graded screen flow rate(s) in L min -1,
- the uncertainty in the above flow rate(s) (normally about 3% of the flow rate
itself),
- 2 to select bimodal with fixed, common GSD,
- 1.5 in response to the prompt for a value of GSD,
- N in answer to the question about default starting values,
- 1 100 in answer to the request for a two starting diameters,
- Y or N, as appropriate, to the question about temperature and pressure,
The output file from the above steps will have the extension .NM2.
1
This is the proper response if the diffusion battery data precedes the graded screen data in the input data
file. Otherwise interchange A and B.
2
This is the proper response if: the four screens were stacked into one holder during the sampling, such
that the air flowed through in the sequence B-C-D-E; the filter was in a separate holder; and the data in
the input file are in the sequence B,C,D,E,X. Otherwise, answer Y to the question about screen rules,
and use these rules to decide how to answer the Gsconfig prompt.

6. MOUDI, alone or with a reference filter. Use UnfoldPS. Before proceeding, review the
input data file and make note of which impactor stages are represented in the file.
(Often the upper stages are not alpha-counted.) Also review the EMLMOUDI.EFF file
and make note of the 50% cut points of the first and last stage for which there is data in
the input file. Type in the following information:

- C to select impactor,
- 40 in answer to the question about smallest size, 1
- 4000 in answer to the question about largest size, 2
- 2 to select lognormal basis functions,
- 1.3 in answer to the question about GSD,
- Y or N, as appropriate, concerning the temperature and pressure,
- EMLMOUDI.EFF in response to the prompt for an info file,
- 1 in answer to the question about particle density, 3
- Y or N, as appropriate, to the questions about data present in the input file,
- Y in answer to the questions about data quality,
- 0 for the number of Twomey iterations,
- 100 for the number of E-M iterations,
- 0.00005 for the convergence criterion,
- N in answer to the question about skipping negative values,
- 0 in response to the prompt about Monte Carlo error study,
- Y in answer to the question about long-form output,
- ENTER in answer to the request for file name,
- Y in answer to the question about short-form output,
- Y in response to the question about 50-line screen.
1
This value should be no smaller than 80% of the 50% cut-point of the last impactor stage for which there
is data in the input file.
2
This value should not exceed 120% of the 50% cut-point of the first impactor stage for which there is
data in the input file.
3
Entering 1 will cause the results to be presented in terms of equivalent unit-density spheres, i.e., the
aerodynamic equivalent diameter. Entering the actual density of the particle will cause the results to be
presented in terms of the Stokes equivalent diameter.

As UnfoldPS runs, the progress of the current calculation is shown near the bottom of
the screen. The upper part of the screen shows the results of the previous calculation.
When finished, the long-form output can be found in a file with extension ending in &, and
the short-form output will be in a file with extension ending in.
7. MOUDI plus Graded Screen Array. Use UnfoldPS. Before proceeding, review the
input data file and the EMLMOUDI.EFF file as described in the last section. Then type
in the following information -

- CB to specify the type of sampler, 1
- 0.5 in answer to the question about smallest size,
- 4000 in answer to the question about largest size, 2
- 2 to select lognormal basis functions,
- 1.3 in answer to the question about GSD,
- Y or N, as appropriate, concerning the temperature and pressure,
- EMLMOUDI.EFF in response to the prompt for an info file,
- 1.5 in answer to the question about particle density, 3
- Y or N, as appropriate, to the questions about data present in the input file,
- BC in answer to the prompt for GSconfig, 4
- the graded screen flow rate in L min -1,
1
This is the correct response if the impactor data precedes the grades screen data in the input file;
otherwise, interchange B and C.
2
This value should not exceed 120% of the 50% cut-point of the first impactor stage for which there is
data in the input file.
3
This value of particle density is approximately correct for indoor aerosols; the results will be g iven in
terms of Stokes equivalent diameter, which is appropriate when combining data from impactors and
diffusion batteries, or graded screens.
4
This assumes that data are available only from screens B and C, and that these two screens were stacked
during sampling, such that the air flowed through in the sequence B-C. Otherwise, read the "screen
rules" to determine the proper entry for GSconfig.

- the uncertainty in the above flow rate (normally about 3% of the flow rate itself),
- Y in answer to the questions about data quality,
- 0 for the number of Twomey iterations,
- 1000 for the number of E-M iterations,
- 0.00005 for the convergence criterion,
- N in answer to the question about skipping negative values,
- 0 in response to the prompt about Monte Carlo error study,
- Y in answer to the question about long-form output,
- Y in answer to the question about short-form output,
- Y in response to the question about 50-line screen.
D. Quality Control.
1. Using a text-viewing or text-editing program, examine the output file from NMsimplx
or from UnfoldPS. Starting at the end of the file, spot-check the column titled
"RawData" to ensure that the input data have been properly matched to the stages of the
sampling device. It will be necessary to consult the RWeENN6 output file to determine
the proper matching.
2. Examine each block of results in the output file. Any block of data that has more than
one negative input datum should be discarded. Examine also the "ChiSqr" value, which
is a measure of the internal consistency of the data. If this number is > 25, the data
block should be discarded unless the reason for the high value can be identified and
fixed.
3. Similarly if the ChiSqr value is < 1, the data block should be discarded because the
uncertainties in the input data are too large to support calculation of the particle size
distribution.

REFERENCES
Knutson, E. O.
"Personal Computer Programs for Use in Radon/Thoron Progeny Measurements"
DOE Report EML-517 (1989)
Knutson, E. O.
"Application of the Expectation-Maximization Algorithm to the Processing of Cascade
Impactor Data: The Method of Lognormal Components"
J. Aerosol Sci., 22, 267-270 (1991)
Maher, E. F. and N. M. Laird

"Algorithm for Reconstruction of Particle Size Distributions from Diffusion Battery
Data"
J. Aerosol Sci., 16, 557-570 (1985)
Solomon, S. B. and T. Ren

"Counting Efficiencies for Alpha Particles Emitted from Wire Screens"
Aerosol Sci. and Tech., 17, 69-83 (1992)
Twomey, S.
"A Comparison of Constrained Linear Inversion and a Iterative Nonlinear Algorithm
Applied to the Indirect Estimation of Particle Size Distributions"
J. Comput. Phys., 18, 188-200 (1975)
2.2.3 RADON AND THORON
2.2.3.1
INTRODUCTION
The procedures and instruments commonly used at EML for measuring radon are
presented here. The main sampling methods are grab, two filter tube, continuous, and
integrating. Both active and passive methods are included. These methods are used in
laboratory applications as well as in situations requiring mobility and portability.

2.2.3.2
GRAB SAMPLING FOR RADON
Three sizes of scintillation flasks, all based on a design described in George (1976), are
used at EML. Typical characteristics are shown in Table 2.1. The flasks are made at EML
from methylmethacrylate stock. The bottom plate, made from sheet, is cemented to the
body, made from tubing. The top plate, also from sheet, slides into the body and is sealed
with an O-ring. The top plate is fitted with two petcock valves. All three flasks are
designed to be counted on 12.7-cm phototubes.
As the radon inside the flask decays, most of the radon progeny that are produced plate
out on the interior surfaces of the flask. The alpha particles from radon and radon progeny
interact with the ZnS(Ag) atoms to produce scintillations which are detected, amplified,
and converted to an electrical signal by the phototube.
A. Flask coating procedure.
In this procedure, we place a thin phosphor coat on all internal surfaces. The thin
coating on the bottom plate adds 15-20% to the sensitivity. The materials and steps used in
this process are listed below.
Coating materials:
1. Silver activated zinc sulfide phosphor (Wm. B. Johnson Associates, PO Box 472, 216
Edgar Ave., Ronceverte, WV 24970).
2. Bonding solution (Caution-Flammable-Use Hood). Dissolve 30 mL of silicone fluid

(Dow Corning, Midland, MI; Silicone Fluid 200) in 285 mL of reagent benzene plus
285 mL of reagent cyclohexane. Stir until the silicone is completely dissolved. This is
enough to coat about 100 flasks.

Coating steps (use a hood):
1. Clean the flask with a nonabrasive cleaner. [A plastic cleaning foam (REN RP-70
cleaner) has been found to be excellent.]
2. Remove cover, add 50 mL of bonding solution, replace cover, close both valves, and
rotate the flask slowly until all surfaces including the bottom are coated. Open valves
and remove cover.
3. Pour out excess bonding mixture into a second clean flask or return to the stock bottle.
Let flask air dry for a few minutes.
4. Add 15-20 g of phosphor, replace cover, and close valves.
5. Shake gently until all surfaces are coated. Open valves and remove cover.
6. Pour out the loose powder and blow off excess phosphor from the flask and from the
cover with clean air.
7. Replace cover and purge the flask with aged (radon free) air or nitrogen for a few
minutes. Close the valves and store the flask for use.
8. When background becomes excessive, wipe out phosphor with clean tissue, clean as
above, and rephosphor.
B. Sampling and counting procedures.
1. Connect a high collection efficiency filter to one valve of the flask to remove
particulates and radon progeny. Connect the other valve to an air pump and draw air at
2-10 L min-1 for 2-5 min for scintillation flasks of 165-2000 mL.
2. Turn off pump and close both valves. An alternate method for filling the flask is to
evacuate it down to 133 Pa (1 mm Hg) of pressure prior to filling with the test
atmosphere.
3. Count the scintillation flask on a 12 cm phototube beginning 3 h after sampling.

4. To convert the counting rate to radon concentration, use the calibration factor (C f)
obtained from a test in a known radon environment and the appropriate decay-
correction. Each scintillation flask should have its own C f which can be influenced by
its size and by the phototube assembly. It is very important that the entire system
(scintillation flask, and phototube) is calibrated as a unit. Typical C f for the three
scintillation flasks used at EML are shown in Table 2.1.
5. Determine the radon concentration at the time of sampling by applying the decay
correction (Df):
0.693 t
Df
exp
exp ( 0.0075 t) (1)
T1/2 for radon
where t is the time in hours from the midpoint of sampling to the midpoint of counting, and
T1/2 is the half-life of radon (91.7 h).
REFERENCE
George, A. C.
"Scintillation Flasks for the Determination of Low-Level Concentrations of Radon"
Proceedings of Ninth Midyear Health Physics Symposium, Denver, Colorado, February
(1976)
2.2.3.3
TWO-FILTER TUBE SAMPLING FOR RADON AND THORON
The two-filter tube sampling method described in this section is used for simultaneous
measurements of airborne radon and thoron (Knutson et al., 1994).

A. Description.
The sampling tube (9.7 cm diameter x 61 cm in length) has two filter heads. The front
end of the tube is fitted with a 10.5-cm filter holder to accommodate two 10.5-cm high
efficiency glass fiber filters mounted in series for the collection of all particulates
including radon and thoron progeny. The back end of the tube is fitted with a 4.7-cm filter
head assembly to hold a 4.7-cm diameter high efficiency Metricel membrane filter paper.
This filter has very low alpha-radioactivity background (0.05 counts min -1) and antistatic
electrical properties. The background counting rate of the back-end filter is critical in
measuring the expected low counting rate from the buildup of radon and thoron progeny
originating inside the tube. The sampling flow rate, ranging from 30-50 L min -1, is high
enough to minimize the loss of 216Po and 218Po atoms to the wall of the tube and to
maximize the collection on the back-end filter.
B. Sampling and counting.
1. Mount two 10.5-cm diameter glass fiber filters in series in the front end of the tube and
a single 4.7-cm Metricel membrane filter in the back end of the tube.
2. Connect the intake of an air pump to the back end of the tube and sample for 5-6 h.
3. At the end of sampling, transfer the back-end filter into a 5-cm diameter gross alpha
scintillation counter and begin to count as soon as possible in short time intervals (5-
10 min) for 4-6 h. One convenient way to do this is to make use of a portable personal
computer equipped with pulse-counting hardware and the software program
ALPHALOG (see Section 2.2.4.6). The sooner the counting begins the better the
precision that is obtained for radon measurements; for thoron, the sensitivity increases
with counting times of several hours.
C. Calculations.
The concentrations of radon and thoron are calculated from the radioactivity measured
on the back-end filter using a computer program JWTI, which is based on the recursion
formula method of Samuelson (1987). This method is very flexible employing different
sampling regimes and counting intervals. The calculated penetration (F f) of 216Po from
thoron and 218Po from radon is governed by the flow rate and the value for the diffusion
coefficient, D, used for these isotopes. The relationship between D and F f is obtained
from Table 2.2, using the value of the parameter µ given by the expression

%xDxL
µ
where
% = 3.14.
D = diffusion coefficient, cm2 sec-1 (0.085 cm2 sec-1)
L = length of tube, cm (61 cm)
Q = sampling flow rate, cm3 sec-1 (500-800 cm3 sec-1)
The value of D = 0.085 cm2 sec-1 is used for very fresh radon progeny. The
concentration of radon or thoron is underestimated by 3%, 4.5%, and 6.0% if the value
used for D = 0.06, 0.05, and 0.043 cm2 sec-1, respectively.
A computer program JWT1 is used to calculate both radon and thoron concentrations
in Bq m-3. The lower limit of detection is 5 Bq m-3 for both radon and thoron. For
concentrations higher than 200 Bq m-3, a smaller two-filter tube can be used (Thomas,
1970).
REFERENCES
Knutson, E. O., A. C. George, P. Shebell and C. V. Gogolak

"EML Thoron Gas Measurements"
Samuelson, C.
"Applications of a Recursion Formula to Air Sampling of Radon Daughters"
Nuclear Instruments and Methods in Physics Research, A262, 457 (1987)
Thomas, J. W. and P. C. LeClare

"A Study of the Two-Filter Method for Radon-222"
Health Phys., 18, 113 (1970)

2.2.3.4
CONTINUOUS RADON MONITORING
Continuous reading radon monitors are ideal for measuring varying concentrations of
radon over a long period of time. The scintillation flask used for radon grab sampling can
be adapted to measure radon continuously by sampling at f1ow rates of 1-2 L min -1 as
described in Thomas and Countess (1979). Any of the three flasks used at EML can serve
this purpose. The flask is mounted on top of the phototube in light-proof housing.
Sample air is drawn continuously through the flask by means of a pump, with a high
efficiency filter mounted inline to remove dust particles and radon progeny. The number
of alpha counts accumulated at the end of each counting interval, usually 30-60 min, is
stored in a computer or printed out on paper tape.
The entire system is calibrated in a continuous operation mode to obtain the

appropriate Cf at a fixed flow rate and at varying radon concentrations. In an
atmosphere in which the concentration of radon changes drastically, the calibration of the
whole system becomes tedious. However, with the aid of modern desk computers the
average radon concentration during the sampling interval can be calculated accurately.
This is accomplished by means of an equation that takes into consideration the number of
counts obtained in preceding sampling intervals (Thomas and Countess, 1979).
The Cf from four continuous 2-L scintillation flask radon monitors used in the EML
radon calibration facility at flow rates of 1 L min -1 range from 0.0019-0.0020 counts min-1
per Bq m-3 (4.2-4.5 counts min-1 per pCi L-1). The range in factors results from differences
in phototubes and scintillation flasks.
REFERENCE
Thomas, J. W. and R. J. Countess

"Continuous Radon Monitor"
Health Phys., 36, 734 (1979)

2.2.3.5
INTEGRATING RADON MONITORS
The activated carbon monitor is used to obtain the average radon concentration over a
1-3 day period of passive sampling. The original design (George, 1984) was based on the
M11 charcoal canister. Although there are currently many variants of the activated car-
bon monitor, the device described below is the one most used at EML.
A. Description.
This monitor consists of the following materials: (1) a metal can with a lid (1.2-cm
diameter by 2.9-cm deep); (2) 75 g of 8-16 mesh activated carbon (Calgon, Pittsburgh,
PA); (3) metal screen (80 mesh) to keep the carbon in place; (4) removable internally
expanding retaining ring to secure the screen; and (5) a strip (35 cm) of vinyl tape for
sealing the lid to the can when closed. After loading and after each use, the carbon
monitor is heated at 100oC for a minimum of 10 h to drive off any previously adsorbed
radon and water.
The counting system consists of: (1) an 8.0-x-8.0 cm NaI(Tl) detector inside a 9-cm lead
shield coupled to a compact multichannel pulse-height analyzer and a printer. The coun-
ting system is operated with the discriminator set to include gamma energies between 0.23
and 0.72 MeV, spanning the peaks of 214Pb (0.242, 0.294, and 0.352 MeV) and 214 Bi (0.609)
MeV. The normal counting period is 10 min.
To determine the counting efficiency of the NaI detection system, a monitoring device
is sealed after spiking with a known quantity of radon or 226Ra. This becomes the standard
source with the proper counting geometry. A different standard source will be required
for any change in the configuration of the monitor. Typically, the efficiency of the EML
canister and counter combination is 0.117 counts per radon atom decay.

B. Calibration.
The monitors must be calibrated because the response depends on the length of
exposure, relative humidity during the exposure, and on the type of carbon used.
(Temperature effects encountered indoors are, however, insignificant because of the
limited temperature range encountered.) Calibration is performed for several relative
humidities from 20-90% and for 1-3 days of exposure. This calibration is required
whenever new samplers are built using a new batch of activated carbon.
Each combination of exposure time and humidity yields a C f calculated from the
following equation:
1000 N
Cf
60 E Rn Df
where
1000 = L m-3,
N = net counting rate (counts min-1),
60 = sec min-1,
E = NaI detector efficiency, typically 0.117 counts sec -1 Bq -1 Rn (0.26

counts min-1 pCi-1), and
Rn = radon concentration in Bq m-3,
Df = decay factor from the midpoint of exposure to the midpoint of

counting (see Equation 1, Section 2.2.3.2).
Typical results are shown in Table 2.3. The amount of water adsorbed, shown in the
left column, was determined from the difference in weights before and after exposure.

C. Use of device.
Before exposure the monitoring device is heated to regenerate it. Exposure times
longer than 3 days should be avoided because water competes with radon adsorption and
the effectiveness of the device as an integrating monitor will diminish.
To calculate the concentration of radon from the measured count rate and
measured water uptake, Equation 2 is applied after solving for radon:with the symbols as
1000 N
Rn
60 E Cf Df
defined before. Use Table 2.3 to obtain the C f. The 1 ) counting error is calculated from
the following expression:
(Gross Counts Background Counts)1/2

)
x 100%
Gross Counts Background Counts
When exposed for 3 days and counted 3 days later, the device described here has a lower
limit of detection of 7.4 Bq m -3. Other versions of the device that contain better adsorptive
carbon can measure radon concentration levels at 3.7 Bq m -3 or less.
REFERENCE
George, A. C.
"Passive Integrated Measurement of Indoor Radon Using Activated Carbon"
Health Phys., 46, 867 (1984)

2.2.3.6
QUALITY CONTROL
To verify the measurement accuracy of all monitoring devices for radon and thoron,
periodic intercomparison measurements are made with pulse ionization chambers (Fisenne
and Keller, 1985). The pulse ionization chambers are the primary calibration instruments
traceable directly to the NIST through use of their standard 226Ra reference solutions. The
accuracy of the thoron concentrations is obtained through intercomparisons (Knutson et
al., 1994).
REFERENCES
Fisenne, I. M. and H. W. Keller

"The EML Pulse Ionization Chamber System for Radon-222 Measurements"
Knutson, E. O., A. C. George, P. Shebell and C. V. Gogolak

"EML Thoron Gas Measurements"
TABLE 2.1
TYPICAL CHARACTERISTICS OF THE THREE SIZES OF EML

SCINTILLATION FLASKS
___________________________________________________
Flask volume (L) 0.165 0.415 2.00
Cf:
counts min-1 Bq m-3 0.022 0.054 0.135
counts min-1 pCi L-1 0.8 2.0 5.0
LLD (Bq m-3) 7.4 3.7 3.0

___________________________________________________

TABLE 2.2
VALUES OF Ff AS A FUNCTION OF µ = % x D x L/Q
µ Ff µ Ff
0.005 0.877 0.25 0.420

0.008 0.849 0.30 0.384
0.010 0.834 0.35 0.349
0.020 0.778 0.40 0.324
0.030 0.737 0.45 0.302
0.040 0.705 0.50 0.282
0.050 0.678 0.60 0.248
0.060 0.654 0.70 0.220
0.070 0.633 0.80 0.220
0.080 0.614 0.90 0.178
0.090 0.596 1.00 0.162
0.100 0.580 1.50 0.110
0.120 0.551 2.00 0.083
0.140 0.525 2.50 0.067
0.160 0.502 3.00 0.056
0.180 0.481 4.00 0.042
0.200 0.462 5.00 0.033

TABLE 2.3
Cf: EFFECTIVE VOLUME SAMPLED AS A FUNCTION OF EXPOSURE

TIME AND WATER ADSORBED
Effective sample volume (L)

for various exposure times
Water adsorbed
(g) 1 day 2 days 3 days
0.500 144 216 259

0.700 143 213 255
1.000 142 210 251
1.500 140 204 246
1.700 138 202 242
2.000 137 199 238
2.500 135 196 233
3.000 132 190 229
3.500 131 187 225
4.000 130 184 220
4.500 127 181 216
5.000 125 179 207
6.000 121 167 199
7.000 118 161 190
8.000 114 153 181
9.000 109 144 173
10.000 105 135 164
11.000 101 127 156
12.000 096 121 151

2.2.3.7
220 222
Rn AND Rn IN SOIL GAS
APPLICATION
This section describes the procedures used to determine soil gas 220Rn and 222Rn
concentrations using commercially-available scintillation cells and photomultiplier tube
apparatus (referred to as "222Rn detector" in the following procedure).
A. Apparatus.
1. Scintillation cells (Scintrex, Ltd., 222-T Snidercroft Rd., Concord, ON, Canada, nee
EDA, Model #RDX-013, or equivalent).
2. Photomultiplier tube and counting apparatus (Scintrex, Ltd., 222-T Snidercroft Rd.,
Concord, ON, Canada, Model #RDA-200, or equivalent).
3. Stainless-steel sampling tubes, 0.95 cm ID, various lengths.
4. Portable battery-operated pump (Du Pont E. I. De Nemours and Co., Route 87 S., PO
Drawer Z, Fayetteville, NC 28302, Model #2500B, or equivalent) capable of
~ 2.0 L min-1 at p of 10 kPa.
5. Flow meter, 0-5 L min-1 (Cole-Parmer, or equivalent).
6. Pressure gauge, 0-25 kPa (Dwyer Instruments, Inc., PO Box 373-T, Michigan City, IN
46360, or equivalent).
7. Short section of Tygon tubing (or equivalent) filled with dessicant held in place by
glass wool, fitted at one end with an in-line filter holder containing Millipore (or
equivalent) 0.8 µm filter to remove progeny from initially entering scintillation cell.
8. Computer program RNTNCAL.FOR (Hutter, unpublished) or equivalent, for

calculating 220Rn and 222Rn concentrations from scintillation cell counts.

B. Procedure.
1. Emplace sampling tubes into the soil using reamer to pound, ensuring no soil is
retained in tube, or alternatively, drill hole using auger and insert tube, tamping soil to
minimize cavities along tube walls.
2. Obtain a 5-min background count for each scintillation cell to be used before the
sample is drawn at the measurement site.
3. Obtain the soil gas sample using a portable battery-operated pump, according to the
apparatus arrangement shown in Figure 2.3, with a flow rate of between 1 and 3 L
min-1 for 1 min. Measure and record the flow rate and the volume of the sample
tubing. The sample is drawn directly into scintillation cells that have been previously
inserted into the 222Rn detector.
4. Turn the pump off, remove the tubes to the scintillation cell and screw on the cap to
the 222Rn detector.
5. Obtain a 1-min count (see Notes 1 and 2).
6. Remove the scintillation cell from the 222Rn detector, and obtain another sample using
a different scintillation cell, or see Note 3 to reuse a cell.
7. Obtain a 5- or 10-min count at least 5 min after the soil gas sample was drawn into the
scintillation cell, and no longer than 3 or 4 days. Typically, these counts are obtained
either on-site at the end of collecting all samples, or within an hour to two at a
convenient (i.e., warm and dry) site.
8. Calculate the concentration of 220Rn and 222Rn, correcting for decay of 220Rn during
sampling (Hutter, 1995). This requires knowledge of the flowrate and sample tube
volume. A computer program, RNTHCALC.FOR, is available to do this calculation.

Notes:
1. The time between the end of pumping and the start of counting must be as short as
possible (< 90 s; 1 1/2 half-lives of 220Rn). Typically, this delay time is about 10 sec.
Record the time between the end of pumping and the start of counting to within ± 1 s.
2. The counts min-1 from the sample must turn out to be at least 3 times the background.
Obtain a new sample if this requirement is not met, either using a different
scintillation cell, or by waiting until the background decreases.
3. If the 5-min count is obtained 5 min after sampling is ended, the cell can then be
purged with outdoor air and a new background count obtained, to be reused for the
next sample, provided that the new background check shows the sample counts min -1
to be at least 3 times the background.
C. QA/QC.
Duplicate samples, defined as measurements performed on the same sampling hole on

the same day ~ 10 to 15 min apart using a different scintillation cell, are performed at a
rate of 1 in 10 for the purpose of assessing measurement precision. Second countings of
samples are performed at approximately the same rate in order to ensure cell integrity
with regard to leakage and to assess statistical counting uncertainties.
Calibrations of scintillation cells/ 222Rn detector apparatus are performed on at least a

semiannual basis using the EML Radon Gas and Radon/Thoron Progeny Facilities for
Testing and Research (see Section 6.2) or other radon chambers. At this time, it is useful
to check for leaks in the scintillation cells by testing for consistency in the count rate, and
by taking into consideration decay over several days. Approximately 1 in 5 cells obtained
from a commercial vendor have been found to leak. Nearly all leaks can be sealed using
epoxy around the window and all valve connections.

REFERENCES
Hutter, A. R.
"A Method for Determining Soil Gas 220Rn (Thoron) Concentrations"
Health Physics, 68 835-839 (1995)
Hutter, A. R.
"220Rn/222Rn Ratios as Indicators of Soil Gas Transport"
(unpublished data)
)ORZ0HWHU
3UHVVXUH
*DXJH &HOOVDQG
FRXQWHU ,QOLQHILOWHUDQG
'HVLFFDQW
3XPS
6DPSOLQJ7XEH
Figure 2.3. Schematic of soil gas sampling arrangement.

2.2.4 RADON AND THORON PROGENY
2.2.4.1
INTRODUCTION
Presented here are the three methods commonly used at EML for determining the
concentration of radon and thoron progeny in air. All three methods - modified Kusnetz,
modified Tsivoglou, and Raabe-Wrenn least squares - are based on collection in a known
volume of air through a filter in a known time period, and on counting the radioactivity
on the filter after sampling. The methods described are suitable for use in the laboratory,
in homes, and in the workplace. The same sampling and counting equipment are used,
but with different counting and calculational procedures.
Units: when specifying the concentration of individual progeny nuclides, the Systeme
Internationale (SI) unit is Bq m -3; when specifying the potential alpha energy
concentration (PAEC) of radon or thoron progeny, the SI unit used is J m -3.
These procedures have also been adopted by the World Health Organization (George,
1993).
2.2.4.2
SAMPLING TRAIN
All three methods require a sampling train such as that shown in Figure 2.4.
A. Air pump and flowmeter.
A portable air pump capable of moving 10-20 L min -1 through a high efficiency filter
is required. The pump should be rugged, light weight, quiet, and operate from the voltage
line in the building. A calibrated flowmeter to measure the flow rate through the filter
holder assembly should be attached upstream of the intake of the pump. Calibration of
the flowmeter is air density dependent and care should be taken if used at different
altitudes. The pump flowmeter train assembly should be calibrated at the same elevation,

and at the same resistance that is caused by the filter and by the other component parts in
the sampling train as shown in Figure 2.4. Never measure the air flow rate from the
exhaust of the pump because of possible leakage in the pump housing.
B. Air filters and filter holder.
Use membrane filters with nominal pore size < 0.8 µm, or glass fiber with a collec-
tion efficiency of > 99.9%. Membrane filters exhibit negligible alpha-particle absorption
during alpha counting. Glass fiber filters allow deeper penetration of particles, but with
the recommended flow rates, face velocity (< 100 cm sec -1), and short sampling period,
particle burial in the filter is negligible. Any other type of filter medium should be
investigated for good surface deposition characteristics. In general, small pore filters
exhibit the best surface collection, but also present the highest resistance to air flow. To
compensate for this, use a higher capacity pump or a larger diameter filter and filter
holder. The diameter of the filter can either be 2.5 or 4.7 cm depending on the size of the
filter holder and the detector counter used. The connecting tubing between pump and
filter holder should be a thick-walled pressure type hose. Filter holders should be of the
open faced type to prevent the loss of radon progeny particles due to plate out upstream
from the filter. The biggest error in measuring radon progeny by collection on a filter is
often from a defective filter holder. To prevent this, make sure the filter holder-filter
assembly is airtight and has the proper O-ring seal.
C. Timing device.
Sample collection timing is very important in the short sampling periods used for
short-lived radionuclides. Errors may be significant if operators rely on their wristwatch
and on their memory.

2.2.4.3
ALPHA PARTICLE COUNTING SYSTEM
A. Description.
Table 2.4 shows the main characteristics of the two alpha-particle counters most used
at EML to measure the alpha activity deposited on a filter. Both counters are designed for
gross alpha (total alpha) counting, in which the alpha particles from 218Po (6 MeV) and
214
Po (7.7 MeV) are counted without discrimination.
Both counting systems consist of a simple scintillation disc (ZnS silver activated
screen) mounted on or close to the face of a photomultiplier tube, and placed in close
proximity to the filter. [In the TH-29-B (see Table 2.4), the scintillator is a separate
Mylar disk coated on one side with ZnS; be sure the coated side faces the filter.] The
photo-multiplier tube and preamplifier are housed in light-tight housing and are
connected to a stable high voltage supply and a scaler.
B. Calibration.
Table 2.5 shows the characteristics of the certified alpha standard source most used at
EML to periodically measure the efficiency of the counting systems. The counting
efficiency is the ratio of the counting rate (in counts sec -1) of the instrument to the known
activity (in Bq) of the standard source. The EML counters described above have an
efficiency of about 48%, but this figure should always be remeasured after the counters
are moved to a field site.
Checking calibration is also a good quality assurance step. Measured efficiencies

which are outside the range 47-49%, or which are not reproducible, are an indication of
equipment malfunction and these counters should not be used.
Because the counters are energy-independent, efficiencies determined with the 241Am
or 239Pu sources (alpha energies 5.53 MeV and 5.15 MeV, respectively) are believed to
apply to radon/thoron progeny as well. For very precise work, the efficiency as measured
above should be multiplied by the factor shown in Table 2.5 to correct for backscatter.
This correction takes into account the fact that the alpha emission from the front face of a
metal plate is slightly higher than from the same activity deposited on a filter.

2.2.4.4
MODIFIED KUSNETZ METHOD
The simplest method is the Modified Kusnetz, in which a 5 min air sample is taken on
a high efficiency filter to be counted for 5-10 min any time between 35-95 min after the
end of sampling. This method differs from the original method (Kusnetz, 1956) in that a
scaler is used in place of a ratemeter and the counting time is longer.
A. Procedure.
Before sampling and counting a sample, the operator should ensure that the entire
sampling train is in good working order and that the counting system is calibrated and
running properly. The counting efficiency of the system and its background counting rate
should be determined as discussed earlier.
Using a 2.5 or 4.7 cm open-faced filter holder, mount a membrane or glass fiber filter.
Attach the filter holder upstream of a calibrated flowmeter with the proper hose and
connect to the intake of an air pump.
Sample air from the environment to be tested for 5 min at a rate of 10-20 L min -1. After
sampling, remove the filter containing the radon progeny from the filter holder and
transfer it to the counting system for analysis. There is no urgency to do this since the
operator has 35 min to commence counting. During that waiting period he/she may wish
to take another sample in another part of the building using a new filter and the same
filter holder and sampling equipment.
The modified Kusnetz method requires a single count of the filtered sample usually
for 10 min in the counting interval from 35-45 min after the end of sampling, or at any
other 10-min intervals between 35-85 min after the end of sampling.

B. Calculation.
The potential alpha energy concentrations (PAEC) can be calculated from the
equation:
PAEC in nJ m-3 = N/(E x Ts x Q x Tf) (1)
where
N = net counts min-1,
E = fractional counter efficiency (counts sec - 1 Bq -1),
Ts = sampling time in min,
Q = sampling flow rate in m3 min-1, and
Tf = time factor given in Table 2.6.
The relative standard deviation of the measurement in % can be calculated from the
following equation.
gross count (cpm) background (cpm)

time counted (min) time counted (min) (2)
)p
x 100
gross counts (cpm) background (cpm)
Example: An air sample was collected for T s = 5 min, at a flow rate of Q = 10 L min -1
(0.01 m3 min-1). The counting was done from 35-45 min after the end of sampling. The
total alpha count in that interval was 4200 counts. The counter background was 0.1
counts min-1 measured for a period of 25 min. The counter efficiency, E, was 0.48. T f at
40 min, which is the midpoint of 35-45 min, is 7.21 obtained from Table 2.6. The total
count in that interval was 4200 counts.

From Equation (1)
(4200/10 0.1) 420

PAEC

2420 nJ m 3.
(0.48 x 5 x 0.01 x 7.21) 0.173
The relative standard deviation of the PAEC measurement is
420 0.1

10 25
)p

0.015 (1.5%).
420 0.1
2.2.4.5
MODIFIED TSIVOGLOU METHOD
The modified Tsivoglou method is more complicated than the Kusnetz, but it yields
additional information: the concentration of individual radon progeny (Thomas, 1972).
A. Procedure.
The sampling procedure is identical to that used for the modified Kusnetz method.
(Actually all three methods can be used with the same filter containing sampled radon
progeny.)
After the end of sampling, remove the filter containing radon progeny from the filter
holder and transfer it to the counting system for analysis. The standard counting intervals
are 2-5, 6-20, and 21-30 min after the end of sampling. These intervals allow adequate
time to transfer the filter into the counting system and record the counts from the different
counting intervals. The technician or the person who performs the test is required to
stand by for 30 min unless he uses automated counting equipment operated by a
computer.

B. Calculation.
The equations needed to calculate the air concentrations from a 5 min sample and for
the standard counting intervals are:
[6.247 Nt(2 5) 3.028 Nt(6 20) 2.857 Nt(21 30)]

C1
(3)
EQ
[0.056 Nt(2 5) 0.776 Nt(6 20) 1.836 Nt(21 30)]

C2
(4)
EQ
[ 0.832 Nt(2 5) 1.224 Nt(6 20) 1.389 Nt(21 30)]

C3
(5)
EQ
[2.011 N t(25) 1.372 N t(620) 3.954 N t(2130)]

Cp
(6)
EQ
where
C1, C2, C3 = the concentrations of 218Po, 214Pb, and 214Bi, respectively (Bq m-3),
Cp = the PAEC (nJ m-3)
Nt(...) = the net counts in the intervals 2-5, 6-20, and 21-30,
E = fractional counter efficiency [(counts min -1) /(disintegrations min-1)],

and
Q = sampling air flow rate, L min -1.
These coefficients were derived using 3.05 min for the half life of 218Po (Martz et al.,
1988). The half lives used for 214Pb and 214Bi were 26.8 and 19.9 min, respectively
(ICRP, 1983).
The standard deviation equations which calculate the precision for each radionuclide
are:

1
S1
[39.0 Nt(2 5) 9.17 Nt(6 20) 8.16 Nt(21 30)]1/2 (7)
EQ
1
S2
[0.003 Nt(2 5) 0.062 Nt(6 20) 3.37 Nt(21 30)]1/2 (8)
EQ
1
S3
[0.69 Nt(2 5) 1.50 Nt(6 20) 1.93 Nt(21 30)]1/2 (9)
EQ
1
Sp
[4.04 Nt(2 5) 1.88 Nt(6 20) 15.6 Nt(21 30)]1/2 (10)
EQ
where
S1, S2, S3 = standard deviation of the 218Po, 214Pb, and 214Bi (Bq m-3),
Sp = standard deviation of the PAEC (nJ m -3),
Nt(...), E and Q were defined earlier.
The coefficients in the above four equations are the squares of the corresponding
coefficients in Equations 3-6. Terms involving the uncertainty of the background count
rate have been omitted because they are seldom significant.
A computer program based on the optimizing technique of Nazaroff (1984) (WWN5,

for a PC; see Table 2.7) has been written to do the calculations in Equations 3-10.
Results can be acquired within 15 sec after the end of counting. The program can also do
these calculations from any three-count radon progeny measurement.
The two outlined counting procedures can be applied to the same filter sample simply
by using two counting regimes in sequence: three counting intervals [(2-5), (6-20), and
(21-30)] for the modified Tsivoglou method; a single counting interval from 35-45 min
after the end of sampling (modified Kusnetz method). This provides a useful check
against errors in transcribing data and in calculations.

2.2.4.6
RAABE-WRENN LEAST-SQUARES METHOD
As used here, the term "Raabe-Wrenn least squares method" refers to a certain
configuration of alpha counters, a computer, hardware, and software for measuring radon
decay product concentrations (Raabe and Wrenn, 1969). This sytem can handle up to 10
samples simultaneously, which is needed when measuring the particle size distribution of
radon progeny particles (Sections 2.2.2.5 - 2.2.2.7). The method is also convenient for
single samples.
A. Components.
1. Up to 10, as needed, drawer-type gross alpha counters, Model TH-29-B or equivalent.
2. A portable personal computer with two free 8-bit expansion slots.
3. Two CIO-CTR05 computer interface boards (Computer Boards 44 Wood Ave.,

Mansfield, MA 02048, 508-261-1123; FAX 508-261-1094) or equivalent, installed in
adjacent slots of the above computer (item 2). One board must be set to address 0300
(hex) and the other to address 0304 (hex).
4. Two 37-pin D-connectors and hoods (Wire Pro, Inc., types 17-10370 and 17-1371;
available from Newark Electronics, 212-963-0289). Install five female K-LOC
connectors (King Electronics, Tuckahoe, NY, 914-793-5000) through the side panel
of each hood, and wire them to the pins corresponding to the five CIO-CTR05 counter
inputs. Note: the D-connectors must be made up in complimentary pairs so both can
be connected to the CIO-CTR05 boards at the same time.
5. Up to 10, as needed, RG-174 coaxial cables with K-LOC connectors (King

Electronics, Tuckahoe, NY, 914-793-5000).
6. Copies of the computer programs ALPHALOG (or ALPHALG2) and RWRENN6;

see Table 2.7.

B. Procedure.
1. Set up apparatus; it is best to arrange the alpha counters in a line, five on either side of
the computer. Install cables and power-packs.
2. Start the computer and make a directory with a name appropriate for the project you
are working on. Copy ALPHALOG and RWRENN6 into this directory. 1
3. Start ALPHALOG; ensure that the computer's time and date are set correctly; when
prompted, rn\un the test using the internal 1000 Hz pulser (a 10-second counting
period is appropriate) to verify that the boards have been properly installed.
4. Skip over the "Enter parameters" step (it is usually more convenient to enter the
parameters during counting).
5. Set the counting period (normally 60 seconds) and the number of intervals (normally
1000) and press Y in answer to the "Ready to Start" prompt. The program will go
into a preview mode, in which counts are collected and displayed — but not saved —
every 10 sec.
6. Collect the filter or particle size samples as described in Sections 2.2.2.5, 2.2.2.6,
2.2.2.7, or 2.2.4.2.
7. Promptly transfer the filters or other sampling substrates into the alpha counters; be
sure that the substrates are placed "dirty side up" and ZnS scintillator disks are placed
"shiny side up."
8. Verify from the computer preview screen that all channels are collecting counts; then
with an eye on the stopwatch, start official counting by hitting ENTER. Make note
of the time at which counting was started.
9. Once the counting is well underway, choose option [F7] to record the parameters
associated with the sample. Enter information when prompted.
1
Or copy these two programs into a directory entitled EOKPROGS and place EOKPROGS into the
PATH statement.

10. After sufficient data has been collected, press [Shift-F10] to stop; 40 min of data is
sufficient for calculating radon progeny, but 240-300 min is needed for calculating
thoron progeny.
11. If the parameters were entered during the data collection period (step 9), press Y to
proceed directly to the program RWRENN6, which calculates the decay product
concentrations. If not, press N, then correct the parameters using an edit program
such as MSDOS EDIT. Then run RWRENN6.
REFERENCES
George, A. C.
"Measurement of Airborne Radon-222 Daughters by Filter Collection and Alpha
Radioactivity Detection"
B. Seifert, H. J. van de Wiel, B. Dodet, I. K. O'Neill (editors)
in: Environmental Carcinogens - Methods of Analysis and Exposure Measurement -
Indoor Air, WHO, IARC Scientific Publications No. 109, Lyon, Vol. 12, pp. 173-179,
March (1993)
ICRP
Radionuclide Transformations: Energy and Intensity of Emissions.
Annals of the International Commission Radiological Protection, ICRP Publication 38,
Vol. 11-13 (1983)
Kusnetz, H. L.
"Radon Daughters in Mine Atmospheres. A Field Method for Determining
Concentrations"
Am. Ind. Hyg. Assoc. Q., 17, 85-88 (1956)
Martz, D. E., R. T. Harris, and G. H. Langner

"The Half-Life of 218Po"
Report UNC-J-002-88, UNC Geotech, Grand Junction, CO (1988)

Nazaroff, W. W.
"Optimizing the Total-Alpha Three-Count Technique for Measuring Concentrations of
Radon Progeny in Residences"
Health Phys., 46, 395-405 (1984)
Raabe, O. G. and M. Wrenn

"Analysis of the Activity of Radon Daughter Samples by Weighted Least Squares"
Health Phys., 17, 593-605 (1969)
Thomas, J. W.
"Measurement of Radon Daughters in Air"
Health Phys., 23, 783-789 (1972)
TABLE 2.4
DRAWER-TYPE ALPHA PARTICLE COUNTERS USED AT EML
Designation TH-29-B Greybox

Built by EML EML
Date of design 1981 1975
Photomultiplier
tube diameter (cm) 5.0 12.7
Largest filter
accommodated (cm) 5 10
Window material None None
Filter-to-window
spacing (mm) 2 3
Typical efficiency (%) 48 48
Estimated dead-time
each pulse (µs) 50 50

TABLE 2.5
ALPHA-EMITTING STANDARD USED AT EML
Identifying marks . . . . . . . . . . . . . . . . . . . . . . . . . . . #16

When obtained . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fall 1981
Where obtained . . . . . . . . . . . . . . . . . . . . . . . . . . . . Oak Ridge National Laboratory
241
Active material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Am
Size of active deposit (mm) . . . . . . . . . . . . . . . . . . . 18
Certifying agency . . . . . . . . . . . . . . . . . . . . . . . . . . . NIST
Certified activity (Bq) . . . . . . . . . . . . . . . . . . . . . . . -
Certified emission rate (alphas sec -1) . . . . . . . . . . . . 92.08
Mounting material . . . . . . . . . . . . . . . . . . . . . . . . . . Stainless steel
Diameter of mount (mm) . . . . . . . . . . . . . . . . . . . . . 25.4
Estimated ratio of emission to activity . . . . . . . . . . 0.504
Condition as of February 1988 . . . . . . . . . . . . . . . . Good
Efficiency multiplier . . . . . . . . . . . . . . . . . . . . . . . . 0.992

TABLE 2.6
TIME FACTORS FOR USE IN THE MODIFIED
KUSNETZ METHOD
Time after sampling* Time

(min) factor
40 7.21
42 7.02
44 6.83
46 6.63
48 6.44
50 6.25
52 6.06
54 5.87
56 5.67
58 5.48
60 5.29
62 5.10
64 4.90
66 4.71
68 4.52
70 4.32
72 4.18
74 4.04
76 3.94
78 3.75
80 3.61
82 3.51
84 3.32
86 3.17
88 3.03
90 2.88
*
Midpoint of counting interval.

TABLE 2.7
COMPUTER PROGRAMS USED AT EML IN CONNECTION WITH
RADON PROGENY MEASUREMENTS
Name Language Machine Method Comments
ALPHALOG.PAS Pascal PC Simultaneous collection of

data from up to 10 alpha
counters
WWN5.PAS Pascal Modified Nazaroff equations (1984) for
Tsivoglou any combination of sampling
and counting times, including
counting while sampling
RWRENN6.BAS GW BASIC PC Least squares Raabe and Wrenn (1969)

Figure 2.4. Sampling train for radon progeny measurements.

2.2.5 ATMOSPHERIC TRACING
2.2.5.1
INTRODUCTION
This section describes the apparatus and procedures used by EML to sample tracer
gases used in studies of long range atmospheric transport. The analysis of the collected
samples is described separately in Section 4.2. Atmospheric tracing is done primarily to
test meteorological models that predict the atmospheric transport and dispersion of
pollutants over distances as far as 3000 km from the source(s). Among other things,
these models are used in assessing the potential for "acid precipitation" in different
regions and under different meteorological conditions.
The tracer gases used in EML atmospheric tracing experiments are:
Global Background
Tracer Gas Acronym (fL L-1)
perfluoromethylcyclohexane PMCH 3.3

total perfluorodimethylcyclohexane PDCH 28.8
perfluoromethylcyclopentane PMCP 3.2
ortho(cis)perfluoro-
dimethylcyclohexane OC-PDCH 0.15
perfluorotrimethylcyclohexane PTCH <0.5
The first two tracer gases were identified by Lovelock (1982) and the others by Dietz
(1987). These gases are nontoxic and chemically stable. They were selected because
they have no natural or anthropogenic source apart from their release during tracing
experiments, and because they are detectable at their background levels (shown above)
using the procedures described here and in Section 4.2.

2.2.5.2
THE PROGRAMMABLE ATMOSPHERIC TRACER SAMPLER
The programmable atmospheric tracer sampler (PATS) (Model RD113, Gilian

Instrument Company, Dawes Highway, Wayne, NJ 07470) is used as the primary
sampler for all perfluorocarbon tracers. The unit, shown in Figure 2.5, is housed in a
waterproof 36 cm x 25 cm x 20 cm container and weighs ~ 7 kg. It consists of two
sections: the lid (air flow module, AFM) and the base (power control module, PCM).
The lid holds 23 sampling tubes, each containing 150 mg of Ambersorb adsorbent
(Rohm and Haas). The Ambersorb absorbs the tracer from the sample air flowing
through the tube. The air flow may be directed through a preselected tube by means of a
multiple port switching valve (Scanivalve, 10222 San Diego Mission Road, San Diego,
CA 92120) which is controlled by the PCM.
The base of the PATS contains a constant flow pump which draws air through the
selected sampling tube. The constant flow pump is based on the EML tethered air pump
system (Latner, 1986), and may be set to draw 10, 20, 30, 40 or 50 cm 3 min -1. The base
also contains programmable timer controls that allow for single or multiple start and stop
times over a 7-day period. These controls are also used for automatic analysis when the
unit is coupled to a gas chromatograph.
Two liquid crystal displays in the base indicate the time of day, the day of the week,
and the tube number, and a digital printer records this information at each tube change.
As a precaution against printer failure, this information is also stored in an integrated
memory circuit module (Polito, 1987) mounted on each lid. The memory module is used
during the gas chromatographic analysis phase (see Section 4.2), and this information is
stored in a computer for inclusion into a data base.
Power is supplied by an internal rechargeable battery which can operate the unit up to
30 days. Longer periods of operation are possible if 110 V A.C. power is available. All
lids are interchangeable and usable with any base, so that after 23 samples have been
collected, a new lid may be substituted to continue sampling.

2.2.5.3
ADSORBENT TUBE BAKE-OUT PROCEDURE
A. Introduction.
Programmable atmospheric tracer sampler (PATS) adsorbent tubes are decontami-

nated (baked out) by resistance heating of each tube at > 400 oC. This method is
applicable to all PATS lids. Up to 10 lids may be baked out at one time (Figure 2.6).
B. Special apparatus.
1. Constant current power supply, Power Mate Corporation Model BPA 2086-V or
equivalent with special interface.
2. Micromaster programmable controller, Model No WP6201-AA-AA or equivalent.
3. Matheson Model 3800 gas pressure regulator or equivalent (two regulators required).
4. PATS bases and lids (up to 10).
5. Primeline (Soltec) two channel strip chart recorder or equivalent.
C. Special gases.
1. Nitrogen, ultra high purity (UHP) (99.999%) or equivalent.
2. Nitrogen, Matheson Purity (99.995%) or equivalent.
D. Procedure.
1. Attach each lid to each base whose batteries have been fully charged. Disconnect all
battery chargers.
2. Insert a jumper in the receptacle labelled Analysis Connector of each base to disable
the sampling pump.

3. Attach the UHP nitrogen line to the To Equalization port of each lid. Set the
equalization nitrogen gas pressure to 207 kPa (30 psig).
4. Plug each lid AFM electrical connector into each base receptacle labelled AFM
Connector.
5. Set the clock time and day of the week of each PATS base and power up each unit.
The clock time is set at the thumbwheel switch marked Set/Time Alarm and the day
of the week by placing the appropriate Day Select switch to On.
6. Manually cycle through each of the 23 tubes using the base manual Valve Step
switch. Cycle each lid at least twice to assure seating of the Scanivalve. Leave the
tube number of each unit at "00" and turn off the power to each unit.
7. Attach the Matheson Purity Nitrogen gas line to the To PCM connector of each lid.
8. Set the UHP nitrogen pressure to 138 kPa (20 psig) and turn the nitrogen gas on.
Adjust the flow to ~ 30 cm3 min-1.
9. For each base, set the thumbwheel switch marked Duration to 0016 and the Sample
Quantity switch to "24". This sets the switching time between tubes and the number
of tubes to be sequentially decontaminated. There are only 23 tubes in each lid,
however, the base must switch to the 24th tube in order to complete the bake-out
cycle.
10. Plug all the electrical jacks into the Desorption Power lid connector.
11. Turn the constant current power supply on and set the current to 16.0 A.
12. Turn on the dual channel strip chart recorder to record the desorption voltage and
current.
13. Quickly turn each unit on, push the PATS base Operate switch to Off, bring the
Alarm toggle switch from Manual to Multi and then back to Manual. Bring the
Operate toggle switch to Run. This procedure should be completed within 1 min for
all 10 bases so that all units will start at the same time.

14. At the next minute, tube number 1 of each unit will switch into position, the current
will be turned on and the tube will be heated to > 400 oC for a 15-min period. The
contaminants will be desorbed into the nitrogen carrier gas stream. At the end of the
15-min heating period the current will turn off. At 16 min, the next tube will advance
into position and the heating cycle will be repeated until all 23 tubes have been
decontaminated.
15. Disconnect all wires and gas lines. Insert a 1/2 hole septum over all lid inlet and
outlet ports and disconnect the lid plug from the base.
2.2.5.4
DEPLOYMENT, SAMPLING, AND RETRIEVAL
Information on the deployment, sampling and retrieval may be found in the report by
Draxler and Heffter (1986), which gives a detailed description of one tracing experiment.
REFERENCES
Dietz, R. N.
"Overview of Perfluorocarbon Tracer (PFT) Technology Applied to Quality Assurance of
ANATEX Tracer Data"
Anatex Model Evaluation Workshop, Orlando, Florida, Oct. 20 and 21 (1987)
Draxler, R. and J. L. Heffter

"Across North America Tracer Experiment (ANATEX), Comprehensive Plan"
National Oceanic and Atmospheric Administration, Air Resources Laboratory, Silver
Spring, MD (November, 1986)
Latner, N.
"TAPS: Tethered Air Pump System"
USDOE Report EML-456 (1986)

Lovelock, J. E. and G. J. Ferber

"Exotic Tracers For Atmospheric Studies"
Atmospheric Environment, 16, 1467-1471 (1982)
Polito, M.
"A Data Acquisition System for Atmospheric Tracer Studies"

Figure 2.5. The programmable atmospheric tracer sampler.

Figure 2.6. Configuration of the PATS lid absorbent tube bake-out system.

2.3 ATMOSPHERIC DEPOSITION
Contact Person(s) : Mathew A. Monetti
2.3.1 SCOPE
EML collects radioactive debris that is dispersed into the atmosphere from nuclear
accidents and from the testing of nuclear weapons using two deposition collectors. These
collectors enable us to measure radioactive deposition at locations far removed from the
source. The collectors and collection methods described here have been used
successfully for many years. Presently there are about 75 sites worldwide at which
monthly collections are made. These samples are routinely radiochemically analyzed for
90
Sr. Following a known or suspected release of radioactivity, sampling and analysis
protocol can be altered in order to determine the arrival time and composition of the
debris.
We provide all the necessary supplies and instructions, in the appropriate language,
and maintain written communication with site operators.
2.3.2 POT COLLECTOR
2.3.2.1
INTRODUCTION
The determination of 90Sr and other radioisotopes contained in fallout can be carried
out on the total material collected in a high-walled pot. The collection of fallout is
simple, but the transfer of all the material in the pot must be done with great care in order
to collect all of the radioactive material and to avoid a buildup of contamination in the
pot, which may influence a subsequent sample.

2.3.2.2
APPARATUS
EML's collectors are stainless-steel pots, 0.076 m 2 in area, but many other high-walled
vessels are equally suitable. The requirements include smooth surfaces that do not absorb
the radionuclides and rounded corners for easy cleaning and durability. The pot collector
is shown in Figure 2.7.
2.3.2.3
DEPLOYMENT, SAMPLING, AND RETRIEVAL
For our program, the pot collector is placed in an open area away from buildings or
overhanging trees and shrubbery. An acceptable location is atop a one or two story
building with a flat roof not shaded by other buildings or trees. The pot is placed outside
on the first of the month and left there for one month. (During months of heavy rainfall,
it may be necessary to remove and evaporate some of the water prior to the end of the
month.)
At the end of the month, the water in the pot is evaporated to ~ 200 mL and
transferred to a 1-L polyethylene bottle. Distilled water is added to the pot and, using a
rubber spatula, the sides and bottom of the pot are scrubbed. The slurry is transferred to
the bottle and the washing is repeated with 1:1 HNO 3, again scrubbing and transferring
the slurry. Then the pot is washed a final time with distilled water and scrubbed. It is
extremely important to transfer all the solid material in the pot to the bottle. If necessary
more than one polyethylene bottle may be used for each month's collection. The bottle(s)
should be carefully labeled with the site location, sample dates, and the monthly
precipitation amount from the nearest recording station.

2.3.3 ION EXCHANGE FALLOUT COLLECTOR
2.3.3.1
INTRODUCTION
Like the pot collector, the ion exchange collector is designed for measuring fallout at
sites removed from the source. At sites where personnel and facilities are at a minimum,
the ion exchange collector is used. The collectors are exposed for monthly intervals and
the collected fallout may then be shipped to a laboratory for analysis. The collector can
be operated without a laboratory facility and consists of a funnel, an ion-exchange
column, and a leveling device (all constructed of polyethylene) mounted in a wooden
housing. The ion-exchange column is packed with paper pulp, ion-exchange resin and a
glass wool plug, and is saturated with water. A utility light fixture with a 100-W bulb
and a 30-m heavy duty extension cord is provided to heat the device in cold climates.
The ion exchange fallout collector is shown in Figure 2.7. A descriptive diagram of the
collector is shown in Figure 2.8.
2.3.3.2
MATERIALS
1. One plywood housing

2. One 30-cm polyethylene funnel
3. Two loaded resin columns, with caps
4. Two tapered caps
5. One leveling tube
6. One threaded T-connection
7. One piece of plastic tubing
8. One wash bottle
9. One set spare caps for mailing
10. One 100-W heating unit, where necessary

2.3.3.3
PREPARATION
The polyethylene ion-exchange column contains glass wool, paper pulp, and cation
exchange resin. The glass wool is the standard laboratory material. The paper pulp is
prepared from Whatman No. 41 filter paper or S&S No. 289 paper pulp by mixing in a
blender with distilled water.
Dowex 50W-X12 cation exchange resin (Bio-Rad Laboratories, Inc., 1000-T Alfred
Nobel Dr., Hercules, CA 94547) 50-100 mesh in hydrogen form is used. The resin is
washed with deionized water.
Glass wool is added to the bottom of each column and cation exchange resin and
paper pulp are added in that order. Approximately 17 cm of glass wool, 50 mL of wet
settled resin and 4 cm of paper pulp are packed into a column filled with distilled water.
Care is taken to prevent the formation of air pockets.
2.3.3.4
COLLECTOR LOCATION
The collector should be located with the same criteria used for selecting a rain gauge
site. These criteria are generally that the collector should be able to receive precipitation
in an open area free of buildings, trees, and other obstructions that might shelter the
collector. In many locations a flat roof is available - this is a suitable location, when the
collector cannot be placed in an open area at ground level.
2.3.3.5
SITE OPERATOR INSTRUCTIONS
1. Remove the ion-exchange column from its mailing tube and retain the tube for return
of sample.

2. With the ion-exchange column inverted (small end up), remove the small cap and
replace with the open tapered cap.
3. Force the short end of the J-shaped tube over the tapered cap and tape the other end to
the column so that the small flexible hose is approximately level with the top of the
tube.
4. Turn the column upright (large end up) and remove the large cap. Screw the column
to the polyethylene funnel and place in the wooden housing. (Retain both caps for
return of sample.)
5. Lead the long flexible tube, which serves as an overflow, through the hole in the side
of the housing.
6. If subfreezing weather is anticipated during the month, hang the heating element from
the eyelet in the housing and switch on during periods when snow or ice may
accumulate in the collector.
7. The collector is left exposed continuously for 1 month, beginning on the first day of
the month.
8. It is important that the resin column be kept saturated with water. If a dry period
extends for several days, examine the column and add water if necessary. A plastic
wash bottle is provided for this purpose. In most areas, tap water is satisfactory.
However, in a few localities where rain water is collected directly for household use,
distilled water should be used.
9. At the end of the observation period, use the wash bottle to rinse down any dust that
has accumulated in the funnel and into the column, and wipe the inside of the funnel
thoroughly with a wet tissue, which is then added to the column.
10. Remove the ion-exchange column from the assembly and replace the caps. (The new
column can be installed at this time.)

11. Note: The column label should contain the station name, the month of exposure, and
the total amount of precipitation recorded by the station during the month.
12. Pack the column in the original mailing tube and return to the analytical laboratory.
2.3.4 WET/DRY DEPOSITION COLLECTOR
2.3.4.1
INTRODUCTION
We examine the wet phase and dry phase of deposition to further understand
atmospheric pollution deposition processes, and the physical and chemical characteristics
of these pollutants. Our measurements of fallout from weapons tests were largely
directed towards stratospheric fallout, which is primarily deposited by way of
precipitation scavenging. Dry deposition processes are also important and, therefore, it is
desirable to measure wet and dry deposition separately.
2.3.4.2
APPARATUS
EML's wet/dry deposition collector is a two-bucket system with a movable peaked

cover designed to expose the wet and cover the dry bucket at the onset of precipitation,
and vice versa (Volchok and Graveson, 1976). There is a conductivity sensor on each
side of the roof. The sensor base plate electrode is separated from the parallel bar
electrode above by a thin (about 0.8 mm) air space. Any electrical flow between the
electrodes activates the motor in the base of the unit and the counter-weighted lid moves
to cover the dry bucket. When the circuit is broken, the cover returns. Heaters are
mounted below the sensors and are activated when the temperature drops below 4 oC to
melt snow or ice accumulations on the sensor, or when the instrument is in the wet
collection mode to evaporate moisture from the sensor. Thus, when properly adjusted,
the wet collector will be exposed only during periods of continuous precipitation.

2.3.4.3
SAMPLING AND DEPLOYMENT
In the past, we have used stainless-steel pots to collect radioactive debris from
weapons tests, and heavy polyethylene buckets to collect trace metals. Since many of
EML's sites are remote from the Laboratory, we have adopted a commercial container
which has a positive closure to prevent leakage during shipment. The opening in the
plastic bucket is about 30 cm in diameter. The sampling containers for these wet/dry
collectors are polyethylene buckets particularly well-suited for shipping because of the
design of the lip and cover [Freund Can Co., 167 West 84th St., Chicago, IL 60620
(As-1137/5541 plastic pail with cover)]. On the underside rim of the cover there is a
groove with an O-ring seal. When the cover is securely hammered onto the bucket with a
rubber mallet, no leakage will occur. The cover is destroyed when it is removed from the
bucket at the Laboratory. The sample buckets are shipped in fiber mailing boxes.
In 1978, EML started to use Aerochem Metrics Model 201 wet/dry collectors
(Bushnell, FL) at some of our sampling sites. This collector is similar in concept and
design to EML's collectors. Both the EML and the Aerochem Metrics collectors are
shown in Figure 2.9. The major mechanical difference is the Aerochem Metrics clutch
system and switching system. EML's collector uses a shear pin to prevent damage to the
motor when the lid is frozen in place. The Aerochem unit has a clutch on the motor drive
of the covering lid. This clutch eliminates the problems caused by frequent shear pin
breakage common to the EML units at windy or cold sites. The switches on the motor
box of the Aerochem Metric unit are mercury-wetted switches, whereas microswitches
are used in our units.
REFERENCE
Volchok, H. L. and R. T. Graveson

"Wet/Dry Fallout Collection"
in: Proceedings of the Second Federal Conference on the Great Lakes, Great Lakes
Commission, pp. 259-264 (1976)

Figure 2.7. Ion-exchange fallout collection and fallout pot collector.
Figure 2.8. Ion-exchange fallout collector.

Figure 2.9. Aerochem metrics wet/dry collector and EML wet/dry collector.

2.4 SOIL
Contact Person(s) : Catherine S. Klusek
2.4.1 SCOPE
Presented in this section are possible uses of soil sampling and some recommended
procedures for this sampling and for the preparation of the samples. An attempt is made
to point out some of the problems that exist in site selection, and the sampling methods
that are available.
2.4.2 SAMPLING OBJECTIVES
2.4.2.1
INTRODUCTION
The sampling of soil is a useful approach to determine the accumulated amounts of

airborne long-lived radioactive and stable contaminants that deposit on the ground. Soil
sampling is, however, of questionable value in attempting to estimate small increments of
deposition over a period of a few years or less. It is not recommended as a routine
method of environmental monitoring except in preoperational surveys.
Historically, soil sampling procedures for radionuclides were modifications of

techniques used in agriculture and engineering. Often, not enough emphasis is placed on
the importance of a proper sampling method to accurately represent the total pollutant
being sampled. The objectives of the project should be well-defined and the degree of
precision required should be established before sampling. The purpose of the project
(deposit, resuspension, root uptake) should dictate the type of sampling (total inventory,
surface sampling, depth profile) used. Site characteristics, such as soil type, topography,
source, and current distribution of the contaminant must be taken into account when
designing the study. Other factors to be considered in the design stage are the uniformity
of the contamination, the required accuracy necessary to provide reasonable results, and
the minimization of cross-contamination.

2.4.2.2
DEPOSITION INVENTORIES
The most direct use of soil measurements is for estimating the inventory of the
material deposited over a given area. EML has used soil analyses in estimating the
deposition of 90Sr (Hardy et al., 1968) and plutonium (Hardy et al., 1973; Krey et al.,
1976a) on a worldwide basis, and in estimating the deposition of 90Sr (Hardy et al., 1972),
137
Cs (Beck and Krey, 1980) and plutonium (Hardy, 1976) northeast of the Nevada Test
Site. Such inventories require the selection of a sufficient number of representative sites,
with the density of the sites depending on the accuracy sought. A statistical sampling
scheme is generally not employed in sampling global fallout because the aerial
distribution and particle size are nearly uniform over large areas (i.e., latitude bands).
Low-level baseline sampling would require the careful selection of sites that serve to
integrate fallout over time.
The most useful measures of the concentration of deposited material in soil relate to
the amount per unit area. Sampling is therefore carried out in such a way that the weight
of the material collected can be directly related to the area sampled and the depth of the
sampling. The analytical results from a weighed aliquot of the soil sample can then be
readily related to area concentration.
An additional requirement is that the sample is taken to a sufficient depth so that all
of the deposited material is sampled. Without previous knowledge of the depth of
penetration, an excessive sampling depth must be selected. This results in dilution of the
radionuclide or other contaminant of interest. If time and cost considerations allow, it is
recommended that a depth profile be taken (see Section 2.4.3.3). An optimum depth for
sampling, which should contain 90-95% of the total material of interest, can then be
selected. In our worldwide 90Sr network we have increased our depth of sampling over
the years from a few centimeters to 30 cm. Even so, at some sites typified by calcareous
soils, the 90Sr has moved deeper than 30 cm. Sampling parameters should be reevaluated
and decisions made on a site basis.
Criteria for site selection. When the accumulated deposition over a given time
period is to be estimated by soil sampling, it is necessary that the area selected for
sampling has been undisturbed for at least the time interval that is of interest. As the time

interval increases, it becomes increasingly more difficult to obtain an accurate history of

the site. In studies of cumulative fallout deposition, areas undisturbed since the early
1950s are sought. Institutional property will have certain advantages over private
property in these cases.
The second criterion, that of representativeness of the sample site, depends on the
surroundings and the meteorological or climatological factors of the area. This generally
requires that the site selected should be at the center of a large, flat open area.
Accumulative areas at the foot of slopes, in low spots or in flooded areas are not suitable.
The site should not be near enough to buildings or trees to be sheltered during blowing
rains. The sampling location should be 100 m or more from dusty roads. A large area of
collection is desirable to make the sample more representative. A surface area of 500-
1000 cm2 is adequate when a composite of 10 cores is taken over a reasonable distance
(~ 30 cm apart).
The third criterion, that the deposited material remain in place, generally requires that
the area be vegetated and have moderate to good permeability. There should be little or
no runoff during heavy rains and no overwash at any time. The soil should have a base
exchange capacity adequate to keep the contaminant from being readily leached into the
ground water. A good grass turf aids in absorption of water and reduces the likelihood of
runoff. Such sites are frequently found on smooth ridge crests, level virgin land, and in
well-kept lawns and grounds around institutional buildings.
At EML, we recommend short-cropped grass sods as the most suitable sampling

areas. Higher stands of vegetation may bias the collections by acting as a filter to remove
airborne material in excess of what would normally be deposited. In wooded areas, the
nonuniform distribution of tree canopies will lead to unevenness in deposition of fallout
materials. Soils having high earthworm activity should be avoided because of uneven
mixing of the soil to considerable depths. Rodent activity also makes an area unsuitable
for sampling (Alexander et al., 1960).

2.4.2.3
DEPOSITION INCREMENT
Incremental estimation of a contaminant through soil sampling and analysis should be

undertaken only after careful planning. Because of the large uncertainties in sampling
and the inherent variability in soil, estimating short-time increments of deposition history
or deposition changes of small degrees is not recommended. When monitoring global
fallout, short-term changes in radiation concentrations are generally small compared to
the variability in the local radionuclide distribution. Direct collections of deposition or of
airborne material are much more specific and yield more information with respect to the
time when contamination occurred.
2.4.2.4
OPERATIONAL OR ACCIDENTAL RELEASES
Following an acute release of a contaminant or an accident at a specific facility,

surface soil sampling soon after the event can be used to define the contamination
contours or distribution pattern. This would require sampling only the top 5 cm of soil,
including the vegetation. Our experience indicates that attempts to sample a shallower
depth results in less reproducible samples. In many areas, a site meeting the criteria for
an optimal sample has a root mat extending several centimeters into the ground, and it is
rarely possible to remove a core <5 cm in depth intact.
In the case of accidental or operational releases, consideration must be given to liquid

effluent as well as airborne particulate deposition. The amount deposited may vary with
direction and distance from the release point. Airborne particle dispersal is affected by
particle size and meteorological patterns. Gaussian plume models which take into
account meteorology, stack height, topography, and deposition velocity of the particles
are used to map local dispersion patterns. The horizontal dispersion of liquid effluent
releases is influenced by the composition and quantity of the liquid, the topography, the
soil type, and the properties of the contaminant of interest.
Sampling techniques used in evaluating acute releases are more site dependent and
methods used for fallout deposition may not be appropriate. Differences in the methods

are dictated by the nature of the distribution of the contaminant in the soil, the range of
particle sizes, and the generally higher levels of releases. Soil sampling in locally
contaminated areas, such as Rocky Flats, can be inventoried by EML methods where the
contaminant was initially made airborne in micron size particles from the source (Hardy
and Krey, 1971).
Criteria for site selection. Wind roses and atmospheric dispersion calculations
provide useful guidance in selecting appropriate soil sampling locations. Figure 2.10
shows a suggested distribution of sampling sites covering the area surrounding a
plant, with emphasis on the downwind direction. This approach to soil sampling was
used by EML at Rocky Flats (Krey, 1976; Krey et al., 1976b). Samples are commonly
collected from a regular grid or a radial pattern, at least close to the facility. When using
such a systematic sampling design, care should be taken to ensure that the repetitive
spacing of the sampling points does not introduce an error in the results. Consideration
should also be given to the likelihood that a grid point can not be used for sampling.
Some alternative random location or selection procedure should be established during the
planning stages. Soil sampling within a 16 km radius should give an adequate
preliminary picture of levels around the plant. It is also suggested that one or more
samples be taken close to the center of the most heavily populated area in the vicinity of
the plant. When sampling at facilities that release activity via tall stacks, sample
locations at considerable distance from the potential release point may be indicated.
The same site selection techniques can be used for a preoperational survey around
a plant. When choosing sampling locations at this early stage, it is desirable to select
areas that can be resampled at a later time, should it become necessary. Samples should
not be taken from the identical location since the sampling depletes the soil and alters the
concentration of the pollutant under investigation. Rather, a sampling plot of several
square meters should be established and samples removed from different areas of the plot.
2.4.2.5
AGRICULTURAL AVAILABILITY
When evaluating soil for uptake availability of a contaminant of interest, it is not

necessary to measure the total deposit but only the amount in the root zone that would be
available to the plant or crop of interest. In most cases this would be the depth of the

plowed layer. In addition to root zone concentration, the extent to which the nuclide or
contaminant is chemically available for uptake must be considered. The availability of
the particular contaminant to the plant is rarely 100%. The processes influencing the
mobility and availability of radionuclides in soil are complex and have been discussed by
several researchers (Schulz, 1965; Russell et al., 1971; Eisenbud, 1987). Routine
procedures for soil sampling will not be appropriate for this type of study because of the
distribution of the nuclide. Field studies of environmental levels of radionuclides in agri-
cultural soils have confirmed the nonuniformity of the concentration distribution due to
mixing of the soil during cultivation and depletion by plant uptake and harvesting (Hardy
and Bennett, 1977).
2.4.2.6
RESUSPENSION AVAILABILITY
There is no standard method to sample for availability of a contaminant in the soil for
resuspension. The direct measurement of the airborne contaminant is the only
sound approach to the problem of evaluating exposure to resuspended material. The
practical problems of the mechanics of sampling make it difficult to take a very shallow
soil sample with reliability. In trying to sample 1 cm or less it is very difficult to take into
account the variation in the ground contour and to reproduce a particular sample. EML
has tested other techniques, such as pressing gummed film to the surface, but these also
have many mechanical difficulties (Krey et al., 1977). Another approach is to measure a
depth profile at the site and plot the contamination as a function of depth. This has been
found in practice to be an exponential, and extrapolation of the curve to zero depth might
give an index of suspendability. This approach is limited by the error introduced if the
shape of the curve as it approaches the surface deviates markedly from an exponential
function. Resuspension concepts and prediction of the degree to which resuspension may
occur have been reviewed (Healy, 1980; Sehmel, 1980).
2.4.3 RECOMMENDED PROCEDURES
A few soil sampling methods will be discussed in this section. Variations on these
techniques or alternate methods (ASTM, 1983a; Bernhardt, 1976; EPA, 1979, 1983;
Gilbert, 1987) may be necessary to accommodate site specific characteristics or the

objectives of the project. The standard EML procedure for collecting soil is described in
the section on core method below, i.e., 10-8.9 cm diameter cores spaced 0.5 m apart on a
flat grassy lawn are collected to a depth of 5 cm, representing an area of 620 cm 2.
In all the procedures discussed, it is important to consider the potential for cross-
contamination. If depth profiles are taken, it may be necessary to decontaminate or
discard tools as different levels of contamination are sampled.
2.4.3.1
CORE METHOD
The procedure described here is designed to obtain samples that will measure the total
amount of an initially airborne contaminant that has fallen out in a given area.
The criteria for selecting an optimal site have been discussed in Section 2.4.2.2.
All analytical values must be related to the surface area sampled. The surface area
and depth define the volume; the weight of the volume of dry soil defines the field bulk
density. These data are necessary to convert to radioactivity concentration per unit
surface area (i.e., Bq m-2).
A recommended procedure is described as follows.
1. Following the selection of an undisturbed site which meets the criteria previously
discussed, lay out a straight line transect about 4.5 m long. If the site is to be re-
sampled at a later time, record distances to fixed landmarks to identify the relative
location of the transect or adopt a systematic scheme or grid.
2. If the vegetation cover is not to be included with the soil sample, or is to be kept as a
separate sample, the vegetation is removed to the surface level.
3. Using the 5 cm depth top soil cutter, press it into the ground without twisting or
disturbing the grass cover or surface soil. This may best be accomplished by stepping
on the rim of the cutter with both shoe heels. If more force is required, a rubber
mallet may be used. Gently twist the handle of the cutter to cleanly remove the top
soil plug. Place the core in a plastic sampling bag.

4. Repeat the process until the desired number of cores have been sampled. We
recommend 10 cores for providing a representative sample (Alexander et al., 1961).
Samples of 20 and 10 core composites were collected in about 10 areas and no
significant differences were found in the estimated 90Sr deposit. Compositing soil
samples provides a larger sample volume and possibly a more representative sample
of the area. Compositing is discussed further in Bernhardt (1976) and Gilbert (1987).
Take 10 top soil cores in a straight line about 30 cm apart, placing the cores in a
plastic bag. (The total area sampled is 620 cm 2.)
5. Sometimes it may not be possible to remove a 5 cm depth plug cleanly because of a

thick root mat. If the top soil and bottom soil are to be combined, a 10 cm or 15 cm
deep cutter may be used to remove the top soil by pounding it part way into the
ground with the rubber mallet, until it is possible to remove the core intact.
6. Next, take the subsoil samples down to the desired depth with the auger. A slight
downward pressure with slow turning will guide the auger. When the cylinder is
about 3/4 full, remove the auger slowly and either tap out or scrape out the soil with a
large flat blade knife. Continue to use the auger until the desired depth has been
sampled. If rocks or roots impede the auger, it may be possible to carefully remove
them. They should be included with the sample. If, however, this destroys the core,
the sample should not be used. It is a useful practice to place the soil from the core as
it is removed into a plastic pail until the entire depth is removed. Then, if the core is
not suitable, it may be poured back into the hole. Only after the entire sample is
successfully removed is the soil added to the sampling bag. Repeat the procedure for
the remaining cores.
7. After collection, label the plastic bag containing the sample, fold, and seal with a
heavy duty stapler. If a portable scale is available, the wet weight can be taken in the
field. Then place the sample in a canvas bag and tie firmly. The label should include
the date, location, and depth.
8. The holes should be filled with top soil to prevent an accident. A new grass cover
will develop in a few weeks. If immediate restoration is necessary, plugs may be cut
from a piece of sod.

Using the above procedure, a site can be sampled in two increments, 0-5 cm and
5-30 cm. This is useful in areas where most of the contamination is in the surface cut of
the soil. In other sampling situations using cores of 10 and 15 cm depth will provide
incremental samples: 0-5, 5-10, 10-15, and 15-30 cm. When attempting this type of
incremental sampling, attention must be given to two sources of error: contamination by
fall-in of soil from the upper layers of more highly contaminated soil as the subsequent
cores are taken from the hole and error in depth due to compaction.
A. Limitations.
Implicit when using the above sampling method is the need to take the sample deep
enough so that all the radionuclide deposited is collected. The extent of vertical
penetration will depend primarily upon the soil type with other factors, such as amount of
annual precipitation and chemical form of the nuclide, playing a confounding role. [See
Section 3.3 Field Gamma-Ray Spectrometry for a discussion of the use of in situ
spectrometry to aid in establishing the depth of penetration.]
There is no simple satisfactory way of sampling powdery, dry, loose, single grain soils
by this core method. It is best to take samples when the soil has enough moisture to be
coherent even if this requires wetting the area to be sampled by sprinkling. An alternate
method for sampling loose soils is to leave the corer in place and scoop out the contents.
Only one composite depth can be taken however, since once the corer is removed the
integrity of the core is lost.
B. Sampling equipment for the core method.
Tools for sampling may be of any material and type that will take a core of equal area
through its entire length. The following equipment are used at EML:
1) Barrel auger - Standard Type No. R-HEO, 8.2 cm ID, with T-handle, Arts Machine
Shop, American Falls, ID.
2) Top soil cutters - 5, 10, 15 cm depth, 8.9 cm ID. Made from 0.155 cm thick cold-
rolled steel. One end sharpened on a lathe, the other end fitted with a welded handle.
3) Other equipment -

Long, flat blade knife for removing cores from auger

Measuring tape (~ 8 m)
File for sharpening top soil cutters
Rubber mallet
Plastic bucket (5 L).
2.4.3.2
TEMPLATE METHOD
Although the core method is preferred, there are areas where the rocks will make it
impossible to use this technique. An alternate method we employ in these areas is to cut
out a 900 cm2 sample using a 31.6 cm square-template for guidance. The soil and rocks
are removed with chisels and scoops down to the desired depth. The rocks are included
and weighed with the sample. The large rocks can be discarded after removing loose dirt.
The remaining smaller rocks are crushed as part of the sample.
This method is comparable to the ring method used by the Nevada Applied Ecology
Group (NAEG) for sampling sandy and rocky soils. Here a 12.7 cm ID ring with a lip to
assure constant depth of penetration is used. The soil adjacent to the exterior of the ring
is removed to the depth of the ring. The confined volume of soil is then transferred to a
plastic bag using an appropriate tool. Depth profile may be drawn using this method by
repeating the steps for each subsequent depth to be sampled. Removal of soil exterior to
the ring is necessary to minimize the possibility of cross-contamination of the deeper, less
radioactive fractions (Fowler et al., 1974). A minimum of five separate samples
(633 cm2) are recommended along a transect and composited for analysis.
A. Sampling equipment for the template method.
Tools for sampling may be of any material that will maintain a rigid shape and
straight edge. The sampling equipment used at EML consists of:
1) A square template 20 cm or 30 cm on the inner edge made of 0.157-cm thick cold-

rolled steel, with holes at the corners,

2) Pins or long nails of corresponding diameter to the corner holes of the template to
anchor the template to the surface,
3) Chisels, knives, and small shovels.
2.4.3.3
TRENCH METHOD
The trench method is used to determine the depth of penetration of a radionuclide or

contaminant or to establish a detailed depth profile. The most suitable area for taking soil
profiles is one where there are no rocks and stones, and very few pebbles. The procedure
works well in sandy loam, loam or loamy sand types of soil (Hardy, 1974; Fowler et al.,
1974). Use of this method in unsuitable areas will result in cross-contamination of lower
profile cuts with higher specific activity subsoil from upper layers. Cross contamination
effects of worms and burrowing insects, cracks from swelling, and other biological and
physical disturbances must be considered.
1. As far as grass cover and terrain are concerned, the site selection criteria previously
described apply. As in the core sampling method, the depth profile samples are taken
so that the weight and depth of the material collected can be directly related to the
area.
2. If the vegetation represents a seasonal growth, it should be clipped to 2.5-5 cm over a

measured area.
3. Lay a tarpaulin (about 0.6 m2) on the ground near the clipped area. Dig a trench of an
appropriate size for ease of access (about 60 cm wide by 90 cm long by 60 cm deep,
about 15-25 cm deeper than the desired sampling depth) immediately adjacent to the
clipped area, placing the dirt on the tarpaulin. Usually the sod can be cut out in
blocks making it easy to replace after sampling.
4. The face of the trench (adjacent to the clipped area) is smoothed from side to side
with a flat blade shovel or mortar trowel, making it perpendicular to the surface.

5. A metal flat-bottomed three-sided pan with sharpened edges on the open side (15 cm
x 15 cm x 5 cm deep; 230 cm2) is pressed into the face from ground surface to 5 cm.
Remove the first cut and seal in a small plastic bag.
6. Cut away the top soil on either side of the cut to make a shelf about 35-cm long by
15-cm wide and 5 cm deep from the surface. Lightly brush away any particles that
may have fallen on the shelf.
7. Again, push the open-end cutting pan into the side and cut out the next incremental
sample. Continue this procedure until the desired depth is reached. The actual depth
of each cut can be determined by placing a two by four on the surface and measuring
to each subsurface.
8. When all the samples have been taken, fill the trench with dirt on the tarpaulinand
replace the sod taken from the trench.

A. Limitations.
A depth profile is only useful for finding the relative vertical distribution of the
radionuclide. Since only 100-300 cm2 of surface area at one spot is sampled when taking
depth increments, the integrated deposit is not necessarily representative of the area.
The trench method is more time consuming and more difficult than taking core
samples. Therefore, researchers rarely sample and composite more than two samples per
trench and rarely take duplicate profiles. However, if care is taken, there will be very
little cross contamination and the data collected in terms of the depth profile will be more
accurate.
Some consideration should be given to the problems introduced by sampling across

soil horizons. Soil horizons differ in chemical and physical properties.
B. Sampling equipment for the trench method.
The sampling equipment used by EML consists of:
1) Three-sided square pan with cutting edges on the open side (15 cm x 15 cm x 5 cm
deep made of 0.157 cm thick cold-rolled steel, welded at the corners);
2) Mortar trowel;
3) Long flat-blade knife;
4) 1.2 m piece of two by four.
2.4.3.4
NONHOMOGENEOUS TERRAIN METHOD
Previous site selection techniques discussed above assure a representative sample by

the homogeneous and undisturbed nature of the location. In geographic areas
characterized by sparse vegetation, wind erosion, and nonuniform drainage, the fallout is

expected to be nonuniformly distributed. A procedure for recovering a representative soil

sample from complex terrain for the purpose of determining the integrated radionuclide
inventory deposited in the area is described in Krey and Klusek (1995). The following
protocol is used in such a nonhomogeneous terrain area.
1. In the area of interest, select a site that is visually representative of the area. An
optimal area would be without excessive rills, washout areas, and gullies that would
indicate areas of intense erosion. If the area is very diverse in landscape,
consideration should be given to subdividing the area and taking samples in each area.
2. Determine the number and types of covers (strata). Some common strata are: open
pavement, trees, shrubs, grass, rocks. Some judgment is required with small trees and
large bushes. Vegetation should be assigned as a cover type if there is a significant
difference in the character or amount of accumulation of soil at their base. It is
preferable to preassign the vegetation to a category before attempting to estimate the
linear percentage to avoid changing the category's characteristic in midcount.
3. Select, at random, a starting point and mark off a 100 m straight line transect in a
randomly selected direction.
4. Using a measure that is a reasonable small unit, i.e., every 0.1 m, count off the
number of meters intersected by each stratum. Estimate the proportion of each cover
along the total transect.
5. Determine the number and method of sampling to be used in each identified stratum.
Samples should be taken in every stratum that represents more than 5% of the total
transect. For each cover type to be sampled:
a) Sample (systematically) by the core method at a fixed interval (e.g., 6 m) along

the transect using the closest sampling location within 0.5 m of the mark.
b) Sample (randomly) each cover type by the template method. It is only feasible
to take two to four samples by this method.

6. The samples taken in a stratum are combined. At this point the soil samples (one per
stratum) can be analyzed:
a) independently to obtain information pertinent to each stratum and the total

inventory estimated by summing the proportional contribution from each
stratum;
b) the soil samples can be composited based on the areal proportion and only this
composite sample for the site is analyzed.
2.4.4 SAMPLE PROCESSING
The procedures to be followed to process a soil sample to obtain a representative

subsample for analysis depend to some extent on the nuclide of interest, the size of the
sample, and the amount of processing already undertaken in the field. Any one of, or a
combination of, the following procedures may be employed. The soil may be crushed to
reduce the size of stones, sieved to remove sample content above a desired size, blended
to obtain a more homogenous distribution of particle sizes, or milled to reduce the
particle size of the soil. If the sample was sieved or split in the field or a small sample
was taken, the preparation process may be eliminated. For some purposes, it is possible
to remove large nonporous stones and not grind them to size, but they must be weighed
separately and an appropriate allowance made. As a general rule, at EML samples are
air-dried, crushed to break up large rocks, blended to allow a representative aliquot to be
removed, and only this subsample is pulverized. The pulverizing reduces the soil to a
standard particle size. Other preparation protocols are addressed in ASTM (1983b).
Global fallout is relatively homogeneous in particle size and distribution in the

sample. When sampling accidental or operational releases, the procedures described here
may not be adequate. Care must be taken that the subsample taken for analysis accurately
represents the total sample. This will depend on the size and the degree of heterogeneity.
Multiple subsampling and multiple analysis may be the only technique available to
adequately define the content of radionuclides in heterogeneous samples.
Care must be taken in all stages of processing to avoid contamination from previously
prepared higher concentration samples. In addition to careful cleaning of the equipment

between samples it is sometimes advisable to run blank samples (e.g., sand) between the
samples being processed. Another technique to minimize cross-contamination is to order
the processing of samples starting with the lowest level samples first. This is difficult to
know in an exact sense, but generally deeper depth samples will have a lower content
than surface samples.
2.4.4.1
DRYING
1. The "excludable" fraction of the sample should be defined, dependent on the

contaminant of interest. Vegetation, root mat, large organic pieces, stones, etc., in
some cases can be discarded. If this is the case, the sample can be screened using a 6
mm sieve or a 10 mesh screen. The appropriate steps of drying process (e.g., Step 3
and/or 5) can then be skipped.
2. If facilities are available, the samples can be dried at 100 oC overnight. Oven drying
has the advantage that most materials will become brittle enough to mill properly.
Otherwise, spread out the sample on a plastic sheet or in trays and allow to air dry.
This will take 3 days to 2 weeks. Turning the soil will facilitate the drying process
especially when the drying area does not allow the soil to be spread in a thin layer.
However, turning is not advised when the rising dust might cause contamination of
other samples.
3. Break up soil aggregates and pull apart the top soil plugs consisting of vegetation and
root mat. Using scissors or clippers, cut up the vegetation so that it is distributed
homogeneously throughout the sample.
4. When completely dry, weigh the entire sample.
5. Remove large rocks, weigh separately, and discard.

2.4.4.2
HOMOGENIZING
When using equipment in this stage of preparation close attention must be paid to
cross-contamination. Machinery should be dismantled and decontaminated between
samples.
1. If the sample contains small rocks or pebbles:
a) crush the entire soil sample, reducing the sample to 6.35 mm, or
b) sieve the entire sample through a 12.7-mm screen.
2. Then blend the entire sample for 15-30 min.
3. Spread out the sample, mark off quarters, and take scoop-fulls from each quarter in a
consecutive manner until about 3 kg has been collected.
4. Pass this subsample of soil through a grinder, ball mill, sieve or pulverizer. The
pulverizer used at EML reduces the soil to <1.3 mm (15 mesh equivalent). Transfer
to a wide-mouth polyethylene bottle.
5. When ready for analysis, roll the bottle to mix the sample thoroughly.
2.4.4.3
RAPID PREPARATION METHOD
An alternate soil sample preparation procedure is employed to allow rapid processing

and aliquoting when gamma-ray spectrometric analysis for short-lived radionuclides is
desired. This procedure was developed to provide timely data from surface soil samples
collected following the Chernobyl reactor accident. After weighing the sample in the wet
state (as received), the entire sample is sieved through a steel mesh screen with square
openings, 1.27 cm on edge. Rocks and pebbles of greater size are brushed and discarded.
Vegetation and root mat are cut to a size (about 0.6 cm) that permits them to pass through

the sieve. The mixture of wet soil and vegetation is homogenized by hand for several
minutes before aliquots of about 100 g are removed. If desired, the remainder of the
sample can then be dried and processed as previously described.
In experiments involving 75 sets of duplicate wet samples, 87% of the samples agreed
with each other to within two standard deviations of the propagated Poisson counting
uncertainties. This indicates a reasonable degree of homogenization of the wet sample.
In addition, the ratio of the deposition values for wet samples to dry pulverized samples
was close to unity for most radionuclides. The homogenization of the wet samples is not
as efficient in mixing the infrequent particles enriched in refractory nuclides, resulting in
a consistent bias toward higher wet values (Krey et al., 1986).
2.4.4.4
PROCESSING EQUIPMENT
The following equipment are used at EML to process soil:
1) Scale - capacity of 50 kg;
2) Sieves - various screen sizes;
3) Splitter - sample reducer, Humbaldt Mfg. Co., Norridge, IL 60656;
4) Crusher - jaw crusher, Morse Bros. Machinery Co., Denver, CO 80214;
5) Blender - twin shell pin intensifier blender, 16 qt capacity, Patterson-Kelly Co., Inc.,
East Stroudsburg, PA 18301;
6) Pulverizer - pulverizing (hammer) mill with #50 Screen, Weber Brothers & White
Metal Works, Inc., Hamilton, MI 49419;
7) Drying oven.

2.4.5 REPRODUCIBILITY
The accuracy of the estimated deposit at any site is related to the representativeness of
the soil sampling and aliquoting, and to the quality of the analysis. The sampling design
should prevent biases and allow errors to be readily determined. A QA program should
be maintained at all stages of the project. A detailed discussion of QA for soil sampling
is presented in Barth et al. (1989) and van Ee et al. (1990).
2.4.5.1
REPRESENTATIVENESS
If the criteria for selecting a soil sampling site are satisfied, the EML sampling
method has been shown to provide reasonable estimates of local and regional fallout.
Integrated fallout of 137Cs, 90Sr, and 239,240Pu have been shown to be quite uniform within
metropolitan areas characterized by the same annual precipitation. The deposition
variability of these radionuclides was <15% (Hardy, 1975). In extensive studies of 90Sr
deposition, 50 paired sites, 2-40 km apart, showed an average difference expressed as a
percent of the mean of <10% (Hardy and Krey, 1971).
Where it can be assumed that there is little gradient in the cumulative fallout within a
city, duplicate soil collection and measurement has inferred a precision of sampling and
analysis of 8% for 137Cs (Beck and Krey, 1980), 9% for 239,240Pu, 3% for the
Pu/239Pu atom ratio, and 4% for the 241 Pu/239 Pu atom ratio (Krey and Beck, 1981) for
240
the determination of these values at any given site.
The statistical analyses of common sampling designs, such as random or systematic

sampling, are discussed in a familiar text such as Cochran (1977).
In cases where the contaminant may not be uniform in size or concentration, the
resulting "hot spots" will be found in some but not all the samples. Uneven physical
distribution of particles or particles with a large range of sizes and concentrations
complicates the collection of a representative sample and subsampling. Gilbert (1987)
discusses different approaches for sampling nonuniformly distributed contamination.

2.4.5.2
ALIQUOTING
Analyses of Utah soils have shown that the prepared soils are sufficiently
homogeneous, after following the procedures described above (air-dry, crush, blend, and
pulverize), that duplicate aliquots agree within two standard deviations of the counting
rate for 137Cs (Beck and Krey, 1980) and the radioassay value for 238Pu, 239,240Pu, and
241
Am (Krey and Beck, 1981). A mean deviation of 7% was found for 426 pairs of
duplicate soil aliquots, representing the subsampling and analytical errors for 90Sr over an
8-y period (Hardy and Krey, 1971).
2.4.5.3
ANALYTICAL ACCURACY
A. Soil standards.
Two standard reference materials are available through the National Institute of
Standards and Technology (NIST, formerly the National Bureau of Standards), SRM
4353 Rocky Flats Soil Number 1 and SRM 4355 Peruvian Soil. SRM 4355 has
nonmeasurable radioactivity concentrations for many fallout radionuclides and is
intended for use as a blank. Upper limits of the radioactive concentrations are given and
can be used to monitor laboratory contamination and background counting rates.
Secondary soil standards, that is, large quantity soil samples that have been dried,
blended and pulverized and aliquots of which have been analyzed by inter- and intra-
laboratory comparisons, are used at EML as the best possible substitute for a primary
standard soil sample for artificial radioactivity. There is no satisfactory way to add a
radionuclide to a soil sample so that it represents the chemical and physical form as it
exists in the field.
B. Blanks.
Soils collected in 1943, and therefore containing no artificial radionuclides, have

served as a quality control blank sample throughout EML's soils programs to monitor
contamination by laboratory handling, reagents, and other possible sources.

REFERENCES
Alexander, L. T., E. P. Hardy, and H. C. Hollister

"Radioisotopes in Soils: Particularly with Reference to Strontium-90"
R. S. Caldecott and L. A. Snyder (Editors)
in: Proceedings of a Symposium on Radioisotopes in the Biosphere, University of
Minnesota, Minneapolis, MN, pp. 3-22 (1960)
Alexander, L. T., R. H. Jordan, R. F. Dever, E. P. Hardy, G. H. Hamada, L. Machta, and

R. J. List
"Strontium-90 on the Earth's Surface "
USAEC Report TID-6567, Office of Technical Information, Washington, D.C., February
(1961)
ASTM
"Sampling Surface Soils for Radionuclides"
Annual Book of American Society of Testing Materials, C-998-83, Vol. 12.01, p. 792
(1983a)
ASTM
"Soil Sampling Preparation for the Determination of Radionuclides"
Annual Book of American Society of Testing Materials, C-999-83, Vol. 12.01, p. 796
(1983b)
Barth, D. S., B. J. Mason, T. H. Starks, and K. W. Brown

"Soil Sampling Quality Assurance User's Guide"
USEPA Report EPA/600/8-89-046, p. 268, March (1989)
Beck, H. L. and P. W. Krey

"Cesium-137 Inventories in Undisturbed Utah Soils - Interim Report on Radionuclides in
Soils of Populated Areas"
USDOE Report EML-375, June (1980)

Bernhardt, D. E.
"Evaluation of Sample Collection and Analysis Techniques for Environmental
Plutonium"
USEPA Report ORP/LV-76-5, Las Vegas, NV (1976)
Cochran, W. G.
Sampling Techniques
John Wiley & Sons, Inc. (1977)
Eisenbud, M.
Environmental Radioactivity
Academic Press, Inc., New York, Third Edition, pp. 84-104 (1987)
EPA
"Sample Collection Manual: Guidelines for Collecting Field Samples"
Environmental Protection Agency, Office of Pesticides Programs, Washington, DC,
March (1979)
EPA
"Preparation of Soil Sampling Protocol: Techniques and Strategies"
Environmental Protection Agency, Office of Research and Development, Report 600/
4-83-020, Washington, DC, August (1983)
Fowler, E. B., R. O. Gilbert, and E. H. Essington

"Sampling of Soils for Radioactivity: Philosophy, Experience and Results"
in: Atmosphere-Surface Exchange of Particulate and Gaseous Pollutants
ERDA Symposium Series 38, CONF-740921, pp. 709-727 (1974)
Gilbert, R. O.
Statistical Methods for Environmental Pollution Monitoring
Van Nostrand Reinhold Company, New York (1987)
Hardy, E. P.
"Depth Distribution of Global Fallout 90Sr, 137Cs, and 239,240Pu in Sandy Loam Soil"
USAEC Report HASL-286, pp. 2-10, October (1974)

Hardy, E. P.
"Regional Uniformity of Cumulative Radionuclide Fallout"
USAEC Report HASL-288, pp. 2-9, January (1975)
Hardy, E. P.
"Plutonium in Soil Northeast of the Nevada Test Site"
USERDA Report HASL-306, pp. 51-85 (1976)
Hardy, E. P. and B. Bennett

"Radionuclide Uptake by Cultivated Crops"
USERDA Report HASL-321 pp. 19-38 (1977)
Hardy, E. P. and P. W. Krey

"Determining the Accumulated Deposit of Radionuclides by Soil Sampling and Analysis"
Los Alamos Scientific Laboratory Report LA-4756, pp. 37-42, August (1971)
Hardy, E. P., P. W. Krey, and H. L. Volchok

"Global Inventory and Distribution of Fallout Plutonium"
Nature, 241, 444-445 (1973)
Hardy, E. P., H. L. Volchok, and P. W. Krey

"Strontium-90 Fallout in Utah"
USAEC Report HASL-257, pp. 71-94, July (1972)
Hardy, E. P., M. Meyers, J. S. Allen, and L. T. Alexander

"Strontium-90 on the Earth's Surface"
Nature, 219, 584-587 (1968)
Healy, J. W.
"Review of Resuspension Models"
W. C. Hanson (Editor)
in: Transuranics Elements in the Environment
USDOE Technical Information Center Report DOE/TIC-22800, pp. 209-235 (1980)

Krey, P. W.
"Remote Plutonium Contamination and Total Inventories from Rocky Flats"
Health Phys., 30, 209-214 (1976)
Krey, P. W. and H. L. Beck

"The Distribution Throughout Utah of 137Cs and 239+240Pu From Nevada Test Site
Detonations"
USDOE Report EML-400, November (1981)
Krey, P. W. and C. S. Klusek

"Soil Sampling in Complex Terrain"
J. Radioanalytical Nuc. Chem., 197, 79-98 (1995)
Krey, P. W., E. P. Hardy, and L. E. Toonkel

"The Distribution of Plutonium and Americium with Depth in Soil at Rocky Flats"
USERDA Report HASL-318, April (1977)
Krey, P. W., E. P. Hardy, C. Pachucki, F. Rourke, J. Coluzza, and W. K. Benson

"Mass Isotopic Composition of Global Fall-Out Plutonium in Soil"
in: Transuranium Nuclides in the Environment, IAEA-SM-199/39, pp. 671- 678 (1976a)
Krey, P. W., E. P. Hardy, H. L. Volchok, L. E. Toonkel, R. H. Knuth, R. Coppes, and

T. Tamura
"Plutonium and Americium Contamination in Rocky Flats Soils, 1973"
USAEC Report HASL-304, March (1976b)
Krey, P. W., C. S. Klusek, C. G. Sanderson, K. M. Miller, and I. K. Helfer

"Radiochemical Characterization of Chernobyl Fallout in Europe"
H. L. Volchok and N. Chieco (Editors)
in: A Compendium of the Environmental Measurements Laboratory's Research Projects
Related to the Chernobyl Nuclear Accident,
USDOE Report EML-460, pp. 155-213, October (1986)

Russell, R. S., B. O. Bartlett, and R. S. Bruce

"Appraisal of the Long-Term Nuclide Contamination Hazard"
D. W. Bensen and A. H. Sparrow (Editors)
in: Survival of Food Crops and Livestock in the Event of a Nuclear War
AEC Symp. Ser. 24 (CONF-700909), Natl. Tech. Info. Service, U.S. Dept. of Commerce,
Springfield, VA, pp. 548-565 (1971)
Schulz, R. K.
"Soil Chemistry of Radionuclides"
Health Phys., 11, 1317-1324 (1965)
Sehmel, G. A.
"Particle Resuspension: A Review"
Environment International, 4, 107-127 (1980)
van Ee, J. J., L. J. Blume, and T. H. Starks

"A Rationale for the Assessment of Errors in the Sampling of Soils"
USEPA Report EPA/600/4-90/013, p. 57, May (1990)

Figure 2.10. A suggested distribution of sampling sites covering the area surrounding a
plant, with emphasis on the downwind direction.

2.5 SEDIMENT
Contact Person : Mathew A. Monetti
2.5.1 SCOPE
Discussed in this section are the methodologies used at EML for obtaining sediment
cores from inland lakes and reservoirs for reconstructing the deposition histories of
energy-related pollutants. Topics included are the relationship of lake bathymetry to core
quality, a general description of the operation of the corer from our specially designed
catamaran, and the procedures for extruding the cores. The catamaran itself is discussed
in Section 6.7.
2.5.2 INTRODUCTION
Lake and reservoir sediments offer unique substrates for investigating the occurrence
of many energy-related pollutants since they are the main "sink" for materials entering
watersheds and may be dated by radioactive methods so as to provide a depositional
history (MARC, 1985). Furthermore, accurate coring, e.g., minimal disturbance of
sediments, is of great importance to paleolimnological investigations, especially those
aimed at reconstructing the deposition history and/or inventories of pollutants deposited
through atmospheric processes. Errors caused by a poorly performing coring system or
by taking sediment cores from locations in lakes that are not representative of
atmospheric deposition (e.g., areas affected by sediment focusing or excessive erosion)
can often lead to an erroneous interpretation of actual events (Heit and Miller, 1987).
To properly assess geochronologies of sediments in a meaningful way, methodologies

must be available for taking large volume, undisturbed sediment cores, so that multiple
parameter analyses can be performed at critical core depths. As stated in Burke (1968),
for the commonly used 4-7 cm diameter sediment corers, increased sample size can be
obtained only by homogenization of longer segments of core, with consequent blurring of
stratigraphic details. For isotopic dating procedures, the demand for really large samples
(>200 g wet weight) presents an even more severe problem. Only by increasing the area
of the column sampled can one improve the sensitivity in the study of sediment horizons.

Unfortunately, most larger area coring devices are of such size and weight that they can
only be used on oceanographic-sized vessels, making them unfit for studies of most lakes
and reservoirs.
As further stated in Burke (1968), the study of vertical profiles of the concentrations
of fallout radionuclides (which have been available for sedimentation only since the early
1950s in most places) also demands efficient sampling of the topmost layers of sediments
and their recovery in situ. Some evidence from studies of more conventionally collected
cores indicates that these upper layers are commonly lost, either by washout at the top of
the core tube or by being swept away from the point of impact by the shock wave of
rapidly falling corers (Sachs and Raymond, 1965). Also, as stated in McIntyre (1971), a
peculiarity of many gravity corers is that the length of the core retrieved may be
considerably less than the penetration depth of the core barrel into the sediment. This is
likely to cause a vertical redistribution of the sediment and hence an erroneous
chronology. Also core tubes having diameters <10 cm are subject to loss of surface
sediment (McIntyre, 1971).
2.5.3 EQUIPMENT DESIGN AND APPLICATION
We have developed a large diameter (21 cm), slow penetration sediment corer, and a
27 ft (7 m) transportable research vessel ("Sedimental Journey") to avoid the pitfalls
described above. This equipment, whose design and construction are described in detail
in Section 6.7, has allowed us to take large volume, undisturbed cores from many
locations in the U.S. and measure increments of sediment as small as 1 cm for a suite of
toxic trace substances and environmental tracers indicative of both natural and
anthropogenic origins. In fact, sediment cores taken with the tripod-sphincter corer have
been shown to be comparable in quality to those taken with the much larger "Soutar type"
box corers which, because of their size, can only be used successfully on oceanographic
vessels (Burke et al., 1983).
Examples of highly resolved sediment cores that can be obtained with our sediment
sampling equipment are shown in Figures 2.11-2.13. Plotted in these figures
is the 137Cs activity per unit area (Bq m-2) versus depth (cm) for sediment cores taken
from Cayuga Lake, Ithaca, NY (Figure 2.11), and Deer Creek Reservoir, Provo, UT
(Figure 2.12). Clearly, the 137Cs distributions closely follow the historic deposition

pattern of 137Cs from atmospheric weapons testing shown in Figure 2.13. The two easily
distinguished 137Cs peaks follow the major cycles of fallout from atmospheric weapons
testing in 1959 and 1963. Furthermore, there is a rapid drop of 137Cs activity in sediments
younger than 1963 following the Nuclear Test Ban Treaty between the U.S. and U.S.S.R.
Lastly, the activity after the onset of atmospheric weapons testing follows closely that of
historic fallout patterns with little debris diffused or mixed below the depth
corresponding to 1951.
Further confirmation of our ability to take quality cores with this system is shown by
the use of the SNAP-9A (Systems for Nuclear Auxiliary Power) Pu isotope signature. In
1964, the U.S. satellite, SNAP-9A, which used 238Pu as a heat source for generating
power, disintegrated after entering the atmosphere of the Southern Hemisphere. As a
result, there was a sharp rise in the stratospheric concentration of 238Pu relative to 239+240Pu
in 1964 in the Southern Hemisphere. The pulse of 238Pu from SNAP-9A did not reach the
surface of the Northern Hemisphere until 1966, at which time a distinct rise in the ratio of
238
Pu to 239+240Pu activity also occurred. It is the increase in this ratio which is used as a
geochronological marker for establishing the year 1966 in a sediment core. This is clearly
shown in Figure 2.14 where the 238Pu/239+240Pu activity ratio increases between 13 and
11.5 cm deep in the sediment core from Cayuga Lake, NY.
The remainder of this section is a description of the procedures that are used by EML
to take sediment cores from inland lakes and reservoirs using the Sedimental Journey and
tripod corer.
2.5.4 PROCEDURES
2.5.4.1
GENERAL OPERATION
Procedures for the preparation and operation of the Sedimental Journey are described
in detail in Section 6.7. The basic coring strategy is to launch the boat and determine the
best sampling sites through a bathymetric survey of the lake or reservoir, obtain the

cores, extrude the cores immediately after their retrieval, and, finally, remove the boat
from the water with the trailer.
2.5.4.2
BATHYMETRIC SURVEY
Bathymetric surveys are always conducted prior to coring since such data are usually
not available. It has been our experience that even when bathymetry is available, it is
usually inaccurate or out of date and hence misleading. This can be a severe problem
because the lack of accurate bathymetric data will almost certainly result in a failure to
locate suitable coring locations within a lake or reservoir.
In general, it has been our aim to take replicate cores from those portions of lake
basins which are the least likely to be affected by processes known to disturb sediments,
such as, excess terrestrial runoff (erosion), sediment slumping, sediment resuspension,
and sediment focusing (Davis and Ford, 1982; Edgington and Robbins, 1977; Heit and
Miller, 1987). In this regard, the bathymetric survey is used to select sites located in
relatively large, hypolimnetic basins, as far away as possible from shoreline areas prone
to erosion. Inlet and outlet areas, as well as locations at the confluence of rivers or close
to dams are also avoided.
For our bathymetric survey work we use a Lowrance graph recorder sonar unit. This
device is capable of accurately graphing a lake bottom to a depth of 300 m (900 ft). Our
location is determined using a micrologic explorer Loran system.
2.5.4.3
SEDIMENT SAMPLING
All of the sediment cores are taken with a sphincter corer with a tripod modification
capable of taking a 21 cm diameter, 90 cm long core. The design and mechanics of the
corer are described in detail in Section 6.7.

The device uses the barrel and nose-cone of the original 21-cm sphincter corer
(Burke, 1968), but is mounted in a tripod (see Section 6.7.4). The operation of the
sphincter is not changed by this design, the tripod frame only provides stability to keep
the corer in a vertical position while it penetrates. This design also allows the corer to be
lowered to the bottom very slowly, with minimal sediment disturbance. The core barrel
is driven into the sediment only by the force of weights mounted on the weight stand (see
Section 6.7.4). Varying the amount of this weight gives control over penetration into
various sediment types. It should be noted that the tripod corer is "manageable" on small
boats and is easily disassembled for transporting or shipping.
The corer is lowered at 100 m min-1 (75 m min-1 in fairly active weather) until it is 5
m from the bottom (observable with the Sonar unit). It is then slowed to 10 cm min -1, or
as slow as the winch will operate, for placement on the bottom. The feet of the tripod
contact the sediment first. The barrel continues to descend, penetrating the sediment by
the force of the weights contained in the weight stand. The core barrel stops its
downward travel when the weight stand comes in contact with the guide ring (see Section
6.7.4.2), or when the resistance of the sediment is sufficient to stop the downward
penetration. When the weight stand comes to a stop, the weight is taken off the spring-
loaded release pin and the pin retracts (see Section 6.7.4). This should be completed
within 60 sec after the corer reaches the bottom. The pull on the wire to retrieve the corer
begins immediately and closes the diaphragms of the core catcher and the top valve.
Stress is taken off the closure wires by a stop which engages the bottom of the release
mechanism where force is exerted during retrieval.
The corer is pulled out of the sediment at the slowest winch speed, or about
10 cm min-1. In the past, pullout forces have not exceeded 4450 N (1000 lb force) and are
generally somewhat lower. After pullout the corer can be retrieved at a rate of
50 m min-1.
2.5.4.4
SEDIMENT EXTRUSION
More than one method has been employed to extrude sediments from the core barrels
since EML started coring in the early 1970s. In all of these methods, the sediments are
always extruded immediately after retrieval. Water retained above the core is siphoned or
pipetted off and may be reserved for analyses. In most cases, contiguous 1 cm increments

are taken from the top of the core to ~ 40 cm, and 2 cm sections are taken thereafter. The
outer ~ 1 cm of each layer of sediment is always discarded, resulting in ~ 19 cm diameter
sections. We have found that if this outer ring of sediment is not eliminated,
contamination may result from surface sediments "dragging down" to subsurface depths
via friction with the core barrel wall or through other physical processes. Lastly,
glassware and covers used for sample storage are prewashed with 1:1 HNO 3, rinsed with
double-deionized water, followed by acetone and methyl-alcohol washes. All of the
glassware is dried and sealed under laminar flow clean stations until the time of use.
Precleaned glass jars are used, which can be obtained from several suppliers.
Prior to extrusion, the length of the core and its distance from the top of the barrel are
measured and noted. After the excess water is removed by siphon or pipette, the
sediment is then carefully removed in 1 cm increments with a large Teflon-coated spoon
bent into an "L" shape. The accuracy of this procedure is ensured by placing the sediment
in precalibrated 16-oz (500 mL) wide-mouth glass jars, and noting the actual extrusion
depth relative to the initial location of the top of the core as measured immediately after
core retrieval. In addition, the core barrels are marked at 5 cm increments for further
calibration; thus, errors in extrusion are identified.
Once the surface sediment is removed, the remaining sediment is usually firm and is
not easily disturbed. The rest of the core can be sectioned in the following manner. A
stainless steel piston is fitted inside the top of the core barrel and contacts the sediment.
While this piston is held in place, the core is laid down on its side, the bottom core
catcher is removed, and another piston is placed into the bottom of the core. The core is
then listed upright again and placed on an extruding stand. Next, the top piston is
removed and the bottom one is pushed up through the core barrel until the sediment
becomes flush with the top of the barrel. The remainder of the sediment is extruded at 1
to 2 cm intervals by pulling the barrel down to designated marks on the attached scale.
The outer ring is removed from the protruding sediment; the rest of the interval is sliced
and packed into sampling jars. Sediment is sectioned in this way to a desired depth or to
the bottom of the core. A description of the construction and design of the extruder used
to section the core is given in Section 6.7.4.
The reproducibility of this technique is demonstrated in Figure 2.15, which compares

137
the Cs distribution in two sediment cores (A and B), taken from separate but nearby
locations (within 0.5 km) in Cayuga Lake, Ithaca, NY. Although the sedimentation rate

was slightly different for the two locations (Heit et al. 1986), as would be expected from
bathymetric variations within a lake basin, even for nearby locations, the 137Cs
distribution patterns were remarkably similar with only small differences occurring
among the major peaks which represent fallout from atmospheric weapons testing in 1959
and 1963. This agreement ( 2 cm) between the patterns of 137Cs distributed in these
independent cores attests to the reproducibility of our current method of sediment
extrusion.
REFERENCES
Burke, J. C.
"A Sediment Coring Device of 21-cm Diameter with Sphincter Core Retainer"
Limnology and Oceanography, 13, 714-718 (1968)
Burke, J. C., R. E. Hamblin, and S. A. Casso

"Tripod Modification Of Sphincter Corer: Construction, Operation, Core Extrusion and
Sampling Efficiency"
Woods Hole Oceanographic Institution Technical Report WHOI-83-36, Woods Hole,
MA 02543, pp. 1-13 (1983)
Davis, M. B. and M. S. Ford

"Sediment Focusing In Mirror lake, New Hampshire"
Limnology and Oceanography, 27, 137-150 (1982)
Edgington, D. N. and J. A. Robbins

"Patterns Of Deposition of Natural and Fallout Radionuclides to Limnological Processes"
J. O. Nriagu (Editor)
in: Environmental Biogeochemistry - Metals Transfer and Ecological Mass Balances
Ann Arbor Science, Ann Arbor, MI, pp. 705-729, Vol. 2 (1977)
Heit, M. and K. M. Miller

"137Cs Sediment Depth Profiles And Inventories In Adirondack Lake Sediments"
Water, Air and Soil Pollution, 3, 243-265 (1987)

Heit, M., Y. L. Tan, K. M. Miller, J. Quanci, C. Marinetti, and S. Silvestri

"The Sediment Chronology and Polycyclic Aromatic Hydrocarbon Concentrations and
Fluxes in Cayuga Lake, NY"
MARC: Monitoring and Assessment Research Centre

"Historical Monitoring"
MARC Report 31, University of London, London, England (1985)
McIntyre, A. D.
"Efficiency of Benthos Sampling Gear"
N. A. Holme and A. D. McIntyre (Editors)
in: Methods for the Study of Marine Benthos
International Biological Program Handbook No. 16, Blackwell Scientific Publications,
pp. 140-146 (1971)
Sachs, P. L. and S. O. Raymond

"A New Unattached Sediment Sampler"
J. Marine Res., 23, 44-53 (1965)

137
Figure 2.11. Cs activity per unit area versus sediment depth for Cayuga Lake,
New York.
Figure 2.12. 137Cs activity per unit area versus sediment depth for Deer Creek
Reservoir, Provo, Utah.

Figure 2.13. Historic deposition pattern of 137Cs in the 40( - 50( latitude band
from atmospheric weapons testing.
238
Figure 2.14. Pu/239 + 240Pu activity ratio in relationship to 137 Cs concentration in the
sediments of Cayuga Lake, New York.

137
Figure 2.15. Cs distribution in two sediment cores taken from nearby locations in
Cayuga Lake, New York.

Section 2.5,
2.6, Vol. I Rev. 0
2.6 URANIUM AND RADIUM IN WATER
Contact Person(s) : Isabel M. Fisenne
2.6.1 SCOPE
A simple method for the field collection of uranium and radium in 10 L of fresh water (tap,
well, river) is described. Similar collection methods for radium are in use elsewhere, notably at
the New York University Institute of Environmental Medicine.
This method has been used to collect uranium and radium from fresh water samples at
environmental levels. The use of the ion exchange collector concentrates the uranium and
radium in the water samples and permits shipment of the samples within national and
international regulations. Water samples collected with this system have been sent to EML from
locations within the continental U.S., the middle East, and Africa.
2.6.2 APPARATUS
The ion exchange collector is a modified version of the fallout collector described in Section
2.3.3. This unit consists of a funnel and ion exchange column constructed of polyethylene. The
funnel is welded to a threaded cap which is attached to the top of the ion exchange column. The
bottom of the column is threaded for a tapered fitting, which in turn has a small cap at the end.
The funnel and the tapered fitting are replaced with standard bottle caps for return shipment to
EML.
2.6.3 PROCEDURE
The column is packed with a plug of glass wool, a 1 cm plug of Whatman No. 41 paper strip
(Note 1), 150 mL of mixed anionic-cationic resin (Note 2), and a top plug of filter paper strip.
The threaded tapered fitting (outlet end of the column) is taped to the column to assure leak-
proof operation during sampling.
The column is attached to a funnel marked for a 10 L volume, it is then placed in a stand and
10 L of the water to be sampled is poured into the funnel. The bottom cap is removed from the
tapered fitting, allowing gravity flow of the water. The collection time is about 3 h.

Section 2.5,
2.6, Vol. I Rev. 0
Upon return to EML, the resin and paper pulp are pushed out of the column body into a
250-mL platinum crucible. The glass wool is discarded. The resin may be analyzed sequentially
for isotopic uranium and radium (see Procedure Se-01, Section 4).
Notes:
1. Filter paper pulp must not be used, as the flow rate through the column is too slow. Narrow
strips cut from filter discs are recommended.
2. The resin is an equal mixture of Bio-Rad AG1-X4 in the H + form (20-50 mesh) and Bio-Rad
AG 50-X8 (20-50 mesh).

Section 2.7, Vol. II Rev. 0
2.7 FOOD
(see Volume II)

Page
3. Radiation Measurements . . . . . . . . . . . . . . . . . 3.1-1
3.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1-1
3.2 Ionization Chambers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-1
3.2.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-1

3.2.2 PIC System Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-1
3.2.2.1 Ion Chamber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-1
3.2.2.2 Electrometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-2
3.2.2.3 Readout Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-3
3.2.3 Data Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-3
3.2.4 Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-4
3.2.5 Inferring Exposure (Dose) Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2-6
3.3 Field Gamma-Ray Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . 3.3-1
3.3.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-1

3.3.2 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-2
3.3.3 Site Selection and Instrument Setup . . . . . . . . . . . . . . . . . . . . . . . 3.3-3
3.3.4 Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-4
3.3.5 Spectrum Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-8
3.3.6 Inventory Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-10
3.3.6.1 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-10
3.3.6.2 Homogeneous Terrain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-11
3.3.6.3 Nonhomogeneous Terrain . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-12
3.3.7 Spectral Stripping for Germanium Detectors . . . . . . . . . . . . . . . . 3.3-14
3.3.7.1 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-14
3.3.7.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-14
3.3.7.3 Determination of Stripping Parameters (f and r) . . . . . . . . . . 3.3-15
3.3.7.4 Stripping Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-16

Page
3.3.8 Sodium Iodide Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-17
3.3.8.1 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-17
3.3.8.2 Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-18
3.3.8.3 Peak Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-18
3.3.8.4 Energy Band Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3-19
3.3.8.5 Total Spectrum Energy Analysis . . . . . . . . . . . . . . . . . . . . . . 3.3-21
3.4 Remote Gamma-Ray Spectrometry Stations . . . . . . . . . . . 3.4-1
3.4.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4-1

3.4.2 Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4-2
3.4.3 Instrumentation Assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4-3
3.4.4 EML Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4-5
3.5 Thermoluminescence Dosimetry . . . . . . . . . . . . . . . . . . . . . . . . . 3.5-1
3.5.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5-1

3.5.2 Special Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5-1
3.5.3 Predeployment Preparation of Chips . . . . . . . . . . . . . . . . . . . . . . . 3.5-4
3.5.4 Environmental Deployment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5-5
3.5.5 Readout and Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5-6
3.5.6 Analysis of Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5-7
3.6 Bonner-Sphere Neutron Spectrometry . . . . . . . . . . . . . . . . . . 3.6-1
3.6.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-1

3.6.2 General Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-1
3.6.3 Personnel and Training . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-2
3.6.4 Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.6-2
3.6.4.1 Description of the System . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-2
3.6.4.2 The Bonner Spheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-3
3.6.4.3 The Response Functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-3

Page
3.6.4.4 Calibrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-3
3.6.4.5 Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-4
3.6.5 Neutron Spectrum Unfolding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-4
3.6.6 Acceptable Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6-5

U.S. Department of Energy 3 - iv
3. RADIATION MEASUREMENTS
3.1 OVERVIEW
Since about 1950, the Environmental Measurements Laboratory has carried out major
research programs directed at the study of ionizing radiation and natural and man-made
radionuclides in the working and in the public environment. Among these studies have
been: (1) the long-term investigation of the atmospheric distribution and ground depo-
sition of radionuclides from global fallout generated by nuclear weapons tests; (2) the
evaluation of the radiation exposure of human populations from these nuclides as well as
those deposited locally by the Nevada weapons tests, those released from nuclear
facilities (including the reactor accidents at Three Mile Island and Chernobyl), and those
normally present from natural sources; and (3) the determination of radiation worker
exposures at particle accelerators, nuclear reactors, and other nuclear facilities. An
important component of these studies has been the development and improvement of
techniques for low-level radiation measurement and data interpretation. In the following
sections, five highly generic measurement systems are described that have been
developed and/or refined at EML, and that have found wide application in environmental
radiation studies. In each case, an essential part of the system is the methodology
associated with detector calibration, measurement procedure(s), and data analysis and
interpretation. The indicated references provide additional details and examples of
applications for the interested reader.

HASL-300, 28th Editon February 1997
3.2 IONIZATION CHAMBERS
Contact Person(s) : Kevin M. Miller
3.2.1 SCOPE
This section describes the design, analysis procedures, calibration, and use of
pressurized ionization chambers (PIC). These instrument systems are used at EML in the
assessment of the penetrating component (gamma plus cosmic-ray secondaries) of the
environmental radiation field. Accurate and highly precise measurements of the total
exposure rate (or dose rate in air) are made of such sources as:
1. cosmic-ray secondary radiation (high energy muons, photons, and electrons) in the
lower atmosphere;
2. natural background radiation from primordial radionuclides (and progeny) in the soil
and air;
3. anthropogenic isotopes associated with
a. direct radiation from nuclear facilities,

b. gaseous effluents from nuclear operations,
c. fallout deposition,
d. residual radioactivity at sites undergoing clean-up.
3.2.2 PIC SYSTEM DESIGN
3.2.2.1
ION CHAMBER
The chamber selected as our standard consists of a 25-cm diameter stainless-steel

sphere with a wall thickness of 2.37 g cm-2 filled to a pressure of 2.5 MPa (25 atmos-
pheres) with ultrapure argon gas. The collecting electrode is a 5-cm diameter hollow
sphere at the center of the chamber supported by a 0.6-cm diameter rod, which in turn is

connected to the chamber shell at the center of a triaxial metal-ceramic seal. The middle
conductor of this seal serves as a guard ring and is kept at true circuit ground. A 300-V
battery is used to provide bias to the outer shell. This voltage along with the large center
electrode results in complete charge collection in fields of up to 10 :Gy h-1.
Smaller versions of this chamber are also routinely used. They consist of an 18-cm
diameter sphere with the same or slightly thicker wall and filling pressures of up to
3.7 MPa. The collecting electrode for these chambers measures 1.9-cm in diameter.
Complete charge collection has been observed at 400 :Gy h-1 with a bias of 300 V.
A complete description of experimental and theoretical investigations involving

various PIC designs can be found in De Campo et al. (1972). Known commercial
suppliers of these PICs are GE Reuter-Stokes (Twinsburg, Ohio 44087) and LND, Inc.
(Oceanside, New York 11572).
3.2.2.2
ELECTROMETER
The ion current from the PIC is measured with a temperature compensated electrom-
eter consisting of a MOSFET (metal oxide semiconductor field effect transistor) and an
operational amplifier using 100% negative feedback from the amplifier output to the
MOSFET input (Negro et al., 1974). Stable voltage regulators, external to the electrom-
eter, are used to provide power. The electrometer itself is small and light enough to
attach directly to the triaxial connector on the PIC and suspend freely without additional
support. This arrangement minimizes mechanical stress on the seal insulators and any
resultant piezo-electric currents. The response to radiation is about 3 fA per nGy h-1 for
the large 2.5 MPa chambers and about half that for the 3.7 MPa small chambers. A glass
encapsulated tera-ohm carbon resistor used in the feedback loop of the electrometer
determines the output sensitivity, generally about 3 mV per nGy h-1, and time response,
generally on the order of a few seconds. The electrometer saturates at somewhat over 5 V,
which translates to about 1700 nGy h-1.

3.2.2.3
READOUT SYSTEMS
Direct observation of the electrometer output voltage is made with a standard

voltmeter. To obtain precise measurements, signal integration is performed by one of
two methods listed below.
A. Survey mode.
For real-time results, a voltage-to-frequency converter with scaler and calibrated

digital readout is used to provide readings with selectable integration times of 4, 40, or
400 sec. This readout system is generally used with the 18-cm diameter chambers in the
form of a two-unit package called a SPICER (small pressurized ionization chamber for
environmental radiation; Latner et al., 1983). The system is battery powered and can be
either held in hand or tripod mounted. Figure 3.1 shows the system in this latter mode of
operation.
B. Monitor mode.
The second read-out method is designed for continuous remote monitoring. It

consists of an analog to digital converter, timing and control circuitry, and a magnetic
tape cassette recorder (Memodyne, Model 201) housed in a weather proof aluminum box
(Cassidy et al., 1974). The ion chamber and electrometer are packaged in a similar box
which sits atop the recorder box during operation in the field as shown in Figure 3.2. The
standard system records the digitized electrometer output voltage every 10 sec, and is
capable of storing up to 17 days of data on a single cassette. Some units have been
modified to allow the option of recording every 10, 20 or 40 sec. An alkaline cell battery
pack provides power for 8 weeks of operation.
3.2.3 DATA ANALYSIS
The magnetic tape cassette is read out with a Memodyne 3122 ABV reader interfaced
to a Hewlett-Packard 9826 computer using a specially developed analysis program
(Gogolak, 1982). The analysis procedure is as follows:
1. A 6 h record of the 10-sec data is read into the computer and displayed on a screen.

2. The data is averaged over 5-min intervals, corrected for the zero reading of the
electrometer and converted to exposure rate via a chamber specific calibration factor.
3. A printout of the 5-min averages as well as the average over each hour is made. The
standard deviation (SD) of the 5-min data for each hour is also computed and printed.
4. Subsequent 6-h records are analyzed and at the end of the tape a summary plot of the
hourly data is made. Bad data sections are then edited and a final printout and plot of
the corrected hourly average and SD data is obtained. The hourly average maximum
and minimum and daily average are also printed for each day along with the average
over the entire period.
5. Permanent storage of the corrected 5-min data is made on a diskette.
6. If desired, the data can be analyzed for any dose due to the passage of a plume
(Gogolak and Miller, 1974). The analysis routine examines the SD of the 5-min data
in each hour and if it is sufficiently high (> 1.7 nGy h-1) it is assumed that a fluctua-
ting plume component was present. A search is then made on each side of the plume
hour for the nearest three background hours indicated by a standard deviation that is
sufficiently low (< 1 nGy h-1). The average background is computed from these 6 h
and subtracted from the total dose in the plume hour to yield the net plume dose.
3.2.4 CALIBRATION
Calibration of the PIC is performed using a National Institute of Standards and

Technology (NIST) certified sealed 37 MBq 226Ra source and a shadow shield technique
(De Campo et al., 1972). The shadow shield method is necessary because it removes the
contribution of the room scatter component which we have found to be on the order of
30% of that from the primary beam. At the same time, it also corrects for any other
constant factors included in the PIC output such as room background, electrometer zero
offset, and " and stress currents. The calibration procedure is as follows:
1. The source is placed in a low mass holder at a height of about 1 m above the floor and
at a distance of 4, 5, or 6 m to the PIC (geometric center), which is at the same height
on a low mass stand.

2. A 30-cm thick lead shield with a cross section measuring 10-x-10 cm is interposed on
a low mass stand so as to intercept all primary rays from the source to all parts of the
PIC through the full thickness of the shield. Alignment is checked with a string with
a dummy source in place. Slight overshielding (a larger shadow) on the order of
1-2 cm is used as this results in a negligible error as opposed to undershielding which
could produce a significant error. The use of a shield with a cross section that is
roughly half that of the PIC is recommended because the shadow size cast will
require the shield to be placed near the midpoint between the source and the PIC thus
minimizing the production and interception of lead fluorescent X-rays and also
allowing a proper alignment which is not too critical to shield placement.
3. The source is placed in its holder and the output signal of the PIC is averaged over a
10- to 30-min time period.
4. The lead shield is removed (leaving its stand in place so as to change the scattering
conditions as little as possible), and the PIC output signal is averaged again over a
10- to 30-min period.
5. The difference between the average signals (reading with shield not in place minus
reading with shield in place) is divided by the exposure rate delivered by the source at
that distance to yield the Ra primary beam calibration factor. This calibration factor
must be adjusted by a small amount for the energy spectrum that will be encountered
for a particular radiation field. For our standard 25 cm-2.5 MPa chamber, this
correction yields a 3% higher sensitivity for a normal background radiation field,
while for the 18 cm-3.7 MPa chamber it is 1% higher.
6. Background readings are taken in the calibration room and in a whole body counter in
both the negative and positive high voltage modes of operation to verify that the
system does not have stress currents present and that there is no high internal
background.

3.2.5 INFERRING EXPOSURE (DOSE) RATE
The total PIC current can be expressed as
R = k c Ic + k tI t + R′
where
kc = the calibration factor for cosmic radiation

Ic = the cosmic radiation exposure rate
kt = the calibration factor for terrestrial radiation
It = the terrestrial radiation exposure rate
RN = the " particle current from contamination in the steel shell (~2 fA for
the 25-cm chamber and 1 fA for the 18-cm chamber)
For our standard chamber, the values of kc and kt are only 1% different so that for
most applications the total exposure rate (Ic + It) is inferred by simply subtracting the "
current from the total current and dividing by the factor corresponding to the dominant
component of the radiation field. (In a strict sense, the quantity "exposure rate" is only
applied to ( rays of certain energies. However, for environmental radiation fields it is
convenient to extend the meaning to include the exposure rate equivalent of ionization in
free air due to cosmic rays.) For expressing the exposure rate in SI units, the appropriate
quantity would be C kg-1 s-1 or A kg-1. Since this is a rather unfamiliar unit, we prefer to
convert the exposure rate to dose rate in air when reporting data in SI units.
A more accurate estimate of It is derived by substituting a value for Ic in the above

equation. To do this, the altitude of a measurement site is determined using a
topographical map or the barometric pressure is measured. The corresponding cosmic-
ray exposure rate (dose rate in air) is inferred using the data presented in Figure 3.3. It
should be noted that Ic will vary with the 11 year solar cycle, being a few percent higher
(lower) at solar minimum (maximum) (O'Brien, 1972).
Although not common with the small freely suspended MOSFET electrometer, stress
currents can result from mechanical pressure on the ionization chamber insulator. The
presence of these unidirectional currents is checked by reversing the high voltage polarity
on the ion chamber shell. After correcting for the electrometer zero offset, the readings

should agree if no stress current is present. If the readings do differ, the true reading is
just the arithmetic average of the two.
REFERENCES
Cassidy, M. E., S. Watnick, V. C. Negro, D. C. Freeswick and R. T. Graveson

"A Computer-Compatible Field Monitor System"
IEEE Transactions Nuclear Science, NS-21, 461 (1974)
De Campo, J. A., H. L. Beck and P. D. Raft

"High Pressure Argon Ionization Chamber Systems for Measurements of Environmental
Exposure Rates"
USAEC Report HASL-260, December (1972)
Gogolak, C. V.
"Collection and Analysis of Environmental Radiation Data Using a Desktop Computer"
USDOE Report EML-398, April (1982)
Gogolak, C. V. and K. M. Miller

"Method for Determining Radiation Exposure Rates due to a Boiling Water Reactor
Plume from Continuous Monitoring Ionization Chambers"
Health Physics, 27, 132-134 (1974)
Latner, N., K. Miller, S. Watnick and R. T. Graveson

"SPICER: A Sensitive Radiation Survey Instrument"
Health Physics, 44, 379-386 (1983)
Negro, V. C., S. Watnick and P. D. Raft

"A Temperature-Compensated Electrometer for Environmental Measurements"
IEEE Transactions Nuclear Science, NS-21, 805 (1974)
O'Brien, K.
"The Cosmic Ray Field at Ground Level"
In: The Natural Radiation Environment II
USERDA CONF-720805-P1, Vol. 1, pp. 15-54 (1972)

Figure 3.1. SPICER system set up for field measurements showing a tripod mounted ion
chamber with an electrometer unit connected via cable to the digital readout
box.

Figure 3.2 PIC system for field monitoring. The chamber and electrometer are housed
in the top box, and the digital recorder unit is contained in the bottom box.

Figure 3.3 Cosmic-ray exposure rate equivalent and dose rate in air as a function of
atmospheric pressure and altitude for mid-latitude.

3.3 FIELD GAMMA-RAY SPECTROMETRY
Contact Person(s) : Kevin M. Miller
3.3.1 SCOPE
This section describes the instrumentation, setup, calibration and analysis for EML's
field (in situ) (-ray spectrometry using high resolution Ge detectors. The specific
application to inventory measurements is described, as well as a spectral stripping routine
for total exposure rate measurements. Methods for low resolution NaI detectors are also
given.
Field spectrometry is used at EML for the rapid identification of radionuclides in the
environment. When the source geometry is taken into account, the concentrations or
inventories (activity per unit area) of these radionuclides in the soil can be inferred along
with the contribution to the above ground exposure rate. Applications have included:
1. the measurement of natural background and weapons test fallout emitters (Lowder
et al., 1964a, b; Beck, 1966; Beck et al., 1964);
2. indoor radiation studies (Miller and Beck, 1984);
3. analysis of power reactor plumes (Gogolak, 1984);
4. the determination of aged fallout levels in terrain with mixed ground cover (Miller
and Helfer, 1985).
5. site characterization for environmental restoration (Miller et al., 1994).

3.3.2 INSTRUMENTATION
Although field spectrometry can be performed with a NaI scintillator, the detector of
choice at EML for most applications is a high resolution hyperpure germanium coaxial
crystal. This type of detector can sustain warmup when not in use, which is a convenient
feature during extended field trips.
Ease of handling is best accomplished with a detector mounted in a cryostat that is

small (hand-held) and which has an all-attitude capability. Ideally, the detector assembly
should be mounted on a tripod with the crystal endcap facing down toward the ground
and the dewar above. This orientation maximizes the flux that will be intercepted and
registered by the detector. However, a standard 17- or 30-L dewar with an upward facing
endcap can still be used without a large loss in efficiency, since most of the flux is
incident at the sidewall of the detector, with the dewar blocking out only a few percent of
the ground area that is effectively being measured. In either the downward or upward
facing geometries, the axis of rotation for the cylindrical crystal is perpendicular to the
ground plane. As such, the detector can be assumed to have a symmetrical azimuthal
response. A "goose neck" cryostat, where the crystal axis is parallel to the ground plane,
should be avoided since this introduces asymmetry and would require making
complicated angular corrections.
Counting times in the field can be reduced by using large volume detectors, however,
the crystal length/diameter ratio is an important consideration as well. The standard
method of measuring the efficiency for a Ge detector is performed with a 60Co source at
25 cm normal to the detector face. As mentioned above, the open field source geometry
is such that most of the flux is incident from the side. Thus, for two detectors that have
the same quoted efficiency, a long thin crystal will yield a higher count rate in the field as
compared to a short wide one. However, length/diameter ratios close to unity would
generally result in less uncertainty in measurements due to flatter angular responses.
A list of detectors that we have calibrated for field spectrometry is given in

Table 3.1. Our current primary detector for field work is the 45% efficient high purity
P-type Ge coaxial mounted in a portable (hand-held) cryostat. It requires a 6 h cool-
down time before becoming operational, although it is normally mated to an overhead
30-L liquid nitrogen dewar with a gravity feed system when stored in the laboratory so
that it is always ready for use. This type of setup also allows the detector to be placed in
a shield and used for sample analysis. Once cooled down and detached from the feeder

dewar, the hand-held cryostat (1.2 L) can be used for as long as 24 h before refilling is
required. For studies involving low energy, a recently acquired detector measures 75%
in relative efficiency and is of N-type Ge with a beryllium window. It has a 3-L dewar
and can be hand-held although it is best suited for tripod mounting.
Generally, measurements are made in the field using a portable battery-powered

computer-based spectroscopy system. High voltage and preamplifier power are supplied
to the detector by the system. Some detectors feature low power preamplifiers which
provide for extended operational time when using battery power in the field. A
spectroscopy grade amplifier is also contained within the system. The complete
spectrometer system can be carried and operated by one person.
3.3.3 SITE SELECTION AND INSTRUMENT SETUP
The detector is placed ~1 m above the ground with the analyzer and operator
positioned a few meters away. The site chosen should be a flat, relatively even and an
open area. Terrain that has obstructions such as boulders, large felled or standing trees,
and any man-made structures should be avoided as these will block the ( flux from the
underlying soil. Extreme ground roughness will result in anomalies since the soil surface
area close to the detector is increased, while the surface contribution from large distances
is reduced. For measurements of fallout radionuclides, the area must be undisturbed in
that water and wind erosion as well as human activity, such as cultivating, would tend to
upset the distribution of any deposited activity. Figure 3.4 shows an example of
equipment placement at a typical field site.
When selecting a site for measurement, the source geometry must be taken into
account. An unshielded detector, placed at 1 m above the ground, samples the photon
flux from a volume of soil out to a radius on the order of 10 m and down to a depth of
about 30 cm, depending upon the photon energy. Figure 3.5 shows a pictorial
representation of the relative ground area contributions to the primary (uncollided) flux at
a height of 1 m for a medium energy (662 keV) source with a typical exponential depth
profile in the soil. This effective "field of view" varies, being somewhat larger (smaller)
for higher (lower) energy sources. Also, activity that is closer to the soil surface will
produce a wider field of view. In effect, a field spectrum samples an area of several
hundred square meters, thus averaging out the local inhomogeneities in the distribution of

the radionuclides. The source being measured is essentially a giant soil sample and
counting statistics for a given spectral absorption peak are obtained in a fraction of the
time required for counting a small collected sample.
A good practice to follow is to make a series of short measurements in an area to

ensure that there is approximate uniformity before collecting a longer spectrum and
obtaining the desired counting statistics. When making measurements of natural
background, or when the exposure rate is dominated by the man-made emitters under
study, this check can be performed with an ionization chamber or a suitably sensitive
survey ratemeter in that uniform exposure rate readings would imply a spatially invariant
source distribution relative to the detector. If the particular radionuclides under study
contribute just a small fraction to the total exposure rate, then the corresponding peak
area count rates should be checked with the spectrometer to ensure uniformity.
3.3.4 CALIBRATION
A complete description of field (-ray spectrometry can be found in Beck et al. (1972)
and Miller and Shebell (1995). To summarize, the exposure rate in air above the ground
is related to the absorption peak counting rate registered by the detector by
Nf N0 Nf φ
= (1)
I φ N0 I
where
No/N is the counting rate from a particular spectrum absorption peak due to a unit
primary photon flux density of energy E incident on the detector along the
detector axis (normal to the detector face).
Nf/No is the correction required to account for detector angular response, and
N/I is the primary photon flux density with an energy E at the detector resulting
from the decay of a particular radionuclide per unit exposure rate at the

detector from all primary and scattered photons originating from this nuclide and any
others present from its radioactive decay series.
The first two terms depend on the particular detector; N/I values depend only on the
source composition and geometry and can be used for any spectrometer calibration.
In a like manner, the concentration or inventory of a particular nuclide is related to

absorption peak counting rate by
Nf N0 Nf φ
= (2)
A φ N0 A
where N/A is the total photon flux density at the detector location per unit
concentration or inventory of the nuclide.
The three factors to compute Nf/I or Nf/A are discussed separately.
A. No/N.
The response to unit flux at normal incidence is evaluated for a detector using various
(-ray point sources. A complete energy response curve from 40 keV to 3 MeV can be
inferred with a set made up with the reasonably long lived isotopes 152Eu, 241Am, 137Cs,
60
Co, and 228Th. The measurement procedure is as follows:
1. Position the source at a distance of at least 1 m and at normal incidence to the

detector face.
2. Calculate the uncollided flux density at the detector effective crystal center, which is
obtained by dividing the ( emission rate by 4 B r2. The value of r is the distance from
the source to the crystal effective center. This can be taken to be the geometric center
for high energy (> 1 MeV) rays and the crystal face for low energy (< 0.1 MeV)
( rays. For the energy range between these two values, an estimate of average
penetration distance can be made based on the absorption coefficient of the crystal.
The ( flux density is also corrected for air and source holder attenuation.

3. Collect a spectrum and determine the full absorption peak count rate.
4. Collect a spectrum without the source present and subtract out from the previously
measured count rate any contribution to the peak from background emitters.
5. Divide the corrected count rate by the flux density to determine No/N.
6. Perform this measurement at different energies with either simultaneous or separate

runs.
7. Plot the values of No/N versus energy on a log-log scale and fit the data to a smooth
curve. Figure 3.6 shows No/N as function of energy above 200 keV for the detectors
listed in Table 3.1. In the energy range shown, the response can be fit to a straight
line on a log-log plot to within ±3%.
B. Nf/No.
The uncollided (-ray flux for a soil half space source geometry is not limited to
angles normal to the detector face. Therefore, the complete flux density response
calibration must account for the fact that a cylindrical Ge crystal when oriented with the
axis of symmetry perpendicular to the ground plane has a variable altitudinal (zenith-
angle) response. The correction factor, Nf/No, is determined from point source
calibrations as functions of energy and angle in the vertical plane and can be calculated
from
Nf
= ∫02
( ) ( ) dθ
x φ θ N θ
(3)
N0 φ N0
where
N(2)/N is the fraction of the total primary flux at zenith angle 2 for a given source
energy and geometry, and

N(2)/N is the response of the detector at angle 2 for the same energy ( ray relative
to the response at normal incidence.
The procedure for determining the values of Nf/No is as follows:
1. Measure the full absorption peak count rate (minus any background contribution to
the peak) using a point source at a fixed distance of at least 1 m to the crystal at 15o
intervals between incident angles of 0o (normal to detector face) and 90o.
2. Plot the relative response N(2)/N versus angle and fit the data to a smooth curve.
3. Evaluate Equation 3 numerically for at least three different source distributions in the
soil (surface plane, 3 cm relaxation depth, and uniform). The angular flux distribution
data can be found in Beck et al. (1972).
4. Repeat Steps 1-3 for several other energies and plot the resultant values of Nf/No
versus energy. The data points can be fit to a smooth curve for each source depth
distribution.
As noted before, a longer crystal would tend to yield a higher count rate in the field,
meaning that the value of Nf/No would be > 1. For the source distributions generally
encountered, more than 80% of the uncollided flux is incident between 2 = 30o-90o
(2 measured from the detector axis normal to the ground interface). Uniformity of the
zenith angular response in this range to within a few percent assures that the value of
Nf/No will not vary significantly with changes in the distribution of flux. In general, a
more uniform response is achieved with a crystal where the diameter is close to the
length dimension. However, the variation in Nf/No for a detector where the crystal
length/diameter is as high as 1.3 or as low as 0.7 would not be expected to be more than
about 20% for energies >200 keV. Figure 3.7 shows angular correction factor data at
three different energies for several detectors in a downward facing geometry and a
uniform source depth profile.
C. N/I and N/A.
The N/I (and N/A) factors are derived from (-ray transport calculations. Tabulations
of these data along with other pertinent information on the make-up of the environmental
( radiation field can be found in Beck et al. (1972), Beck and de Planque (1968), and
Beck (1972). A complete set of exposure rate values (I/A) for close to 200 common

fission and activation isotopes at various exponential depth distributions in the soil can be
found in Beck (1980).
Notes:
1. The inference of exposure rates from nuclides located in the ground does not require
a precise knowledge of the distribution with depth or of the exact soil density or
composition. This property results because the observed peak count rate in a field
spectrum is essentially a measure of the uncollided flux, and although this quantity
and the exposure rate produced by it and the associated scattered flux varies
significantly with the source depth distribution and soil characteristics, the ratio of
these two quantities, N/I, does not. Thus, even a crude estimate of source distribution
should not lead to a sizeable error in the exposure rate.
2. In lieu of a complete experimental calibration of a Ge detector for field spectrometry,

generic factors may be substituted at energies > 200 keV (Helfer and Miller, 1988).
The only parameters needed to apply this semiempirical calibration method are the
manufacturer's quoted efficiency at 1332 keV (5-45%), the crystal length/diameter
ratio (0.5-1.3), and the detector orientation in the field (upward or downward facing).
The accuracy of the derived factors is estimated to be ±10% for energies > 500 keV
and ±15% for energies between 200 and 500 keV.
3.3.5 SPECTRUM ANALYSIS
In many situations, the built-in peak area estimate features of state-of-the-art

analyzers are used in providing quick results in the field. Prominent peaks are identified
in a bench-mark spectrum and the appropriate regions of interest are set up. On certain
analyzers, function keys are programmed using the net peak area, counting time and
calibration factor (Nf/I and Nf/A) to provide instantaneous readout of exposure rate and
concentration or inventory.
For more complete data reduction, a small computer is interfaced to the analyzer to
run a spectrum analysis program. If desired, a totally portable system may be configured
using a battery-powered laptop computer. Our standard analysis program (Gogolak and
Miller, 1977; Gogolak, 1982) performs the following:

1. Based on a two point energy calibration as set by the operator, certain peaks which
are characteristic of typical environmental spectra are identified, namely:
a. the 186, 295, 352, 609, 1120 and 1765 keV peaks in the 238U series;
b. the 583, 911, 966 and 2615 keV peaks in the 232Th series;
c. the 1460 keV peak of 40K;
d. the 662 keV peak of 137Cs.
These peaks are defined by set energy bands where the left and right channel markers
are representative of the Compton continuum.
2. The counts between the energy boundaries for each of the above peaks are summed.
The background counts in three channels on each side of a peak are averaged and the
result is used as an estimate of the baseline under the peak. This is multiplied by the
number of channels in the peak and subtracted out from the total counts in the peak
band to yield the net peak counts.
3. Detector specific calibration factors are applied to convert from peak count rate to
exposure rate and concentration or inventory.
4. A printout is made listing count rates, converted quantities and associated statistical
counting errors.
5. Permanent storage of the spectrum is made on either magnetic tape or diskette.
6. As an option, an automated search is performed to identify any peaks present in the

spectrum. Data such as nuclide, half-life, (-ray intensity and associated energy are
printed out using a library of nearly 400 principal (-ray energies that are seen in the
environment (Section 5, this Manual). Any peak can be quickly analyzed by using an
optional automated continuum strip.
7. The program enters an interactive phase where the operator examines any additional
peaks, checks the results of the automated routine, or investigates any unusual or
unexpected features of a spectrum.

3.3.6 INVENTORY MEASUREMENTS
3.3.6.1
APPLICATION
A field (-ray spectrum can also provide an estimate of the amount of activity per unit
area of soil surface for nuclides which have been deposited on the ground. To do this, a
knowledge of the source distribution in the soil is required in order to relate the mea-
sured total absorption peak count rate to the incident unscattered photon flux and then to
the activity in the soil in a manner analogous to that used for natural emitters.
The activity profile with depth for deposited nuclides in undisturbed soils can be
represented by an exponential function,
S = S0 e (
- α / ρ ) ρz
(4)
where
S is the activity per cm3 at depth z cm,

So is the activity per cm3 at the soil surface,
" is the reciprocal of the relaxation length in cm-1, and
D is the in situ soil density (g cm-2).
The cumulative activity, or inventory I, integrated to depth z' is, then,
z′
I = ∫o dz=
So
α [ − α / ρ ρz′
] [
1 −e ( ) = I o 1 − e ( )
α / ρ ρz′
] (5)
where Io is the total inventory integrated to infinite depth.

3.3.6.2
HOMOGENEOUS TERRAIN
In the case of a freshly deposited nuclide, the depth parameter is infinite corres-
ponding to a plane source distribution and a relaxation length of zero. In practice, the
effects of ground roughness bury the source somewhat. Even on what appears to be flat
terrain, we apply an "/D value of 6.25 cm2 g-1, which at a typical soil density of 1.6 g cm-3
corresponds to a relaxation depth of 0.1 cm. Values of "/D for aged global fallout 137Cs
have been found to range from a high of 1.0 for an evergreen forest floor to a low of 0.03
for a flood irrigated lawn. At a soil density of 1.6 g cm-3, these correspond to relaxation
lengths of 0.6 and 21 cm, respectively. More typical values of "/D tend to range from
0.05-0.1 for open field sites and 0.2-0.5 for wooded or desert areas.
Values of the unscattered flux and its angular distribution at 1 m above the
ground have been tabulated for exponentially distributed sources in the soil for various
energies and "/D values (Beck et al., 1972). Using Equation 2, where the term A now
represents the inventory (activity per unit area), the detector response can be calculated
for a particular nuclide as a function of "/D. If the nuclide has two reasonably strong (
lines well separated in energy, the value of "/D can be inferred from the ratio of the
measured fluxes.
In the case of a monoenergetic source such as 137Cs, the value of "/D can be
determined experimentally as follows:
1. A 62 cm2 or similar large area corer and auger is used to extract soil samples from
different depth intervals (see Section 2.4) depending upon the expected activity
distribution. For example, if the profile is expected to be shallow, the depth intervals
can be 0-2.5, 2.5-5, and 5-30 cm, while if it is expected to be deep, intervals of 0-5
cm, 5-10 cm, and 10-30 cm can be used. More than one core can be taken, in which
case the samples from the same depth are composited. The depth of the soil core
should be sufficient to include essentially all of the deposited activity so that Io can be
determined.
2. An aliquot of a sample from each depth increment is counted on a high resolution Ge

detector to determine the concentration of the radionuclide of interest.

3. The activity per unit area for each depth is computed from the product of the con-
centration and the sample mass for that depth increment divided by the area of the
sample.
4. A fit to Equation 5 is then applied, the variables being Io - I, the integrated activity per
unit area and DzN, the gross in situ mass per unit area down to depth zN. Graphically,
this can be performed by plotting the log(Io - I) versus Dz and fitting a straight line
through the points, weighting the points near the surface more heavily since this is
where most of the activity is contained. The slope of this line is just "/D.
Note:
Although the inventory is determined using the soil sample data itself, it is quite
useful to corroborate this estimate with the field spectrum. The soil cores may represent
an area of a few hundred square centimeters, while the field data represent the average
over several hundred square meters.
3.3.6.3
NONHOMOGENEOUS TERRAIN
For areas where the fallout is suspected of being unevenly distributed across the
ground, representative inventory measurements can still be made by relying on the fact
that a field spectrum averages out the local inhomogeneities in the source geometry. This
more generalized method is applied to cases such as the measurement of aged fallout in
the desert southwest of the U.S. where blowsand tends to shift from bare soil and collect
under vegetative cover. A complete description can be found in Miller and Helfer
(1985). The basic steps include:
1. Soil samples in depth increments are collected from the different types of ground
cover present (grass, brush, bare soil, etc.).
2. The samples are counted and a depth profile for each type of ground cover is obtained
using the procedure outlined above for homogeneous terrain.

3. If the depth profiles are significantly different, the approximate percentage of ground
cover of each type is determined within a 15 x 15 m square centered at the detector.
This can be performed using a combination of tape measurements and eye estimates
to approximate the dimensions of any patches of grass or shrubs and trees out to their
drip line, or to where there is an obvious change in soil characteristics, and then
calculating the total area of each particular type of cover.
4. The conversion factor to apply to the peak count rate in order to obtain an inventory
estimate is given by
 x i  −1
< g > = ∑  (6)
 i gi 
where
<g> is the average full absorption peak count rate to inventory conversion factor
for an infinite half space source distribution with randomly spaced segments
of different types of ground cover, each of which has its own characteristic
nuclide depth distribution and inventory (inventory per unit count rate),
xi is the fraction of the total inventory associated with the i-th type of ground
cover,
gi is the full absorption peak count rate to inventory conversion factor for an
infinite half-space source distribution with a measured depth profile
characteristic of the i-th type of ground cover (inventory per unit count rate).
Note:
The value of <g> exhibits a dependence on the relative inventory mix for the different
ground covers which can only be determined through soil sampling. Nonetheless, the
value of <g> must fall within the range of the individual values of gi. Generally, this
range is not large. Although the inventory may typically vary by a factor of two for the
different ground covers, the variation in the conversion factor for the different depth

profiles associated with these ground covers will average <30%. This is particularly true
for sites where the fallout is near the soil surface because the conversion factor does not
vary strongly with the depth profile for values of "/D > 0.2.
3.3.7 SPECTRAL STRIPPING FOR GERMANIUM DETECTORS
3.3.7.1
APPLICATION
A stripping operation can be applied to a Ge detector spectrum which has been

collected in free air in order to obtain the ( flux density as a function of energy
(Miller, 1984). This flux spectrum can be readily converted to an independent estimate
of the free air exposure rate or be used to make energy response corrections to other
radiation measuring devices. This technique has particular applications to indoor
radiation measurements, where the flux distribution is not easily predicted because of the
complex and generally unknown ( source geometry.
3.3.7.2
THEORY
A count registered by the detector can be caused by the full or partial absorption of an
incident photon or by the passage of a cosmic ray produced charged particle. In order to
obtain a measure of the incident photon flux spectrum, the partial absorption and cosmic-
ray events must be subtracted out and then the full absorption efficiency curve of the
detector can be applied.
The stripping operation can be expressed as:
( )
L
N 1′ = N 1 − ∑ f ij r j −1 N j′ − N c (7)
j=i+1

where
NiN, NjN are the counts in an energy band due to the total absorption of incident ( flux,
Ni is the observed counts in an energy band due to all sources,
L is the energy band containing the highest energy ( line (generally
2.615 keV),
fij is the fraction of the continuum counts at energy band i due to the partial
absorption of incident ( flux at energy band j,
rj is the ratio of total counts to full absorption peak counts for incident flux at
energy band j, and
Nc is the counts in band i due to cosmic-ray events, assumed to be constant in any
energy band and given by
N C = (E 2 − E1 + 1)
E2
−1
∑ Ni (8)
i=E1
where
E1, E2 are the lower and upper energy bands of a pure cosmic-ray energy (generally 3-
4 MeV).
3.3.7.3
DETERMINATION OF STRIPPING PARAMETERS (f and r)
Factor f - For the factor f, a multiple step function fit is used wherein the region
below the Compton edge is divided into 10 equal size energy bands and the region above
the Compton edge is divided into four equal bands. The fraction of the total counts in the
continuum in each band can be experimentally determined for a particular detector by
examining the shape of the continuum below a full absorption peak from a mono-
energetic ( source. Although the shape of the continuum is a function of the energy and

incident angle of the ( ray, it is not overly sensitive to these variables, particularly at the
higher energies which contribute the most to the exposure rate.
Factor r - In the same manner that the full absorption peak efficiency is determined
for a detector (see Procedure 3.3.4 for No/N), the total efficiency can be determined and
its ratio computed. However, effectively monoenergetic sources must be used and room
background must be subtracted from the entire spectrum. Like the full absorption peak
efficiency, the total efficiency varies with incident angle for a cylindrical detector.
However, the ratio of the two, r, varies more smoothly and is not a strong function of the
incident angle. A single angular correction factor can therefore be applied which is
representative of the higher ( energies which weigh heavily in the exposure rate
computation. This factor can be obtained by assuming an isotropic radiation field and
averaging over the entire 4 B solid angle. Although, in practice, the radiation field may
not be isotropic, a reasonable approximation to this ideal can be created by accumulating
a spectrum with the detector oriented in different directions, thus averaging out the
angular dependence. To accomplish this, we routinely count for equal lengths of time
with the detector pointing in six different directions, that is, each way along three
orthogonal axes.
3.3.7.4
STRIPPING OPERATION
The stripping operation is performed on a portable PC using Basic and takes < 1 min
to complete. It proceeds as follows:
1. The spectrum is calibrated using two energy-channel points supplied by the operator.
2. The spectrum is compressed from 4000 channels to 400 channels for faster
computation.
3. The spectrum is stripped of the cosmic-ray events.

4. The spectrum is stripped of partial absorption events for equal size energy bands of
10 keV each and starting at the band containing the highest energy ( line (generally
2.615 keV), where NN = N - Nc. Succeeding lower energy bands can then be
computed based on the Nj' values from any higher band.
5. The spectrum of counts which remains after the stripping operation is completed is
converted to the incident flux density energy distribution by applying the full
absorption peak efficiency of the detector. As in the case of the factor r, an angular
correction based on the assumption of isotropic incidence must be applied.
6. The ( exposure rate is computed by integrating across the spectrum the product of the
energy, flux density, and mass energy absorption coefficient for air at each energy
band.
Note:
Intercomparisons between the spectral stripping method and our own instruments and
standard procedures, as well as with those of the Japanese Atomic Energy Research
Institute, have shown good agreement (Nagaoka, 1987). Based on these measurements,
we conservatively estimate an upper limit in the total systematic error of ±5% when this
method is applied to spectra at background levels. The statistical error was determined to
be < ±2% (at the 1 F level) for a 1-min spectrum at typical background levels.
3.3.8 SODIUM IODIDE DETECTORS
3.3.8.1
APPLICATION
Although no longer used routinely by EML for field (-ray spectrometry, NaI
detectors are nonetheless capable of yielding satisfactory results particularly for natural
background measurements. Like the case for Ge detector measurements, full absorption
analysis can be applied to a NaI field spectrum. In addition, there is the technique of
"energy band" analysis as well as "total spectrum energy" analysis. A complete
description of these methods can be found in Beck et al. (1972).

3.3.8.2
EQUIPMENT
The NaI detectors (usually 4-x-4 in cylindrical crystals attached to matched

photomultiplier tubes) are coupled through an emitter-follower preamplifier. Either a
battery powered portable or 120 V AC vehicle-based analyzer with at least 400 channels
is used to collect the spectra. NaI detectors are usually covered (in addition to the
manufacturer's standard thin aluminum or stainless steel window) by a 6-mm bakelite
shield to reduce the ß-ray contribution to the Compton continuum as well as to moderate
thermal stresses. The NaI detector is transported in a rugged, foam-cushioned box to
minimize mechanical and thermal shock.
3.3.8.3
PEAK ANALYSIS
For NaI spectrometry, the No/N should be obtained with source energies as close as
possible to those environmental sources to be evaluated, usually the energies associated
with the 238U and 232Th series, 40K, and 137Cs. The resulting No/N versus E data do not
represent the usual NaI response curve, because the analysis of absorption peaks does not
lead to accurate estimates of the actual peak areas, unless one engages in a complex
computer program for spectral stripping. NaI peak areas are determined in essentially the
same manner as those from Ge detectors, though only a few absorption peaks are
measurable due to the relatively poor resolution. Cross-calibration of a NaI detector with
the more accurate Ge detector can be very helpful.
3.3.8.4
ENERGY BAND ANALYSIS
When the naturally-occurring nuclides associated with the 238U and 232Th series and
40
K predominate at a field site, the simplified "energy band" method of analysis can be

applied. In this method, the spectrum energy is calculated as the product of the counts
per channel times the energy represented by each channel in bands of channels. The
energy bands are centered on the 1.46 MeV 40K, the 1.76 MeV 214Bi, and the 2.62 MeV
208
Tl peaks. The response in each bin can then be represented by the following equations.
E1 = u1U + k1K + t1T + I1
E2 = u2U + k2K + t2T + I2 (9)
E3 = t3T + I3
where E1, E2 and E3 are the measured "energy" values for some arbitrary counting period;
U, K and T represent the exposure rates to be measured; the constants represent the
distribution of spectrum energy per unit exposure rate among the three energy bands; and
I1, I2 and I3 are the cosmic-ray contributions. The three equations relating the U, K and
Th exposure rates to the energy bands are determined by solving Equation 9 and
evaluating the coefficients from regression analyses of a large number of field spectra for
which exposure rates had been determined from absorption peak analyses.
The following approximate equations apply for a nominal 10.16 x 10.16 cm NaI
detector, shielded with 6-mm Bakelite, though calibration of individual detectors is
preferred.
U = 0.4 E1N - 0.2 E3N
K = 0.08 E1N - 0.06 E2N - 0.02 E3N (10)
T = 0.3 E3N
and
I = ETN/37

where I is the total exposure rate from natural radioactivity in soil, and
1.32 MeV < E1N < 1.60 MeV,

1.62 MeV < E2N < 1.90 MeV,
2.48 MeV < E3N < 2.75 MeV,
0.15 MeV < ETN < 3.40 MeV,
the E values being in GeV per 20-min counting period. The primes indicate that the
energy contributions from cosmic rays must be subtracted before Equations 10 are
used.
Energy band analysis is performed quickly in the field by interfacing the

multichannel analyzer to a portable computer. Using interactive software (Gogolak and
Miller, 1977), the basic steps include:
1. The spectrum is read into the computer and the operator provides a two point energy
calibration (usually the positions of the 1460 keV 40K and 2615 keV 208Tl peaks) and
the altitude to the nearest thousand feet (for the cosmic-ray corrections).
2. The above equations are applied.
3. A printout is made of the total exposure rate and the contributions for 40K and the 238U
and 232Th series.
3.3.8.5
TOTAL SPECTRUM ENERGY ANALYSIS
The exposure rate in air is proportional to 4 N(E) (:e/D) EdE, where N(E) is the flux
of ( rays of energy E and :e/D is the mass absorption coefficient in air. Between a few
hundred keV and several MeV, :e/D is fairly constant. Also for low energies, the
probability of an incident photon being totally absorbed by a large NaI detector is fairly
high (on the order of 50-100% from 100 keV to 1 MeV). About 75% of the exposure rate
from the soil is due to emitters between 100 keV and 1500 keV. This and the fact that
the spectrum of ( rays from natural emitters is fairly invariant to the exact proportions of
U, Th and K in the soil, indicates that the total "spectrum energy" is a reasonable measure

of free air exposure from natural radioactivity in the soil. A large NaI or similar detector
measures the flux to a fairly high degree of accuracy and, even though sensitivity
decreases somewhat at higher energies due to the escape of secondary scattered photons,
this decrease tends to be compensated by correspondingly smaller values of :e/D for
energies above 1 MeV relative to values below 1 MeV.
Unlike many NaI hand-held survey instruments, which depend on the assumption that
the counting rate above some bias level is proportional to the exposure rate, the total
energy technique requires only that the counts in a channel be proportional to N (E) (:e/D)
for that energy, and is, therefore, less sensitive to spectral changes. For example, a NaI
survey meter might indicate that the exposure rate from a unit flux of 60 keV photons as
being almost equal to the exposure rate from a unit flux of 1460 keV photons. This
would occur since the 1460 keV pulse would be recorded due to the high probability of a
Compton collision in the detector even though many of the secondaries would escape the
crystal. In the total energy technique, the higher energy counts are weighted by the
energy deposited and reflect their relative contribution to the exposure rate more
correctly. The slightly larger total absorption at 60 keV reflects the larger value of (:e/D)
relative to higher energy ( rays.
The spectrum "energy" calibration factors for 10.16 x 10.16 cm detectors are
determined in two ways:
1. The detectors are exposed to a known point source of 226Ra in the laboratory and the
measured exposure rate is compared to an ionization chamber reading. The
measurement should be corrected to account for the fact that the rays from the point
source are incident along the detector axis.
2. A comparison of measurements of "spectrum energy" from actual field spectra is

made with simultaneous ionization chamber measurements for different
environmental radiation fields.
The two methods give essentially the same calibration factors.
REFERENCES
Beck, H. L.

"Environmental Gamma Radiation from Deposited Fission Products, 1960 - 1964"

Health Physics, 12, 313-322 (1966)
Beck, H. L.
"The Physics of Environmental Gamma Radiation Fields"
J. A. S. Adams, W. M. Lowder, and T. F. Gesell (Editors)
In: The Natural Radiation Environment II, CONF-720805-P1, pp. 101-134 (1972)
Beck, H. L.
"Exposure Rate Conversion Factors for Radionuclides Deposited on the Ground"
USDOE Report EML-378, July (1980)
Beck, H. L. and G. de Planque

"The Radiation Field in Air Due to Distributed Gamma-Ray Sources in the Ground"
USAEC Report HASL-195, May (1968)
Beck, H. L., W. J. Condo and W. M. Lowder

"Spectrometric Techniques for Measuring Environmental Gamma Radiation"
USAEC Report HASL-150, October (1964)
Beck, H. L., J. A. De Campo and C. V. Gogolak

"In Situ Ge(Li) and NaI(Tl) Gamma-Ray Spectrometry for the Measurement of
Environmental Radiation"
USAEC Report HASL-258, July (1972)
Gogolak, C. V.
"Collection and Analysis of Environmental Radiation Data Using a Portable Desktop
Computer"
USDOE Report EML-398, April (1982)
Gogolak, C. V.
"Rapid Determinations of Noble Gas Radionuclide Concentrations in Power Reactor
Plumes"
Health Physics, 46, 783-792 (1984)
Gogolak, C. V. and K. M. Miller

"New Developments in Field Gamma-Ray Spectrometry"

USDOE Report EML-332, December (1977)
Helfer, I. K. and K. M. Miller

"Calibration Factors for Germanium Detectors Used for Field Spectrometry"
Health Physics, 55, 15-29 (1988)
Lowder W. M., H. L. Beck, and W. J. Condo

"Spectrometric Determination of Dose Rates from Natural and Fall-Out
Gamma-Radiation in the United States, 1962-63"
Nature, 202, 745 (1964a)
Lowder W. M., W. J. Condo and H. L. Beck

"Field Spectrometric Investigations of Environmental Radiation in the U.S.A."
In: The Natural Radiation Environment, University of Chicago Press, Chicago, IL,
pp. 597-616 (1964b)
Miller, K. M.
"A Spectral Stripping Method for a Ge Spectrometer Used for Indoor Gamma
Exposure Rate Measurements"
Miller, K. M. and H. L. Beck

"Indoor Gamma and Cosmic Ray Exposure Measurements Using a Ge Spectrometer
and Pressurized Ionisation Chamber"
Miller, K. M. and I. K. Helfer

"In Situ Measurements of 137Cs Inventory in Natural Terrain"
In: Environmental Radiation '85, Proceedings of the Eighteenth Midyear Topical
Symposium of the Health Physics Society, pp. 243-251 (1985)
Miller, K. M. and P. Shebell

"In Situ Gamma-Ray Spectrometry - A Tutorial for Environmental Radiation Scientists"
USDOE Report EML-557, October (1995)
Miller, K. M., P. Shebell and G. A. Klemic

"In Situ Gamma-Ray Spectrometry for the Measurement of Uranium in Surface Soils"

Health Physics, 67, 140-150 (1994)
Nagaoka, T.
"Intercomparison Between EML Method and JAERI Method for the Measurement of
Environmental Gamma Ray Exposure Rates"

Table 3.1
Ge DETECTOR SPECIFICATIONS
Resolution Dimensions
Serial Cryostat Efficiency at 1332 DxL Peak/
Manufacturer No. Code Type orientation (%) (keV) (mm) L/D+ Compton
*
Princeton 484 P1 Ge(Li) 4 L, 2.9 1.70 36 x 20 0.56 23.0
Gamma-tech downward
514 P2 Ge(Li) 4 L, 12.2 2.43 43 x 44 1.02 30.0

downward
1039 P3 Ge(Li) 17 L, 27.9 2.36 59 x 47 0.80 35.9

upward
1545 P4 Ge(Li) 17 L, 22.3 2.10 56 x 54 0.96 49.5

upward
1030 P5 P-type Ge 2 L, all 21.7 1.77 59 x 35 0.59 52.0

attitude
**
EG & G 23-N-37VB O1 N-type Ge 30 L, 35.3 1.96 55 x 65 1.18 59.4
Ortec upward
25-N-1514 O2 N-type Ge 30 L, 35.4 1.73 55 x 73 1.31 67.9

upward
26-P-70P O3 P-type Ge 1.8 L, all 45.0 1.80 60 x 79 1.31 73.0

attitude
33-TN30860A - N-type Ge 3 L, all-attitude 75.0 1.95 71 x 79 1.11 74.8
*
Princeton Gamma-Tech, Inc., 1200 State Road, Princeton, NJ 08540
**
EG & G Ortec, 100 Midland Road, Oak Ridge, TN 37830
+
Ge crystal length/diameter ratio

Section 3.3, Vol. I
HASL-300, 28th Edition
Figure 3.4. Typical field site for conducting in situ (-ray spectrometry showing placement of tripod
mounted portable Ge detector and battery-powered multichannel analyzer.
Figure 3.5. Schematic representation of the relative ground area contributions to the primary flux at
1 m above the ground for an exponentially distributed source with an energy of 662 keV
and where "/D = 0.21 cm2 g-1.

Section 3.3, Vol. I
Figure 3.6. Count rate per unit incident flux at normal incidence (No/N) as a function of energy for
seven of the detectors listed in Table 3.1.
Figure 3.7. Angular correction factor (Nf/No) as a function of Ge crystal length/diameter (L/D) ratio at three different
energies for a downward facing detector for a uniform with depth source profile in the soil.

3.4 REMOTE GAMMA-RAY SPECTROMETRY STATIONS
Contact Person(s) : Colin G. Sanderson
3.4.1 SCOPE
EML's global studies are comprised of a Global Fallout Program, a Surface Air
Sampling Program, and a Remote Atmospheric Measurements Program (Sanderson et al.,
1994). These programs currently represent EML's effort to sample, measure, and study
radionuclides in the lower troposphere and their deposition on the earth's surface (Larsen
et al., 1994).
Using remote atmospheric measurement systems (RAMS) in RAMP, EML is able to

measure gamma-ray emitting radionuclides having short half-lives, such as 7Be, that have
been collected by drawing air through highly efficient filters, see Procedure 2.2.2.2. The
gamma-ray spectrum is transmitted to ARGOS communications systems flown aboard
polar-orbiting National Oceanic and Atmospheric Administration (NOAA) satellites,
retransmitted to ground stations, and recovered via a telephone link by EML's computer.
The recovered sodium iodide (NaI) gamma-ray spectrum is automatically resolved using
a linear least squares program with a library of 18 possible gamma-ray emitting
radionuclides. The last background spectrum received is also included in the library.
When the analysis is complete, the results are written to a report file and a computer mail
message is issued to report the completion of the analysis.
Once a RAMS station has been set up, its weekly operation requires <1 h of an
operator's time. Each week one sample, one calibration, and one background is counted.
Each month the weekly air filter samples are sent to the University of Miami and the
computer floppy disk is sent to EML.

3.4.2 COMPONENTS
A. Gamma-ray detector.
A 12.7 cm x 10.2 cm diameter integral inline NaI(Tl) gamma-ray detector with 241Am
doping for gain stabilization is used in the RAMS. The photopeak produced by the 241Am
alpha particles should approximate a 3.5 MeV gamma ray.
B. Lead shield.
The copper-lined shield is composed of 12 interlocking steel and lead rings with a
sample holder drawer at its base. The rings are 27 cm in diameter at the lower half and
22 cm for the top half of the shield and weigh either 20 kg or 9 kg, depending on the size.
C. Heated environmental chamber.
A heated environmental chamber is used to house the lead shield, NaI detector, multi-
plying phototube, and preamplifier. The temperature inside the chamber is set ~ 5oC
above the highest expected ambient temperature.
D. Lead-acid gel-cell batteries and DC charger (power supply system).
The power supply system provides primary and backup battery power to the RAMS.
This system uses: a transformer to convert 240-V power to 120 V (if required); sealed,
lead-acid gel-cell batteries; and battery chargers. The EML-designed power supply can
sustain 8 h of continuous operation when a line power failure occurs.
E. Multichannel analyzer (MCA).
The portable MCA used in the RAMS has the following features: 4096 channel,
battery operated, CRT display, preamplifier power, detector high voltage, RS232 input/
output. Davidson Model #2056-C MCA or equivalent is used.

F. Laptop computer.
A computer with backlite LCD display, either dual floppy, one fixed and one floppy
disk, at least one RS232 and one parallel port, 512K memory, and simple 12-V DC
operation are required.
G. Satellite transmitter and antenna.
A 2 W, 401.650 MHz transmitter, 30.5 m of low-loss cable and an omnidirectional

quadrafilar helix antenna are used to transmit the gamma-ray data to the ARGOS
satellites. Polar Research SITRA-1 or SITRA-2 or equivalent is used.
Figure 3.8 shows a block diagram of EML's second generation NaI RAMS.
3.4.3 INSTRUMENTATION ASSEMBLY
A. Lead shield and NaI detector.
Place the removable bottom of the environmental chamber on a table or floor that will
support about 200 kg. The shield parts are numbered for assembly. Place the lead base
(1) on the indicated circle. Place lead ring (2) on top of (1) and lead ring (3) on top of (2).
Align these rings so that the sample drawer fits properly. Continue to install lead rings
(4), (5), and (6). Next, install the small copper insert, the NaI gamma-ray detector with
preamplifier attached, and then the large copper housing. Add lead rings (7), (8), (9),
(10), and (11). Finally, place the lead plug (P) on top of the shield and place the
environmental chamber over the completed shield.
B. Equipment rack.
Place the RAMP system power supply on the top shelf of the equipment rack, passing
the cables through the hole in the back of the shelf. Place the MCA on the center shelf
and connect the cables from the NaI gamma-ray detector preamplifier to the "0 TO 1250
V POSITIVE H.V.," "PULSE INPUT," and "PREAMP POWER." Place the
serial/parallel two-way converter to the left and to the back of the bottom shelf.

Hang the transmitter on the two screws on the back of the equipment rack. Connect
the printer cable to the computer printer port. The other end of this cable is connected to
the PARALLEL side of the serial/parallel two-way converter.
Connect a 25-pin RS232C cable to the SERIAL side of the serial/parallel two-way
converter and to the 25-pin connector on the transmitter. Use tape to secure this cable to
the back of the equipment rack.
Connect the 9-pin end of an RS232C cable to the computer, connect the other end of
this cable to the 25-pin I/O Port RS232C on the MCA. Connect the antenna cable to the
transmitter and the ARGOS antenna.
*** WARNING ***
The power switch on the back of the RAMP system power supply must be in the
down (OFF) position and the ARGOS antenna connected to the transmitter before
proceeding. The transmitter will be damaged if power is applied without a load on the
antenna connector. Connect one end of the AC power cord to the inside of the
environmental chamber, connect the other end to the multioutput AC extension box.
Connect the RED power plug from the RAMP system power supply to the computer.
Connect the BLACK power plug with the hole in the center from the RAMP system
power supply to the MCA.
*** WARNING ***
Very carefully connect the BLACK miniature phone power plug from the RAMP
system power supply to the serial/parallel two-way converter. It is possible to cause a
short circuit and blow an internal fuse if this plug is not inserted properly.
Connect the AMP lock power connectors to the transmitter.
Connect the AC power cord of the RAMP system power supply to the multioutput
AC extension box.

Power the RAMP system power supply with the switch on the back of the unit.
Power the MCA and perform setup as follows:
Press SETUP on the MCA.

Press the UP ARROW.
Press YES eight times or until BAUD RATE=9600 appears again.
Press the UP ARROW.
Press YES six times or until PARITY=8+NONE appears again.
Insert the SYSTEM DRIVE A disk into drive A on the right side of the computer.
Insert a formatted data disk into drive B on the left side of the computer.
Power the computer. The switch is toward the back on the right side. The computer
will self-test, load, and execute "1RAMP," the RAMS control program.
The system is now ready for operation. Set the clock as described in Appendix A and
perform the steps described in Appendix B. In the event of problems, go to Appendix C
for system troubleshooting. Appendix D gives the schedule of routine operation.
3.4.4 EML QUALITY CONTROL
All data records being received from Service ARGOS are monitored by EML
personnel daily to ensure that all sites are transmitting valid data. This includes almost
continuous monitoring of EML VAX mail messages by EML personnel during the
normal work day. All completed spectra received from Service ARGOS are also
examined daily. Calibration spectra are computed and plotted as received. Background
spectra are plotted and visually compared with previous background spectra. The results
of the analyses of the sample spectra are examined for quality of fit and for the likelihood
of fission products. The cause of excessively high quality of fit or fission product
likelihood is determined, corrected, and a reanalysis is then performed.
All hard copy and computer files, both original data and results of analyses, are
maintained at EML.

REFERENCES
Larsen, R. J., H.-N. Lee, M. Monetti and C. G. Sanderson

"EML's Global Sampling Programs"
Proc. of the Conference on Atmospheric Chemistry, American Meteorological Society,
Boston, MA (1994)
Sanderson, C. G., N. Latner and R. J. Larsen

"Environmental Gamma-Ray Spectrometry at Remote Sites with Satellite Data
Transmission"
Nuclear Instruments and Methods, A239, 271-277 (1994)
Latner, N., C.G. Sanderson, V.C. Negro, S. Wurms and N. Chiu

“AUTORAMP - An Automatic Unit for Unattended Aerosol Collection, Gamma-Ray
Analysis and Data Transmission from Remote Locations”

Figure 3.8. Block diagram of EML’s second generation NaI RAMS.

APPENDIX A
OPERATION PROTOCOL
CONTROL PROGRAM MENUS
When the RAMP control program starts, there are four possible operations.
I - for initial setup,

C - for system clock reset,
G - for MCA gain check, or
A - for data acquisition.
INITIAL SETUP
Press the 'I' key on the computer. Enter the local date and time in the format as shown
on the screen. Press ENTER. If the entry is correct, press the 'Y' key on the computer. If
the entry is incorrect, press the 'N' key on the computer and reenter the correct local date
and time.
If the 'Initial Setup' is entered in error, press the 'Q' key to quit this routine.
The default values displayed can be accepted by pressing ENTER. Press the 'Y' key
to accept this value, or 'N' to enter a new value.
CLOCK RESET
It is very important that the date and time displayed in the upper-left corner of the
screen is correct to within 1 h. If the date and time should change by more than 1 h, it
must be reset. Press the 'C' key on the computer and enter the current local date and time

in the format as shown on the screen. Press ENTER. If the entry is correct, press the 'Y'
key on the computer. If the entry is incorrect, press the 'N' key on the computer and
reenter the correct local date and time.
DATA ACQUISITION - CALIBRATION
Press the 'A' key on the computer for data acquisition. When the 'A' key is pressed,
there will be five possible operations.
S - for sample count,

B - for background count,
C - for calibration count,
P - to return to previous menu.
The first set of data obtained by the system must be a calibration count. Place a
Coleman lantern mantle into the drawer of the RAMS counter and start data collection by
pressing the 'C' key on the computer. The computer will automatically set up the analy-
zer and begin data collection. The calibration data should be collected for at least 4 h.
Stop the calibration count by pressing the 'S' key, then the 'Y' key, and then the 'T' key.
The calibration data will then be recorded on the floppy disk and transmitted to the
ARGOS satellite. Remove the Coleman lantern mantle from the drawer of the RAMS
counter.
DATA ACQUISITION - BACKGROUND
Press the 'A' key on the computer for data acquisition. When the 'A' key is pressed


Background data must be collected after the calibration and before any samples.
Remove the Coleman lantern mantle from the drawer of the RAMS counter and replace
with a BACKGROUND filter. Start data collection by pressing the 'B' key on the
computer. The computer will automatically set up the analyzer and begin data collection.
The background data should be collected at least overnight. Stop the background count
by pressing the 'S' key, then the 'Y' key and then the 'T' key on the computer. The
background data will then be recorded on the floppy disk and transmitted to the ARGOS
satellite.
DATA ACQUISITION - SAMPLE
Press the 'A' key on the computer for data acquisition. When the 'A' key is pressed,

After one calibration and one background data set have been collected, exposed air
filter samples can be counted.
Prepare for sample data collection by pressing the 'S' key. Enter the following
information when requested on the computer screen.
Date & time that sample collection started.

Date & time that sample collection ended.
Reading of running time meter when sample collection started.
Reading of running time meter when sample collection ended.
Reading of pressure meter when sample collection started.
Reading of pressure meter when sample collection ended.
Temperature when sample collection started.
Temperature when sample collection ended.

Please refer to Appendix D for a schedule of when SAMPLES, CALIBRATIONS,

and BACKGROUNDS should be counted.
When instructed, place the folded sample air filter into the drawer of the RAMS
counter and start data collection by pressing any key on the computer. The computer will
automatically set up the analyzer and begin data collection.

APPENDIX B
FIELD QUALITY CONTROL
POWER SUPPLY METERS
Each voltmeter should read about 14 V.
The MCA ammeter should read about 0.7 A with the display OFF and about 1.0 A
with the display ON.
The laptop ammeter should read about 0.3 A with the display OFF and about 0.5 A
when the display is ON.
The transmitter/converter ammeter should read about 0.3 A. Every 3 min when the
transmitter is active this ammeter will read about 0.8 A for a second. This meter
deflection is a good indication that the transmitter is operating.
LIGHT EMITTING DIODE (LED) INDICATORS
A red LED on the parallel/serial converter should be on, as it indicates the unit is
powered.
A green LED on the MCA indicates that the battery is charging properly. If this LED
should become red, a fault condition exists and EML must be notified by TELEX or
FAX, but no operator action is required.
The three LEDs on the power supply should be on, as they indicate that the battery
chargers are operating.

APPENDIX C
SYSTEM TROUBLESHOOTING
Once the system has been set up and is running, it should continue to do so
indefinitely. There are a number of error traps built into the computer software program.
If an error occurs and is trapped by the program, a message will be displayed indicating
what action the operator should take.
Power for the transmitter/converter is protected with a 5 A internal fuse. If the LED
on the serial/parallel two-way converter is not illuminated, and the transmitter/ converter
meters indicate no voltage, this fuse may need to be replaced. In order to replace this
fuse, the cover for the RAMP system power supply must be removed. The fuse holder is
at the back of the left side of the unit. Spare fuses have been supplied with the backup
equipment.
If none of the power supply LEDs are lit, the ammeters read 0 and the voltmeters read
between 12 and 13 V, then the AC fuse at the back of the unit must be replaced to restore
the AC (main) power. The batteries inside the power supply will continue to provide
power for the RAMS for about 8 h.
If the computer does not respond, press 'CTRL,' 'ALT,' and 'DEL' at the same time.
This will reset the computer and restart the program. Press the 'A' key, then either the 'C,'
'B' or 'S' key, as appropriate.
If the computer has entered the DOS operating mode as indicated by the DOS prompt
A>, type 1RAMP and press ENTER to restart the program. Press the 'A' key, then either
the 'C,' 'B' or 'S' key, as appropriate.
If the MCA has been turned off or has lost power for a long time, it will be necessary
to reset the high voltage and to recycle the baud rate and parity so that communications
with the computer can be established. Proceed as follows:
Press SETUP on the MCA.

Press the UP ARROW.

Press 'YES' eight times or until 'BAUD RATE=9600' appears again.
Press the UP ARROW.
Press 'YES' six times or until 'PARITY=8+NONE' appears again.
Press END.
Use 'CTRL,' 'ALT,' and 'DEL.' (This will reset the computer and restart the program.)
When the RAMP control program starts, there will be four possible operations.
I - for initial setup,

C - for system clock reset,
A - for data acquisition.
Press the 'I' key on the computer. Accept the default values displayed by pressing
ENTER. Press the 'Y' key to accept these values. The high voltage will automatically be
set to the correct value by the initial setup routine.
Computer software problems can develop if: 1) the MCA amplifier gain is beyond
the range that the computer can correct; 2) the MCA gain setting when the unit was
packaged for shipment was preset to an invalid value; and 3) the internal temperature of
the environmental chamber was not set at 88oF. The MCA gain can be checked and
adjusted as follows.
Press the 'G' key on the computer keyboard. "THE CURRENT GAIN VALUE IS"
message will be displayed. After a few seconds, the current gain value will also be
displayed. If the gain is very different from the preset value, enter the preset value and
press the ENTER key on the computer. Press ENTER on the computer to leave the
current gain value unchanged.
The MCA gain can also be reset automatically by the software. The procedure is as
follows:
From the initial menu, press 'I' for initialization.

Enter the correct local date and time.
When prompted for a GAIN value, enter the word RESET.

Follow the instructions on the computer screen.
If the data that is being transmitted is not received by EML in New York City, EML
will inform site operators by TELEX or FAX and ask operators to TELEX or FAX the
status of the RAMS. After EML has determined the correct resolution of the problem,
instructions will be communicated to site operators.

APPENDIX D
SCHEDULE FOR ROUTINE OPERATION
MONDAY - Transmit the SAMPLE count started on Friday by sequentially

pressing the S, Y, and T keys on the computer.
Remove the exposed sample filter from the RAMP counter, write the
date of transmission on the filter label under Notes, and mail the filter
to the University of Miami.
Place the Coleman lantern mantle into the RAMP counter and start
data collection by sequentially pressing the A and C keys on the
computer.
WEDNESDAY - Transmit the CALIBRATION count started on Monday by sequentially

pressing the S, Y, and T keys on the computer.
Remove the Coleman lantern mantle from the RAMP counter; store
mantle.
Place the unexposed background filter into the RAMP counter and
start data collection by sequentially pressing the A and B keys on the
computer.
Change RAMP air filter and record pump data as outlined in Appendix
A; store filter.
FRIDAY - Transmit the BACKGROUND count started on Wednesday by

sequentially pressing the 'S', 'Y,' and 'T' keys on the computer.
Remove the unexposed background filter from the RAMP counter;

store filter.

Fold and place the exposed filter sample collected on Wednesday into
the RAMP counter and start data collection by pressing the 'A' and 'S'
keys on the computer. Enter the data requested by the computer.
MONTHLY - At the end of each month, replace the data disk in Drive B of the
computer and mail the old disk to EML.

3.5 THERMOLUMINESCENCE DOSIMETRY
Contact Person(s) : Gladys Klemic
3.5.1 SCOPE
Research at EML is directed toward advancements in environmental applications of

thermoluminescence dosimetry (TLD). This includes investigations of problems
associated with low-level measurements of the gamma- and cosmic-ray natural
background (de Planque and Gulbin, 1985; Julius and de Planque, 1984; Gulbin and
de Planque, 1983, 1984), as well as techniques for the separation of neutron and gamma
components from artificial sources (Klemic et al., 1996). EML organizes the
International Intercomparisons of Environmental Dosimeters, a voluntary program of
testing and research on integrating dosimeters for the measurement of environmental
radiation (Klemic et al., 1995; Maiello et al., 1990a,b, 1995; de Planque and Gesell,
1986) that attracts participants from around the world.
Consistent procedures for the preparation, packaging, recordkeeping and readout,

along with many QC checks, are necessary to obtain reliable results. The procedures
described here have been shown to result in high quality measurements that are suitable
for low-level environmental radiation monitoring and for TLD research purposes (see
also American National Standards Institute Report, ANSI N545-1975, and the future
release of ANSI N13.37, which will replace it).
3.5.2 SPECIAL APPARATUS
1. TLD phosphors:
Lithium fluoride dosimeters - 7LiF:Mg,Ti chips are used for most applications. They are
3.2 x 3.2 x 0.89 mm, 24 mg chips manufactured by Harshaw/Bicron Co., 6801 Cochran
Rd., Solon, OH 44139-3395 (TLD-700).

Aluminum oxide dosimeters - Al2O3:C chips are presently used only for research
purposes. They are 5 mm in diameter and 1 mm thick and are manufactured by
Victoreen, Inc., 6000 Cochran Rd., Solon, OH 44139-3395 (Model 2600-80).
Calcium fluoride chips and bulb dosimeters - EML's historical experience has included
bulb-type dosimeters and other types of chips such as CaF2:Mg (Gulbin and de Planque,
1983; Gulbin and de Planque, 1984); however, these phosphors are not presently in use
and will not be covered here.
2. Annealing equipment:
High temperature furnace* - A furnace with constant temperature capability up to 1000oC
(manufactured by Blue M Electric Co., Blue Island, IL 60406) is used for high
temperature annealing.
Low temperature furnace - This furnace is maintained at 100oC for low temperature
annealing (manufactured by Fisher Isotemp, Pittsburgh, PA 15219).
Planchet - An EML-designed, platinum-plated copper planchet is used for chip anneal-

ings. The tray is indented so that chips may be identified by placement (see Figure 3.9).
Brass heat sink - A brass heat sink, 5 x 5 x 21 cm, is mounted on an aluminum base that
is placed on steel unistrut bars to allow uniform cooling of chips (see Figure 3.9).
3. Controlled lighting:
Gold fluorescent lights with no ultraviolet emissions.
Dark room shades.
Incandescent bulbs, including a 25-W red bulb for minimal lighting.
4. 137Cs source:
A 2 Ci collimated NIST traceable 137Cs source is used for calibration. Usual exposure
distance is 2 m, where the beam is uniform within a radius of at least 3.0 cm.
*A new controlled atmoshpere oven (manufactured by GS Lindberg/Blue M., Watertown, WI) has recently been installed for
research but it is not yet in regular use.

5. TLD readers:
The TLD reader room is air-conditioned to maintain a constant temperature (~ 20oC)
year-round. Three TLD readers are presently in use:
EML reader - This reader was built by EML and has been in use since 1971. It uses
linear pan heating and measures the TL signal with a high-gain, low-noise photo-
multiplier tube cooled to 15oC below room temperature. An internal light source is used
to verify the electronic stability of the system. Power is applied to a heating element
silver-soldered to a thin silver heater pan. The chip is positioned manually and centered
in the pan by a removable platinum-plated, stainless-steel disk with a central hole for the
TLD. This disk suppresses the infrared signal from the heater pan and provides a
reproducible geometry for chip placement. Heating parameters are adjustable up to a
maximum temperature of about 550oC. Purified nitrogen gas flows through the heating
chamber at a rate of about 2.4 L min-1 to suppress any nonradiation induced TL signal. A
strip chart records the glow curve and temperature profile with a selected glow peak
region of interest indicated by pen offsets. The integral "counts" in this region is
indicated on a numerical display.
Victoreen Model 2800M - A commercially available reader with many of the same
features as the EML reader using updated technology, it will eventually replace the aging
EML reader. Readout data can be sent to a printer or personal computer.
Automatic hot gas reader (TNO) - Built by Radiologische Dienst TNO at the Netherlands
Organization for Applied Research, this reader is different from the other two, both in
heating methods and chip handling. It uses three jets of preheated nitrogen gas (about
190oC constant temperature, not a linear profile) for reproducibility and speed. Chips are
handled automatically at a rate of 150 per hour up to 1000 chip readings. Readout
parameters and output are controlled and stored by a personal computer. This reader is
especially suitable for large-scale studies and routine monitoring.
6. Lead shield:
A 10-cm thick lead shield is used to store TLDs after preparation or before readout.

3.5.3 PREDEPLOYMENT PREPARATION OF CHIPS
A. Batch preselection.
Before chips are to be used for measurements, a set (typically 200 to 300 chips) from
a single manufacturing batch is tested for uniformity as follows:
1. Clean and anneal chips as described in Section B.
2. Give chips a single exposure to 137Cs (typically on the order of 70 µGy in air, or
8 mR).
3. Read out the chips (see Table 1 for readout parameters).
4. Assign chips with readings that agree to within 30% of each other to the same group.
Outliers should be flagged and removed from the group. (Note: A tighter criterion of
5-10% may be used for special applications.)
5. Assign each chip a unique identification number to be permanently retained.
B. Cleaning/annealing.
1. Manually clean individual chips before each use with methanol and a cotton swab,
handling chips with forceps or a vacuum pen under appropriate lighting conditions
(see Table 3.2) (Freeswick and Shambon, 1970).
2. Anneal chips as follows:

LiF: 1 h at 400oC, 1-min cool-down on heat sink, followed by 2 h at 100oC.
Al2O3: 10 min at 400oC.
3. Cool chips to room temperature on heat sink.
4. Store chips in the lead shield if they are not going to be used immediately. Keep
careful records of the date and time that the chips are placed in the lead shield, as well
as when they are removed for deployment.

C. Dosimeter packaging.
Packaging should be light-tight, moisture proof, and thick enough to provide

electronic equilibrium and to shield against environmental beta radiation. The EML
dosimeter consists of a commercially available black lucite box in which additional black
lucite pieces have been bonded in place to provide depressions for holding the individual
chips (see Figure 3.10). It has outside dimensions of 2.9 x 2.9 x 0.9 cm. Each chip is
surrounded by lucite with a minimum thickness of 2.8 mm (about 320 mg cm-2). A
dosimeter usually consists of five chips, though the container can hold up to 10 chips. To
ensure water-tightness, the lucite box is placed inside a thin plastic bag which is heat
sealed or secured with fiber tape.
3.5.4 ENVIRONMENTAL DEPLOYMENT
Environmental TLDs are usually deployed for 1-3 months. A preselected uniform
batch (see Section 3.5.3.A) with enough TLDs to cover at least three monitoring cycles is
maintained exclusively for use in environmental monitoring (i.e., while one set is in the
field, there are enough dosimeters for two replacement sets). A set of environmental
dosimeters for a monitoring cycle includes six control dosimeters prepared with the field
dosimeters, as described in Section 3.5.3.B. All dosimeters are stored in the lead shield
after preparation until they can be deployed, noting date and time. Two of the controls
will be used to determine the exposure rate in this shield (STORAGE CONTROLS) and are
thus stored there for the duration of the field cycle. The other four are used for
calibration of the system (CALIBRATION CONTROLS) and will be discussed in Section
3.5.5.D.
If the field site is far from the laboratory, it is necessary to use additional controls to
account for exposure received in transit (TRANSIT CONTROLS). These controls must be
kept with the field dosimeters at all times except during field deployment, when they
must be kept somewhere where the exposure rate is known or can be measured
independently.
The dosimeter is hung 1 m above the ground, away from large structures that may
provide shielding or additional exposure (see Figure 3.11). Usually the dosimeter is left
hanging freely to rotate in the wind for isotropic angular exposure. At the end of the field
cycle, the dosimeters are returned to the lead shield until they are read out, and a
replacement set is deployed in the field.

3.5.5 READOUT AND CALIBRATION
A. Reader checkout.
1. Prepare the reader for use by setting the appropriate reader parameters as shown in
Table 3.2.
2. Check the reader's dark current, the heating chamber current (background of empty
chamber), and the response of the reader to the internal light source.
3. Read out a test chip several times to check for anomalous results.
B. Preread annealing.
1. Remove the FIELD dosimeters from the lead shield, noting the date and time.
2. Perform a preread anneal for LiF chips at 100oC for 10 min. (No preread anneal is
used for Al2O3 chips.)
C. Initial readout.
1. Read out one chip from each FIELD dosimeter. After it returns to room temperature,
the chip is read a second time to measure the background of the system.
2. Temporarily discontinue readout at this point to prepare the calibration dosimeters.
D. Calibration.
Four dosimeters are used to calibrate the system during readout. Two of these are
from the set originally prepared at the start of the field cycle, and two are taken from the
set of replacement dosimeters just prepared. Thus, while each prepared set includes four
calibration dosimeters, two will be used right away to calibrate the returning field set and
the other two are stored in the lead shield for the duration of the field cycle to be used at
the following readout. The calibration is performed as follows:
1. Examine the range of reader net counts from the initial readout of each field
dosimeters to determine the calibration exposures to use. Choose three calibration
exposures to bracket the readings given by the field dosimeters and to provide a

check on the linearity of the system. (The approximate counts per unit exposure is
known from previous readouts.)
2. Remove the CALIBRATION CONTROLS from the lead shield, noting the date and time of
retrieval.
3. Give one CALIBRATION CONTROL an exposure that is expected to yield net counts in
the range of the lowest result found for the FIELD dosimeters. Another CALIBRATION
CONTROL is given an exposure corresponding to the highest reading, and the other
two receive an exposure in the middle of this range.
E. Resuming readout.
1. Remove the STORAGE CONTROL dosimeters from the lead shield, noting the date and
time.
2. Anneal all of the control dosimeters in the case of LiF TLDs (the four CALIBRATION
o
CONTROLS as well as the two STORAGE CONTROLS) for 10 min at 100 C.
3. Intersperse the STORAGE CONTROL and CALIBRATION CONTROL dosimeters among the
FIELD dosimeters. Read out one chip from each dosimeter before going to the next
chip in any dosimeter. (This provides a QC check against any variations in the
system during readout.)
3.5.6 ANALYSIS OF RESULTS
An interactive program that runs on a personal computer (written in Fortran) handles

the data analysis. A sample input file is shown in Appendix A. It includes for each
dosimeter: date and times of preparation, deployment, return, and readout; gross counts;
background counts; and time of exposure to the cesium source. The program determines
the field exposure by correcting for exposure received in storage as measured by the
storage controls and then converting counts to exposure by using the calibration controls.
The user is given the option of rejecting outliers, and the statistical error is propagated
throughout each step in the calculation. The program returns the net field exposure and
exposure rate and the field deployment time for each field dosimeter. It also gives
information about the exposure rate in storage, the calibration factor, and any rejected

readings. A sample output file is shown in Appendix A. Details of the calculations are
given below.
A. Computing net counts and standard error.
The mean net counts for each dosimeter is:
n
X = ∑ (x i ) ÷ n
i=1
where
xi = gross counts - background counts of ith chip.
n = number of chips per dosimeter (n = 5 usually).
The standard error of the mean for each dosimeter is:
n
∑ ( x i − X)
2
σ
errx = = i-1
n n(n -1)
B. Outlier check.
The program checks for outliers among the individual chip readings in a dosimeter.
Two different criteria are used:
1. "Extreme Values" - Individual chip net counts that are > 150% or < 50% of the
dosimeter average X are flagged. This test would find missing chips or noise spikes.
2. "r Test" - This is an outlier test for gaussian distributions (Proschan, 1969). The net
counts for the five chips are ranked in order of smallest to the largest, such as x1, x2,
x3, x4, x5. If the ratio r = (x2 - x1) ÷ (x5 - x1) is larger than 0.780, chip x1 is flagged.
Similarly if the ratio r = (x5 - x4) ÷ (x5 - x1) is larger than 0.780, chip x5 is flagged.
This is a more sensitive test that can identify outliers that would be missed by the
extreme value test. While it is redundant for values beyond 150% of the mean, it

could miss the very low extreme values so both tests are needed. (Proschan describes
more sensitive tests to apply when more than 7 chips are used.)
In either criterion, the user is then given the option of omitting flagged chips from
the analysis. No chips are automatically rejected: the final decision is made by the user.
(In practice data are rarely rejected, and then usually for obvious reasons.) If a chip is
rejected, the mean net counts and standard error are recalculated for that dosimeter, and a
note appears in the output file.
C. Storage exposure rate correction factor.
S= 1 ( 2 ) (X SC1 + XSC2 ) ÷ t SC
where
S = storage correction factor,
XSC1 = mean net counts for STORAGE CONTROL #1,
XSC2 = mean net counts for STORAGE CONTROL #2, and
tSC = time storage controls were in lead shield (calculated by subroutine from
dates in input file)
The standard error is propagated through this calculation as:
1
errS =
2 t SC
(err 2
SC1 + errSC2
2
)
With errSC1 and errSC2 being the standard error of the storage controls as defined in
Section A above. (The error associated with the storage time is negligible, estimated at
< 0.01%.)
D. Calibration factor.
 1 4
C= 
 4
∑ (X CCi − St CCi ) ÷ exposure CCi
i =1
where
C = calibration factor,
XCCi = mean net counts of CALIBRATION CONTROL #i

tCCi = time ith CALIBRATION CONTROL was kept in lead shield (calculated by
subroutine from dates in input file),
exposureCCi = cesium exposure given to ith CALIBRATION CONTROL (calculated from
decay corrected known source strength and time of exposure).
The standard error propagated through this calculation is then:
1 4  errCCi
2
+ errS2 t CCi
2

errC = ∑  exposure 2 
4 i=1  CCi 
(Uncertainties in cesium calibration exposure are treated as systematic rather than

statistical errors and are treated separately.)
The program also performs a linear regression on the corrected counts vs. exposure
for the four calibration dosimeters. The goodness of fit is a check on the linearity of the
system and the slope may be compared to C.
E. Field exposure.
The field site exposure (f) is a function of the quantities calculated above. The
algorithm used by the program to calculate field site exposure may be summarized as:
F = f (X F, t F , S, C) =
(X F −S t F )
C
where
XF = mean FIELD dosimeter counts
tF = time FIELD dosimeters were kept in a lead shield (calculated by

subroutine from dates in input file),
F. Error analysis.
Total uncertainty = statistical error at 95% confidence + estimated systematic error

While the standard error was propagated through all the above calculations using the
analytical propagation of error formulas, for the last step it is easier to calculate the
statistical error numerically as shown below (Bevington and Robinson, 1992).
Statistical err = 2.776 (a 2

+ b2 + c2 )
where
2.776 = 95% confidence interval for 5 chips
(4 degrees of freedom)
a=
([X F + errF ] − St F )
−
(X F − St F )
C C
b=
( X − (S + err )t ) − (X
F F F F − St F )
C C
c=
(X F − St F )
−
(X F − St F )
C + errC C
Systematic error is estimated on a case-by-case basis and added linearly to the

statistical error for reporting the final results. The estimated systematic uncertainty
associated with EML's cesium source is 2.5%.
G. Situations involving transit controls.
In cases where TRANSIT CONTROLS are required, the field exposure (Section E)
calculation would instead be:
F = (X F − T) / C

where
T = mean TRANSIT dosimeter counts corrected for exposure received in

storage.
If it happens that the TRANSIT CONTROLS are stored in the same lead shield as the
other storage controls during the field cycle (time = tF ), then
T = (X T − St F )
where
XT = mean TRANSIT dosimeter counts.
More likely the TRANSIT CONTROLS will be stored in a different lead shield near the field
site, in which case the storage exposure must be measured by some other means.
REFERENCES
"American National Standard Performance, Testing, and Procedural Specifications for

Thermoluminescence Dosimetry (Environmental Applications)"
American National Standards Institute Report, ANSI N545-1975 (1975)
Bevington, P. R. and D. K. Robinson

"Data Reduction and Error Analysis for the Physical Sciences"
Second Edition, McGraw-Hill, Inc., New York, p. 49 (1992)
de Planque, G. and T. F. Gesell

"Environmental Measurements with Thermoluminescence Dosemeters - Trends and
Issues"
de Planque, G. and J. F. Gulbin

"The Effects of Moisture on LiF TLDs and Its Consequences for Environmental
Measurements"

Proceedings 18th Midyear Health Physics Symposium, pp. 307-315, January (1985)
Freeswick, D. C. and A. Shambon

"Light Sensitivity of LiF Thermoluminescent Dosimeters"
Health Physics, 19, 65 (1970)
Gulbin, J. F. and G. de Planque

"An Investigation of Field Fading in LiF (TLD-700) in an Environmental Monitoring
Program"
Gulbin, J. F. and G. de Planque

"Ten Years of Residential TLD Monitoring"
Julius, H. W. and G. de Planque

"Influence of Annealing and Readout Procedures on Fading and Sensitivity Changes in
LiF for Temperatures and Humidities Typical for Environmental and Personnel
Dosimetry"
Klemic, G.A., N. Azziz and S.A. Marino

“The Neutron Response of Al2O3:C, 7LiF: Mg, Cu, P, and 7LiF:Mg, Ti TLDs”

Klemic, G.A., J. Shobe, T. Gesell and P. Shebell

"Results of the Tenth International Intercomparison of Environmental Dosemeters"
Maiello, M., J. F. Gulbin, G. de Planque and T. F. Gesell

"8th International Intercomparison of Environmental Dosimeters"
Radiation Protection Dosimetry, 32, 91-98 (1990a)
Maiello, M., J. F. Gulbin, G. de Planque, and H. Thompson Heaton

"Ninth International 'Mini' Intercomparison of Environmental Dosemeters: A Further
Analysis of the Data"
Proschan, F.
in: Precision Measurement and Calibration
Ku, H. H. (ed.)
Selected NBS Papers on Statistical Concepts and Procedures
NBS Special Publication 300, Vol. 1, pp. 349-354 (1969)

TABLE 3.2
SUMMARY OF TLD PARAMETERS USED
ANNEALING
Predeployment Prereadout
400oC 1h 100oC 10 min
LiF
100oC 2h
Al2O3 400oC 10 min none
LIGHTING CONDITIONS
LiF no UV: gold fluorescent or incandescent
Al2O3 darkroom
READ OUT Linear Heating: Victoreen Reader

Integration
Starting Temp Heating Rate Heating Time Period*
LiF 100oC 10oC sec-1 30 sec ~ 10 - 20 sec
Al2O3 100oC 10oC sec-1 20 sec ~ 5 - 20 sec

Table 3.2 (Cont'd)
READ OUT Linear Heating: EML

Heating Rate Maximum Integration Period*
Temperature (adjusted visually)
LiF 10oC sec-1 ~ 330oC peaks 3,4 &5
Al2O3 10oC sec-1 ~ 300oC whole peak
READ OUT Constant Temperature Hot Gas: TNO

Heating Time Integration Period*
LiF 11 sec 1.3 - 10.0 sec
Al2O3 13 sec 1.7 - 12.0 sec
*Integration period adjusted as needed to include entire peak.

Figure 3.9. EML-designed planchet used for chip annealings, shown on brass heat
sink. Chip identity is retained by position in planchet.
Figure 3.10. EML's light-tight lucite dosimeter package (320 mg cm-2), shown

Figure 3.11. EML dosimeter deployed at field site. Lucite box is sealed in plastic
bag to protect from moisture, and hung ~ 1 m above ground.

APPENDIX A
SAMPLE INPUT FILE Environmental TLD Measurements

INTO LEAD RET. LEAD Counts Cs Expos
SITE ID SHIELD DEPLOYED SHIELD READ OUT GROSS BKD min
Shrm 3140 02/21/93 02/26/93 04/27/93 10/20/93 430 36 0.00

19:23 15:55 07:37 09:45 425 32
417 34
414 30
447 38
Roof 3100 02/21/93 03/01/93 05/25/93 10/20/93 534 35 0.00
19:23 15:20 12:45 09:45 507 33
556 28
536 36
550 36
Chstr 3110 02/21/93 02/23/93 05/19/93 10/20/93 808 29 0.00
19:23 14:45 12:00 09:45 812 36
806 29
803 30
783 34
Chstr 3120 02/21/93 02/23/93 05/19/93 10/20/93 811 30 0.00
19:23 14:45 12:00 09:45 802 30
764 34
739 38
764 33
Sphr 3130 02/21/93 03/01/93 05/25/93 10/20/93 319 35 0.00
19:23 15:20 12:45 09:45 349 31
333 30
338 30
347 31
Stor 3200 02/21/93 00/00/00 00/00/00 10/20/93 265 29 0.00
Ctl 19:23 00:00 00:00 09:45 257 32
264 27
267 32
253 29
Stor 3190 02/21/93 00/00/00 00/00/00 10/20/93 241 32 0.00
Ctl 19:23 00:00 00:00 09:45 269 36
329 32
244 32
239 32
Calib 1 3150 02/21/93 00/00/00 00/00/00 10/20/93 478 31 3.50
19:23 00:00 00:00 09:45 511 32
471 35
489 39
486 36
Calib 2 3160 02/21/93 00/00/00 00/00/00 10/20/93 656 31 6.0
19:23 00:00 00:00 09:45 643 30
675 34
618 41
643 34
Calib 3 3000 04/23/93 00/00/00 00/00/00 10/20/93 614 30 6.0
13:00 00:00 00:00 09:45 598 34
610 32
666 38
597 30
Calib 4 3050 04/23/93 00/00/00 00/00/00 10/20/93 771 28 9.0
13:00 00:00 00:00 09:45 798 31
791 32
777 32
796 29

APPENDIX A (Cont'd)
SAMPLE OUTPUT FILE
Environmental TLD Measurements (with statistical uncertainty at 1 F)
SITE DEPLOYMENT NETmR EXPOSURE RATE :R/h FIELD h
Shrm 2-26-93 4-27-93 9.12 6.37 ± .25 (3.9%) 1431.70
Roof 3-01-93 5-25-93 14.53 7.13 ± .22 (3.1%) 2037.42
Chstr 2-23-93 5-19-93 24.68 12.11 ± .29 (2.4%) 2037.25
Sphr 3- 1-93 5-25-93 6.73 3.30 ± .17 (5.2%) 2037.42
Stor. Corr. Factor: .0448 ± .00150 cts/h (3.4%)
Ave. Calibration Factor: 25.028 ± .428 cts/mR (1.7%)
Lead Shield Exp. Rate: 1.789 ± .067 micro-R/h (3.8%)
SITE SN Net Cts Store h Cor. Cts err % err sd %sd
Shrm 3140 422.60 4342.67 228.19 ± 8.0 (1.1%) 10.5 4.58
Roof 3100 531.00 3736.95 363.71 ± 9.5 (1.5%) 17.3 4.75
Chstr 3110 784.90 3737.12 617.60 ± 10.0 (1.1%) 26.3 4.26
Sphr 3130 335.80 3736.95 168.51 ± 8.3 (1.8%) 13.6 8.08
Stor Ctl 3200 255.40 5774.34 255.40 ± 3.4 (1.3%) 7.5 2.94
Stor Ctl 3190 261.60 5774.34 261.60 ± 17.0 (6.5%) 38.0 14.53
Calib 1 3150 482.40 5774.34 223.90 ± 11.2 (1.5%) 15.9 7.12
Calib 2 3160 645.00 5774.34 386.50 ± 12.5 (1.4%) 20.0 5.17
Calib 3 3000 614.20 4316.72 420.95 ± 13.2 (1.9%) 25.8 6.13
Calib 4 3050 782.20 4316.72 588.95 ± 8.8 (0.8%) 13.3 2.26

APPENDIX A (Cont'd)
SAMPLE OUTPUT FILE continued

______________________________________________________________________________
..........CALIBRATION INFORMATION..........
Name SN Expos mR cts/mR err %err
Calib 1 3150 9.229 24.260 ± 1.216 (5.0%)
Calib 2 3160 15.821 24.429 ± 0.787 (3.2%)
Calib 3 3000 15.821 26.607 ± 0.836 (3.1%)
Calib 4 3050 23.732 24.817 ± 0.371 (1.5%)
Fit to line:
slope = 25.084 (cts/mR)

y intcpt = -0.05930
rnorm = 28.031
ierr = 0
The following packets had outlier data rejected:
(none)

Section 3.6 , Vol. I Rev. 0
HAS L-300, 2 8th Edition February 1997
3.6 BONNER-SPHERE NEUTRON SPECTROMETRY
Contact Person(s) : Paul Goldhagen
3.6.1 SCOPE
Described here are EML's moderated multisphere neutron spectrometers, also known
as Bonner sphere neutron spectrometers, and the general principles of their use in neutron
spectrometry. These spectrometers are used to measure neutron fields:
1. That result from cosmic-ray interactions in the atmosphere (Hajnal et al., 1971;
Nakamura et al., 1987);
2. In the containment of pressurized nuclear reactors (Hajnal et al., 1979; Nakamura

et al., 1984; Sanna et al., 1980);
3. Around unmoderated (fast) reactors (Griffith et al., 1984; Hoot s and Wadsworth,
1984).
4. In plutonium facilities (Harvey and Hajnal, 1993).
5. Fusion test reactors (Kugel et al., 1994a,b).
3.6.2 GENERAL DESCRIPTION
The primary Bonner sphere spectrometer system consists of 12 moderated poly-

ethylene spheres equipped with boron-trifluoride proportional counters. The spectro-
meters are usable either in parallel or in the independent mode. In the parallel mode, all
the spheres are exposed simultaneously to the neutron field, while in the independent
mode they are exposed sequentially. Sufficient detail is given here for the basic
methodology; the references cited should be consulted for additional information (Aldrich
et al., 1981; Awschalom and Sanna, 1985; Cross and Ing, 1987).

At EML, neutron spectrometry is carried out on an occasional basis, usually to answer

specific research requirements or questions. Consequently, there are not rigidly defined
procedures. Considerable expertise and judgement are required to perform Bonner sphere
spectrometry, and this section should be considered as a guide rather than a specific
procedure.
3.6.3 PERSONNEL AND TRAINING
The procedures described in this section should be conducted and/or supervised by an

experienced physicist or nuclear engineer and that individual should be thoroughly familiar
with the content of the references cited in this section.
3.6.4 METHODOLOGY
3.6.4.1
DESCRIPTION OF THE SYSTEM
Bonner sphere spectrometers have been used extensively in radiation protection

practices to determine neutron spectral distributions around particle accelerators, nuclear
power stations and other nuclear facilities, as well as in cosmic-ray neutron research for
over two decades. The Bonner sphere spectromet er system is very useful since it is
simple, portable, has an isotropic response, covers a wide energy range, and the data can
be unfolded and interpreted fairly easily (Bramblett et al., 1960).
One drawback of this method is the low energy resolution. This is partially due to t he
fact that the statistical fluctuations in the number of collisions in the neutron slowing down
processes are large, and t he capture reactions are completely indistinguishable from one
another. This results in loss of information about the primary neutron energy and,
consequently, low resolution.

3.6.4.2
THE BONNER SPHERES
The 12 Bonner spheres are: one bare and one 0.075-cm Cd covered 5.08-cm diameter
boron-trifluoride spherical proportional counter, and 10 spherical polyethylene mode-
rators of 7.62-cm, 7.85-cm, 10.01-cm, 10.24-cm, 12.75-cm, 14.94-cm, 15.24-cm, 19.96-
cm, 25.04-cm and 30.07-cm diameters, respectively, with spherical proportional counters
placed at the centers.
3.6.4.3
THE RESPONSE FUNCTIONS
The Bonner sphere spectrometer response functions must be calculated. The calcu-
lations should be performed using different numerical methods (such as those incor-
porated in the ANISN and MORSE codes), different evaluated neutron cross section sets,
and different energy bining. The response functions of the boron-trifluoride counter
equipped Bonner spheres are calculated using DTF-IV and by ANISN transport codes in
the adjoint mode. The calculated detector response functions are considered sufficiently
accurate if the results obtained using different cross section sets and transport codes differ
by only a few percent for the entire energy region (Burgart and Emett, 1972; Maerker et
al., 1971).
3.6.4.4
CALIBRATIONS
The Bonner sphere spectrometer calibrations, whenever possible, should be performed

with the National Institute of Standards and Technology (NIST) monoenergetic neutron
beams, and the normalization of the overall response functions should be performed using
252
Cf spontaneous fission neutron sources. At EML, the 252Cf calibrations are performed
in an open air calibration facility, where the air and ground scattering contribution in the
worst case amounts to only 3% at 1 m source-to-detector separation (Hajnal et al., 1970;
Hunt, 1984a,b).

3.6.4.5
ELECTRONICS
Since the boron-trifluoride counters are not sensitive to ß or ( radiation, a simple

electronic setup is sufficient: a proportional counter is connect ed to a preamplifier and the
signal is fed to a linear amplifier, followed by a discriminator and a scaler to record the
number of capture reactions. The scaler readouts can be recorded on tape, or in an
appropriate logbook.
3.6.5 NEUTRON SPECTRUM UNFOLDING
The result of a set of measurements with Bonner spheres is a set of 12 count rates for
the 12 detector configurations. A mathematical method known as unfolding is used to
obtain a neutron spectrum from these data. This is accomplished using a computer
program entitled TWOGO developed at EML (Hajnal, 1981).
The relative count rates obtained for a set of 12 counts made with the Bonner spheres
are a function of the energy distribution of the neutron field. The unfolding code provides
a reasonable estimate of neutron fluence rate as a function of energy, i.e., a neutron
spectrum (Ing and Makra, 1978). The user of TWOGO provides an estimate of the shape,
called trial vector, of the neutron spectrum and the computations performed by TWOGO
iteratively adjust the spectrum to fit or be consistent with the data. The computations rely
on the use of the data available in t he literature regarding the response of the detector in
its various configurations, as a function of neutron energy. Estimates of the relative errors
of individual counts are used as weighting factors during the iterative fitting process.
Several indices are computed with the TWOGO program that serve to measure the
goodness of fit of the unfolding process. These indices are based on determining the
degree of agreement between the data obtained by observation. That is, count rates due
to neutrons for each of the detector configurations, and synthetic counts or estimates of
these same parameters obtained by folding together the response matrix and the spectrum
obtained by the unfolding process.

3.6.6 ACCEPTABLE SOLUTION
A solution can be called exact, approximate, or appropriate (Gold, 1964). Exact

solutions may have zero errors, and might look reasonable. However, they may have
unphysical characteristics, such as oscillations, and the "tail-wags-the-dog syndrome"
might appear. Usually, the unfolded data should not be expected to have too good a fit, at
least not better than the error of the input data. In general, the trial vectors should contain
the features of the neutron spectra one can expect from the physics of the problem.
Similarly, the smoothing functions, if any, have to be properly chosen. Appropriate
solutions can be obtained from good measurements, and considerable experience is needed
to judge just when a reasonable spectral solution is reached.
REFERENCES
Aldrich, J. M., D. L. Haggard, G. W. R. Endres, J. J. Fix, F. M. Cummings,

M. R. Thorson and R. L. Kathren
"Evaluating Existing Radiation Fields"
Pacific Northwest Laboratory Report PNL-3536, Richland, WA (1981)
Awschalom, M. and R. S. Sanna

"Application of Bonner Sphere Detectors in Neutron Field Dosimetry"
Radiation Protection Dosimetry, 10, 89 (1985)
Bramblett, R. L., R. I. Ewing and T. W. Bonner

"A New Type of Neutron Spectrometer"
Nuclear Instruments and Methods, 9, 1 (1960)
Burgart, C. E. and M. B. Emmett

"Monte Carlo Calculations of the Response Functions of Bonner Ball Neutron
Detectors"
Oak Ridge National Laboratory Report ORNL-TM-3739, Oak Ridge, TN (1972)

Cross, W. G. and I. Ing

"Neutron Spectrometry"
In: The Dosimetry of Ionizing Radiation
Kase, K. R., B. E. Bjarngard and F. A. Attix (Editors)
Academic Press, Vol. II, pp. 91-169, Orlando, FL (1987)
Gold, R.
"An Iterative Unfolding Method for Response Matrices"
USAEC Report ANL-6984, Argonne National Laboratory, Argonne, IL (1964)
Griffith, R. V., C. J. Huntzinger, and J. H. Thorngate

"Neutron Spectra as a Function of Angle at Two Meters from the Little Boy
Assembly"
Lawrence Livermore National Laboratory Report UCRL-90178, Livermore, CA (1984)
Hajnal, F.
"An Iterative Nonlinear Unfolding Code: TWOGO"
Hajnal, F., J. E. McLaughlin and R. Oeschler

"Technique for Determining Moderated-Neutron Instrument Characteristics"
USAEC Report HASL-222 (1970)
Hajnal, F., J. E. McLaughlin, M. S. Weinstein and K. O'Brien

"Sea-Level Cosmic-Ray Neutron Measurements"
USAEC Report HASL-241 (1971)
Hajnal, F., R. S. Sanna, R. M. Ryan and E. H. Donnelly

"Stray Neutron Fields in the Containment of PWRs"
International Atomic Energy Agency Report IAEA-SM-242/24, STI/PUB/527,
Vienna (1979)
Harvey, W. F. and F. Hajnal

"Multisphere Neutron Spectroscopy Measurements at the Los Alamos National
Laboratory Plutonium Facility"

Hoots, S. and D. Wadsworth

"Neutron and Gamma Dose and Spectra Measurements on the Little Boy Replica"
Lawrence Livermore National Laboratory Report UCRL-90095, Livermore, CA (1984)
Hunt, J. B.
"The Calibration of Neutron Sensitive Spherical Devices in Non-Isotropic Neutron
Fields"
Radiation Protection Dosimetry, 9, 105 (1984a)
Hunt, J. B.
"The Calibration of Neutron Sensitive Spherical Devices"
Radiation Protection Dosimetry, 8, 239 (1984b)
Ing, H. and S. Makra

"Compendium of Neutron Spectra in Criticality Accident Dosimetry"
International Atomic Energy Agency Report, IAEA Technical Report Series No. 180,
Vienna (1978)
Kugel H. W., G. Ascione, S. Elwood, J. Gilbert, L. P. Ku, J. Levine, K. Rule,

N. Azziz, P. Goldhagen, F. Hajnal and P. Schebell
"Measurements of TFTR D-T Radiation Shielding Efficiency"
in: Fusion Engineering and Design, Proceedings of the Third International Symposium
of Fusion Nuclear Technology, Los Angeles, CA., September (1994a)
Kugel, H. W., J. Gilbert, D. Hwang, M. Lewis, J. Levine, L. P. Ku, K. Rule,

F. Hajnal, N. Azziz, P. Goldhagen, G. Klemic and P. Shebell
"TFTR Radiation Contour and Shielding Efficiency Measurements During D-D
Operations"
in: Fusion Technology, Proceedings of the Eleventh Topical Meeting on the Technology
of Fusion Energy, American Nuclear So ciety, September (1994b)
Maerker, R. E., L. R. Williams, F. R. Mynatt and N. M. Greene

"Response Functions for Bonner Ball Neutron Detectors"
Oak Ridge National Laboratory Report ORNL-TM-3451, Oak Ridge, TN (1971)

Nakamura, T., T. Kosako and S. Iwai

"Environmental Neutron Measurements Around Nuclear Facilities with Moderated-
Type Neutron Detector"
Nakamura, T., Y. Uwamino, T. Ohkubo and H. Hara

"Altitude Variation of Cosmic Ray Neutrons"
Sanna, R. S., F. Hajnal, J. E. McLaughlin, J. F. Gulbin and R. M. Ryan

"Neutron Measurements Inside PWR Containments"

.
4. ANALYTICAL CHEMISTRY

New York, NY 10014-4811

U. S. Department of Energy 4-i
Page
4. Analytical Chemistry . . . . . . . . . . . . . . . . . . . 4.1-1
4.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1-1
4.2 Atmospheric Tracer Technology . . . . . . . . . . . . . . . . . 4.2-1
4.2.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2-1

Procedure:
ATT-01 Gas Chromatographic Determination of
Perfluorocarbon Tracer
4.3 Inorganics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3-1
4.3.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3-1

4.3.2 Elemental Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3-2
Procedures:
Anions-01-E Anions - Ion Chromatography (see Volume II)
Ca-01-E Calcium - Atomic Absorption Spectrometry (see Volume II)
Ca-02-E Calcium - Permanganate Titration of the Oxalate
(see Volume II)
F-01-E Fluoride in Soil and Sediment - Specific Ion Electrode
Measurements (see Volume II)
Hg-01-E Mercury - Atomic Absorption Spectrometry (see Volume II)
NH3--01-E Ammonium in Water and Precipitation Samples -
Autocolorimetry (see Volume II)
Sr-01-E Strontium - Atomic Absorption Spectrometry (see Volume II)
U-01-E Uranium in Urine - Fluorimetry (see Volume II)
4.3.3 Multielemental Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3-3
Procedures:
M-01 Cadmium and Lead in Human Excreta and
Composite Diet Samples - Atomic Absorption
Spectrometry (see Volume II)

U. S. Department of Energy 4 - ii
Page
M-02 Precipitation and Lake Water Samples - Physical
and Chemical Measurements (see Volume II)
M-03 Trace Metals - Atomic Absorption and/or
Emission Spectrometry (see Volume II)
4.4 Organics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4-1
4.4.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4-1

Procedure:
OR-01 PAH and PCDD/Fs in Sediment - GC/MS
4.5 Radiochemical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5-1
4.5.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5-1

4.5.2 Radiometrology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5.2-1
Procedures:
A-01-R Alpha Radioassay
B-01-R Beta Radioassay
Ga-01-R Gamma Radioassay
4.5.3 Quality Control and Detection Limits . . . . . . . . . . . . . . . . . . . . . . 4.5.3-1
4.5.4 Radiochemical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5.4-1
Procedures:
Am-01-RC Americium in Soil
Am-02-RC Americium-241 in Soil - Gamma Spectrometry
Am-03-RC Americium in Water, Air Filters, and Tissue (see Volume II)
Am-04-RC Americium in QAP Water and Air Filters - Eichrom’s
TRU Resin
Am-05-RC Americium in Water and Air Filters (see Volume II)
Am-06-RC Americium and/or Plutonium in Vegetation
Fe-01-RC Iron in Aqueous Samples - Dual-DPM Mode Liquid
Scintillation Analysis
3
H-01-RC Tritium in Water - Acid Electrolysis (see Volume II)
3
H-02-RC Tritium in Water - Alkaline Electrolysis (see Volume II)
3
H-03-RC Organically Labeled Tritium - Combustion Procedure

U. S. Department of Energy 4 - iii
Page
(see Volume II)
3
H-04-RC Tritium in Water - Liquid Scintillation Counting
Pb-01-RC Lead-210 in Bone, Food, Urine, Feces, Blood, Air,
and Water
Pb-02-RC Determination of 210Pb in Bone Ash by
Measurement of 210Po
Po-01-RC Polonium in Water and Urine
Po-02-RC Polonium in Water, Vegetation, Soil, and Air Filters
Pu-01-RC Plutonium in Air Filters
Pu-02-RC Plutonium in Soil Samples (see Volume II)
Pu-03-RC Plutonium in Soil Residue - Total Dissolution Method
Pu-04-RC Plutonium in Tissue (see Volume II)
Pu-05-RC Plutonium in Tissue - Solvent Extraction (see Volume II)
Pu-06-RC Plutonium in Urine (see Volume II)
Pu-07-RC Plutonium in Large Urine Samples (see Volume II)
Pu-08-RC Plutonium in Vegetation and Tissue - Nitric/Hydrochloric
Acid Method (see Volume II)
Pu-09-RC Plutonium in Vegetation and Tissue - Nitric/Sulfuric
Acid Method (see Volume II)
Pu-10-RC Plutonium in Water
Pu-11-RC Plutonium Purification - Ion Exchange Technique
Pu-12-RC Plutonium and/or Americium in Soil or Sediments
Note: For Plutonium in Vegetation see Am-06-RC.
Ra-01-RC Radium-226 in Bone Ash
Ra-02-RC Radium-226 - Emanation Procedure
Ra-03-RC Radium-226 in Soil, Vegetation Ash, and
Ion Exchange Resin
Ra-04-RC Radium-226 in Tap Water, Urine, and Feces
Ra-05-RC Radium-224 in Urine (see Volume II)
Ra-06-RC Radium-226 in Urine and Water
Rn-01-RC Radon-222 in Air and Breath Samples
Sr-01-RC Strontium-89 (see Volume II)
Sr-02-RC Strontium-90 (see Volume II)

U. S. Department of Energy 4 - iv
Page
Sr-03-RC Strontium-90 in Environmental Matrices
Sr-04-RC Strontium-90 in Water Containing Other Radioisotopes
by Cerenkov Counting
Sr-05-RC Strontium-90 in Environmental Water Samples
Tc-01-RC Technetium-99 in Water and Vegetation (see Volume II)
Tc-02-RC Technetium-99 in Water - TEVA Resin
Th-01-RC Thorium in Urine (see Volume II)
U-01-RC Enriched Uranium in Urine (see Volume II)
U-02-RC Isotopic Uranium in Biological and Environmental Materials
U-03-RC Isotopic Uranium in Bone Ash
U-04-RC Uranium in Biological and Environmental
Materials (see Volume II)
Y-01-RC Standardization of Yttrium Carrier
4.5.5 Generic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5-5

Procedures:
G-01 Electrodeposition of the Actinides: Mitchell Method
G-02 Electrodeposition of the Actinides: Talvitie Method
G-03 Microprecipitation Source Preparation for Alpha
Spectrometry
G-04 Preparation of Microprecipitation Sources for Reanalysis
4.5.6 Sequential Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5-6
Procedures:
Se-01 Isotopic Uranium and Radium-226
Se-02 Isotopic Uranium, Isotopic Thorium and Radium-226
Se-03 Americium, Plutonium and Uranium in Water

U. S. Department of Energy 4-v
4.1 OVERVIEW
During the past 40 years, EML has developed analytical procedures for the
determination of specific gases, inorganic and organic constituents, and radionuclides.
The procedures in this section are subdivided into three general categories: gases,
organics, and radionuclides. All of the procedures have been written in a detailed manner
to provide the user with sufficient information to obtain a quantitative result which is
accurate, precise, free from chemical interference and contamination with specified
detection capabilities. These procedures are presently used at EML to obtain data for
ongoing and future research programs.
The procedures described in the gases subsection have been used primarily for the
Laboratory's atmospheric tracer program. These procedures are highly specific for this
application, with detection limits on the order of 10-15.
The procedures described in the organic subsection have been applied primarily to the
analysis of certain organic compounds in sediment or soil. Primary emphasis has been
the determination of polyaromatic hydrocarbons (PAHs) at low concentrations for
pollutant history studies conducted at EML. Separation, purification, and concentration
procedures are fully described, including expected analyte recovery for these matrices and
sample sizes.
The last subsection is devoted to radionuclide measurements and radiochemical

procedures. The radionuclide measurement techniques are described for alpha, beta, and
gamma detection types of equipment. Information about background corrections,
efficiency determination, and quality control methods and limits of detection are also
included. The radiochemical procedures described are designed for various
environmental matrices. The sample preparation portion introduces the procedure so that
representative, homogeneous, and equilibrated samples are obtained. Next, separation
and purification techniques are described to obtain a radiochemically pure sample.

Measurement techniques, including limits of detection, quality control or special

procedural precautions are also included.
Further information about these procedures can be obtained from the individual listed
as the principal contact person.

4.2 ATMOSPHERIC TRACER TECHNOLOGY (ATT)
4.2.1 SCOPE
For over a decade EML has participated in a number of atmospheric tracer

experiments designed to provide dynamic modelers with large data bases to verify,
modify, or develop computer simulations of atmospheric transport and diffusion of
energy-related pollutants over long distances. The tracer technology involves the release
of perfluorocarbon tracers at controlled and known rates from a source(s) into the
atmosphere under well-documented meteorological conditions, and measuring the tracers
at very low concentrations at various distances from the release point(s).
We will present here the analytical procedure for the determination of the perfluoro-
carbon tracers (PFTs), perfluoromethylcyclopentane (PMCP), perfluoromethyl-
cyclohexane (PMCH), ortho(cis)dimethylcyclohexane (OC-PDCH), perfluorodimethyl-
cyclohexane isomer (PDCH), and perfluorotrimethylcyclohexane (PTCH). The PFTs are
quantitatively determined by gas chromatography/electron capture detection.

ATT-01, Vol. I Rev. 0
ATT-01
GAS CHROMATOGRAPHIC DETERMINATION OF

PERFLUOROCARBON TRACERS
Contact Person: Raymond J. Lagomarsino
APPLICATION
This procedure is applicable to tracers adsorbed on Ambersorb adsorbent

contained in stainless steel tubes in the programmable atmospheric tracer sampler (PATS)
lids (described in Section 2.2.4.2).
The procedure (Dietz, 1986) involves the heating of the PATS tubes (described in
Section 2.2.4.2) to 400oC by resistance heating and desorbing the PFTs and ambient air
impurities (halocarbons) into the carrier gas. The compounds pass through a temperature
programmed precut column (heated by resistance heating) where the high boiling point
impurities are retained. The low boiling point impurities and the PFTs are partially
separated by the precut column. Further decontamination of the lighter impurities is
accomplished by catalytic reduction using a first stage palladium catalyst maintained at
200oC and by venting the impurities to the atmosphere by proper timing of the carrier gas
switching valves. A trap containing Florisil (FL) adsorbent is opened and the partially
purified PFTs are adsorbed. Subsequent rapid resistance heating of the trap to 200oC
injects the PFTs into the carrier gas of the main chromatographic column system. The
desorbed tracers are further purified by passage through two palladium catalyst beds
maintained at 200oC, and a Nafion permeation dryer. The purpose of the dryer is to
remove moisture and halogenated acids produced by the catalytic reduction. The PFTs
are then chromatographically separated by the main column and detected by the electron
capture sensor. Details of the pneumatics configuration are shown in Figure 1.

U.S. Department of Energy Page 1 of 22
SPECIAL GASES
1. 5% ultra high purity (UHP) (99.999%) hydrogen in UHP (99.999%) N2 carrier gas.
2. Compressed air to operate the valve actuators.
3. UHP (99.999%) N2.
4. Primary calibration standards consisting of a mixture of the four tracers: perfluoro-

methylcyclopentane, perfluoromethylcyclohexane, ortho-(cis) perfluoro-
dimethylcyclohexane (with isomers), and perfluorotrimethylcyclohexane.
a. 1.0 µL L-1 of each tracer in UHP (99.999%) N2.

b. 10 nL L-1 of each tracer in UHP (99.999%) N2.
c. 0.1 nL L-1 of each tracer in UHP (99.999%) N2.
d. 1.0 pL L-1 of each tracer in UHP (99.999%) N2.
SPECIAL APPARATUS
1. Gas chromatograph, modified Varian Vista 6000 or equivalent with Ni-63 electron
capture detector and 1 mV recorder or data acquisition system.
a. Main column 15 cm x 3.2 mm: stainless steel packed with

0.1% SP-1000 on Carbopack C, 80/100 mesh.
b. Precut column 53 cm x 3.2 mm thin walled stainless steel

tubing packed with Unibeads 2S, 80/100 mesh.
c. Florisil trap 11.5 cm x 1.6 mm thin walled stainless steel

tubing packed with FL, 60/100 mesh.
d. Catalyst 1% palladium on polyethylenimine/SiO2 (Royer

Pd Catalyst), 20-40 mesh beads.
e. Carrier gas purifiers activated charcoal, 13X molecular sieve and O2

traps.

2. PATS, power control module (base).
3. Matheson Model 3800 gas regulators or equivalent.
4. Power Mate Corporation Model BPA 2086-V constant current power supply or
equivalent.
5. Primeline (Soltec) two channel strip chart recorder or equivalent to monitor the PATS
adsorbent tube desorption current and FL trap desorption temperature.
A. Gas chromatograph operating conditions.
Carrier gas flow main column system - 22 cm3 min-1

precut column system - 15 cm3 min-1
Catalyst temperature 200oC (Injectors A and B)
Column temperature main column - 160oC

precut column - temperature programmed - 80oC
to 160oC at 160o min-1
Detector temperature 200oC
Compressed air set at 276 kPa (40 psig) to actuate switching

valves
Nitrogen set at 207 kPa (30 psig) for PATS lid Scanivalve
equalization pressure

B. Gas chromatograph relay assignments.
Relay No. Assignment
1 V1, sample valve (SV)
2 V2, precut valve (PCV) for changing the direction of

the precut column (PCC) carrier gas flow.
3 V3, flow direction valve (FDV) for loading FL trap and

purging catalyst B.
4 V4, FL trap valve (FTV).
5 Desorption power - High heat.
6 Desorption power - Low heat.
7 PATS tube/FL trap power routing relay.
8 Auxiliary power to precut column (PCC) for High

temperature. Relay Off for Low temperature.

C. Timed relay automation programming.
Method Analysis Aux. temp. (oC)

Method time integrated Relay Relay precut
No. (min) time (min) On Off column) Remarks
1 .00 .00 85
.01 .01 3,7 8 V3 (FDV) On, FL Trap

relay On. Auxiliary power
to PCC Off.
.02 .02 4 V4 (FTV) On (FL Trap

Open)
.05 .05 5 High heat On FL Trap
.08 .08 6 5 Low heat On FL Trap, High

heat Off
.35 .35 4,6 V4 (FTV), (FL Trap Off),

heat Off
.40 .40 7 FL Trap relay Off
3.00 3.00 Total run time

3 .00 3.00 80
.01 3.01 2 V2 (PCV) On, PCC low

Forward
.10 3.10 1,5 V1 (SV) On, High heat On
4 .00 5.00 8 160 Auxiliary Power to PCC On
.60 5.60 3 V3 (FDV) Off
.65 5.65 4 V4 (FTV) (Trap Open)
1.50 6.50 1,5 V1 (SV) OFF, High heat

Off
4.50 9.50 4 V4 (FTV) (Trap Closed)
4.60 9.60 2 V2 (PCV) Off (precut

Column Back-Flush)
5 .00 11.20 145 PCC in Back-Flush,

Catalyst B purge
.60 11.80 Total run time

D. Setting the gas chromatograph.
1. Set the 5% UHP hydrogen in UHP N2 carrier gas pressure regulator to

690 kPa (100 psig).
2. Set the main column pressure to 276 kPa (40 psig) and adjust the main column flow
to 22 cm3 min-1 using a calibrated flowmeter or soap bubble spyrometer. Set the
precut column pressure to 104 kPa (15 psig). This pressure should give carrier gas
flows of 15 cm3 min-1 at vents 1, 2, and 4.
3. Adjust the Nafion permeation dryer purge gas flow rate at vent 3 to
~ 30 cm3 min-1.
4. Input all GC operating conditions and the timed relay program for each method as
specified in Section 4.2.3.3. Method 2 is not used because it is a permanent gas
chromatograph memory default method.
5. Set the constant current power supply to 14-14.25 A.
E. Determination.
1. Attach the PATS lid containing the samples to the PATS base. Plug in the lid AFM
connector into the base receptacle labelled AFM Connector.
2. Set the base sample Duration rotary switches to 0013 (13.0 min) and the Sample
Quantity (number of tubes) to 24. This sets the switching time between tubes and
the number of tubes to be sequentially analyzed. The number of tubes desired is 23;
however, the analysis sequence is such that the PFTs from a sample are not injected
into the main column until Method 1 of the next analysis sequence. Turn the Power
Switch of the base to On.
3. Plug the constant current power supply jack into the lid receptacle labelled Power
Desorption.
4. Attach the UHP N2 gas line to the lid connector labelled To Equalization and set the
tank regulator pressure at 207 kPa (30 psig). Its purpose is to equalize the pressure to
prevent the lid Scanivalve plates from separating. Pressurize the Scanivalve and

manually step through each of the 23 tubes by rapidly pushing the Valve step switch
to assure that the Scanivalve plates are properly seated. Step to tube number "00" and
leave at that tube number.
5. Pull off the lid filter at the connector labelled To SV and attach the polyurethane
tubing purge gas outlet from V1 (SV) to this connector. Attach the V1 (SV)
polyurethane tubing carrier purge gas inlet line to the lid connector labelled To PCM.
This connects the GC carrier gas lines to the lid.
6. Turn on the constant current power supply and the two-channel strip chart recorder.
7. Turn on the compressed air, set at 276 kPa (40 psig), to operate the valve actuators.
8. To start the analysis cycle, push the PATS base Operate switch to Off, bring the
Alarm toggle switch from Manual to Multi then back to Manual and finally move
the Operate toggle switch to Run. Tube No. 1 will advance into position, the gas
chromatograph will start and run through its automated sequence consisting of four
methods.
Method 1: The FDV (V3) and FTV (V4) valves are energized and the FL trap
containing the PFTs from the previous sample is heated. The desorbed PFTs are
injected into the main column system (Figure 2). The precut column is in the back-
flush mode.
Method 3: SV (V1) and PCV (V2) are energized to place the precut column carrier
gas flow into the forward position. Heat is applied to the PATS sample tube to desorb
the sample (Figure 3).
Method 4: The desorbed PFTs pass through the precut column, the column is heated
to 160oC at a rate of 160oC min-1. V3 is placed in standby and V4 is energized to
allow effluent from the precut column to flow through the FL trap where the PFTs are
adsorbed (Figure 4). V1, V2, and V4 rotate to standby, forcing the precut column
carrier gas path into the back-flush mode.

Method 5: The precut column temperature is lowered to 145oC with continued back-
flush to elute the residual higher boiling components out of vent 1 to the atmosphere
(Figure 5).
9. At the end of 13 min, the next sample tube will step into position. This sequence will
continued until all 23 sample tubes have been desorbed and analyzed.
10. Record the chromatogram. A typical chromatogram of an ambient air sample

containing tracers is shown in Figure 6.
11. Integrate the tracer peaks corresponding to their appropriate retention times. Apply
the appropriate response factor corrections obtained from the analysis of working
standards prior to the analysis of each batch of samples. Obtain the tracer volumes
from the appropriate calibration curves and convert to concentrations using the
sample collection volume.
12. The retention times are based upon the start of the 13-min run. The expected
retention times are as follow:
Perfluoromethylcyclopentane (PMCP) - 1.47 min

Perfluoromethylcyclohexane (PMCH) - 2.25 min
Ortho(cis)perfluorodimethylcyclohexane (OC-PDCH) - 3.60 min
Meta-para perfluorodimethylcyclohexane (MP-PDCH)* - 4.17 min
Meta(cis)perfluorodimethylcyclohexane (MC-PDCH) - 4.43 min
Para(trans)perfluorodimethylcyclohexane (PT-PDCH) - 4.84 min
Perfluorotrimethylcyclohexane (1-PTCH) - 9.20 min
Perfluorotrimethylcyclohexane (2-PTCH) - 9.73 min
_______________
*Combination of the meta(trans) and para(cis) perfluorodimethylcyclohexane.

LOWER LIMIT OF DETECTION
Lower limit of detection (LLD) is defined here as that amount which gives detector
response equal to three times the noise level (ACS, 1980). The LLDs are:
Perfluorocarbon LLD (fL)
PMCP 2.7
PMCH 4.0
OC-PDCH 2.2
MP-PDCH 2.1
MC-PDCH 2.0
PT-PDCH 4.0
PTCH 3.9
DATA ACQUISITION AND REDUCTION
A. Computer hardware.
1. IBM personal computer AT with a minimum of 512 kilobytes system memory,

20 megabyte hard-disk drive, 5 1/4 inch floppy disk drive, enhanced graphics adapter
card, graphics memory expansion card (64K) or equivalent.
2. IBM enhanced color display monitor offering 640 by 350 screen resolution and
keyboard or an equivalent monitor and keyboard.
3. Nelson Series 760 intelligent A/D interface box or equivalent.
4. Citizen Model MSP-20 printer or equivalent.
5. Standard IEEE-488 (GPIB) cable.
6. Dysan 5 1/4 inch high-capacity, 96 TPI floppy diskettes or industry equivalent.

B. Computer software.
1. Nelson Analytical Corp. Model 2600 chromatography software package. Other

software vendors provide equivalent packages.
2. Nelson Analytical Corp. Model 2660 peak summary tables software (optional).
3. Nelson Analytical Corp. Model 2670 batch reprocessing software (optional).
C. General procedure.
The electron capture detector (ECD) signal from the Vista 6000 gas chromatograph is
monitored in real time by the Nelson intelligent interface offering 20 bit precision. The
interface digitizes the detector signal and stores the values in its memory. When the data
are available in the interface and the operating program is the 2600 software ACQUIRE
on the IBM AT, the data is transmitted to the computer according to the METGEN
method. The software detects peaks, determines their baselines, integrates these peaks,
and then calculates the component concentrations. Three data files are created for each
sample. They are distinguished by their file extensions: .PTS, .HDR, and .ATB. In the
.PTS file, raw chromatographic mV data are saved in binary form, while in the .HDR file,
parameters for sample identification pertaining to that raw data are stored in ASCII form.
The peak heights and/or peak areas obtained from integration, as determined by the
method, are stored in the .ATB file. Baselines different than those specified in the
method may be drawn using the software's timed events capability. The values from the
reintegration may be overwritten in the .ATB file. A schematic of the data acquisition
and data reduction system is shown in Figure 7.

CALIBRATION
A. Standards preparation.
Presented here is a procedure for the preparation of PFT standards for both instrument
calibration and daily working standards. The daily standards are analyzed prior to the
analysis of a batch of samples to determine response factor corrections resulting from
changes in electron-capture sensitivity. This method is applicable to PATS lids
(described in Section 2.2.4.2).
B. Special apparatus.
1. Matheson Model 3800 gas pressure regulator or industry equivalent.
2. Nupro Model SS-4BMG gas flow regulating valve or industry equivalent. Caution:
Low concentrations of tracer material could be adsorbed with other type valves.
3. A complete PATS unit consisting of a base (PCM) and a baked-out lid (AFM).
4. Teledyne-Hastings-Raydist Model HBM-1A bubble spyrometer or industry

equivalent, NIST traceable.
5. A 1A cylinder containing 1 fL L-1 each of PMCP, PMCH, OC-PDCH and PTCH in

UHP N2.
C. Sample preparation.
1. Plug the battery charger into the port labelled Chg.Jack and a jumper in the
receptacle labelled Analysis. The purpose of the jumper is to disable the sampling
pump. Set the thumbwheel switches to the following settings:
a. Set Time/Alarm: set to the appropriate time of day.
b. Duration: set to the time in minutes desired for each tube to remain in line
position.

c. Sample Quantity: set to 24. The sample quantity (23 in this instance) must always
be set for one more tube than is physically present on a lid.
d. Day Select: place to the On position for the appropriate day of the week.
2. Plug the lid connector into the base receptacle marked AFM Connector and turn the
Power Switch of the base to the On position.
3. Set the Matheson purity N2 tank pressure to 207 kPa (30 psig) and attach the
3.2 mm polyurethane tubing line from the cylinder to the equalization inlet port
labelled To Equalization on the lid. Open the N2 supply to pressurize the Scanivalve
and manually cycle through each of the 23 tubes. This is done by a rapid push of the
Valve step switch. Make sure that the LCD display indicates that tube "00" is in line
after this is completed.
4. Attach the 3.2 mm polyurethane tubing from V2 of the standard gas flow control
system (Figure 8) to the lid port labelled To SV.
5. Set the pressure of the standard cylinder containing the PFTs to 207 kPa (30 psig).
Slowly open the regulator valve (V1) to permit tracer gases to flow into the PATS lid
through the Nupro Flow Control Valve (V2).
6. Connect the 3.2 mm polyurethane tubing from the outlet of the lid labelled To PCM
to a calibrated flowmeter and adjust V2 to obtain 50 cm3 min-1.
7. Remove the calibrated flowmeter and replace with the bubble spyrometer.
8. Using a stopwatch, time a soap bubble to travel from 0 to the 100 cm3 marks. Record
the time and convert minutes and seconds to a pure minute time frame.
9. The quotient of 100 and the time is the flow rate of a mixed tracer gas.
10. If the flow rate is <49.0 or above 51.0 cm3 min-1, fine adjust the needle valve to obtain
~ 50 cm3 min-1.
11. Repeat Step 8 at least four times. The precision of the average of the four
measurements should be within 2%.

12. Disconnect the tubing from the outlet of the lid to the bubble spyrometer.
13. To load daily working standards, set the Duration to 0002 (2 min) to load 100 fL of
tracers onto each tube.
14. A signal must be given to inform the PATS logic to start the time sequence that
indexes the first tube into position. To start the sequence push the Operate toggle
switch to Off, move the Alarm toggle switch from Manual to Multi to Manual and
finally push the Operate switch to Run.
15. The first tube will switch into line and 100 cm3 of PFT gas will flow through the tube
over a 2-min period. At the end of the 2-min period, the next tube will switch into
position. This cycle will continue for 23 tubes. The actual volume of each PFT
adsorbed on each tube is calculated by multiplying the average of the four
measurements of flow rate obtained from Step 11 by time and by the value of the
standard of each tracer affixed to the standard (fL).
n
Volume of PFT added = ∑ fi / n × fL standard × time
i=l
where fi is the value of the ith flow measurement in cm3 min-1.
16. After tube "00" appears on the tube LCD, push the Operate switch to Off and shut all
cylinder valves.
17. Disconnect all tubing and place a 1/2 hole septum over the lid inlet and outlet ports.
18. Disconnect the lid plug from the base and remove the entire lid from the base.
19. For preparing standards up to 5 x 106 fL, the same loading procedure is followed by
using the appropriate standard for the desired range of tracer quantities and setting the
flow rate and time. The PATS base time setting may be increased during a run so that
by extending the time, increased tracer quantities may be loaded from one adsorbent
tube to the next. For constructing a calibration curve, the standards are prepared in
triplicate. Data (peak height or area) obtained from the analysis of the standards in

the 102 to 106 fL range are fitted by a 6th-order polynomial. A linear fit is applied
below 100 fL.
REFERENCES
Dietz, R. L.
"Preliminary Operating Manual, Brookhaven National Laboratory Addendum to a
Modified Varian Model 6000 GC"
Private Communication (1986)
Subcommittee on Environmental Analytical Chemistry, American Chemical Society

(ACS), Committee on Environmental Improvement (1980)
"Guidelines for Data Acquisition and Data Quality Evaluation in Environmental
Chemistry"
Anal. Chem., 52, 2242-2248 (1980)

Figure 1. Pneumatics configuration of the perfluorocarbon tracer gas chromatograph.

Figure 2. Method 1: carrier gas flow paths - Florisil trap desorption.

Figure 3. Method 3: carrier gas flow paths - PATS sample adsorption.

Figure 4. Method 4: carrier gas flow paths - absorption of PFTs on Florisil trap.

Figure 5. Method 5: carrier gas flow paths - precut column back-flush.

Figure 6. Chromatogram of a 72 L ambient air sample containing perfluorocarbon tracers.

Figure 7. Schematic diagram of the data acquisition and data reduction system.

Figure 8. PFT standard sample preparation system.

4.3 INORGANICS
4.3.1 SCOPE
The inorganic procedures previously presented in this section are not currently in use
and are now in Volume II. These procedures were adapted for inorganic constituent
analyses in air filter extract, water, rain water, and certain soils and sediments. Atomic
absorption spectrometry is used for determination of metals, ion chromatography for
specific anions, and a specific ion electrode is used for fluoride determination. These
procedures have been thoroughly tested; accuracy, precision, and lower limits of detection
have been established. Effects from interferences and contamination are detailed in each
appropriate procedure.

U.S. Department of Energy 4.3-1
4.3.2 Elemental Analyses

Anions-01-E, Vol. II Rev. 0
Anions-01-E
ANIONS - ION CHROMATOGRAPHY

(see Volume II)

Ca-01-E, Vol. II Rev. 0
Ca-01-E
CALCIUM - ATOMIC ABSORPTION SPECTROMETRY

(see Volume II)

Ca-02-E
CALCIUM - PERMANGANATE TITRATION OF THE OXALATE

(see Volume II)

F-01-E, Vol. II Rev. 0
F-01-E
FLUORIDE IN SOIL AND SEDIMENT - SPECIFIC

ION ELECTRODE MEASUREMENTS
(see Volume II)

Hg-01-E, Vol. II Rev. 0
Hg-01-E
MERCURY - ATOMIC ABSORPTION SPECTROMETRY

(see Volume II)

NH3--01-E, Vol. II Rev. 0
NH3--01-E
AMMONIUM IN WATER AND PRECIPITATION SAMPLES -

AUTOCOLORIMETRY
(see Volume II)

Sr-01-E, Vol. II Rev. 0
Sr-01-E
STRONTIUM - ATOMIC ABSORPTION SPECTROMETRY

(see Volume II)

Section Vol.
U-01-E, 4.3.3,
II Vol. I Rev. 0
U-01-E
URANIUM IN URINE - FLUORIMETRY

(see Volume II)

4.3.3 Multielemental Analyses

M-01, Vol. II Rev. 0
M-01
CADMIUM AND LEAD IN HUMAN EXCRETA AND COMPOSITE DIET SAMPLES

ATOMIC ABSORPTION SPECTROMETRY
(see Volume II)

M-02
PRECIPITATION AND LAKE WATER SAMPLES -

PHYSICAL AND CHEMICAL MEASUREMENTS
(see Volume II)

M-03
TRACE METALS - ATOMIC ABSORPTION AND/OR

EMISSION SPECTROMETRY
(see Volume II)

Sec tion 4 , Vo l. II Rev. 0
H A S L - 3 0 0 , 2 8 t h E d i ti o n April 1996
4.4 ORGANICS
4.4.1 SCOPE
The organic pollutants studied at EML are combustion related. Of particular interest
are pollutants which are toxic, resistant to natural degradat ion, and that accumulate in the
environment. Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzo-p-
dioxins and dibenzofurans (PCDD/Fs) fit into this category and have been analyzed at
EML in sediment samples (Tan et al., 1993).
The anthropogenic PAHs in the environment are formed primarily by pyrolysis of

carbonaceous materials and the major source is the combustion of fossil fuels. Various
combustion processes, especially those involving chlorinated aromatic compounds,
generate PCDD/Fs. These compounds are of particular interest to DOE because, besides
being combustion originated, they are quite persistent chemicals and can spread
throughout the environment. Some PAH and PCDD/F isomers are highly carcinogenic.
The study of these compounds in sediments is important as they can reveal the magnitude
of contamination, as well as their origins and historical inputs.

U . S . D e p a r t m e n t of E n e r g y 4.4 - 1
OR -01, Vol. I Rev. 0
HAS L-300, 2 8th Edition F e b r u a r y 19 9 7
OR-01
PAH AND PCDD/Fs IN SEDIMENT - GC/MS
Contact Person(s) : Yulin L. Tan
APPLICATION
This procedure can be applied to the analysis of sediment for three-ring to six-ring
polycyclic aromatic hydrocarbons (PAHs) and tetra- to octa- polychlorinated dibenzo-p-
dioxins and dibenzofurans (PCDD/Fs).
Many organic compounds, including PAHs and PCDD/Fs, that exist in complex
compositions in sediments can be extracted into organic solvents such as methylene
chloride. From the extract, the PAHs can be isolated from other organics by silica gel
adsorption column chromat ography and Sephadex LH-20 gel permeation column
chromat ography, and the PCDD/Fs can be isolated by silica gel adsorption column
chromatography, acid/base wash, and alumina adsorption column chromatography.
Individual PAHs and PCDD/Fs in these isolated fract ions can be further separated and
identified with a gas chromatograph/mass spectrometer (GC/MS) by GC retention times
and mass spectra. Internal standards of labeled stable isotopes serve the purpose of
quantification and quality control.
SPECIAL APPARATUS
1. Hewlett-Packard (3000-T Hanover St., Palo Alto, CA 94304) 5988 GC/MS with on-
column injector.
2. HP 5890 GC/Kratos CONCEPT 1S (Barton Dock Road, Unmston, Manchester, M31

2LD UK) high resolution MS with on-column injector.
3. Labconco (8111-T Prospect, Kansas City, MO 64132) chemical carcinogen glove

box.

4. Cahn Inst ruments, Inc. (16207-T S. Carmenita Rd., Cerritos, CA 90701), automat ic
electrobalance.
5. Whatman Soxhlet extraction thimbles, 33 x 80 mm, cleaned by Soxhlet extraction with

CH2Cl2.
6. Buchi rotary evaporator (Brinkmann, Westbury, NY 11590).
7. Fused silica capillary columns, bonded with DB-5, 30 m x 0.25 mm i.d., 0.25 : m film
(J & W Scientific Inc., Folsom, CA 95630).
8. On-column syringes.
9. Amberized microflex tubes, 5 mL and 1 mL.
10. Milli-Q reagent grade water system (Millipore Corp., 80-T Ashby Rd., Bedford,
MA 01730).
11. Volumetric flasks, 25 mL, l50 mL, 300 mL.
12. Narrow mouth amber glass bottles, 60 mL, with Teflon-lined screw caps.
13. Glass columns (40 cm x 19 mm i.d.), for gel permeation chromatography, with Teflon
stopcocks and 250-mL reservoirs having 24/40 female joints for 24/40 stoppers.
14. Filter paper, Whatman No. 41, 2.5 cm, cleaned by Soxhlet extraction with CH 2Cl2.
15. Soxhlet extractors, medium size.
16. Heavy-duty explosion proof centrifuge, Model EXD (Forma Scientific, Inc.,
Box 649, Millcreek Rd., Marietta, OH 45750).
17. Baker Bond SPE glass Teflon columns and adapters (J. T. Baker, 222-T Red School
Lane, Phillipsburg, NJ 08865).
18. 60-mL separatory funnels with Teflon stopcocks and stoppers.

19. Separatory funnel shaker.
20. Glass columns (14 cm x 5.5 mm i.d.), for alumina column chromatography, with
Teflon stopcocks and 50-mL reservoirs.
SPECIAL REAGENTS
1. Distilled in glass - methylene chloride, hexane, and toluene (Burdick and Jackson,
Muskegon, MI 49442).
2. PAH solutions - in the Labconco glove box, put about 100 : g each of the following
standard PAHs (from various suppliers: Aldrich, P.O. Box 335, Milwaukee, WI
53201; Analabs, North Haven, CT 06473; Ultra Scientific, North Kingston, RI 02852;
and Community Bureau of Reference (BCR), Brussels, Belgium) into separate 5-mL
amberized microflex tubes:
phenanthrene, anthracene, 1-methylphenanthrene, fluoranthene, pyrene,

1-methylpyrene, benzo(ghi)fluoranthene, benz(a)anthracene, chrysene, triphenylene,
benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(k)fluoranthene, benzo(e)pyrene,
benzo(a)pyrene, perylene, indeno(1,2,3-cd)pyrene, dibenz(a,c)-anthracene,
dibenz(a,h)anthracene, benzo(ghi)perylene.
Dissolve each of the PAHs into 5 mL of CH2Cl2.
3. SRM-1647 (priority pollutant PAHs, NIST).
4. PAH standard solution - using the Cahn 25 automatic electrobalance in the Labconco
glove box, quantitatively weigh an amount of about 5 mg each of the following PAHs
into a 50-mL volumetric flask:
phenanthrene, anthracene, 1-methylphenanthrene, fluoranthene, pyrene,

1-methylpyrene, benzo(ghi)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene,
benzo(e)pyrene, perylene, indeno(1,2,3-cd)pyrene, dibenz(a,h)anthracene,
benzo(ghi)perylene.

Disso lve the weighed PAHs with 50 mL of toluene so that the concentration of this
primary standard solution contains about 100 : g mL-1 for each PAH. Transfer the
solution to a 60-mL narrow mouth amber glass bottle with a Teflon-lined screw cap
and store in a refrigerator. Mix quant itative amounts of the primary standard and
SRM-1647. The mixture is analyzed as PAH calibration solutions by measuring the
molecular ions of the PAHs with GC/MS according to Steps 1-8 of Determination,
Section A. Calibrate the concentrations of each PAH in the standard solution based on
the PAH concentrations in SRM-1647. Use the method of standard additions for
PAHs that are present in both solutions. For PAHs present only in the standard
solution, response factors of neighboring PAHs in the gas chromatogram are used.
5. Labeled PAH solution - Using the Cahn 25 automatic electrobalance in the Laconco
glove box, quantitat ively weigh an amount about 2 mg each of the following
deuterated PAHs into a 50-mL volumetric flask:
anthracene, fluoranthene, pyrene, chrysene, benzo(e)pyrene, perylene,

benzo(ghi)perylene
Dissolve the weighed deuterated PAHs in 50 mL of toluene.
6. PAH calibrat ion solutions - Mix and dilute the labeled PAH solution and the PAH
standard solution with toluene to make five calibration solutions. All five calibration
solutions contain 5 : g mL-1 of each deuterated PAHs with various concentrations of
native PAHs at 1 : g mL-1, 2 : g mL-1, 5 : g mL-1, 10 : g mL-1, and 25 : g mL-1.
7. Native PCDD/F stock solutions containing: 2378-TCDF, 12378-PnCDF, 123478-

HxCDF, 1234678-HpCDF, OCDF, 2378-TCDD, 12378-PnCDD, 123678-HxCDD,
1234678-HpCDD, and OCDD, 1 mg mL -1 each in toulene.
8. PCDD/F spiking solution - mix and dilute labeled PCDD/F solutions:
13
C6 2378-TCDF, 13C6 23478-PnCDF, 13C6 123478-HxCDF, 13C12 1234678-HpCDF,
C12 2378-TCDD, 13C12 12378-PnCDD, 13C12 123678-HxCDD, 13C12 1234678-
13
HpCDD, and 13C12 OCDD from Cambridge Isotope Laboratory (Woburn, MA 01810)
with toluene so t hat the spiking solution contains 100 ng mL-1 each of the labeled
PCDD/Fs.

9. PCDD/F calibration solutions - mix and dilute the PCDD/F spiking solution and the
native PCDD/F stock solutions with toluene to make six calibrat ion solutions. All six
calibration solutions contain 10 ng mL-1 of each labeled PCDD/Fs in the PCDD/F
spiking solution with various concentrations of each of the native PCDD/Fs listed in
Step 7 at 1 ng mL-1, 2 ng mL-1, 5 ng mL-1, 10 ng mL -1, 25 ng mL -1, and 50 ng mL -1.
10. Sulfuric acid, ACS reagent (Fisher Scientific, 52 Faden Rd., Springfield, NJ 07081).
11. KOH solution, 20% by weight in Milli-Q water.
12. Copper powder - electrolytic purified (Fisher Scientific, 52 Faden Rd., Springfield, NJ
07081), freshly activate before use by soaking in 6N HCl for 5 min then rinsing
thoroughly with Milli-Q water, followed by methanol.
13. Sephadex LH-20, Sigma Chemicals Co. (P.O. Box 14508, St. Louis, MO 63178) -
swell overnight in 1:1 methanol-methylene chloride before column packing.
14. Silica gel, 100-200 mesh, EM Science (480-T Democrat Rd., Gibbstown, NJ 08027),
Grade 923, cleaned by Soxhlet extraction with methylene chloride, activated at 120 oC
overnight, then stored in a desiccator.
15. ICN alumina B, activity 1 (ICN Pharmaceuticals, Inc., 3300-T Hyland Ave., Costa
Mesa, CA 92626) cleaned by Soxhlet extraction with methylene chloride, activated at
150oC overnight, then stored in a desiccator.
16. Glass beads, 0.5 mm, cleaned by Soxhlet extraction with CH 2Cl2.
17. Zero gases, He, H2, air, and N2 (Matheson Gas Products, 30-T Seaview Dr., P.O. Box
1587, Secaucus, NJ 07096).
18. Perfluorotributylamine, Hewlett-Packard calibration compound.
SAMPLE PREPARATION
A. Sediment handling.
1. Centrifuge the watery sediment and decant off the excess water.

2. Dry the sediment in a freeze dryer.
3. Pulverize the dried sediment in a mortar and pestle and then sieve with a No. 40
(0.425 mm) sieve to remove stones and extraneous material. The fines are collected
for analyses.
B. Extraction.
1. Place the fine sediment in a cleaned Whatman extraction thimble, 33 x 80 mm.
2. Spike appropriate amounts of labeled PAH and labeled PCDD/F solutions close to
those of the estimated analytes.
3. Soxhlet extract the sample with CH2Cl2 for 30 h.
4. Concentrate the extract to dryness with a rotary evaporator at room temperature.
C. Silica gel adsorption chromatography and sulfur removal.
1. Pack 250 mg of clean activated silica gel in an empty SPE glass Teflon column
between two Teflon fritted disks. Tap gently for a tight packing and make sure the
top of the column is evenly packed and closely held by the Teflon-fritted disk.
2. Pack 1000 mg of cleaned and activated silica gel in another empty SPE column as
above.
3. Reactivate the two columns overnight at 120oC.
4. Prior to using, allow the columns to cool in a desiccator.
5. Place a piece of Whatman No. 4l filter paper, ca. 1 cm I.D., onto the top of the Teflon
disk of the 250 mg silica gel column, add about 0.5 g of activated copper powder,
place a second piece of filter paper on top of the powder.

6. Transfer the dried residue (Step B4 of Sample Preparation) onto the copper powder
topped 250 mg silica gel column with 2 x 0.5 mL of CH2Cl2. Dry the wetted column
tho roughly with dry N2 after each transfer.
7. Wet the 1000 mg column with hexane.
8. Attach sampled 250 mg column to the top of the 1000 mg column with a Teflon
column adapter.
9. Wash the t wo-column assembly with 3 mL of hexane, and discard the wash.
10. Elute the columns with 10 mL of hexane followed by 7 mL of 60% CH2Cl2 in hexane
into two separate 25-mL round bottom flasks for PCDD/F and PAH fractions,
respectively.
11. Evaporate the PAH fraction to dryness at 35oC under reduced pressure with a rotary
evaporator.
D. Acid/base wash.
1. Transfer the PCDD/F fraction in 10 mL of hexane from Step 10 of Section C, into a

60-mL separatory funnel, add 10 mL of concentrated H2SO4.
2. Shake the funnel and contents with a separat ory funnel shaker for 2 min.
3. Centrifuge the funnel for 30 s.
4. Drain off the lower aqueous layer.
5. Add second 10 mL of H 2SO4 into the funnel and repeat Steps 2-4.
6. Add 10 mL of Milli-Q water, shake briefly by hand, and repeat Steps 3-4.
7. Add 10 mL of 20% KOH solution into the funnel, and repeat Steps 2-4.
8. Add second 10 mL of 20% KOH solution and repeat Steps 2-4 once and Step 6 twice.

9. Transfer the hexane layer into a 25-mL round bottom flask and concentrate to dryness
with a rotary evaporator at 35 oC.
E. Alumina column chromatography.
1. Place a small amount of glass wool at the bott om of the glass column for alumina
column chromatography.
2. Pack 2.5 mL of activated alumina into the column and reactivate overnight at 150oC.
3. Prior to use, cool the column in a desiccator. Once cool, add a 3-mm thick layer of
dry Na2SO4.
4. Transfer the residue from Step 9 of Section D with 2 x 0.5 mL of hexane onto the top
of the Na2SO4 layer. Drain the column until the meniscus reaches the sodium sulfate
layer after each transfer.
5. Wash the column with 45 mL of hexane and discard the wash.
6. Elute the column with 4 mL of 60% CH2Cl2 in hexane.
7. Collect the eluent and concentrate to dryness on a rotary evaporator at room

temperature.
F. Gel permeation chromatography.
1. Place a piece of Whatman No. 41 filter paper, 17 mm in diameter, on the fritted glass
disc of the gel permeation column. Wet the filter paper with a few drops of methanol
so that the paper adheres to the fritted glass disc.
2. Pour in a layer of about 1 mL of glass beads to hold the filter paper onto the fritted
glass disc.
3. Fill half the column with the eluting solvent, 1:1 methanol-methylene chloride.

4. Pour in the swelled Sephadex LH-20 to form a 37-cm tall column. After the solvent is
drained to the top of the gel, place a piece of Whatman No. 41 filter paper, 17 mm in
diameter, on top of the column and add a 1-cm thick layer of glass beads.
5. Transfer, dropwise, the PAH fraction (Step 11 of Section C) with t hree to five
portions of 0.5 mL each of the eluting solvent onto the column. Spread the drops
evenly over the top of the column and drain off each transferring solution before
adding the succeeding portions.
6. Elute with 1:1 methanol-methylene chloride and discard the first 75 mL of the eluent.
Collect the following 30 mL of eluent and dry it with a rotary evaporator at room
temperature.
7. Regenerate the column by washing with an additional 50 mL of eluting solvent. Keep

the column in the solvent and seal the reservoir with a 24/40 stopper.

DETERMINATION
A. PAHs.
1. Set the HP5988 GC/MS parameters as follows:
Parameters Description
GC Column J & W Scientific, Inc., fused silica capillary

column (see Special Apparatus)
Oven temperature program from initial 60o to 150 oC, at 32oC min-1,
then from 150o to 280 oC at 4oC min-1, and
hold at 280oC for 30 min
Carrier gas He, head pressure 20 psi.
Injection mode On-column
Ionization mode Electron impact
Emission 300 : A
Electron energy 70 eV
Ion source temperature 150oC
2. Tune the MS with a calibration compound, perfluorotributylamine.
3. Set the MS at scan mode and mass scan range at 50-500.
4. Inject 0.5 : L of each PAH solutions (Step 2 of Special Reagents).
5. Immediately start the GC oven temperature program, and acquire the data during the
GC run.

6. Determine the GC retention times of each PAH from the total ion chromatograms.
7. Switch t he MS to the SIM mode, set the masses of the molecular ions of labeled and
native PAHs in calibration solutions (St ep 6 of Special Reagents) to be acquired in
their retention windows.
8. Inject 1 : L of each PAH calibrat ion solution and acquire the ion abundances of the
selected ions at the SIM mode. Repeat five times.
9. Establish the calibration curve for each native PAH by plotting the molecular ion
abundance ratios of native to labeled PAHs vs. their co ncentration ratios in the
calibration solutions. For native PAHs without labeled counterparts, data from
neighboring labeled PAHs in the total ion chromatograms are used. The slopes of
these curves are the response factors, F.
10. Repeat Step 3.
11. Redissolve the residue of the PAH fraction (Step 6 of Section F) into a small amount
of methylene chloride and inject 1 : L of the solution into the GC/MS.
12. Repeat Step 5.
13. Identify the PAHs in the PAH fraction by their retention times and mass spectra,
considering there are superimposed spectra of spiked labeled PAHs on some of the
native PAHs.
14. Repeat Step 7.
15. Inject 1 : L solution of PAH fraction and repeat Step 5.
16. Calculate the molecular ion abundance ratios of native to labeled PAHs, r.
17. Determine the co ncentrations of native PAHs, C, from the weight of the sample, W,
amount of spiked labeled PAHs, w, the ion abundance rat ios and response factors, F,
as:

B. PCDD/Fs.
1. Set the Kratos 1S CONCEPT parameters as follows:
Parameters Description
GC column J & W Scientific, Inc.; fused silica capillary

column (see Special Apparatus)
Oven temperature program Hold at initial 80oC for 1 min, program

from 80-200oC at 30oC min-1, then go to
280oC at 5oC min-1 and to 300oC at 15oC
min-1
Carrier gas He, head pressure 20 psi
Injection mode On column
Ionization mode Electron impact
Electron energy 30-40 eV
Source temperature 250oC
Trap current 500 : A
Resolution 10,000 (10% valley definition)
2. Tune the MS with a calibration compound, perfluorotributylamine.
3. Under t he GC oven temperature program, acquire the mass spectra of the native
PCDD/Fs in stock solution (St ep 7 of Special Reagents) at scan mode, mass range
50-500. Establish the retention windows of PCDD/Fs with the acquired spectra and
published results (Ryan et al., 1991).
4. Set the MS at the SIM mode and acquiring ions with masses M (molecular mass with
all 35Cl) and M+2 (molecular mass with one 37Cl and the rest 35Cl) for both native and

labeled tetra- to penta- PCDD/Fs isomers and M+2 and M+4 (molecular mass with
two 37Cl and the rest 35Cl) for both native and labeled hexa- to octa- PCDD/Fs isomers
in their respective retention windows.
5. Inject 0.5 : L of each PCDD/F calibration solutions (Step 9 of Special Reagents),

start the GC oven temperature program, and acquire the ion abundances of the
selected ions at the SIM mode.
6. Establish the calibration curves for each native PCDD/F by plotting the ion abundance
ratios of native to labeled PCDD/F vs. their concentration ratios in the calibration
solutions. The slopes of these curves are response factors, F1.
7. Redissolve the residue of PCDD/F fraction (Step 7 of Alumina Column

Chromatography) into a small amount of toluene and inject 0.5 : L of the solution into
the GC/MS.
8. Repeat Step 4.
9. Inject 0.5 : L of solution made in Step 7 and start GC/MS run as Step 5.
10. Identify the PCDD/Fs in the PCDD/F fraction by their retention times (Ryan et al.,
1991) and ion abundances.
11. Calculate the ion abundance ratios of native to labeled PCDD/Fs, r1.
12. Determine the concentrations of native PCDD/Fs, C1, from the weight of the sample,
W, amount of spiked labeled PCDD/Fs, w1, the ion abundance ratios of native to
labeled PCDD/Fs, r1, and F1, as:

The recovery of PAHs and PCDD/Fs from the whole sample preparation is ~ 50%.
The detection limit varies from 1 to 3 pg for three-ring to six-ring PAHs on the HP5988
GC/MS, and 0.2 to 0.5 pg for tetra- to octa-PCDD/Fs on the HP5890 GC/Kratos
CONCEPT 1S MS.
REFERENCES
Ryan, J. J., H. B. S. Copnacher, L. G. Panopio, B. P.-Y. Lau, and J. A. Hardy

"Gas Chromato graphic Separations of All 136 Tetra- to Octa-Polychlorinated-p-dioxins
and Polychlorinated Dibenzofurans on Nine Different Stationary Phases"
J. of Chromatography, 541, 131-183 (1991)
Tan, Y. L., A. Kong, and Y. Chiu

"Sample Preparation for Analyzing Polycyclic Aromatic Hydrocarbons and
Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in Sediment by Gas
Chromatography/Mass Spectrometry"
Estuaries, 16, 427-432 (1993)

Section 4.5. Vol. I Rev. 0
4.5 RADIOCHEMICAL
4.5.1 SCOPE
Described in this section are the radiochemical procedures currently in use at EML.
These procedures have been constantly updated for the past 40 years to reflect current
separation technology and measurement techniques. The radiochemical procedures are
usually written for a distinct environmental matrix since chemical interferences and
contamination levels vary according to sample type.

Section 4.5. Vol. I Rev. 0
4.5.2 Radiometrology

U.S. Department of Energy 4.5.2 - 1
A-01-R, Vol. I Rev. 0
A-01-R
ALPHA RADIOASSAY
CALIBRATION OF ALPHA-EMITTING RADIONUCLIDE

SOLUTIONS AND SOURCES
A. Application.
The methods for primary and secondary calibrations of "-emitting solutions and
sources are described for detection systems in use at EML.
B. Description of the system.
Primary calibrations of "-emitting radionuclide solutions and sources are performed

at EML with a 2B windowless (internal) gas flow proportional detection system. A
commercially obtained stainless steel counter with a three-position turntable and gas flow
indicator (a bubbler) is capable of accepting samples up to 5.08 cm (2 in) diameter. A
heavy walled cylindrically shaped active volume contains a loop anode of stainless steel
wire. An EML designed and built preamplifier is connected directly to the top of the
detector. The preamplifier acts as an impedance matching device for pulses from the
detection volume to an electronic scaler. High voltage from a 0-5000 V regulated power
supply is applied to the anode through a cable connection on the preamplifier. The signal
from the anode passes through the preamplifier and a cable into an electronic scaler. The
duration of the measurement interval is controlled with an electronic timer. Methane
(99.99% chemically pure) is used as the counting gas.
Any source to be measured must be of a conducting material. In practice, all sources

measured at EML in this system are on metal backings, usually platinum, stainless steel
or aluminum.

C. Traceability to the National Institute of Standards and Technology (NIST).
Each day the detection system is used, its operating characteristics are checked with a
NIST standard reference material (SRM) U3O8 source. After thoroughly flushing the
system with the counting gas, a voltage plateau is determined with the NIST source.
Generally, the plateau is 500-600 V in length at applied voltages of 2300-2900 (+). The
slope of the voltage plateau is checked and should be < 1% per 100 V with methane as
the counting gas. The operating voltage selected is 100 V below the upper "knee" of the
plateau. The NIST source is measured for 2000 sec, sufficient for a 1 s Poisson standard
deviation (SD) of the measurement of < 0.5%. The background count rate is determined
at the same operating potential for 2000 sec. The background count should be 4-5 counts
or about 0.003 counts sec-1 (cps). The net count rate obtained by subtracting the
background count rate from the total count rate of the standard source measurement is
compared with the certified NIST value. (Total count rate refers to the [sample +
background] count rate.) The NIST certified value is given in terms of " particles sec-1 in
a 2B configuration. This means that the " backscatter factor is part of the certified value
and no correction needs to be made for this source characteristic. The EML value
obtained must agree with the NIST certified value (within the error of the measurement)
before other sources are measured.
As a further check of this procedure, when NIST "-emitting SRM sources are
purchased, they are treated as unknowns and measured as described above. The value
obtained at EML is then compared with the certified value.
Failure to obtain a flat or a long voltage plateau or failure to agree with the certified
source value are immediate indicators of problems in the detection system which must be
remedied before proceeding with additional measurements.
D. EML source preparation.
A system for the primary calibration of "-emitting solutions and sources is

maintained at EML because all the nuclides required for in-house programs may not be
available as NIST SRMs at any given time and it is cost effective. Both NIST SRM
solutions and sources are initially expensive and the cost of recalibration by NIST is
often equal to or more than the original cost. Since all EML "-emitting solutions and
sources are recalibrated at least once a year, the cost of NIST recertification would be
prohibitive.

Electrodeposited sources of "-emitting radionuclides are prepared on 17 mm diameter

virgin platinum discs. These sources, once calibrated, are used as standards to determine
the detection efficiencies of "-scintillation counters and solid-state "-spectrometry
systems. In general, the activity of these sources is 15-20 Bq (450 pCi or 1000 dpm).
The procedure for obtaining a "working standard" source is to measure the NIST SRM
U3O8 source and background as described above, obtain a voltage plateau for the source
to be calibrated, and measure the source at the proper plateau voltage for 2000 sec. The
net count rate of the source is converted to an activity unit using the detection efficiency
of 52%. A Poisson error term is calculated and attached to the activity value.
The calibration of an "-emitting solution differs from that for electrodeposited

sources only in the method of source preparation. It is the practice at EML that sources
from the solution to be calibrated be prepared in triplicate. The source mounts are 24 mm
diameter virgin platinum discs. The solution to be calibrated must be essentially carrier-
free. The activity of the solution should be on the order of 160-1600 Bq g-1. To
minimize " absorption in the source, a weighed amount of a Teflon suspension is
transferred to the disc from a polyethylene transfer pipette (see Specification 7.11).
About 30 :g of Teflon beads are delivered in the 0.1-g aliquot. A weighed aliquot of the
solution to be calibrated is dispensed from the transfer pipette directly into the Teflon
suspension bead. As a check on possible self-absorption in the dried source, aliquot
weights are varied from 0.1-0.2 g in the triplication procedure. The sources are slowly
dried near a heat lamp.
After the 2B proportional detection system has been checked as described above, the
first source is heated in an alcohol burner flame just until the Teflon vaporizes. This
drives off any residual waters of hydration which could cause self-absorption in the
source. The flamed source is immediately placed in the methane atmosphere. A voltage
plateau is obtained and the source is measured as described above. This procedure is
repeated for the remaining sources. The activity and Poisson counting error are
calculated for each source and corrected for the aliquot weight to obtain the activity g-1 of
solution. A Gaussian mean and SD are calculated from the triplicate source
measurements. The Gaussian SD is usually < 1%.
Dilutions of the calibrated solution may then be prepared by weight for use in various
EML programs.
ALPHA SCINTILLATION MEASUREMENTS

A. Application.
The procedure was developed for " measurements of air dust samples and chemical
precipitates. Perhaps its largest application has been in the determination of 222Rn and
220
Rn concentrations from air filter samples. Routine applications include the
determination of the " nuclide concentrations of low-level solutions and measurement of
total " activity of radiochemically separated samples and investigations of materials for
commercial uses.
The advantages of the use of ZnS(Ag) on Mylar phosphor discs were enumerated by
Hallden and Harley (1960) and are paraphrased here.
Samples are measured with uniform high efficiency, since the sample is in direct
contact with the phosphor and photomultiplier tube (PMT).
The phosphor sees only the sample and the face of the PMT, yielding a lower
background than other "-scintillation systems and proportional counters.
Samples are completely enclosed, readily handled and stored without loss of sample
integrity or cross contamination.
Counter maintenance is negligible, since the system cannot be contaminated under

ordinary conditions.
Samples need not be conducting as with internal gas proportional counters.
Filter samples are held flat without curling or buckling producing a uniform counting
configuration.
B. Description of the detection systems.
Essentially all " scintillation detection systems use ZnS(Ag) as the phosphor. There
are basically two types of " scintillation counters in use at EML for total "
measurements, those accommodating samples using ZnS(Ag) on Mylar (Hallden and
Harley, 1960; see Specification 7.11), and those with the phosphor applied as a powder to
the face of a PMT tube (Curran and Baker, 1948).

The EML "-scintillation counters were designed and built by EML's Instrumentation
Division (now the Technical Program Services Division). The EML "-scintillation
counters accommodate the 2.54 cm (1 in) diameter nylon ring and disc sample mounting
system (see Specification 7.2). The sample to be measured is placed on the nylon disc.
A 2.4 cm (15/16 in) diameter die-cut phosphor disc is placed against the sample, a strip
of Mylar film (see Specification 7.3) is overlaid and the assembly is locked together with
a nylon ring.
A spring-loaded 2.54 cm (1 in) diameter PMT is housed in a light tight, anti-magnetic

shield, facing downward. The sample ring and disc assembly is placed in a space in a
pullout drawer. The drawer is closed and a knob turned to the "up" position, placing the
sample assembly in direct contact with the PMT. An emitter follower network is built on
the base of the PMT. The high voltage supply for the PMT is an integral part of the EML
Instrumentation Division's double width nuclear instruments modules (NIM) scaler-timer
assembly.
It should be noted that the "-scintillation phosphor discs were and are intended for
single use, that is, they and most of the samples are disposable as a unit.
C. Calibration of the instruments.
The detection efficiencies of the EML "-scintillation counters are determined by

measuring electrodeposited "working standard" sources prepared at EML. The sources
are traceable to the NIST through the process described in Section C, Traceability to
NIST.
Measurements with single emitter sources with energies ranging from 3-6 MeV show
that the detector response is independent of the energy of the " particle. Sources of 226Ra
and 228Th in equilibrium with their short-lived progeny were measured in the 2B
proportional counter and then mounted and measured in the "-scintillation detection
systems. After applying the detection efficiency obtained from the "working standards",
the values obtained by "-scintillation counting agreed with those of the 2B proportional
counter within the error of the measurements. This implies that the detection efficiencies
of the "-scintillation counters are independent up to 9 MeV.
Background count rates are determined for the materials commonly used in EML
programs. These include platinum discs and cellulose, polystyrene and glass fiber filters.
To determine the "true" background count rates of the systems, so called "nylon

background" measurements are performed in which the phosphor is placed in direct

contact with the nylon disc. This is especially useful when assessing the performance of
each new batch of phosphors. Typical background count rates for these materials are
shown below.
Material Background Count Rate (cpm)
Nylon 0.001 ± 0.001

Polystyrene filter 0.001 ± 0.001
Cellulose filter 0.002 ± 0.002
Glass fiber filter 0.100 ± 0.010
Platinum disc (17 mm dia.) 0.012 ± 0.002
The background count rates are determined for measurement intervals of

1000 min or more.
The average detection efficiency determined from measurements of a "working

standard" source electrodeposited on platinum is 51%. The source is measured twice
weekly for a 100-min counting interval.
Quality control charts are maintained for the background count rates and the detection
efficiencies of the "-scintillation counters. The means and SDs of each type of
measurement are calculated on a monthly basis.
SOLID-STATE ALPHA SPECTROMETRY
A. Application.
The solid-state "-spectrometry systems are used primarily to determine the

concentrations of radionuclides in chemically separated samples. Virtually all
radiochemical analyses for "-emitting radionuclides are performed with an isotopic
tracer. For the transuranic nuclide determinations, the following tracers are used at EML:
236
Pu, 242Pu, and 243Am. Tracers used in the determination of naturally-occurring
radionuclides are 208Po, 209Po, 229Th and 232U.
The systems are also used to determine the radiopurity of radionuclide solutions.
B. Description of the detection systems.

The solid-state "-spectrometry systems used at EML are divided into two groups of
four detectors, one group is devoted to transuranic measurements and the other to natural
radionuclide measurements. Both groups have several elements in common. All
components of the systems are commercially available except as noted.
Four vacuum chambers are served by a single beltless vacuum pump. The interior
diameters of the vacuum chambers allow samples to be placed as far as 5 cm from the
detector. The sample holder, which may be moved vertically, has been modified at EML
to an open drawer-slide arrangement. The drawer is locked in place and the slide, with a
2.54 cm diameter by 2 mm deep indentation to accommodate the sample mount, is
removable. The sample is placed on a mount, the mount is placed in the indentation, and
the slide is then replaced in the open drawer arrangement. This sample holder
arrangement eliminates problems of source to detector geometry. The two kinds of solid-
state detectors in use at EML will be discussed below. Voltage to the detectors is
supplied by individual regulated power supplies. Each detector has a charge sensitive
preamplifier and a linear amplifier. Signals from the detectors are directed through a
router into a 4096 multichannel analyzer. One analyzer serves four detectors with data
collection divided into four 1024 channel segments. A hard copy of the data is obtained
with a high speed printer.
All "-spectrometry data are reduced "by hand" which ensures immediate and
individual review of the spectra. By this practice, difficulties with the spectrometry
systems or the samples are quickly noted and remedied.
The solid-state " detectors are operated at about 10 keV per channel, covering an
energy range of about 3-13 MeV. By this practice, all " emitters present in a sample can
be identified from their energies. (Virtually all " emitters, both natural and artificial are
within this energy range.)
Because EML is primarily involved in the measurement of low-level environmental

samples, the most common measurement period by " spectrometry is 5000 min. This
time unit will be used in describing some of the characteristics of the detection systems.
The solid-state detectors in use at EML for research programs are conventional 500
mm2 active area silicon surface barrier detectors. The resolution of the detectors, as
measured routinely with EML prepared "working standard" sources, is 40-45 keV
(FWHM). The systems are calibrated with "mixed " standards" prepared by micro-
precipitation with NdF3 (Hindman, 1983; Sill, 1981) on polystyrene filters. The back-

ground count rates determined with "blank" micro-precipitates in the energy regions of
interest are generally 1 to 2 counts 5000 min-1. The emitter mixture of the standards is
238,239,242
Pu, 244Cm. The standard and sample measurements are performed at a distance of
1 mm from the lip of the detector housing. At this distance the average detection
efficiency is 40%.
The detection efficiencies and resolution obtained with microprecipitated standards

were checked against those obtained with electrodeposited standards and no differences
were found.
The multichannel analyzers used for "-spectrometry measurements have been

thoroughly tested by EML's Instrumentation Division to ensure stability over long
measurement periods (5000-10,000 min). The stability of the systems is aided by placing
them in a temperature controlled room. It is important to note that the room temperature
needs to be stable. It is fluctuations in temperature that cause the detector response to
shift or drift.
A commercially available hardware/computer controlled system is used for routine

measurements. There are eight vacuum modules, each housing a 500 mm2 ion implant
detector. To accommodate the software requirements of the system, the detectors are
calibrated with NdF3 microprecipitated "working standards" containing only two
emitters, 242Pu and 244Cm. The resolution of the detectors is about 50 keV FWHM and
the detection efficiency about 40%. Background count rates are similar to our research
systems.
B. Calibration of the alpha-spectrometry systems.
The detection efficiencies of the "-spectrometry systems are determined by

measuring microprecipitated "working mixed standards" prepared at EML. The activity
of the standards is determined by "-scintillation counting on systems calibrated with
sources traceable to NIST through the process described in Section C, Traceability to
NIST.
Measurements with single emitter sources with energies ranging from 3-6 MeV have
shown that the energy and detection efficiency responses of silicon surface barrier
detectors are constant. Sources of 228Th in equilibrium with its short-lived progeny were
measured and the activities of the individual progeny were the same within the error of
the measurements. This provided empirical information that the energy response of the

detectors is constant up to 9 MeV and implies that the detection efficiencies are also
constant.
It is the practice at EML to measure the background count rate of the detectors each
weekend and during the week if the work load permits. Typical background count rates
for the detectors are given above. The background count rates of the systems invariably
increase with time due to recoil atoms depositing on the face of the solid-state detectors.
It has been the experience at EML that the background count rates become unacceptable
after two years of use. The only effective method of reducing the background count rates
is to place the detectors in a high vacuum provided by a liquid nitrogen cooled diffusion
pumping system over a weekend.
Each "working mixed standard" source has a total activity of about 15 Bq. The
standards source is measured for 50 min before and after each sample measurement. The
standard source measurements provide three important pieces of information: the
detection efficiency, the detector resolution, and the energy calibration. Deviations from
normal operating conditions in any or all of these characteristics are immediately
investigated. These quality control records are very important in establishing the norm
for each detector system.
REFERENCES
Curran, S. C. and W. R. Baker

"Photoelectric Alpha-Particle Detector"
Rev. Sci. Instrum., 19, 116 (1948)
Hallden, N. A. and J. H. Harley

"An Improved Alpha-Counting Technique"
Anal. Chem., 32, 1861-1862 (1960)
Hindman, F. D.
"Neodymium Fluoride Mounting for Spectrometric Determination of Uranium,
Plutonium and Americium"
Anal. Chem., 55, 2460-2461 (1983)
Sill, C. W. and R. L. Williams

"Preparation of Actinides for Alpha Spectrometry without Electrodeposition"

Anal. Chem., 53, 412-415 (1981)

Ba-01-R, Vol. I Rev. 0
Ba-01-R
BETA RADIOASSAY
Contact Person(s) : Isabel M. Fisenne and Salvatore Scarpitta
CALIBRATION OF BETA-EMITTING RADIONUCLIDE SOLUTIONS
A. Application.
The methods for the primary calibration of emitting radionuclide solutions and
routine measurements are described for detection systems in use at EML.
B. Description of the system.
Primary calibrations of $-emitting radionuclide solutions are performed at EML with

gas flow 4B $-proportional and 4B $-proportional-4B ( coincidence detection systems.
The commercially obtained aluminum proportional counters have a stainless steel wire
anode in each half-cylinder. The total interior volume is 50 cm3. The source mount is an
aluminum washer, 3.8 cm in diameter with a 1.8-cm diameter center hole and four 0.3-cm
holes in the rim to allow gas to flow between the halves with the source mount in place.
The counting gas is 99.99% chemically pure methane, and the flow through the chamber
is monitored with a bubbler. An EML designed and built emitter follower preamplifier is
connected directly to the anodes. Signals from each half of the chamber are summed
prior to further amplification. The amplifier is arranged to deliver triggered pulses to an
electronic scaler. High voltage is supplied by a 0-5000 V regulated power supply. The
chambers exhibit rather long (600 V) and flat (<0.5% per 100 V) counting plateau. The
4B $ detection system is unshielded and has a background rate of 0.7 counts sec-1 at
3500 V, the usual operating voltage.
In the 4B$-4B(-coincidence detection system, the chamber is mounted between two

7.6 x 12.7 cm NaI(Tl) crystals. The entire detection assembly is lead shielded. The
upper crystal is pneumatically raised and lowered to permit access to the chamber. The
signals from the two crystals are summed, amplified, and processed through a single

channel analyzer, and simultaneously recorded into a scaler and a multichannel analyzer.
High voltage to the crystals is supplied by a single 0-1500 V regulated power supply. As
described above, the signals from the chamber are summed and amplified, but then split
into the variable coincidence gate and a scaler. The output signals from the variable
coincidence gate unit are fed into a third scaler. The three scalers are controlled by a
master timer.
A detailed discussion of the 4B$-(-coincidence method can be found in the National

Council on Radiation Protection and Measurements Report No. 58 (NCRP, 1985).
C. Traceability to the National Institute of Standards and Technology (NIST).
Traceability to NIST is difficult since suitable standard reference material (SRM)

sources are not available for many radionuclides. Our approach over the years has
simply been to recalibrate NIST SRM solutions or solutions obtained from commercial
vendors who are traceable to NIST using EML source preparation techniques and
detection systems. Except for discrepancies caused by differences in the use of decay
scheme parameters, the EML results are in agreement with the certified values within the
error of the measurements.
D. EML source preparation.
Two kinds of supporting films for the source mounts are used in the proportional
counters, which are described below.
The first type of film support is prepared from clear vinyl paint* and is used with pure
beta emitters with a maximum energy >0.25 MeV. It has been established
experimentally, using NIST and commercial vendor certified standard solutions of 45Ca,
that the detection efficiency of this emitter is 100% for the source mounts described
below.
About 0.1 mL of paint is dropped onto a 1-cm deep layer of clean cold water in a
50 cm x 75 cm tray, painted matte black on the interior surfaces. The paint spreads
across the surface of the water and the film thickness is estimated visually, by color. A
clear or light gray film is ~ 5 :g cm-2, white is 10 :g cm-2, and yellow is 20 :g cm-2, which
*
Flat Vinyl Ink 3900-99-Clear, obtained from: Colonial Printing Ink Co., 180-T East Union Ave.,
East Rutherford, NJ 07073

has been determined experimentally. At EML, the 10 :g cm-2 films are used as they
provide the necessary strength, while still remaining extremely thin. The film is lifted
from the surface of the water with a wire loop and placed over the aluminum washer.
This thin film planchette is dried and then given a thin gold coating of about 10 :g cm-2
on one side by vacuum evaporation in a small sputterer unit. Self- absorption in the
source mount is minimized using a technique developed at EML (Hallden and Fisenne,
1963). A 0.1-g aliquot of a Teflon bead suspension in water* (100 :g of Teflon g-1) is
placed onto the nonconducting side of the film. The radioactive solution to be
standardized is delivered by weight from a polyethylene transfer pipette into the Teflon
bead suspension on the film. In general, a 0.1-g weight of the radionuclide solution is
used in the preparation of a source. The source is air dried and then gold coated to
produce an entirely conducting mount.
The second kind of source mount is a 2-:m thick film of polycarbonate** that is glued
to the aluminum washer. These mounts are used for measurements by 4B$-4B(-
coincidence counting, which will correct for the absorption within the film. The
remainder of the source preparation procedure is the same as described for 4B$
measurements. (Note: The thin vinyl films will only tolerate an HCl solution of <1N.
The stronger polycarbonate will withstand HCl concentrations of up to 6N. In addition,
the polycarbonate source mounts can be dried gently under a heat lamp.) The graph
below shows the 4B$ counter detection efficiency versus $- or $+ endpoint energies for
sources mounted on polycarbonate films.
The primary radionuclide solution should be essentially carrier-free. The primary

radionuclide solution to be calibrated is diluted to a concentration on the order of
1700 Bq g-1. The calibration is performed with triplicate source measurements. The
voltage plateau for each source is determined in order to select the proper counting
voltage. The activity and Poisson counting error are calculated for each source and
corrected for the aliquot weight to obtain the activity g-1. Other corrections appropriate to
the particular radionuclide decay scheme are made from the 4B$-(-coincidence
measurements. A Gaussian mean and SD are calculated for the triplicate sources.
Appropriate dilutions of the calibrated solution are prepared for distribution within
EML for various programs.
*
Vanflex Teflon Emulsifier #30; obtained from: Interchem Corp., 120 Route 17N, Suite 115-T,
Paramus, NJ 07652
**
KIMFOIL; obtained from: Kimberly-Clark Corp., Schweitzer Division, Lee, MA 01238

LOW BACKGROUND GAS-FLOW PROPORTIONAL COUNTING SYSTEM
A. Application.
The only routine beta analysis conducted at EML is the determination of 90Sr by
measurement of 90Y. These measurements are performed in the LB4100TM (Oxford
Instruments Inc., Nuclear Measurements Group, 601 Oak Ridge Turnpike, Oak Ridge,
TN 37831-2560) low background counting system. This system is also utilized for gross
alpha/gross beta determination in water and air filter samples.
B. Description of the detection system.
The LB4100 is a four drawer, 16 detector, low background counting system that is
intended for gross counting of ", $ and low energy x-ray emitters. The detectors are of
the gas-flow proportional type. The detector slide accepts samples prepared in solid form
on disks either 2.54 cm or 5 cm in diameter. Two drawers (of four detectors each) are
equipped with 5 cm detectors, which are used for gross alpha/gross beta determinations.
The other two drawers are equipped with 2.54 cm detectors that are used for counting the
90
Y samples. The detectors are mounted on a 2.54 cm Whatman No. 42 filter paper and
are covered with Mylar fastened with a ring and disc assembly.
Each sample detector is the signal source for a counting channel. Each detector
activates a counting channel independently of the others. Each channel has its own time
control. The channels are individually deadtime corrected. The interface between the
counter and the user is a computer and its keyboard.
C. Calibration of the detection system for 90Y determinations.
The detectors are checked for energy plateaus and source (90Sr) efficiencies prior to
use or when the gas tank is changed. The background is also measured prior to use with
yttrium oxalate blanks. If the instrument is idle for an extended period of time, crosstalk
and yttrium oxalate efficiencies are checked. The counters are standardized with 90Y
oxalate with detection efficiencies of ~ 40%.

LIQUID SCINTILLATION MEASUREMENTS
A. Application
The conventional liquid scintillation (LS) counting systems used at EML are
designed to detect and measure low-energy (e.g., 3H, 14C) to high-energy beta particles
(i.e., 90Y, 106Rh), and alpha particles. Samples containing mixtures of radionuclides that
emit either alpha, beta, or conversion electrons are detected and quantified using
variations of the LS counting technique. Depending on the LS cocktail, the alpha
detection efficiency is generally > 95%, whereas the beta detection efficiency is
dependent on energy, spectral shape and cocktail. Typically, beta particles with
maximum energies > 0.250 MeV are detected with >90% counting efficiency.
One variation of the LS counting technique used at EML is Cerenkov counting

(Scarpitta and Fisenne, 1996), which is an adjunct to LS counting that does not require a
LS cocktail. Cerenkov counting in aqueous samples is applicable to beta particles with
endpoint energies in excess of 0.263 MeV. The Cerenkov counting efficiency (CCE) is
typically 30% per MeV for beta particles with endpoint energies above the Cerenkov
threshold; alpha particles are not detected.
Another variation of the LS technique utilized at EML is photon-electron rejecting

alpha liquid scintillation spectrometry (PERALS), which is designed specifically for low-
level liquid scintillation alpha detection where beta/gamma interferences are eliminated
and a high degree of sensitivity is desired.
The three counting methods described above require a clear liquid sample that can be
counted in a short period of time (1 to 2 h). Presented in the following sections are
descriptions of these methods.
B. Description of the detection system
EML's Packard Tri-Carb-2250CA LS instrument is a multitasker unit for quantitative

detection of alpha, beta, positron, and conversion electron radiation. The system may be
preprogrammed to select any of the 15 unique programs stored on the computer disk. The
instrument can be operated in one of four counting modes: 1) conventional LS, 2) dual-
DPM, 3) full spectrum analysis, or 4) efficiency tracing. The system provides computer

controlled data reduction of counting results after each sample or after every batch of
samples identified by the user.
The scintillation detector well is located underneath the sample changer. Samples are
automatically lowered into the detector well. The detector assembly consists of two
facing bi-alkali high performance photomutiplier tubes, each coupled to an optical
chamber. The shielding assembly consists of a light-tight detection chamber, magnetic
shielding and 5 cm of lead to reduce the effect of external radiation.
Spectrum analysis forms the basis of the Packard LS system. Typically, a beta
particle will take a few nanoseconds to dissipate all of its energy in the scintillation
solution. This results in an analog pulse rising to its maximum amplitude and falling to
zero. The amplitude of the analog pulse is converted to a digital value. The conversion
is achieved in a high speed analog to digital converter (ADC), and the digital value,
which represents the beta particle energy, is the memory slot of a 0-2000 keV spectrum
analyzer. The conversion by the ADC is linear so that during the measurement of a
sample, the spectrum analyzer will accumulate counts representing the complete energy
spectrum of the radionuclide. The spectrum analyzer is calibrated in units of keV, and
the user can select one of three regions of interest over a range of 0-2000 keV.
Quenching, in general terms, refers to interferences with any of the steps of energy
transferred from the solvent (where most of the energy from the ionizing radiation is
initially deposited) to the scintillant and subsequent light transmission to the PMT. When
a sample is quenched, the spectrum usually is shifted toward the lower energy regions,
resulting in an increase in counts (i.e., apparent increase in counting efficiency) in any
low energy preset regions of interests. In most cases, a correction for this effect may be
performed.
A quench-efficiency curve must be established for a given nuclide and scintillator

cocktail if the sample differs in chemical composition from the reference standard used to
calibrate the instrument. A series of quenched samples, containing a known constant
activity for the nuclide of interest, are prepared with a measured volume of scintillation
cocktail. Successively increasing amounts of a chemical quenching agent are added to
the samples. The samples are then measured for spectrum analysis. A description of the
quench corrections and dual-dpm analysis can be found in Scarpitta and Fisenne (1996).

C. Calibration of the system.
The LS stability and operational acceptance criteria are checked first before running
any standards or samples. This is accomplished by counting the background, and a 3H
and 14C standard provided by the instrument manufacturer using an appropriate
spreadsheet program. The count rate is then compared with the quality control charts
developed at EML for this instrument. Descriptions of the cocktail selection,
determination of window settings, and detection efficiencies can be found in Scarpitta
and Fisenne (1996).
D. Cerenkov Counting
Cerenkov radiation occurs when charged particles pass through a dielectric medium
(liquid) where there is an exchange of energy from the charged particle to the molecules
of the medium (Haberer, 1966). The exchange energy produces local electronic
polarizations in the medium if the charged particle is moving at velocities comparable to
the velocity of light in the medium. When these polarized molecules return to their
normal state, the excess energy is released as electromagnetic radiation known as
Cerenkov radiation.
A threshold energy exists for the production of Cerenkov radiation and it is a function
of the refractive index, n, of the medium. For water (n = 1.33) the lower energy limit of
electrons for the production of Cerenkov radiation is 0.263 MeV (Berger and King,
1985). With beta emitters, the maximum energy, Emax, has to substantially exceed this
value because of the broad beta energy spectrum. Photoelectrons and Compton electrons
from gamma emitting nuclides, having energies in excess of the threshold energy, can
also be measured by Cerenkov counting. Some nuclides which can be measured by
Cerenkov counting are 32P, 35S, 36Cl, 40K, 59Fe, 89Sr, 90Sr/Y, 106Rh(Ru), 137Cs, 210Pb/Bi,
234m
Pa (progeny of 238U via 234Th), and 99Tc.
Cerenkov counting is an adjunct to LS analysis that does not require a scintillating

cocktail. Various wavelength shifters (Haberer, 1966; Karamanos et al., 1975) have been
used to enhance the CCE by 10-20% using commercially available LS spectrometers.
Wave shifters are organic substances that shift the Cerenkov photon energies from a
region of low detector sensitivity to a region of high detector sensitivity.
Standardized solutions, containing the equivalent of about 17 Bq (1000 dpm), are

dispensed gravimetrically, in triplicate, into either 20 mL plastic or low borosilicate glass

vials. Each vial was counted for 15-30 min with window settings of 0-50 keV for
Cerenkov counting so that the 1 sigma counting error is <2%.
For Cerenkov counting, water is typically used as the solvent. The average
instrument background, using 20-mL plastic vials containing 3-18 mL of ultra-pure water
is 0.225 ± 0.018 counts sec-1 (cps) for a 0-50 keV region of interest. The average
background count rate for glass vials (0.346 ± 0.010 cps) is about 30% higher than that
obtained using plastic vials. Based on replicate background measurements, the lower
limit of detection for a 1 h count at the 95% confidence level, using water as a solvent, is
0.024 cps (1.44 cpm) and 0.028 cps (1.70 cpm) for plastic and glass vials, respectively.
For specific alpha/beta applications, see Scarpitta and Fisenne (1996).
E. PERALS Spectrometry
EML's PERALS spectrometer (Ordela, Inc., 1009 Alvin Weinberg Drive, Oak Ridge,
TN 37830) which is a single sample stand-alone Nim Bin type unit. The unit is
interfaced to a personal computer which is capable of functioning as a multichannel
analyzer. The PERALS technique employs a LS detector with a pulse-shape
discriminator for beta-gamma rejection (>98%) and direct extraction of the alpha activity
of interest into 2 mL of a water insoluble organic phase containing the scintillator. The
discriminator takes advantage of the longer decay time of light produced by alpha
particle interactions to select the alpha pulses for spectrometry and reject those from
beta-particle or gamma-ray events.
The choice of commercially available extractants (ETRAC Corporation) and

chemical composition of the aqueous phase allows for selectivity and flexibility in
sample preparation (McDowell and McDowell, 1994). The degree of beta/gamma
rejection allows an instrument background (with a blank scintillator in the detector) of
0.001 cpm or less over the entire alpha energy range (3-5 MeV). The advantages of the
PERALS method are that it: 1) is extremely sensitive, 2) has a high alpha counting
efficiency (100%), 3) requires a count time of 1-4 h per sample or less depending on the
sample activity, and 4) generates a very small amount of organic waste (<2 mL per
sample).

REFERENCES
Berger, S. and M. King

“A Simple Method for Quantifying 32P in Submicroliter Samples”
Biotechniques, 9, 38-46, Jan.-Feb. (1985)
Haberer, K.
“Measurement of Beta Activities in Aqueous Samples Utilizing Cerenkov Radiation”
Packard Technical Bulletin No. 16, Packard Instrument Co., Downers Grove, IL, January
(1966)
Hallden, N. A. and I. M. Fisenne

“Minimizing Self-absorption in 4-Counting”
Int. J. Appl. Rad. and Isot., 14, 529-532 (1963)
Karamanos, R., J. Bettany and D. Rennie

“Lead-210 Assay in Soil and Plant Material Using Cerenkov Radiation”
Canadian. J. Soil Sci., 55, 407-13 (1975)
McDowell, W. J. and B. L. McDowell.

Liquid Scintillation Alpha Spectrometry.
CRC Press, 2000 Corporate Blvd., N.W. , Boca Raton, FL (1994)
National Council on Radiation Protection and Measurements

A Handbook of Radioactivity Measurements Procedures
NCRP Report No. 58, Bethesda, MD (1985)
Scarpitta, S. C. and I. M. Fisenne

"Cerenkov Counting as a Complement to Liquid Scintillation Counting"
Appl. Radiat. Isot., 47, 795-800 (1996)
Scarpitta, S. C. and I. M. Fisenne.

“Calibration of a Liquid Scintillation Counter for Alpha, Beta and Cerenkov Counting”

Ga-01-R, Vol. I Rev. 0
Ga-01-R
GAMMA RADIOASSAY
APPLICATION
This procedure is used for the nondestructive measurement of (-ray emitting

radionuclides from a variety of environmental matrices by high resolution germanium
(Ge) detector (-ray spectrometry and NaI(Tl) detector (-ray spectrometry. It is ap-
plicable to nuclides emitting (-rays with energies > 20 keV for Ge detectors and 50 keV
for NaI(Tl) detectors. For typical counting systems and sample types, activity levels of
about 40 Bq are easily measured and sensitivities as low as .002 Bq can be achieved for
many nuclides. Count rates in excess of 2000 counts sec-1 (cps) should be avoided
because of electronic limitations. High count rate samples can be accommodated by
dilution or by increasing the sample to detector distance.
The procedure is used for either qualitative, quantitative or relative determinations.

In tracer work, the results may be expressed by comparison with an initial concentration
of a given nuclide which is taken as 100%. For radioassay, the results may be expressed
in terms of known standards for the radionuclides known to be present. In addition to the
quantitative measurement of (-ray radioactivity, (-ray spectrometry can be used for the
identification of specific emitters in a mixture of radionuclides. General information on
radioactivity and the measurement of radiation has been published. Information on the
specific application of (-ray spectrometry is also available in the literature.
DESCRIPTION OF THE SYSTEM
Gamma-ray spectra are measured at EML with modular equipment consisting of a

detector, an amplifier, a pulse-height analyzer, memory, and a permanent data storage
device. Lithium-drifted germanium, Ge(Li), or high purity Ge detectors (p-type or

n-type) are used for the analysis of complex (-ray spectra because of their excellent
energy resolutions. These Ge detectors, however, are characterized by high cost and
require cooling with liquid nitrogen. Thallium activated sodium-iodide crystals, NaI(Tl),
can be operated at ambient temperatures and are often used at EML as (-ray detectors in
spectrometer systems. However, their energy resolutions limit their use to the analysis of
single nuclides or simple mixtures of a few nuclides.
Upon completion of the (-ray assay, the spectral data are interpreted and reduced to
nuclide activities in Bq (disintegrations per second) or related units suited to the
particular application. At this time, the spectral data may be inspected on the CRT to
identify the (-ray emitters present. This is accomplished by reading the channel number
from the x-axis and converting to (-ray energy by multiplying by the appropriate
keV/channel (system gain). If the system is calibrated for 1 keV per channel with
channel zero representing 0 keV, the energy will be equal to the channel number. The
channel number or (-ray energy in keV is usually displayed on the CRT. Identification
of nuclides is aided by catalogs of (-ray spectra and other nuclear data tabulations.
Because of the reduced spectral resolution obtained with NaI(Tl) detectors, this technique
can only be applied to samples of single nuclides or very simple combinations of
nuclides.
Data reduction of spectra taken with Ge spectrometry systems is usually

accomplished by integration of the photopeaks above a definable background (or
baseline), and by subsequent activity calculations using a library that includes data such
as nuclide name, half-life, (-ray energies and associated abundance (intensity or
branching ratios). Computer programs for data reduction of NaI(Tl) detector data have
been used extensively at EML. Data reduction of spectra involving mixtures of nuclides
is usually accomplished by least-square fitting routines to a library of standard spectra of
the individual nuclides acquired under individual conditions.
Variation of the physical geometry of the sample and its relationship with the detector
will produce both qualitative and quantitative variations in the (-ray spectrum. To
adequately account for these geometry effects, calibrations are designed to duplicate all
sample counting conditions including source-to-detector distance, sample shape and size.
Electronic problems, such as erroneous deadtime correction, loss of resolution, and

random summing, may be avoided by keeping the gross count rate below 2000 cps and
also by keeping the deadtime of the analyzer below 5%. Total counting time is governed

by the radioactivity of the sample, the detector-to-source distance, and the acceptable
Poisson counting uncertainty.
In complex mixtures of (-ray emitters, the degree of interference of one nuclide in the
determination of another is governed by several factors. If the (-ray emission rates from
different radionuclides are similar, interference will occur when the photopeaks are not
completely resolved and overlap. If the nuclides are present in the mixture at markedly
different levels of activity, nuclides of higher energies that are predominant can cause
serious interferences with the interpretation of minor, less energetic, (-ray photopeaks.
The complexity of the analysis method is due to the resolution of these interferences and,
thus, one of the main reasons for computerized systems.
Cascade summing may occur when nuclides that decay by a (-ray cascade are
analyzed. Cobalt-60 is an example; 1172 and 1333 keV (-ray from the same decay may
enter the detector to produce a sum peak at 2505 keV or a count in the continuum
between the individual peaks and the sum peak; thus, causing the loss of counts from one
or both of the other two peaks. Cascade summing may be reduced by increasing the
source-to-detector distance. Summing is more significant if a well-type detector is used.
Random summing is a function of counting rate and occurs in all measurements. The
random summing rate is proportional to the total count squared and the resolving time of
the detection system. For most systems, random summing losses can be held to < 1% by
limiting the total counting rate to 1000 cps.
The density of the sample is another factor that can affect quantitative results. Errors
from this source can be avoided by preparing the standards for calibration in solutions or
other matrices with a density comparable to the sample being analyzed. Another
approach is to apply attenuation corrections to all calibration standards and samples
based on sample weight, known volume, (-ray path length and average atomic number of
the sample matrix.

APPARATUS
A (-ray spectrometer consists of the following components:
A. Detector assembly.
1. Germanium detector - The detector should have a volume of at least 50 cm-3, with a
full width at one half the peak maximum (FWHM) < 2.2 keV at 1332 keV, certified
by the manufacturer. A charge-sensitive preamplifier using low noise field effect
transistors should be an integral part of the detector assembly. A convenient support
should be provided for samples of the desired form. Vertical systems allow the
standard/sample to be placed directly on the detector end cap.
2. NaI(Tl) detector - The sodium iodide crystal, activated with about 0.1% thallium
iodide, should contain < 5 :g g-1 of K and should be free of other radioactive
materials. The crystal should be attached and optically coupled to a multiplier
phototube. (The multiplier phototube requires a preamplifier or a cathode follower
compatible preamplifier with the amplifier.) The resolution (FWHM) of the
assembly for the photopeak of 137Cs should be < 7% for a 75-mm by 75-mm detector.
3. Shield - The detector assembly should be surrounded by an external radiation shield

made of massive metal, equivalent to 102 mm of Pb in (-ray attenuation capability.
It is desirable that the inner walls of the shield be at least 127 mm in distance from
the detector surfaces to reduce backscatter. If the shield is made of Pb or a Pb liner,
the shield must have a graded inner shield of 1.6 mm of Cd or tin lined with 0.4 mm
of copper, to attenuate the 88 keV Pb (-rays. The shield must also have a door or
port for inserting and removing samples.
4. High-voltage power/bias supply - The bias supply required for Ge detectors usually
provides a voltage up to 5000 V and 1 to 100 :A. NaI(Tl) detectors require a high-
voltage power supply of a range of usually from 500 to 3000 V and up to 10 mA to
operate the multiplier phototube. The power supply should be regulated to 0.1% with
a ripple of not more than 0.01%. Line noise caused by other equipment should be
removed with filters and additional regulators.

5. Amplifier - A spectroscopy amplifier compatible with the preamplifier and with the
pulse-height analyzer should be used.
B. Data acquisition and storage equipment.
1. Data acquisition - A multichannel pulse-height analyzer (MCA) or stand-alone

analog-to-digital converter (ADC) under software control of a separate computer,
performs many functions that are required for (-ray spectrometry. An MCA or
computer collects the data, provides a visual display, and outputs final results or raw
data for later analysis. The four major components of an MCA are the ADC, the
memory, control, and input/output. The ADC digitizes the analog pulses from the
detector amplifier. The magnitude of these pulses is proportional to the energy of the
photon deposited in the detector. The digital result is used by the MCA to select a
memory location (channel number) which is used to store the number of events which
have occurred with that energy. Simple data analysis and control of the MCA is
accomplished with microprocessors. These processors control the input/output,
channel summing over set regions of interest, and system energy calibration, etc.
2. Data storage - Because of the use of microprocessors, modern MCAs provide a wide
range of input and output (I/O) capabilities. Typically, these capabilities include the
ability to transfer any section of data to one or more of the following: terminal, line
printer, cassette tape, floppy or hard disk, X-Y plotter, and to computer interfaces via
a serial or parallel port.
SAMPLE/STANDARD CONTAINERS
Sample mounts and containers must have a convenient reproducible geometry.

Considerations include commercial availability, ease of use and disposal, and the
containment of radioactivity for protection of the personnel and working environment
from contamination. The evaporation of liquid samples to dryness is not necessary and
liquid samples up to 1 L may be used. Massive samples may cause significant self-
absorption of low energy (-rays and may degrade the higher energy (-rays. A ß absorber
consisting of about 6 mm of Al, Be, or plastic may be used for samples that have a
significant ß activity and high ß energies.

CALIBRATION AND STANDARDIZATION
This section describes the analysis of mixtures of radionuclides with Ge detectors or

single or simple mixtures of radionuclides with NaI(Tl) detectors. If complex mixtures
of radionuclides are to be analyzed with NaI(Tl) detectors, refer to page 2 of this
procedure.
A. Preparation of apparatus.
Follow the manufacturer's instructions, limitations, and cautions for the setup and the
preliminary testing of all of the spectrometry equipment to be used in the analysis. This
equipment would include, as applicable: detector, power supplies, preamplifiers,
amplifiers, multichannel analyzers, and computing systems.
Place an appropriate volume of a standard or a mixed standard of radionuclides in a

sealed container and place the container at a desirable and reproducible source-to-
detector distance. For environmental analysis, most standards/samples are counted at the
detector end cap. The standard should provide about 100 cps in the peaks of interest and
should be made up of standard sources traceable to a nationally certified laboratory. In
all radionuclide measurements, the volumes, shape, physical and chemical characteristics
of the samples, standards and their containers must be as identical as practicable for the
most accurate results.
B. Energy calibration.
The energy calibration (channel number of the MCA versus the (-ray energy) of the
detector system is accomplished at a fixed gain using standards containing known
radionuclides. The standards should be in sealed containers and should emit at least four
different (-ray energies covering the range of interest, usually 50 keV to 2000 keV in
order to test for system linearity. Some commercially available nuclides suitable for
energy calibration are: 210Pb, 46.5 keV; 241Am, 59.5 keV; 109Cd, 88 keV; 141Ce, 145 keV;
51
Cr, 320 keV; 137Cs, 662 keV; 54Mg, 835 keV; 22Na, 511 and 1275 keV; 88Y, 898 and
1836 keV; 60Co, 1173 and 1332 keV; equilibrated 226Ra, 186, 352, 609, 1120, and 1765
keV. A mixed (-ray standard for energy and efficiency calibration is also commercially
available. This standard can be obtained in solid form in a user supplied container. The
radionuclide purity of the standards should be verified periodically to ensure against

accidental contamination or the presence of long-lived impurities by comparing the

observed spectra with the spectra published in the literature.
A MCA should be calibrated to cover the range of interest. If the range is 50 to 2000
keV, the gain of the system should be adjusted until the 137Cs photopeak, 662 keV, is
about one-third full scale. Leaving the gain constant, locate at least three other
photopeaks of different energies, covering the same range. Determine and record the
MCA channel number corresponding to the maximum count rate for each of the four
energies. Germanium detectors will have a linear relationship if the equipment is
operating properly. Similarly, MCAs and NaI(Tl) detectors being produced today are
capable of producing an almost linear energy response. Samples should not be analyzed
if this relationship is not obtained. Follow the appropriate manufacturer input
instructions for the determination of the slope and intercept. During each day in which
the spectrometry system is being used to analyze samples, the above sequence of
operation shall be repeated using at least two different energies. If the slope and
intercept are essentially unchanged, the energy calibration data remain valid. If an
appreciable change in the slope or intercept is evident, the entire calibration procedure
must be rerun.
C. Photon detection efficiency calibration.
Accumulate an energy spectrum using sealed, calibrated radioactivity standards in a

desired and reproducible counting geometry. At least 10,000 net counts (total counts
minus the compton continuum and ambient background) should be accumulated in each
full-energy (-ray peak of interest.
Correct the radioactivity standard source (-ray emission rate for the decay from the
time of standardization to the time at which the count rate is measured.
Calculate the full-energy peak efficiency Ef as follows:
Ef = Np/Ng
where
Ef = full-energy peak efficiency (counts per (-ray emitted),

Np = net (-ray count in the full-energy peak of interest (cps), and
Ng = (-ray emission rate (rays sec-1).

If the standard source is calibrated as to activity, the (-ray emission rate is given by:
Ng = A*Pg
where
A = number of nuclear decays per second, and

Pg = probability per nuclear decay for the (-ray.
For Ge detectors, plot the values for the full-energy peak efficiency versus (-ray
energy. The plot will allow the determination of efficiencies at energies for which
standards are not available, and will show that the algorithms used in computerized
systems are providing valid efficiency calibrations.
Once the efficiencies have been determined, it is unnecessary to recalculate them

unless there is a change in resolution, geometry, or system configuration.
SAMPLE MEASUREMENTS
After the spectrometer system has been set up, the energy and efficiency calibrations
are performed, then the unknown sample can be measured.
Following the general concepts of quantitative analytical chemistry, transfer the

sample to the specimen container and position it in the same manner as was done during
system calibration.
Measure the sample for a period of time long enough to acquire a (-ray spectrum
which will meet the minimum acceptable counting uncertainty.

PEAK AREA CALCULATIONS
Spectral data obtained with a Ge detector are only corrected for background when
these peaks may alter the final results. In many experiments, the background may not
affect the results but is still monitored to ensure the integrity of the system.
The underlying aim of this procedure is to subtract the continuum or baseline from
the spectral data where it underlies a photopeak of interest. For operator-directed calcu-
lations, the choice of the baseline level may be straightforward. The simplest way, using
a plot of the spectral data, is to draw a straight line, using judgement and experience, that
best describes the baseline. Then the baseline data can be read directly from the plot and
subtracted.
Photopeaks lying on a sloping baseline or one with curvature will be analyzed,

independent of the method, with increased uncertainty. Use of data from these peaks
should be limited to those cases where there is no other alternative. Photopeaks that
overlap with each other will also increase the uncertainty of the final result.
In order to determine nuclide concentrations, the photopeak areas corrected for

background and interferences are divided by the count time and efficiency for the energy
of the (-ray being calculated to give photons sec-1 for the peak of interest. If, as is the
case for some nuclides, the branching ratio is not accurately known and a direct calibra-
tion was made with the same nuclide, the branching ratio and efficiency will be one
number that converts cps to Bq sec-1 for the nuclide and photopeak of interest. If not, the
photons sec-1 are converted to disintegrations sec-1 by dividing the photons sec-1 by the
photons per disintegration, for the nuclide and photopeak of interest. The results are then
corrected for attenuation or decay, or both.
Canberra Industries MicroSampo Version 2.0 (a commercial software package) is

used at EML to perform these calculations.
While the uncertainty due to counting and calibration may represent a significant
proportion of the total uncertainty in the measurement, systematic uncertainties should be
determined and included in the above calculation. Systematic uncertainties include, but
are not limited to, reproducibility of sample position, peak analyses, decay calculations,

background subtraction, pulse pile-up, cascade summing corrections, and self-absorption

corrections.
ANALYSIS OF COMPLEX MIXTURES

OF NUCLIDES WITH NAI(Tl) DETECTORS
Because of the inherent energy resolution of NaI(Tl) detectors, (-ray peaks in

complex mixtures of nuclides may not be separated sufficiently for quantification as
outlined above. It may not even be possible to visually locate individual peaks if their
energies are similar or their intensity is too low in relation to other (-rays present in the
spectrum. Complex mixtures of as many as 10 to 20 radionuclides can be quantified
mathematically with computer programs using linear least squares techniques.
When using these techniques, care should be given to the following parameters.
A. System gain and zero energy channel.
The exact gain and zero energy channel of the spectrometer must be monitored and
recorded. If the computer analysis program performs gain and/or baseline (zero energy
channel) corrections on sample data, then the library of standards data must be obtained
under uniform and precise calibration conditions.
B. Library standards.
The least squares analysis technique is a linear combination of all of the data
contained in the standards library. Therefore, the standards library must contain a spectra
of every component in the sample; in addition, these spectra must be obtained from the
purest radionuclides available.
C. Counting of library standards.
All (-ray spectra will contain a background component. The activity of the library
standards must be high enough so that this background component will be insignificant,
even though all computer programs make some kind of a background correction.

The duration of the counting period for the standard library spectra should be long
enough to obtain statistically valid data, but it should be short enough so that analyzer
gain and baseline drifts are insignificant.
The activity of the library standards should be chosen so that the counting rates of the
predominant photopeaks are all about the same.
A very important data evaluation technique to be used with a least squares program is
a superimposed plot of the original sample data and the computed spectral data. A plot of
residuals (the difference between the original and computed spectra) is also very
important. The residuals plot is very sensitive to errors that are caused by omitting
radionuclides present in the sample from the library standards.
SAMPLE MEASUREMENTS
After the spectrometer system has been set up, the energy calibrations performed, and
individual pulse-height spectra for nuclides expected to be present in samples are
obtained, then the unknown specimens can be measured and quantified.
Following the general concepts of quantitative analytical chemistry, transfer the

sample to the specimen container and position it in the same manner as was done during
system calibration. Measure the sample for a period of time long enough to acquire a (-
ray spectrum which will meet the minimum acceptable counting uncertainty.
COMPUTER CALCULATIONS
WLSQ is an EML least squares Fortran computer program that can be run on a VAX
or IBM-compatible PC to resolve complex spectra.
Systematic uncertainties include, but are not limited to: reproducibility of sample
position, peak analyses, decay calculations, background substraction, pulse pile up,
cascade summing operations, and self-absorption corrections.

The uncertainty obtained from the least squares analysis can be substituted for the
uncertainty in counting and should be included to obtain an overall uncertainty of the
analysis. The uncertainties obtained from the least squares analysis are the square roots
of the diagonal elements of the inverse matrix used to solve the linear set of simultaneous
equations representing the sample spectra.
QUALITY CONTROL
The following quality control procedures are required so that the (-ray spectrometers
maintain their energy calibrations. In addition, the systems are to be monitored so that
degradation in performance will be noticed as soon as possible.
A. Daily calibration checks.
The energy calibration of each Ge (-ray detector is determined daily with a mixed
nuclide source consisting of 241Am and 60Co.
In order to maintain an energy calibration of 0.5 keV/channel, count the Am-Co

source to obtain well-defined peaks. The 59.5 keV (-ray line from 241Am should fall in
channel 119. The 1332.5 keV (-ray line from 60Co should fall in channel 2665.
If the 241Am and 60Co peaks do not fall in the correct channels, first adjust the DC
offset of the amplifier so that the 59.5 keV (-ray line falls in channel 119. Then adjust
the fine gain of the amplifier so that the 1332.5 keV (-ray line falls in channel 2665.
Recount the Co-Am calibration standard to verify the peak positions and readjust the
amplifier if necessary.
The energy calibration of each NaI(Tl) (-ray detector is determined daily with a
nuclide source consisting of 207Bi.
In order to maintain an energy calibration of 10 keV/channel, count the 207Bi source

to obtain well-defined peaks. The 570 keV (-ray line should fall in channel 57. The
1064 keV (-ray line should fall in channel 106.

If the 207Bi peaks do not fall in the correct channels, first adjust the DC offset of the
amplifier so that the 570 keV (-ray line falls in channel 57. Then adjust the fine gain of
the amplifier so that the 1064 keV (-ray line falls in channel 106.
Recount the 207Bi calibration standard to verify the peak positions and readjust the
amplifier if necessary.
B. Weekly efficiency calibration and resolution checks.
Each week the same 137Cs calibration standard is counted, recorded, analyzed, and the
date is entered into a permanent data base for each (-ray spectrometry system.
Count the 137Cs calibration standard in the same manner as unknown samples.
Record the data for permanent storage and perform the usual data reduction analysis.
Enter the results of the analysis (Bq) and the resolution of the 137Cs peak (full width at
half maximum in keV) in the (-quality control data base.
Report any deviation from the expected values before samples are analyzed. If
remedial action is necessary, the cause and solution of the problem must be recorded in
the laboratory logbook. A complete recalibration must be performed if any remedial
actions have been taken.

Section 4.5.3, Vol. I Rev. 0
4.5.3 Quality Control and Detection Limits

4.5.3 QUALITY CONTROL AND DETECTION LIMITS
QUALITY CONTROL
Quality control (QC) must be included in all aspects of a radiochemical measurement,

from the collection of samples to the reporting of data. The exact QC practices that are to
be used as part of the radiochemical procedures will vary somewhat, depending upon the
chemical and radiological characteristics of the analyte. Some of the general
requirements of a QC system for procedures are described here. Where the peculiarities
of an analyte necessitate that modifications be made in these requirements, these
modifications are discussed in the subsection after the analytical procedure for that
analyte. The QC procedures described here are termed "internal" in that they are initiated
by the analyst. Similarly, "external" QC procedures should be initiated by project leaders
introducing QC samples "blind" into the sample stream. Data from both the internal and
external QC procedures must be maintained and tabulated by the party initiating the
procedures to document the continuing adequacy of the analytical work.
The QC practices used during radiochemical analyses are intended to assure the
analyst that the determinations are under control. They involve continuous testing of
those processes that influence the extent to which the results of the analyses remain
within the required limits of precision and accuracy. The QC samples that are analyzed
consist of five types: instrument calibration standards, blank samples, control samples,
"spiked" samples, and replicate samples.
Instrument calibration standards are certified reference materials used primarily to

calibrate the measurement apparatus. Standards for radioactivity measurements are
discussed in Section 4.5.2. A key requirement of such materials is that they be traceable
to the National Institute of Standards and Technology or to other recognized
organizations.
Blank samples are commonly "reagent blanks" that are prepared by beginning with
deionized water or an empty sample container. All appropriate reagents are added to the
sample in the proper sequence and the normal steps involved in the analysis are followed.
Ideally, the blank samples would be the same matrix as the routine sample but without

U. S. Department of Energy Page 1 of 17
the analyte of interest. Normally, the activity of each routine sample is corrected by
subtracting the reagent blank activity from it to obtain net activity. All the uncertainties
of the measurements obtained throughout the analytical procedure should be propagated
when calculating the uncertainty of the final result. However, very often only the
Poisson errors of the counts of the reagent blank and of the sample are propagated when
they are the most significant contributors to the total uncertainty.
Control samples contain known concentrations of the analyte. If possible, they

should be the same matrix as the routine samples, and they should have concentrations in
the same range as the routine samples. They usually are samples that are included by the
analyst in the sample batches to be analyzed, and their values should be known with an
uncertainty better than that which will be required of measurements of the routine
samples.
"Spiked" samples are prepared by adding a known amount of the radionuclide of

interest to blank samples or to samples that have already been analyzed in order to
provide a matrix with a known activity.
Replicate samples usually consist of two or more aliquots of homogeneous solid,

liquid or gas samples. Individual samples that are measured by nondestructive
techniques, such as (-ray spectrometry, may be measured more than once to obtain
replication of the data.
Analytical instruments, such as analytical balances, must be calibrated regularly. The

standards that are used to calibrate any instrument should be traceable to the National
Institute of Standards and Technology (NIST), when possible. A record of instrument
performance must be maintained by the instrument operator. A record must be kept of
any modifications that are made in an instrument, and such modifications must be
approved by the analyst's supervisor beforehand and must conform to the safety standards
and practices that are specified in the EML Safety Manual.
For most radiochemical procedures, QC samples are added to make up between

10-20% of the sample stream. It is good analytical practice to process high-level and
low-level samples in independent batches whenever possible to minimize the possibility
of cross contamination. When samples of very low activity are to be analyzed, blank
sample analyses and instrument background measurements should be increased.

The best estimates of a reagent blank or blank sample activity, instrument background
count rate and detection efficiency are obtained from the mean value of replicate
determinations. Whenever possible, the mean and standard error of the replicate
determinations should be used in calculating a final value.
ESTIMATING THE LOWER LIMIT OF DETECTION
Counting data are like other analytical data in that a series of measurements of
background, for example, should show a Gaussian distribution like that in Figure 1. The
standard deviation (SD) for the distribution will give an estimate of how well additional
background measurements will approach the original mean. In most environmental
analyses, however, we cannot afford the luxury of multiple analyses or even duplicates.
Fortunately, counting data follow the Poisson distribution and it is possible to estimate
the SD from a single measurement. This SD of counting can be used in the same way as
the Gaussian SD to establish a confidence interval about the mean value. For example, if
the confidence interval chosen is ±1 SD, additional measurements should fall into this
interval 68% of the time. An interval of ±2 SD would contain the new value 95% of the
time.
Thus, if we establish a background with its associated SD for a counting system, this
should give us a way of estimating our lower limit of detection (LLD). For example, a
sample count > 1 SD above background should indicate the presence of activity 84% of
the time. In the other 16%, there would be a false positive. If the limit of 2 SD is used,
the values would be 97.5% real and 2.5% false with 3 SD, 99.85% and 0.15%. This
seems to be very simple, but it does not consider the fact that the sample counts also
would have a distribution.
The interaction of the two distributions becomes more important as environmental

analyses tend toward lower levels of radioactivity. As the activity decreases, the counter
background or method blank has to be subtracted from the gross count, and estimating
the precision of these measurements and also the limit of detection for a procedure
becomes slightly more difficult. Where the total count on a sample approaches the
background count, you have a situation as in Figure 2 where the two distributions
overlap. [This form of showing the detection limit for counting was given by Healy
(1956).]


Pasternack and Harley (1971) developed a procedure for calculating what they
defined as the LLD, the smallest amount of sample activity that will yield a net count for
which there is a confidence at a predetermined level that activity is present. This concept
was only practical for ( counting in the original form since they required that the number
of counts be sufficient for the Poisson distribution to approach the Gaussian distribution
so that Gaussian statistics could be used.
However, the approximation is valid down to a few total counts. Thus, the
calculations can be applied to any detection system.
The LLD can be approximated as
LLD – (k" + k$)s0

where
k" is the value for the upper percentile of the standardized normal variate
corresponding to the preselected risk for concluding falsely that activity is present
("),
kß is the corresponding value for the predetermined degree of confidence for
detecting the presence of activity (1- ß), and
s0 is the estimated standard deviation for the net sample activity.
A still shorter approximation may be made if the values of " and ß are set at the same
level and if the gross activity and background are very close. In this case:
The equation then becomes,

The values of k for common "'s are:
" 1-ß k 2k
0.01 0.99 2.327 6.59

0.02 0.98 2.054 5.81
0.05 0.95 1.645 4.66
0.10 0.90 1.282 3.63
0.20 0.80 0.842 2.38
0.50 0.50 0.000 0.00
Routinely, an " value of 0.05 is used at EML for calculating the LLD. The LLD will
be provided at the end of each procedure, if appropriate.
The simplest possible case is one where the sample activity is zero. It is sometimes
not realized that if a series of counts is taken on such a system, that half of the net values
should be less than zero. Negative counts are not possible, of course, but when there is a
blank or a background, the entire scale is shifted up and the situation becomes one where
half of the sample counts on a zero activity sample would be less than background. This
negative net count occurs frequently in low-level measurements, causing considerable
concern, but such results are to be expected.
Thus, if we have a counter with a background of 0.003 counts sec-1 (cps) and we
count the sample and background for 24000 sec, then
s = 72 = 8.5
b
If we set " at 0.05, accepting a 5% chance of a false positive result for a sample
having no activity,
LLD = (4.66)(8.5) = 40 counts
or ~ 0.002 cps.
Since the simplified formula used sets k" = kß, we are also accepting the chance that
we will detect activity when it is present, 95% of the time, but will miss it 5% of the time.

If a 50% chance of finding activity is accepted, the LLD is zero. This is to be

expected from the previous qualitative description.
The original paper of Pasternack and Harley (1971) applied the LLD concept to
multicomponent ( spectrometry with NaI detectors. They noted particularly the decrease
in sensitivity as the number of components in the mixture increased, and observed a
decrease when the number of radionuclides in the library was increased, even when the
actual sample contained only a single component.
Multicomponent " spectrometry can be performed in accordance with the procedures

of Fisenne et al. (1973). Solid state "-spectrometry calculations are simpler, since
overlapping spectra are less common. The basic principle is that an interfering
radionuclide effectively increases the background for the nuclide sought.
Examples of LLD calculations for three typical measurement situations are given for
illustrative purposes in the appendix.
ZERO LEVELS
A. Introduction.
When the measurement of background yields a positive value, its variance and SD
may be calculated based on Poisson counting statistics. In any subsequent measurement
of a sample, the net activity and its SD may be evaluated to determine whether significant
radioactivity is present.
A special case arises when neither counter background nor sample activity is
detectable over a reasonably long counter interval. It is of practical interest to be able to
quantitate the upper limit of radioactivity that could be present in this sample and yet
yield this result, since increasingly more environmental nuclide measurements may fall
into this category.

The measurement and identification of low levels (< 0.0001 Bq/sample) of "-emitting
nuclides by spectrometry represents a specific example. This measurement is performed
with a silicon surface barrier or ion implant detector. Any background counts measured
in these detectors usually fall within the energy intervals corresponding to naturally
occurring nuclides, primarily radium and its progeny. The background count rate for
these detectors usually ranges from 0-5 counts per 6x104 sec in any of the energy
intervals containing peaks of the U series, Pu isotopes and most other " emitters of
interest.
Thorium-232 is a special case, since the energy interval at which it appears

(3.9 MeV) normally exhibits very low background. For example, a measurement for
232
Th yielded zero counts in 3x105 sec and zero background counts over a similar count
interval. It is of value to calculate rigorously an upper limit of 232Th activity which could
be present in such a sample. Two examples are given here. One, where the counting
interval is fixed and the other where the count time can be calculated based upon a
desired fixed value for the upper limit of activity in the sample (Harley and Fisenne,
1976).
B. Predetermined count interval.
We may apply the binomial distribution to a group of No atoms to calculate the

probability that there will be no " decays in counting interval, t.
The binomial distribution for the probability of x number of disintegrations out of a

total of No atoms is:
N0 !
Pr ( x) = p x q (N0 −x) (1)
(N - x)! x!
0
where
Pr(x) = probability of x disintegrations during time, t,

N0 = initial number of radioactive atoms,
p = probability that an atom will decay in time, t, and
q = probability that an atom will not decay in time, t.

Since the probability, q, that an atom will not decay is:
q = e −λ t
then,
(
p = 1- e −λ t )
and
(1- e -λ t ) (e )
N0 ! x-λ t N 0 -x
Pr(x) =
(N 0 - x)! x!
The probability of no disintegrations in time t is then:
N0 !
( ) (e )
0 -λ t N 0
Pr ( 0) = 1- e -λ t = e -λ N 0t (2)
N 0 0!
Because the detector efficiency is <100%, there is also the possibility that one or
more disintegrations occur but that they are not detected. If the detector efficiency is G
and one disintegration occurs, the probability of no count being detected is (1-G). If two
disintegrations occur, the probability of zero counts is (1-G)2. In general, whenever x
disintegrations occur, the probability that zero counts will be seen is (1-G)x. Then the
probability that one or more of No atoms present disintegrates during time, t, but that
none is detected is:
Pr (1) ⋅ (1 - G ) + Pr (2) ⋅ (1 - G )2 + Pr (3) ⋅ (1 - G )3 + ... (3)
From (1), the probability of one disintegration occurring is:
N0 !
Pr (1) = (1- e -λ t )1 (e -λ t )N0 −1 (4a)
(N 0 -1)! 1!

The probability of two disintegrations occurring is:
N 0!
Pr (2) = (1- e -λ t )N0 -2 (4b)
(N 0 - 2)! 2!
and so on.
If the assumption can be made that t is small and that No is much greater than one,
then Pr(1), Pr(2), etc., simplify to:
(
Pr (1) ≅ N 0 (λ t ) e -λ N 0t
-1
) (5a)
N0N0
Pr (2) = (λ t )2 (e -λ N 0t ) (5b)
2!
N0N0N0
Pr (3) = (λ t )3 (e -λ N 0t ) (5c)
3!
The probability for observing zero counts is the sum of the probabilities for no
disintegration to occur plus those for the occurrence of one or more disintegrations which
are not detected.
P = Pr (0) + Pr (1) ⋅ (1-G ) + Pr (2) ⋅ (1-G )2 + Pr (3) ⋅ (1-G )3 + ...
≅ e -λ N 0t + λ N 0 te -λ N 0t (1- G ) +
[λ N t(1- G)]
0
2
e -λ N 0t + ...
2!
≅ e -λ N 0t

1 +
λ N 0 t(1- G )
+
[
λ N 0 t(1- G ) ] 2
+
[λN t(1- G)]
0
3

+ ...
 1! 2! 3! 
 

≅ e - λN o t ⋅ e + λN o t(1-G) (6a)
≅ e - λN o tG (6b)
8NotG is the number of counts to be expected during the interval t.
We would like the occurrence of zero counts, when activity is actually present, to
have a small probability. If this probability is arbitrarily set to 0.05 so that zero counts
will be detected only 5% of the time, when No atoms are actually present and the
counting interval is t minutes, then (6b) becomes:
e -λ N 0tG = 0.05
λ N 0 tG = -1n( 0.05)
1
( λ N 0 ) = A 0 = - tG 1n(0.05) (7)
3
A0 =
tG
where 8No = Ao is the upper limit of sample activity in Bq at the 95% confidence level,
when t is in seconds and G is expressed as fractional efficiency.

C. Predetermined upper limit of activity.
It may be of interest to establish the counting time required to determine that a chosen
upper limit of activity is present. Solving (7) for the counting time yields:
3
t= (8)
A 0G
As an example, the measured data for the 232Th sample will be used. The efficiency
of the surface barrier detector is 0.30 and zero counts were recorded in 3x105 sec. From
(7):
3 -5
A = = 3 x 10 Bq
0 ( 5
)
3 x 10 (0.3)
(9)
The upper limit of activity in this sample is thus 3x10-5 Bq at the 95% confidence
level.
BACKGROUND NOT ZERO
All of the above expressions apply equally well to background activity. It is possible
that either a background count did not occur during the count interval or that one or more
occurred but were not detected. In this case, the upper limit to background activity is the
same as that calculated in (9), except that there is no efficiency for background and the
background activity is expressed as counts sec-1. Expression (9) would then become:
3 -5 -1
= 1 x 10
(3 x 10 )
A G= counts sec
0 5

Then according to the convention at EML, any value of net activity equal to zero would
be evaluated in comparison with:
-5 -5
1x10 1x10 -6 -1
S net = 5 + 5 = 8 x 10 counts sec
3x10 3x10
and the activity would be reported as:
-6
≤ 8 x 10
,
0.3
or # 2x10-5 Bq at the 95% confidence interval.1
*This convention would be used for reporting single values. For averaging purposes, the actual value of
the net activity, positive or negative, would be used.

REFERENCES
Fisenne, I. M., A. O'Toole and R. Cutler

"Least Squares Analysis and Minimum Detection Levels Applied to Multi-component
Alpha Emitting Samples"
Radiochem. Radioanal. Letters, 1, 5-16 (1973)
Harley, N. H. and I. M. Fisenne

"Reporting Results of Radioactivity Measurements at Near Zero Levels of Sample
Activity and Background"
USERDA Report HASL-306, pp. 43-50 (1976)
Healy, J. W.
in: Proceedings of the Second Annual Meeting on Bioassay
USAEC Report WASH-736, September (1957)
Pasternack, B. S. and N. H. Harley

"Detection Limits for Radionuclides in the Analysis of Multi-Component Gamma Ray
Spectrometer Data"
Nuclear Inst. and Methods, 91, 533-540 (1971)

APPENDIX
LOWER LIMIT OF DETECTION2
In the analyses of samples for naturally occurring radionuclides, it is rare that the
sample activity and background are the same. Reagent blanks processed through the
chemical procedure will show activity in excess of the background of the detection
system. Multiple measurements of the background and multiple reagent blank analyses
are used to obtain the respective standard errors of these variables. In this case, the
equation is
1/2
 
S s = Sgross + S BK 2 + S Bl 2  (1)
 
where
Sgross = the mean background plus mean reagent blank counts for a specified
counting time,
S BK = the standard error of the background from multiple measurements (n),
corresponding to the same counting time as above, ([sBK2]/[n])1/2, and
S B1 = the standard error of the blank from multiple analyses (n), also with the same
counting time, ([sBl2]/[n]½).
Then, the LLD at the 95% confidence level is
( )
LLD 95% = k a + k S s = 3.29 S s
b
(2)
*
Taken from Pasternack and Harley (1971).

where
k" = the preselected risk for concluding falsely that activity present. At the 95%
confidence level (") = 1.645, and
k$ = the predetermined degree of confidence for detecting the presence of activity.

At the 95% confidence level (1-$) = 1.645.
Thus, at LLD95%
k" = k$ = 1.645
and (k" + k$) = 3.29
The LLD95% must be converted to activity (Bq) using the appropriate conversion
factors.
3.29 SS
LLD 95% (Bq ) = (3)
(CT) (∈)(Y)
where
CT = the counting time or counting interval in seconds,
, = the detection efficiency of the measurement system (counts sec-1 Bq-1), and
Y = the average radiometric or chemical yield obtained for the separation

method.
The applications of Equations 1 and 3 to solid state "-spectrometry measurements are

illustrated below.
In 239Pu measurements, a manmade radionuclide, there is no measurable blank and the

mean background count from multiple measurements is used. Then, the term sBl does
not appear and Equation 1 reduces to

sS = [s gross + s Bk2]1/2 (4)
For this situation sgross is the mean background counts and sBk is the standard error of
multiple measurements.
Given the following variables:
counter efficiency: 40%

counter background
(in the 239Pu energy region): 3.3 x 10-5 ± 1.7 x 10-5 counts sec-1
(0.002 ± 0.001 counts min-1)
tracer yield: 75%
counting time: 60,000 s (1,000 min)
sS = (2 + 1 counts)½ = (3 counts)½ (5)
and
(
3.29 3 counts )
1/ 2
LLD 95% = = 0.0003 Bq
( )(
60000 sec 0.40 counts sec
-1
Bq
-1
) (0.75 yield)
In 210Po measurements there usually is a measurable blank and all variables in

Equation 1 must be taken into account.
Given the following variables:
counter efficiency: 40%

counter background
(in the 210Po energy region): 8.3 x 10-5 ± 5.0 x 10-5 counts sec-1
(0.005 ± 0.003 counts min-1)

blank: 1.6 x 10-4 ± 1.0 x 10-4 Bq

(5.0 x 10-5 ± 3.3 x 10-5 counts sec-1)
(0.003 ± 0.002 counts min-1)
tracer yield: 80%
counting time: 60,000 s (1,000 min)
Again, mean background from multiple measurements and the mean reagent blank
from multiple analyses are to be used.
sS = [(5+3 counts) + (2 counts)2 + (3 counts)2]½ = 4.6 counts
3.29 (4.6 counts)

LLD 95% = = 0.0008 Bq
(60000 sec) (0.40 cps Bq -1 ) (0.80 yield)
The LLD can be reduced by: (1) increasing the number of background and reagent
blank measurements, assuming these do not increase over time; (2) increasing the
counting time; (3) increasing the counting efficiency; and (4) increasing the sample yield.

4.5.4 Radiochemical

Americium

Am-01-RC, Vol. I Rev. 0
Am-01-RC
AMERICIUM IN SOIL
Contact Person(s) : Anne Berne
APPLICATION
This procedure is applicable to soils which contain americium deposited from

worldwide fallout and some nuclear activities.
Americium is leached from the soil with HNO3 and HCl and simultaneously
equilibrated with 243Am tracer. The soil is processed through the plutonium separation
steps using ion exchange resin according to Procedure Pu-11-RC. If determination of
plutonium is desired, an appropriate plutonium tracer should be added along with the
243
Am tracer. Americium is collected with a calcium oxalate precipitation and finally
isolated and purified by ion exchange. After source preparation by microprecipitation,
the 241Am is determined by alpha spectrometry using 243Am tracer to provide recovery
data.
SPECIAL APPARATUS
1. For microprecipitation, see Procedure G-03.
2. Ion-exchange columns - see Specification 7.5.
SPECIAL REAGENTS
1. Americium-243 tracer solution, about 0.15 Bq g-1 in dispensing bottle - standardize

for total disintegration rate. Measure purity on an " spectrometer.

2. Bio-Rad AG 1-X8 resin (100-200 mesh) - see Specification 7.4.
4. 4M ammonium thiocyanate solution - dissolve 304 g of NH4SCN in deionized

distilled water and dilute to 1 L. To purify the 4M NH4SCN, place 4 L of solution in
a 5 L polyethylene beaker. Add 25 mL of Bio-Rad AG 1-X4 resin (100-200 mesh)
ion exchange resin, and mix for 1 h with a magnetic stirrer. Allow the resin to settle
and filter by gravity through Whatman No. 40 filter paper. Repeat the addition of the
resin and filtration steps twice more to remove all Fe+3 from the 4M NH4SCN. Store
the purified 4M NH4SCN in a polyethylene bottle.
5. 0.4M NH4SCN - 0.3M HCl - dilute 100 mL of purified 4M NH4SCN to 500 mL with
water, then add 25 mL HCl and dilute to 1 L. Make 2 L of solution for 10 samples.
6. Calcium carrier solution, 100 mg mL-1 - dissolve 25 g CaCO3 in a minimum of HNO3

and dilute to 100 mL.
7. Iron carrier, 100 mg mL-1 - slowly heat 100 g of iron powder in 500 mL of HCl until
reaction ceases. Carefully and slowly add 100 mL of HNO3 while stirring. Cool and
dilute to 1 L.
8. Oxalate wash solution - dissolve 10 g of oxalic acid to make 1 L of solution (~ 1%

solution).
SAMPLE PREPARATION
1. Weigh 1000 g of soil into a 4-L beaker. Add a weighed amount (about 0.03 Bq) of
243
Am tracer.
2. Slowly add 900 mL of HNO3. Control the foam with the addition of a few drops of
n-octyl alcohol. When the reaction subsides, add 300 mL of HCl. Allow the mixture
to react at room temperature, then heat on a low temperature hot plate overnight with
occasional stirring.

3. Dilute to 1:1 HNO3 and filter through Whatman No. 42 filter paper into a 3-L flask.
Wash with 1:1 HNO3. Retain the filtrate. Return the residue and filter to the original
beaker.
4. Add 900 mL of HNO3 and wet ash the filter paper. Maintain the HNO3 volume.
Cool and add 300 mL of HCl to the residue and heat on a low temperature hot plate
for about 3 h with occasional stirring. Cool and allow to settle overnight.
5. Filter and wash as in Step 3. Combine the filtrate with the filtrate from Step 3.
Return the residue and filter to the original beaker.
6. Repeat Step 4.
7. Filter and wash as in Step 3. Combine the three filtrates and discard the residue.
8. Decompose any organic matter in the extract by heating with repeated additions of
HNO3, covering the sample with a watch cover and letting the sample reflux.
Concentrate until salting out begins to occur. Add an equal volume of water. If
solution is not clear, proceed to Step 9, otherwise go to Step 14.
9. If any siliceous matter is present, filter by gravity over an 18.5 cm Whatman No. 42
filter paper. Wash the residue with 1:1 HNO3. Reserve the filtrate.
10. Transfer the filter paper with the residue to the original beaker and ash the paper with
100 mL of HNO3. Repeat two or three times, then transfer the residue into a 100-mL
platinum dish using 1:1 HNO3.
11. Add 5-25 mL of HF and 5-25 mL of HNO3 to the platinum dish and evaporate on a
medium temperature hot plate. Repeat the addition of the HF/HNO3 and the
evaporation process two or three times. Rinse the walls of the platinum dish with 1:1
HNO3 and evaporate. Repeat three times. Evaporate to dryness. Dissolve with 1:1
HNO3 and evaporate to dryness.
12. Dissolve the residue in 1:1 HNO3 and filter by gravity through a Whatman No. 42
filter paper. Add the filtrate to the solution from Step 9. Discard the filter and any
residue.

13. Heat the combined solution (with the addition of HNO3 if necessary) to complete the
oxidation of any organic materials. Evaporate to near dryness. Redissolve in 1:1
HNO3 and stir to get a clear solution, adding 1:1 HNO3 as necessary.
14. Proceed to Procedure Pu-11-RC, ion-exchange purification saving the column

effluents for Americium Determination.
AMERICIUM DETERMINATION
1. Evaporate the americium effluents to incipient dryness. Redissolve in a minimum

amount of 1:1 HNO3, dilute with four volumes of water.
2. Add 5 mL of calcium carrier solution (500 mg of calcium) and 50 g L-1 of oxalic acid
to the sample while stirring with a magnetic stirrer. (The total volume of the sample
solution can be estimated using the markings on the beaker, and the amount of oxalic
acid to be added is calculated using that volume.)
3. Adjust the pH of the solution to 2.0 - 2.5 with NH4OH using pH paper as an indicator
and continue to stir for 30 min. Remove the magnetic stir bar.
4. Cool and let stand until precipitate settles and solution clears (for more than 6 h or
overnight). Check for completeness of precipitation using a drop of saturated H2C2O4
solution. Aspirate (or decant), using a disposable transfer pipette and suction, as
much liquid as possible without disturbing the precipitate. Transfer the precipitate to
a 250-mL centrifuge bottle using oxalate wash solution (see Note 1). Balance the
bottles on a double pan balance and centrifuge for 10 min at 2000 rpm. Decant and
discard the supernate.
5. Break up the precipitate with a stirring rod and wash the precipitate with the oxalate
wash solution. Centrifuge, decant and discard the wash. Repeat wash. Redissolve
the precipitate in a minimal amount (50-70 mL) of concentrated HCl (redissolve the
precipitate in ~200 mL of HNO3 a final time and proceed to Step 8). (Note:
Dissolution is easier if the centrifuge bottle is placed in a hot water bath and stirred
with a glass rod).

6. Transfer the dissolved precipitate to the original 600-mL beaker. Add enough water
to make ~ 1M solution. Add 50 g L-1 of oxalic acid.
7. Repeat Steps 3 through 6 until supernate is colorless.
8. Transfer the dissolved precipitate to the original beaker and heat to destroy the
oxalate ion. Evaporate to near dryness. Dissolve in minimum 1:1 HNO3. Transfer to
centrifuge bottle using water to complete the transfer.
9. Add enough water to make ~1M HNO3. Warm the solution in a 90/ hot water bath
and add 0.2 mL iron carrier solution (20 mg iron).
10. With the centrifuge bottle in the hot water bath adjacent to a hood, adjust the pH of
the solution to 8-9 with NH4OH while stirring with a glass rod. Allow solution to
digest in a hot water bath for 20 min.
11. Cool in a cold water bath, rinse, and remove the glass rod. Balance the bottles on a
double pan balance and centrifuge for 40 min at 2000 rpm.
12. Decant (or aspirate) and discard the supernate. Add 10 mL concentrated HCl to
dissolve the Fe(OH)3 pellet. Add four drops 30% H2O2 to oxidize any Mn present,
followed by 100 mL of water. Heat in the water bath for 30 min to get rid of the
excess H2O2 .
13. Repeat Steps 10 to12 three times. Reprecipitate, centrifuge and redissolve. The final
precipitate should be redissolved in HNO3.
14. Transfer to a 250-mL beaker, evaporate to dryness, add 20 mL HNO3, and evaporate
to dryness again.
15. Dissolve the wet-ashed residue in 40 mL 1:1 HNO3. Cool in an ice-water bath. Add
0.6-1.0 g NH2OH A HCl, dissolve, and let the solution react for 15 min. Cover with a
watch glass. Heat on a low temperature hot plate to decompose unreacted NH2OH A
HCl, then bring to a gentle boil for 1-2 min. Cool and pass the solution through a 1:1
HNO3 ion-exchange column (see Note 2). Collect the effluent in a 400-mL beaker.
Wash the column with 150 mL of 1:1 HNO3, and collect in the beaker.

16. Evaporate the sample in the 400-mL beaker to dryness. Convert to HCl by adding
20-30 mL of HCl at a time, heat to almost dryness, and repeat the HCl addition and
evaporation at least three times. Evaporate again and dissolve the final residue in
30 mL of HCl. Pass this solution through a 12N HCl ion exchange column (see Note
3). Collect the effluent in a 250-mL beaker. Wash with 100 mL of HCl, and collect
in the 250-mL beaker.
17. Evaporate to dryness. Dissolve in 1-2 mL of HCl. Cool thoroughly. Add 40 mL of

4M NH4SCN and stir immediately. Stir the sample and pass the solution through a
4M NH4SCN column (see Note 4). Discard the effluent.
18. Wash the column with 200 mL of 4N NH4SCN solution. Discard the wash solution.
19. Elute the americium into a 250-mL beaker with 180 mL of 0.4N NH4SCN - 0.3N
HCl. Evaporate to dryness on a low temperature hot plate overnight. Discard the
resin.
19. To remove NH4+ salts, place the beaker on an iron tripod and heat slowly with a cool
Bunsen flame. After ~ 0.5 h, increase the flame temperature and continue heating to
remove all NH4+ salts and S, then heat briefly to dull red heat. This step requires
~ 1-1.5 h.
20. Cool to room temperature. Add 25 mL of HNO3 and boil slowly for a few minutes.
Cautiously add 1 mL of 30% H2O2 and evaporate the solution to dryness.
21. Convert the residue to Cl- by adding 1 mL of HCl and evaporating to dryness twice
and proceed to microprecipitation.
Notes:
1. If a centrifuge is not available, centrifugation can be replaced by filtering and wet

ashing the filter paper and precipitate in HNO3
2. Preparation of 1:1 HNO3 Column. Position a plug of glass wool at the base of an 11-
mm o.d. column. Transfer with deionized distilled water, 15 mL of wet settled Bio-

Rad AG 1-X8 resin (100-200 mesh) to the column and allow it to settle. Place a
second plug of glass wool on top of the resin and with the stopcock open allow the
H2O level to reach the top of the upper plug. Pass 150 mL of 1:1 HNO3 through the
resin bed in three 50-mL portions or enough so that the effluent tests free of Cl- ion
using dilute silver nitrate solution, allowing the level of each portion to reach the top
of the upper glass wool plug.
3. Preparation of HCl Column. Position a plug of glass wool at the base of an 11-mm
o.d. column. Transfer 10 mL of wet settled Bio-Rad AG 1-X4 resin (100-200 mesh)
with deionized water to the column and allow it to settle. Place a second plug of
glass wool on top of the resin and with the stopcock open allow the H2O level to
reach the top of the upper plug. Pass two 50-mL volumes of HCl through the resin
bed and allow each to reach the top of the upper glass wool plug.
4. Preparation of NH4SCN Column. Position a plug of glass wool at the base of an

11-mm o.d. column. Transfer with deionized distilled water, 15 mL of wet settled
Bio-Rad AG 1-X4 resin (100-200 mesh) to the column and allow it to settle. Place a
H2O level to reach the top of the upper plug. Pass 100 mL of purified 4M NH4SCN
through the resin bed in two 50-mL portions, allowing the level of each portion to
reach the top of the upper glass wool plug.
MICROPRECIPITATION
See Microprecipation Source Preparation for Alpha Spectrometry, Procedure G-03.
DATA PROCESSING AND ANALYSES
For alpha spectrometry measurements, please see Procedure A-01-R.

LOWER LIMIT OF DETECTION (LLD)
Counter Efficiency (%) 25

Counter Background (cps) 15x10-6
Yield (%) 50
Blank (cps) -
LLD (400 min) (mBq) 1

LLD (1000 min) (mBq) 0.5
LLD (5000 min) (mBq) 0.3

Am-02-RC
AMERICIUM-241 IN SOIL - GAMMA SPECTROMETRY
APPLICATION
This procedure is capable of determining small amounts of 241Am in large volume soil
samples. The lower limit of detection for 600-800 g of soil in a Marinelli beaker is 0.74
mBq for a 1000-min count.
Americium-241 decays with the emission of ( rays at 11.9, 13.9, 17.8, 20.8, 26.4,
and 59.5 keV. The 59.5 keV ( ray, which has an abundance of 35.9%, can be measured
in soil with commercially available germanium (Ge) semiconductor (-ray detectors and
600 mL Marinelli beakers. Gamma-ray attenuation corrections are required if the
calibration source and the sample are in a different matrix or are of different densities.
SPECIAL APPARATUS
1. Hyperpure Ge (-ray detector, shield, and associated electronics.
2. Multichannel analyzer.
3. Marinelli beaker - see Specification 7.22.
SPECIAL REAGENT
Americium-241 calibration solution, about 2.50 Bq mL-1.
SPECTROMETER CALIBRATION

1. Transfer 600 mL of standardized 241Am solution to a Marinelli beaker.
2. Set the spectrometer energy calibrations at 0.5 keV/channel and count the standard
until 10,000 or more counts are accumulated in the channels corresponding to 58.0 to
61.5 keV.
3. Record the count time and the channel-by-channel data corresponding to 56.0 to
63.5 keV.
SAMPLE PREPARATION
1. Transfer 600 mL of prepared soil to a Marinelli beaker.
2. Accumulate sufficient counts in the 59.5 keV 241Am peak to achieve the desired
counting statistics.
3. Record the count time and the channel-by-channel data corresponding to 56.0 to
63.5 keV.
DETERMINATION
If computer calculation techniques are used to determine peak areas from spectral
data, the same techniques must be used for both calibration standards and samples.
However, in most instances, simple peak integration by channel summing is sufficient.
The net count in the 241Am peak = A - B - C.
where
A = sum of counts in the 8 channels from 58.0 to 61.5 keV
B = sum of counts in the 4 channels from 56.0 to 57.5 keV

C = sum of counts in the 4 channels from 62.0 to 63.5 keV
B and C are the leading and trailing edges of the photopeak and represent the background
upon which the photopeak is superimposed.
The net 241Am counts, AmC, corrected for attenuation equals
A/e-(:dAw)
where
A = observed net counts in the 241Am peak,
:d = attenuation constant for Marinelli beaker (see Note below),

for H2O, :d = 0.000427 cm2 g-1
for soil, :d = 0.000533 cm2 g-1
w = weight in g of the standard or sample.
The 241Am detector efficiency at 59.5 keV,
Efficiency = (AmC/t)/(AcA600)
where
AmC = net 241Am counts of the standard, corrected for attenuation, and
t = standard count time (sec).
241
Ac = Am activity of standard (Bq mL-1).
The Bq 241Am in the sample = (AmC/t)/Efficiency

where
AmC = net 241Am counts of the sample, corrected for attenuation, and
t = sample count time (sec).
Note:
The Marinelli beaker attenuation constant (:d = 0.000533 cm2 g-1) is for soil of
normal composition. Soils or ores composed of high atomic number elements will
require a different constant. For example, a 1% U ore will attenuate the 59.5 keV ( ray
to 7% more than normal soil and the correct :d would be 0.000677 cm2 g-1.

Am-03-RC, Vol. II Rev. 0
Am-03-RC
AMERICIUM IN WATER, AIR FILTERS, AND TISSUE

(see Volume II)

Am-04-RC
AMERICIUM IN QAP WATER AND AIR FILTERS -

EICHROM’S TRU RESIN
Contact Person(s) : Anna Berne
APPLICATION
The following procedure has been applied to the preparation, separation, and analysis
of spiked water and air filter samples that contain americium but not lanthanides (Berne,
1996). Lanthanides, if present, will not be removed by this method and will significantly
reduce the resolution of the "-spectrograph. Combined with Procedure Pu-11-RC, this
procedure allows for the sequential determination of plutonium and americium. Other
researchers have applied TRU Resin methods to other matrices (Horowitz et al., 1990).
The procedure is used in the EML Quality Assessment Program (QAP; Sanderson and
Greenlaw, 1996).
The water and air filters are equilibrated with 243Am and processed through the
plutonium separation steps using ion exchange resin according to Procedure Pu-11-RC.
If determination of plutonium is desired, an appropriate plutonium tracer should be added
along with the 243Am tracer. The eluate from the ion exchange column containing
americium (and all other ions, except plutonium) is evaporated, redissolved, and loaded
onto a TRU Resin extraction column. The americium (and curium, if present) is
separated and purified on the column and finally stripped with dilute nitric acid stripping
solution. Microprecipitation is used to prepare for " spectrometry.
SPECIAL REAGENTS
1. Americium-243 tracer solution, about 0.15 Bq g-1 in dispensing bottle - standardize

for total disintegration rate. Measure purity on an " spectrometer.

U. S. Department of Energy
Page 1 of 4
2. TRU Resin 2 mL ion extraction columns or equivalent or can be prepared from TRU
Resin, Eichrom Industries, Inc., 8205 Cass AV, Suite 107, Darien, IL 60561. Place
a plug of glass wool in the bottom of a polyethylene transfer pipette (see
Specification 7.7). Add slurried TRU Resin (0.5 g). Assemble immediately before
use.
3. Column feed solution, 0.5M Al(NO3)3 in 2M HNO3 - place 18.76 g of

Al(NO3)3A9H2O in a 100-mL volumetric flask and add 2M HNO3 to the mark. Shake
to mix thoroughly.
4. 2M HNO3 - 125 mL HNO3 diluted to 1 L with water.
5. 1M HNO3 - 62.5 mL HNO3 diluted to 1 L with water.
6. 0.025M HNO3 - 25 mL 1M HNO3 diluted to 1 L with water.
SAMPLE PREPARATION
See Procedure Pu-01-RC, air filters or Procedure Pu-10-RC, water.
1. Collect the sample and the wash effluent from Step 4, Ion Exchange Separation,
Procedure Pu-11-RC, and evaporate almost to dryness. If necessary, sometime
during the evaporation process transfer the solution to a smaller beaker. The final
residue should be contained in a beaker not larger than 50 mL. Add 3 mL of 0.5M
Al(NO3)3 in 2M HNO3 to each residue and heat very gently to dissolve.
2. Prepare an ion extraction column.
3. Wash the resin with 15 mL of 2M HNO3, and discard the effluent.
4. Load the column with the sample solution from Step 1. Wash the beaker with 3 mL
of column-feed solution and add to the column. Discard the effluent.

Page 2 of 4
5. Rinse the column with 8 mL of 2M HNO3, followed by 8 mL of 1M HNO3, and

discard the effluents.
6. Elute the americium fraction with three 3-mL aliquots of 0.025M HNO3, and collect
the eluate in a 50-mL beaker.
7. Evaporate the eluate to dryness. Convert the residue to the chloride form by adding
5 mL of HCl three times and evaporating to dryness at a low temperature.
8. Prepare the sample for " spectrometry by microprecipitation (see Procedure G-03).
DATA PROCESSING AND ANALYSIS
For " spectrometry, see Alpha Radioassay, Procedure A-01-R.
LOWER LIMIT OF DETECTION (LLD)*

Counter Background (cps) 1.6x10-5
Recovery (%) 80
Blank (cps) -
LLD ( 400 min) (mBq) 0.5
LLD (1000 min) (mBq) 0.3
LLD (5000 min) (mBq) 0.1
*Reagent blanks must be analyzed with each set of samples.
REFERENCES

Page 3 of 4
Berne, A.
“Use of EIChrom’s TRU Resin in the Determination of Americium, Plutonium and
Uranium in Air Filter and water samples.”
Sanderson, C. G. and P. Greenlaw

“Semi-Annual Report of the Department of Energy, Office of Environmental Restoration
and Waste Management, Quality Assessment Program”

Page 4 of 4
Am-05 RC, Vol. II Rev. 0
Am-05-RC
AMERICIUM IN WATER AND AIR FILTERS

(see Volume II)

Page 1 of 1
Am-06-RC
AMERICIUM AND/OR PLUTONIUM IN VEGETATION
APPLICATION
This procedure is applicable to vegetation which contain americium deposited from

worldwide fallout and some nuclear activities. It is most effective when used on dried
finely powdered samples of vegetation.
The vegetation is either dry ashed in a ceramic crucible using a muffle furnace or wet
ashed with nitric acid. Wet ashing requires considerably more time and must be carefully
attended to due to the highly reactive nature of vegetation. The sample is further digested
with hydrofluoric acid to dissolve silicate compounds. Plutonium is separated by ion
exchange and determined by alpha spectrometry. Americium is collected with a calcium
oxalate precipitation and finally isolated and purified by ion exchange. After source
preparation by microprecipitation, the 241Am is determined by alpha spectrometry using
243
Am tracer to provide recovery data.
SPECIAL APPARATUS

Page 1 of 8
SPECIAL REAGENTS
1. Americium-243 tracer solution, about 0.15 Bq g-1 in a dispensing bottle-standardize

for total for total disintegration rate (and/or 236Pu tracer solution - a standard solution
containing ~0.15 Bq g-1 in a dispensing bottle). Measure purity on an "
spectrometer.
2. Anion exchange resin, Bio-Rad AG 1-X8 resin (100-200 mesh) - see Specification
7.4.
3. Anion exchange resin, Bio-Rad AG 1-X4 resin (100-200 mesh) - see Specification
7.4.
4. TRU Resin 2 mL ion extraction columns or equivalent or can be prepared from TRU
Resin, Eichrom Industries, Inc., 8205 Cass AV, Suite 107, Darien, IL 60561. Place
a plug of glass wool in the bottom of a polyethylene transfer pipette (see
Specification 7.7). Add slurried TRU Resin (0.5 g). Assemble immediately before
use.
5. 0.5M Al(NO3)3 in 2M HNO3 - place 18.76 g of Al(NO3)3@9H2O in a 100-mL

volumetric flask and add 2M HNO3 to the mark. Shake to mix thoroughly.
6. 2M HNO3 - 125 mL nitric acid diluted to 1 L with water.
7. 1M HNO3 - 62.5 mL nitric acid diluted to 1 L with water.
8. 0.025M HNO3 - 25 mL 1M HNO3 diluted to 1 L with water.
9. Calcium carrier solution, 100 mg mL-1 - dissolve 25 g CaCO3 in a minimal amount

of concentrated HNO3, dilute to 100 mL.
the reaction ceases. Carefully and slowly add 100 mL of HNO3 while stirring. Cool
and dilute to 1 L.
11. Oxalate wash solution - dissolve 10 g of oxalic acid to make 1 L of solution (~ 1%

solution).
12. Hydroxylamine hydrochloride, NH2OHAHCl.

SAMPLE PREPARATION
A. Dry ashing
1. Weigh an aliquot of < 10 g vegetation into a tared 250-mL porcelain crucible. (Note:
After ashing, several aliquots can be combined to provide adequate sample size.)
Place each crucible in a muffle furnace with the crucible cover slightly ajar.
Increase the temperature of the furnace at a rate of 0.80/C min -1 to 250/C. Maintain
this temperature for 30 minutes. Increase the temperature at a rate of 10/C min -1 to
600/C. Maintain the temperature for 960 min to completely ash sample. Cool the
crucible and weigh to determine percent ash. Ash content for replicate crucibles
should vary by not more than 4%. If the ash content of an individual sample is
lower by more than 4%, sample loss should be assumed and that sample discarded.
2. Place a known amount (approximately same amount as 241Am in the sample) of

243
Am tracer (and/or 236Pu tracer solution) in a 400-mL beaker containing a small
amount of 1:1 HNO3. Transfer ashed vegetation to the beaker using 1:1 HNO3 to
dissolve the ash and rinse the crucible. Transfer as many aliquots to the beaker as
needed to meet the detection requirements.
3. Cover with a watch glass and reflux on a hot plate until there is no evidence of
remaining organic matter, adding HNO3 or H2O2 as necessary.
4. Evaporate to near dryness. Add 50 mL 1:1 HNO3. Filter by gravity through a

Whatman No. 42 filter paper, washing with 1:1 HNO3 into a beaker. Continue with
Step 5 below.
B. Wet ashing
1. Weigh an aliquot of vegetation into an appropriate sized beaker. (For a 100-300 g

sample, use a 3000-mL beaker.) Add a known amount (approximately the same
amount as expected of 241Am in the sample) of 243Am tracer solution (and/or 236Pu
tracer solution).
2. Slowly add 500 mL of 1:1 HNO3. Control the foaming, if necessary, with the
addition of a few drops of n-octyl alcohol. Cover with a watch glass and place on a

low temperature hot plate overnight, maintaining a slow reaction and stirring as
necessary to break up the foam. Gradually increase the temperature of the hot plate,
adding HNO3 and maintaining refluxing until the reaction is complete as indicated
by the lack of brown nitrogen oxide gas.
3. Slowly add enough HCl to equal one third the volume of HNO3 still in the beaker.
Allow the mixture to react at room temperature for 15 min, cover with a watch glass,
then heat on a low temperature hot plate overnight with occasional stirring.
4. Remove the sample from the hot plate, add an equal volume of water. Allow the
sample to cool to room temperature. Filter by gravity through a large Whatman No.
42 filter paper into a beaker. Wash with 1:1 HNO3.
5. Retain the filtrate and evaporate to near dryness. Return the residue and filter to the
original beaker. Add 100 mL HNO3, cover with a watch glass and place on a
hotplate to reflux until colorless. Change the watch glass to a ribbed watch glass and
evaporate to near dryness.
6. Transfer the digested filter with the residue to a 250-mL Teflon beaker using 1:1
HNO3. Evaporate to dryness. Add 15 mL of HNO3 and 15 mL of HF to the beaker
and evaporate to near dryness on a medium temperature hot plate. Repeat the
addition of the HF/HNO3 and the evaporation process two or three times.
7. Add 30 mL HNO3 and evaporate to dryness, repeat twice, rinsing the walls of the
beaker with acid. Add 20 mL HNO3. Add 20 mL of water. Cool. Filter by gravity
through a Whatman No. 42 filter paper into the beaker with the filtrate from Step 5.
Rinse with 1:1 HNO3.
8. Evaporate filtrate to dryness. Redissolve in 30 mL 1:1 HNO3. Proceed to Ion

Exchange Purification for Plutonium Determination, Procedure Pu-11-RC, saving
the column effluents for Americium Determination.

1. Evaporate the americium containing effluents in a beaker to incipient dryness.

Redissolve in a minimum amount (20-100 mL) of 1:1 HNO3, dilute with four
volumes of water.
2. Add 5 mL of calcium carrier solution (500 mg of calcium) and 50 g L-1 of oxalic

acid to the sample, while stirring with a magnetic stirrer. The total volume of the
sample solution can be estimated using the markings on the beaker, and the amount
of oxalic acid to be added is calculated using that volume.
3. Adjust the pH of the solution to 2.0 - 2.5 with NH4OH using pH paper as an
indicator and continue to stir for 30 min. Remove the magnetic stir bar.
4. Cool and let stand until precipitate settles and solution clears. Check for
completeness of precipitation using a drop of saturated H2C2O4 solution. Aspirate as
much liquid as possible without disturbing the precipitate. Transfer precipitate to a
250-mL centrifuge bottle using oxalate wash solution (see Note 3). Balance the
bottles on a double pan balance and centrifuge for 10 min at 2000 rpm. Discard the
supernate.
5. Wash the precipitate with the oxalate wash solution. Centrifuge and discard the
wash. Repeat wash. Redissolve the precipitate in a minimal amount (50-70 mL) of
concentrated HCl. (Note: Dissolution is easier if the centrifuge bottle is placed in a
hot water bath and stirred with a glass stirring rod.)
6. Transfer the precipitate to the original beaker. Add ~3 volumes of water, 50 g L-1 of
oxalic acid, and reprecipitate the oxalate with NH4OH at a pH of 2.5-3.5 (see Step
3).
7. Cool the solution, aspirate, transfer to a centrifuge bottle, centrifuge, wash and
redissolve the precipitate (repeat Steps 4 and 5).
8. Transfer the solution to original beaker. Add ~3 volumes of water, 50 g L-1 of oxalic
acid, and reprecipitate the oxalate at a pH of 2.5-3.5 with NH4OH (see Step 3).

9. Cool the solution, aspirate, transfer to a centrifuge bottle, centrifuge, wash and
redissolve the precipitate in ~200 mL of concentrated HNO3.
10. Transfer the solution to the original beaker and heat to destroy oxalate ion.
Evaporate to near dryness. Dissolve in 1:1 HNO3 and transfer to the centrifuge
bottle.
and add 200 :L iron carrier solution (20 mg iron).
12. Adjust the pH of the solution to 8-9 with NH4OH, while stirring with a glass rod.
Leave the solution in a hot water bath to digest for 20 min.
13. Cool in a cold water bath, rinse and remove the glass rod. Balance the bottles on a
14. Aspirate the supernate and discard. Add 10 mL of concentrated HCl to dissolve the
Fe(OH)3 pellet, four drops of 30% H2O2 to get rid of any Mn, followed by 100 mL of
water, and heat in the water bath for 30 min to get rid of excess H2O2.
15. Reprecipitate, centrifuge and redissolve. Repeat Steps 12 to 14 three times.

Reprecipitate, centrifuge and redissolve. The final precipitate should be dissolved in
1:1 HNO3.
16. Transfer to a 250-mL beaker, evaporate to dryness, add 20 mL 1:1 HNO3, and
evaporate to dryness again.
17. Dissolve the residue in 40 mL 1:1 HNO3. Cool in an ice-water bath. Add 0.6-1.0 g
NH2OHAHCl, dissolve, and let react for 15 min. Cover with a watch glass. Heat on
a low temperature hot plate to decompose unreacted NH2OHAHCl, then bring to
gentle boil for 1-2 min. Cool and pass the solution through a 1:1 HNO3
ion-exchange column (see Note 1). Collect the effluent in a 400-mL beaker. Wash
with 150 mL of 1:1 HNO3, and collect in the beaker.
18. Evaporate the sample in the 400-mL beaker to dryness and treat several times with
concentrated HCl. Dissolve the residue in 30 mL HCl. Pass this solution through a

concentrated HCl ion exchange column (see Note 2). Collect the effluent in a
250-mL beaker, and wash with 100 mL of HCl. Evaporate and proceed to
microprecipitation if no residue is visible. If residue remains, continue with Step 19.
19. Evaporate to dryness transferring the sample to a 50-mL beaker when volume is
sufficiently diminished. Add 10-mL HNO3 and evaporate to dryness. Add 3 mL
0.5M Al(NO3)3 in 2M HNO3 to each residue and heat very gently to dissolve.
20. Prepare a TRU Resin column. Wash the resin with 15 mL 2M HNO3, and discard
the effluent.
21. Load the sample (see Step 19) on the column. Drain to the top of the resin. Wash
the beaker with 3 mL 0.5M Al(NO3)3 in 2M HNO3 and add to the column. Discard
the effluent.
22. Rinse the column with 8 mL 2M HNO3, followed by 8 mL 1M HNO3, and discard
the effluents.
23. Elute the americium with three 3 mL aliquots of 0.025M HNO3 into a 50-mL beaker.
24. Evaporate eluate to dryness. Convert the residue to the chloride form by adding 3-4
mL HCl. Evaporate to dryness. Redissolve in HCl and evaporate two more times.
Proceed to microprecipitation.
Notes:
1. Preparation of 1:1 HNO3 Column. Position a plug of glass wool at the base of an
11-mm o.d. column. Transfer 15 mL of wet settled Bio-Rad AG 1-X8 resin (100-
200 mesh) to the column with deionized distilled water, and allow to settle. Place a
second plug of glass wool on top of the resin, and with the stopcock open allow the
H2O level to reach the top of the upper plug. Pass 150 mL (or enough so that the
effluent tests free of Cl- ion) of 1:1 HNO3 through the resin bed in three 50-mL
portions, allowing the level of each to reach the top of the upper glass wool plug.
2. Preparation of HCl Column. Position a plug of glass wool at the base of an 11-mm
o.d. column. Transfer 10 mL of wet settled Bio-Rad AG 1-X4 resin (100-200 mesh)
with deionized water to the column, and allow to settle. Place a second plug of glass

wool on top of the resin, and with the stopcock open allow the H2O level to reach the
top of the upper plug. Pass two 50-mL volumes of HCl through the resin bed and
allow each to reach the top of the upper glass wool plug.

ashing the filter paper and precipitate in HNO3.
MICROPRECIPITATION
See Microprecipitation Source Preparation for Alpha Spectrometry, Procedure G-03.

Yield (%) 50
Blank (cps) -

LLD (1000 min) (mBq) 0.5
LLD (5000 min) (mBq) 0.3

Iron

Fe-01-RC, Vol. I Rev. 1
HASL-300, 28th Edition May 1999
Fe-01-RC
IRON IN AQUEOUS SAMPLES - DUAL-DPM MODE LIQUID

SCINTILLATION ANALYSIS
Contact Person(s) : Ada Kong and Raymond J. Lagomarsino
APPLICATION
The procedure is applicable for the determination of 55Fe in water samples prepared
for the EML Quality Assessment Program (QAP, Greenlaw, 1998). The 55Fe, which
decays by electron capture, is determined from an aliquot of the spiked solution
containing a mixture of alpha, beta and gamma emitting radionuclides. Beta emitting 59Fe
(Emax = 0.475 MeV) tracer is added to the sample as the yield determinant prior to the
precipitation of Fe(OH)3. Following two anion exchange separations to remove
interferences, the sample activities (as FePO4 ) are measured in a commercially available
liquid scintillation counter that is operated in the dual-dpm mode. A single count, in a
calibrated instrument, provides the quench corrected activity concentrations of 55Fe in a
sample based on recovered 59Fe (Scarpitta and Fisenne, 1996). The procedure has been
adapted from an ASTM (1990) method.
SPECIAL APPARATUS
1. Disposable ion exchange columns, pre-filled with AG1-X8 Resin (100 - 200 mesh) -
Bio-Rad Laboratories, 2000 Alfred Nobel Drive, Hercules, CA 94547-9980, or
equivalent.
2. Disposable 4.0 cm (h) x 0.6 cm (d) ion exchange columns (empty) - Bio-Rad
Laboratories or equivalent.
3. Liquid scintillation counter - Packard Tri-Carb 2250CA, Packard Instrument Co.,

Downers Grove, IL 60515, or equivalent.
4. 20-mL low K borosilicate liquid scintillation glass vials.
5. Vortexer - Scientific Industries, Inc., Bohemia, NY 11716, or equivalent.
6. Centrifuge, IEC Clinical Model containing a four place trunnion-type horizontal rotor
and 40-50 mL capacity shields, or equivalent.

SPECIAL REAGENTS
1. Anion exchange resin, AG1-X8 (50-100 mesh).
2. Cerium carrier: 1 mg mL-1 - CeCl3 in 2M HCl.
3. Cesium carrier: 1 mg mL-1 - CsCl in 2M HCl.
4. Cobalt carrier: 1 mg mL-1 - CoCl2 in 2M HCl.
5. Iron carrier: 5 mg mL-1 - FeCl3 in 2M HCl.
6. Manganese carrier: 1 mg mL-1 - MnCl2 in 2M HCl.
7. Strontium carrier: 1 mg mL-1 - SrNO3 in 2M HCl.
8. Zinc carrier: 1 mg mL-1 - ZnCl2 in 2M HCl.
9. 10M HCl - dilute 833 mL of conc HCl to1 L with water.
10. 6M HCl - dilute 500 mL of conc. HCl to1 L with water.
11. 4M HCl - dilute 333 mL of conc. HCl to1 L with water.
12. 0.5M HCl - dilute 42 mL of conc. HCl to1 L with water.
13. 0.01M HCl - dilute 20 mL of 0.05M HCl to1 L with water.
14. 8M HNO3 - dilute 500 mL of conc. HNO3 to1 L with water.
15. Ultima Gold liquid scintillation cocktail - Packard Instrument Co., Downers Grove,
IL 60515.
16. Ammonium phosphate, 0.5M - dissolve 66 g of (NH4)2HPO4 in 1 L of H2O.
17. Quenching agent (e.g., chloroform, nitromethane, carbon tetrachloride, etc.).
18. 59Fe tracer solution in 0.1 N HCl, about 17 Bq gm-1 in a dispensing bottle (1.7 Bq per
sample).
19. 55Fe standard solution - NIST SRM or equivalent.
20. Aerosol OT solution - 1%.

SEPARATION
1. Weigh out 1.7 Bq (~100 dpm) of 59Fe tracer for each sample and reference standard.
2. Add the 59Fe yield tracer, 1 mL (5 mg mL-1) of Fe+3 carrier solution and 1 mL each (1
mg mL-1) of Ce, Cs, Co, Mn, Sr and Zn holdback carriers to an aliquot of the sample
in a 40-mL centrifuge tube (see Note 1).
3. Prepare a reagent blank by adding the Fe+3 carrier and the holdback carriers in a 40-
mL centrifuge tube, but without 59Fe tracer.
4. Add 1.7 Bq of 59Fe tracer and 1 mL of Fe+3 carrier to a 20 mL glass scintillation vial
labeled "59Fe Reference Tracer." Set the "59Fe Reference Tracer" aside until Step 18.
5. Add NH4OH to the samples and blank until the pH is >10 to precipitate the combined
hydroxides. Digest in a hot water bath with occasional stirring for ~ 20 min. Cool,
add several drops of 1% Aerosol solution and centrifuge at 2000 rpm for
approximately 5 min. Decant and discard the supernate.
6. Add 10 mL of water and breakup the precipitate with a stirring rod. Add several
drops of 1% aerosol solution and centrifuge at 2000 rpm for ~ 2 min. Decant and
discard the wash.
7. Dissolve the hydroxide precipitate in 3 mL of HCl and heat in a hot water bath with
occasional stirring until the precipitate is completely dissolved, then cool the solution
to room temperature.
8. Condition an ion-exchange column containing 3 mL of Bio-Rad AG1-X8 (100-200

mesh) resin by passing 30 mL of conc. HCl through the column. Tap the column to
speed the flow and to assure the packing of the resin.
9. Pass the sample solution from Step 7 through the column. Collect the effluent in a
50- mL beaker.
10. Wash the column with 10 mL volumes of each of the following acids: 10M HCl; 6M
HCl; and 4M HCl to remove Mn, Cs, Ce, Sr, and Co. Collect the three washes in the
50-mL beaker. Discard the effluent and combined washes.
11. Replace the 50-mL beaker with a clean 50 mL beaker. Elute the iron with exactly
10 mL of 0.01M HCl. The solution should be yellow.
12. Add 10 mL of HNO3 to the eluted sample from Step 11 to produce an 8M HNO3
solution.

13. Prepare a second ion-exchange column containing 3 mL of Bio-Rad AG1-X8 (50-100

mesh) resin and condition the resin by passing 30 mL of 8M HNO3 through the
column.
14. Pass the 8M HNO3 sample solution through the second column. Collect the effluent in
a 100 mL labeled beaker. Wash the column with10 mL of 8M HNO3. Collect the
wash with the eluent (the wash should completely remove the iron from the column as
evidenced by the absence of the yellow color in the effluent). Discard the column
which contains plutonium, uranium and zinc.
15. Add 10 mL of 0.5M (NH4)2HPO4 to the beaker containing the iron eluate and add
NH4OH until the pH is ~3.0. Gently heat the beaker on a hot plate for ~ 20 min with
occasional stirring to completely precipitate iron as FePO4.
16. Remove the beaker from the hot plate, cool, and transfer the mixture to a 40 mL
centrifuge tube using H2O to rinse the contents of the beaker into the centrifuge tube.
Centrifuge at 2000 rpm for ~ 2 min. Decant and discard the supernate. Add 10 mL of
H2O, break up the precipitate with a stirring rod, and heat in a hot water bath for
~ 10 min. Cool, transfer the precipitate and wash to solution to a 20 mL scintillation
vial whose cap has been labeled with the sample identification number. Use H20 to
rinse the contents of the centrifuge tube into the scintillation vial. Cap the vial and
centrifuge the scintillation vial for ~ 2 min (see Note 2). Decant and discard the
wash.
17. Dissolve the precipitate in the scintillation vial in 2 mL of 0.5M HCl (the total
volume should not exceed 2 mL of 0.5M HCl) and gently heat on a hot plate to obtain
a clear solution.
18. Add 1 mL of 0.5M HCl to the 59Fe reference tracer from Step 4 to bring the total
volume to 2 mL, then add 6 drops of conc. phosphoric acid.
19. Dispense 15 mL of Ultima Gold liquid scintillation cocktail to each vial, cap, and
vortex for 20 sec. Wipe the external surface of each vial with an alcohol soaked
tissue. Allow the samples to dark adapt in the refrigerated liquid scintillation counter
for 30 min prior to counting.

20. Proceed to Determination.
Notes:
1. If the sample aliquot volume is greater than the capacity of the centrifuge tube, use a
beaker of appropriate capacity to accommodate the sample. Add the carriers and 59Fe
yield tracer, evaporate on a hot plate to approximately 30 mL, transfer to a 40-mL
centrifuge tube, then proceed to Step 5.
2. Centrifuge the sample in the scintillation vial using the specified centrifuge. The vial
may be lifted from the shield with forceps.
DETERMINATION
A. Instrument window settings (see Notes 1 and 2).
1. Prepare unquenched 55Fe and 59Fe standards in the 20 mL scintillation vials.
2. Set the instrument energy regions for 55Fe (Region A), 59Fe (Region B) using the
guidance found in the applicable liquid scintillation counter manual.
3. Optimize the energy regions using the guidance found in the instrument operating
manual. Alternately, use Steps 4 to 6.
4. Perform a spectral analysis using the 55Fe standard and visually adjust the energy
range of Region A (0-7 keV, 55Fe) to maximize the count rate and to minimize the
width of the energy range. (Note: A balance between the count rate and the energy
range should be obtained).
5. Perform a spectral analysis using the 59Fe standard, and visually adjust the energy
range of Region B (8-500 keV, 59Fe) to maximize the width of the energy range
(Note: A balance between the count rate and the energy range should be obtained).
6. Utilizing the full window, set a third region, Region C (0-2000 keV).
55
B. Fe Calibration, Efficiency as a function of Quenching (see Notes 1, 2 and 3).
1. Weigh an aliquot (0.1 g) of an 55Fe standard solution in a 20 mL scintillation vial.

The aliquot of the tracer standard should contain sufficient activity (i.e., 17 Bq) to
give a counting error of < 1% for a 15 min counting period.
2. Pipette various volumes of a quenching agent (i.e., nitromethane) into separately

labeled vials, each containing the tracer standard, to obtain a range of quenching from
high to low efficiency. (Note: The following are examples of quenching agent

volumes: 0.01, 0.02, 0.03, 0.04, 0.06, 0.08 mL.) Record standard information
(including: identification number, aliquot weight, activity concentration, reference
date, etc.).
3. Prepare a vial labeled “zero” that does not contain a quenching agent.
4. Dispense enough scintillation cocktail into each glass vial to make up the final
volumes equal to the sample set to be analyzed (e.g., 17 mL).
5. Cap and vortex the labeled scintillation vials for 10 to 20 sec. Clean the exterior of
the vials by wiping with ethanol and a paper towel, and refrigerate in the dark for at
least 15 min.
6. Load the six aqueous quench standards from Step 2 into the counting rack with the
first sample labeled as “zero.” Select the dual-dpm mode from the main program
menu. Key in: a) the number of standards per set for 55Fe, b) the activity per sample
(dpm), c) the reference date of the standards as MM/DD/YY, d) the half-life of
55
Fe = 2.73 years, 23915 h, and e) low-level count mode (optional).
7. Set the instrument window for 55Fe and 59Fe as established in “instrument window
settings.”
8. Count the quench standards, typically for 15 min (or until 1% counting statistics are
obtained), in each of the three regions selected on the liquid scintillation counter.
9. The net count rate for each quench standard vial is calculated automatically by
subtracting the background (zero) count rate in Region A from the total count rates in
Region A.
10. The efficiency (Eff) (see Note 4) is also determined automatically for each quenched
sample in units of counts min-1/disintegration min-1 by dividing the net activity
measured in count min-1 by the calculated activity added in dpm. Also, the
uncertainty in the efficiency, sigma (Eff), should be estimated for each vial.
11. The efficiency curve is generated by the instrument which plots Ln(Eff) versus the
QIP.
12. A least squares fit on the plot may be performed. The coefficients (a) and (b) or the
equation
Eff = a exp[b * QIP]
(obtained from the intercept [Ln a] and the slope [b]), and the fitting coefficient, R2,
should be recorded.

13. A complete instrument calibration for 55Fe should be performed annually (Note 3).
59
C. Fe Calibration, Efficiency as a function of Quenching (see Notes 1, 2 and 3)
1. Calibrate the instrument for 59Fe in an identical fashion to 55Fe (Steps B1 to B12),
except that a tracer solution of 59Fe is used instead of the 55Fe standard solution, and
count rates are measured in Region B rather than Region A.
2. Establish a curve of the ratio of the count rate of each standard of 59Fe in Region A
(0-7 keV) to the count rate in Region B (8-500 keV) to QIP. This is to adjust the
sample count rate of the 55Fe in Region A because of spectral overlap of the 59Fe into
Region A.
3. Steps 6 to 11 of the 55Fe calibration above should be followed, with the exception that
the half-life of 59Fe is used.
4. A complete instrument calibration for 59Fe should be performed annually (see Note
3).
Notes:
1. Before counting the samples and blanks, the appropriate window settings are
determined for each of the two regions of interest (i.e., 55Fe, 59Fe). Steps A1 to A6 are
performed once, after which the appropriate parameters are manually set in the liquid
scintillation counting instrument.
2. Check the liquid scintillation counter’s stability before running the standards and
samples. Measure the instrument background and the 3H and 14C standards provided
by the instrument manufacturer using the “SN” (system normalization) counting plug.
The instrument software contains an appropriate spreadsheet program that compares
the count rate of these standards with previously determined standard data according
to criteria currently in use at EML.
3. A complete instrument recalibration is required if any major component of the

instrument is replaced.
4. The efficiency curve is a plot of the counting efficiency as a function of the quench
index parameter (QIP). The QIP is determined internally by the instrument, using a
133
Ba source, and is also known as the automatic external standardization (AES)
number or the transformed spectral index of the external standard (t/SIE). A sample
aliquot is prepared with a measured volume of a scintillation cocktail that is then
placed in a programmed liquid scintillation analyzer, which is operated in the dual-
dpm counting mode.

PREPARATION OF SAMPLE LIQUID SCINTILLATION COUNTING VIALS
1. Mark the appropriate glass liquid scintillation vials with the sample identification on
the cap.
2. Dispense an appropriate amount (e.g., 15 mL) of the scintillation cocktail into each
scintillation vial containing the dissolved sample from Step 17 (Separation). A
separate vial containing 2 mL of water serves as “background” (Note: Check the
samples for phase separation. If phase separation is evident, solubilizing or
complexing agents will be required to produce a stable solution.). Clean the exterior
of the vials by wiping with ethanol and a paper towel.
3. Load the samples into the counting rack with the the reagent blank from Step 3
(Separation) as the first sample in position “zero”.
4. Use the Packard Instrument counting protocol plug No. 1 which is delegated for
55
Fe/59Fe counting.
5. Select the “use curve” option from the count mode menu under the dual-dpm mode
when counting samples for 55Fe.
CALCULATIONS
Calculate the 55Fe activity in the sample on the reference date using the following
equation:
55
Fe Activity, Bq L-1 =
[a - (b ∗ c)] ∗ 1000
E ∗ W ∗ D ∗ R ∗ 60
where:
a = net count rate in the 55Fe region of interest, cpm (Region A)
b = net count rate in the 59Fe region of interest, cpm (Region B)
c = spectral overlap factor obtained from 59Fe (Region A)/59Fe (Region B) versus the
quench curve
E = 55Fe counting efficiency obtained from the 55Fe quench curve
W = sample weight, g

D = decay factor, e-0.693t/T, where
t = elapsed time from collection
T = half live of 55Fe, 2.73 years
e = base of natural logarithms
R = 59Fe recovery (dpm 59Fe of sample/dpm 59Fe of the reference tracer)
Alternately, when using the “dual-isotope” counting mode, calculations may be

performed internally by the liquid scintillation software and the results are given in dpm.

Counter Efficiency (% Max) 47
Counter (cps) 0.157 (0 - 7.0 keV)
Background
Yield (59Fe) (%) 85
Blank (cps)
LLD (60 min) (Bq) 0.08

REFERENCES
ASTM Designation: D-4922-89

Standard Test Method for Determination of Radioactive Fe in Water. ASTM Committe
D19, 100 Barr Harbor Drive, West Conshohocken, PA 19428 (1998).
DeFilippis, S.
“55Fe and 59Fe: A Qualitative Comparison of Four Methods to Liquid Scintillation
Activity Analysis”
Radioactivity Radiochemistry, 2, 14-21 (1991).
Greenlaw, P.
“Semi-Annual Report of the Department of Energy, Office of Environmental Restoration
and Waste Management, Quality Assessment Program”


Section 4.5 .4, Vol. I Rev. 0
Tritium

U . S . D e p a r t m e n t of E n e r g y
3
H- 01- RC , Vo l. II Rev. 0
H A S L - 3 0 0 , 2 8 t h E d i ti o n F e b r u a r y 19 9 7
3
H-01-RC
TRITIUM IN WATER - ACID ELECTROL YSIS

(see Volume II)

U . S . D e p a r t m e n t of E n e r g y Page 1 of 1
3
3
H-02-RC
TRITIUM IN WATER - ALKALINE ELECTROLYSIS

(see Volume II)

3
H A S L - 3 0 0 , 2 8 t h E d i ti o n F e b r u a r y 19 9 7
3
H-03-RC
ORGANICALLY LABELED TRITIUM - COMBUSTION PROCEDURE

(see Volume II)

3
H-04- RC, V ol. I Rev. 0
3
H-04-RC
TRITIUM IN WATER - LIQUID SCINTILLATION COUNTING
Contact Person(s): Salvatore C. Scarpitta
APPLICATION
The procedure is used for the rapid determination of tritium by liquid scintillation
(LS) spectrometry. It applies to all clear liquid samples and it can be completed in a short
period (1 to 2 h) once efficiency curves have been established. The procedure is designed
for a Tri-Carb 2250CA LS counter using Insta-Gel XF cocktail and it requires distillation
of the samples so that they are free of salts and other interfering radionuclides.
The 3H spectral range or window setting is first defined. The counting efficiencies are
then determined by using efficiency curves (quench curves). The efficiency curve is a plot
of the counting efficiency as a function of the quench index parameter (QIP). The QIP is
also known as the automatic external standardization (AES) number or the transformed
spectral index of the external standard (tSIE). A sample aliquot is prepared with a
measured volume of a scintillation cocktail that is then placed in a programmed LS
counter for spectrum analysis.
SPECIAL APPARATUS
1. Packard Tri-Carb 2250-CA LS spectrometer
2. Low 40K borosilicate glass scintillation vials
3. Glass distillation apparatus
4. Refrigerator
5. Tritium source - sealed 20-mL scintillat ion vial with cocktail.

3
6. Carbon-14 source - sealed 20-mL scintillat ion vial with cocktail.
7. Background source - sealed 20-mL scintillation vial with cocktail.
8. Glass containers - where 3H is of concern to minimize evaporative loss of water.
SPECIAL REAGENTS
1. Standardized solutions of 3H water
2. Inst a-gel-XF or equivalent scintillation cocktail
3. 30% H2O2
4. Ethanol (95%)
5. Quenching agent - e.g., chloroform, nitromethane, carbon tetrachloride, nitric acid,

etc. (Note: Some of the quenching agents listed are highly toxic and/or are
carcinogens, e.g., carbon tetrachloride, and the safety of handling and disposal is the
responsibility of the user.)
INTERFERENCES
1. Perform a 3H distillation if information more accurate than gross tritium is needed.
2. Reanalyze samples with excessively high count rates (e.g., > 1,000,000 counts min-1)
using less sample material. (Note: When using this procedure, the calculated 3H
concentration may be higher than the actual concentration because of possible
interferences from other low-energy beta emitters and the beta continuum of high-
energy beta particles.)
3. Add several drops of 30% H2O2 to the vial to bleach the sample if quenching causes
the efficiency to drop to one fourth of the highest efficiency. (Note: Deep color in the
samples may cause severe quenching that will lower the counting efficiency.)

3
DETERMINATION
A. Window settings. (see Note 1)
1. Prepare unquenched 3H standards in the same geometry as the analytical samples. Set
the energy regions for 3H (Region A) using the guidance found in the applicable LS
counter manual.
2. Optimize the energy regions using the guidance found in the operat ing manual (the
figure of merit is a common way to optimize the regions of interest). Follow Step 3 as
an alternate.
3. Perform a spectrum analysis using the 3H standard, and visually adjust the energy
range of Region A (0 to 19 keV, 3H) to maximize the count rate and minimize the
energy range. A balance between the count rate and the energy range should be
obtained (see Note 2).
Notes:
1. Determine the 3H window settings before counting the samples and backgrounds.
2. If the sample is not distilled there may be interference from low energy beta particles
with the same energy as 3H, as well as from the beta continuum from high energy beta
particles.
B. Efficiency as a function of quenching. (see Note)
1. Use a small volume (10-50 : L) of 3H tracer solution that has sufficient activity to give
a counting error of < 1%. Prepare approximately 6-8 standards.
2. Record the tracer information (including volume, activity concentration, reference

date, etc.). In order t o obtain a range of quenching from high to low efficiency,
pipette various volumes of the quenching agent (i.e., nitromethane) into vials,
separately labeled. The following quenching agent volumes are presented as an
example: 0, 0.01, 0.02, 0.03, 0.05, and 0.08 mL. (Note: Do not use deionized water
to dilute the aqueous standard to a volume consistent with the sample set preparation.)

3
3. Dispense enough scintillation cocktail into each glass vial to make up the final
volumes consistent with the sample set to be analyzed (e.g., 15 mL).
4. Cap and shake vigorously the scintillation vials for 10 to 20 sec. Wipe the vials clean
with 95% ethanol and a paper towel. Refrigerate the vials for at least 10 min.
5. Check the stability and operational order of the LS counter before running the
standards and the samples. This can be done by: counting the background, the 3H
standard, and the 14C standard provided by the instrument manufacturer; using an
appropriate spreadsheet program; and then comparing the count rate of these
standards with previously determined standard data according t o criteria currently in
use.
6. Count a background sample (prepared similarly to the standards) and the 3H standards
for 30 min (or unt il 1% counting statistics are obtained) in the regions selected on the
LS counter. Record the corresponding energy regions given by the instrument.
7. Calculate the net count rate for each vial by subtracting the prepared background
count rates in Region A from the measured gross count rates in Region A.
8. Determine t he beta efficiency (Eff$) for each vial in units of count per min/
disintegrations per min by dividing the net activity measured in counts min-1 by the
calculated activity added in dpm. Also, estimate the uncertainty in the $ -efficiency,
, -(Eff) for each vial.
9. Generate the $ -efficiency curve by plotting Ln(Eff$) versus the QIP. (Note: Many LS
counting systems are equipped with programs to generate efficiency curves. To use
these applications, the operating manual should be referenced.)
10. Perform a least squares fit on the plot. Record the coefficients (a) and (b)
for the equation Eff = a exp(b* QIP) and the fitting coefficient, R. Obtain
the QIP from the intercept [Ln a] and the slope [b].
Note: Establish efficiency curves (efficiency vs. QIP) by using artificially quenched
standards. Check the efficiency curves annually and regenerate them if any major
component of the instrumentation is replaced.

3
SAMPLE PREPARATION
1. Mark the sample identification on the appropriate scintillation vials with ink that is not
removable using ethanol.
2. Pipette a known amount (e.g., 2.0 - 5.0 mL) of each sample into the appropriate
scintillation vials.
3. Dispense an appropriate amount (e.g., 15 mL) of scintillation cocktail into each

scintillation vial.
4. Secure the cap onto each of the scintillation vials, then shake the vials vigorously for
10 to 20 sec. Wipe each vial on the outside with a paper towel wet with ethanol to
remove any fingerprints.
5. Refrigerate the samples for at least 10 min before counting. (Note: The samples may
also need to be “dark adapted” to minimize the potential for delayed scintillations.
This can be accomplished by postponing the start of counting for 10-15 min.)
6. Prepare a background sample in the same manner as the samples. A prepared

background sample is one that is developed using stable compounds (e.g., dead
water), and has a matrix as similar as possible to that of the samples being analyzed.
7. Count the sample for an appropriate time (e.g., 10 min) in the energy regions specified
in Determination, Step 7. Record the QIPs given by the instrument. Return the
samples to a well-ventilated area and store until disposal when the sample counts are
completed.
CALCULATIONS
Perform the calculations internally with the LS software when using the DPM mode,
or refer to EPA-600 4-80-032, Method 906.0 (Krieger and Whittaker, 1980).

3
REFERENCE
Krieger, H. L. and E. L. Whittaker

“Prescribed Procedures for Measurements of Radioactivity in Drinking Water”
U. S. Environmental Protection Agency EPA-600 4-80-032, Method 906.0, August
(1980)

Lead

Pb-01 -RC , Vol. I Rev. 0
Pb-01-RC
LEAD-210 IN BONE, FOOD, URINE,

FECES, BLOOD, AIR, AND WATER
APPLICATION
This procedure is applicable to samples of bone, food, urine, feces, blood, air, and
water and is based on the solvent extraction of a lead bromide complex into Aliquat-336
(Petrow and Cover, 1965; Morse and Welford, 1971).
Lead-210 is isolated from most interferences. Its progeny 210Bi is separated from
210
Pb, and the $ activity is measured radiometrically after ingrowth.
SPECIAL APPARATUS
1. Atomic absorption (AA) spectrometer.
2. Aluminum foil - 7.2 mg cm-2.
3. Rings and discs - see Specification 7.2.
4. Mylar film - see Specification 7.3.
5. Teflon filter holder.
6. Combination magnetic stirrer and hot plate.
7. Plastic scintillation phosphors - see Specification 7.9.

SPECIAL REAGENTS
1. Aliquat-336, methyltricapryl-ammonium chloride (Henkel Corporation, 2430 N.

Huachuca Dr., Tucson, AZ 85745-1273), 3:7 in toluene and washed twice with an
equal volume of 1.5M hydrobromic acid.
2. Hydrobromic acid 48%.
3. Hydrobromic acid 3.0M - 340 mL of 48% HBr L-1 of water.
6. Toluene.
7. Standard Pb solution - 1000 : g mL-1.
8. Lead carrier: 20 mg Pb mL -1 - 32 g Pb(NO3)2 L-1 in 1:19 HNO3.
9. Bismut h carrier: 10 mg Bi mL -1 - 23.2 g Bi(NO3)3@5 H2O L-1 in 1:19 HNO3.
SAMPLE PREPARATION
A. Water.
1. To daily collections of 20 L of tap water add 100 mL of HNO3 and evaporate to about
100 mL (see Note 1).
2. Add 100 mL of HNO3 and transfer to a 400-mL beaker. Complete the destruction of
organic material and evaporate to near dryness.
3. Add 50 mL of 10% HNO3 to the beaker and warm to affect dissolution of any residue.

4. Coo l the solution to room temperature and t ransfer the sample solution to a 100-mL
volumetric flask. Bring the solution to volume with 10% HNO3.
5. Pipette 1 mL of sample solution into a 10-mL volumetric flask. Bring the solution to
volume with 10% HNO3. Reserve this solution to determine the stable Pb content of
the sample by AA spectrometry (see Note 2).
6. Return the sample solution in the 100-mL volumetric flask (Step 4) to the 400-mL
beaker. Add 1 mL of Pb carrier and evaporate the solution to dryness.
7. Add 100 mL of 3M HBr to the sample beaker and warm the solution. Cool the
solution to room temperature and proceed with the Determination.
B. Urine, blood, feces and air filters.
1. Measure 2-L of urine and transfer to a 3-L beaker. Place a measured volume of blood
or 24 h fecal sample in a 1-L beaker. Place the air filter in a 600-mL beaker (see
Note 1).
2. Destroy most of the organic material by carefully heating with HNO3. Hydrogen
peroxide can be used to complete the oxidation of organic material (see Note 3).
3. Add 50-mL of 10% HNO3 to the beaker and warm to affect dissolution of any residue.
4. Cool the solution to room temperature and t ransfer the sample solution to a 100-mL
6. Transfer the sample solution in t he 100-mL volumetric flask (Step 4) to the 400-mL
7. Add 100 mL of 3M HBr to the sample beaker and warm the solution. Cool the
solution to room temperature and proceed with the Determination.

C. Bone (see Note 4)
1. Weigh 20 g of bone ash and transfer to a 400-mL beaker.
2. Dissolve the ash in about 80 mL of 3M HBr and warm to complete the dissolut ion.
volumetric flask. Bring the solution to volume with 3M HBr.
5. Transfer the sample solution in t he 100-mL volumetric flask (Step 3) to the 400-mL
beaker and add 1 mL of Pb carrier.
6. Proceed with the Determination.
D. Food.
1. Depending upon food type, freeze drying should be used to remove excess water prior
to wet ashing the sample (see Note 1).
2. Destroy most of the organic material by carefully heating with HNO3. Hydrogen
peroxide can be used to complete the oxidation of organic material (see Note 3).
3. Add 50 mL of 10% HNO3 to the beaker and warm to affect dissolution of any residue.

6. Transfer the sample solution in the 100-mL volumetric flask (Step 3) to the 400-mL
7. Add 100-mL of 3M HBr to the same beaker and warm the solution. Cool the solution
to room temperature and proceed with the Determination.
Notes:
1. It is necessary to analyze reagent blanks with each batch of samples t o correct the
210
Pb results.
2. The stable Pb content of some samples may be high enough to contribute a significant
fraction to the total stable Pb measured by AA. This would result in an inflated
estimate of the Pb carrier yield.
3. Hydrogen peroxide contains measurable and variable amounts of st able Pb and should
be used sparingly.
4. It has been shown at this Laboratory that no 210Pb loss occurs from bone dry ashed
below 700oC (Fisenne, 1994). The absence of 210Pb loss was determined for three
bone types — ribs, vertebrae, and femur. It is the practice at EML to dry ash bones
for 210Pb analyses at 550oC.
DETERMINATION
1. Transfer the 3M HBr solution to a 250-mL separatory funnel containing 75 mL of

Aliquat-336.
2. Shake for 30 sec. Let the phases separate and discard the aqueous (lower) phase.
3. Wash the organic phase three times with 50-mL portions of 0.1M HBr and discard all
washes (lower phases).
4. Wash the organic phase twice with an equal volume of water. Transfer the washed
organic phase to a suitable disposal container.

5. Combine the strip solutions in a 400-mL beaker and add 100 mL of HNO3.
6. Wait for any reaction to subside and heat gently until the organic residue is destroyed.
Evaporate the solution to ~ 10 mL.
A. First milking.
1. Transfer the sample to a 40-mL centrifuge tube with water. Add 1 mL of Bi carrier.
2. Adjust the pH of the sample to 8 with NH4OH.
3. Stir the sample and heat in a hot water bath.
4. Cool and centrifuge the tube for 10 min. Decant and discard the supernate.
5. Disso lve the precipitate with five drops of HCl.
6. Add 40 mL of water and heat with constant stirring.
7. Cool and centrifuge for 10 min. Decant and reserve the supernate in a 250-mL beaker.
8. Repeat Steps 5-7 twice more, combining the supernates. Discard the precipitate.
Record the time and date for ingrowth of 210Bi.
9. Add 1 mL of Bi carrier and 3-5 mL of HCl to the combined supernates. Reduce the
volume to <100 mL.
10. Cool, transfer to a 100-mL volumetric flask and bring to volume with 0.5N HCl.
11. Pipette 1 mL of sample into a 10-mL volumetric flask. Bring to volume with 0.5N
HCl.
12. Measure the quantity of Pb in both the sample and the separated Pb fraction in the 10-
mL volumetric flasks on an AA spectrometer at 283 : m. (The calibration curve
should have a working range of 0-50 :g mL-1.)
13. Subtract the Pb content of the dissolved sample and the reagent blank from the total
Pb content determined in Step 12 to obtain the Pb carrier yield.
14. Allow 2-3 weeks for ingrowth of 210Bi into the main portion of the sample (Step 10).
B. Second milking.
1. Transfer the solution from the 100-mL volumetric flask to a 250-mL beaker and
evaporate to about 15 mL.
2. Transfer the sample to a 40-mL centrifuge tube and adjust the pH to 8 with NH4OH.
Centrifuge the tube for 10 min. Decant and discard the supernate.
3. Disso lve the precipitate with five drops of HCl and bring volume of sample to 30 mL
with H 2O. (Record the time and date for decay of 210Bi.)
4. Heat with constant stirring in a hot water bath. Cool and centrifuge the tube for
10 min. Reserve the supernate for additional 210Pb analysis in a 150-mL beaker.
5. Dissolve the precipitate with five drops of HCl and dilute to 30 mL with water.
6. Heat in a hot water bath with constant stirring. Cool and centrifuge the tube for
10 min. Combine the supernate with that from Step 4.
7. Dissolve the precipitate with five drops of HCl. Stir and dilute to 30 mL with water.
8. Heat the tube in a hot water bath with constant stirring. Cool, filter with suction on a
preweighed 2.4 cm Whatman No. 42 filter paper using a Teflon filter holder.
9. Wash the t ube and the precipitate with water and alcohol. Dry the paper and
precipitate for 30 min at 110oC in a drying oven.
10. Cool and reweigh the filter to determine weight of BiOCl precipitate.
11. Mount the filtered sample on a nylon ring and disc, covering the sample with
aluminum foil (7.2 mg cm-2), a plastic scintillation phosphor and Mylar film.
12. Measure the 210Bi on a low-level $ -scintillation counter. (Record the time and date for
decay of 210Bi.)

210
13. Standardize the counter with a known amount of 210Pb from which Bi has been
separated and prepared in the same way as the sample.
The 210Pb activity of the sample is calculated using the following formula:
Bq of 210Pb =
where
Rs = net counting rate of the sample,

Y1 = yield factor for Pb carrier,
Y2 = yield factor for Bi carrier,
E = counter efficiency factor,
G = growth factor (growth of 210Bi from first milking to final milking), and
D = decay factor (decay of 210Bi from final milking to time of counting).

A B
Counter efficiency (%) 35 -

Counter background (cps) 0.005 -
Yield (%) 80 80
LLD (400 min) (Bq) 0.01 0.007

LLD (1000 min) (Bq) 0.005 0.005
A = 210Pb separation, 210Bi ingrowth, 210Bi separation.

B = 210Bi separation o nly.
REFERENCES
Fisenne, I. M.
"Lead-210 in Animal and Human Bone: A New Analytical Method"
Env. Int., 20, 627-632 (1994)
Hursh, J. B. (Editor)
USAEC Report AECU-4024, November (1958)
Morse, R. S. and G. A. Welford

"Dietary Intake of 210Pb"
Health Phys., 21, 53-55 (1971)
Petrow, H. G. and A. Cover

"Direct Radiochemical Determination of Lead-210 in Bone"
Anal. Chem., 37, 1559-1660 (1965)

Pb-02-RC
DETERMINAT ION OF 210Pb in BONE ASH BY

MEASUREMENT OF 210Po
APPLICATION
The procedure has been tested for sample weights of up to 15 g of bone ash.
Lead-210 may be determined in bone samples which have been dry ashed at
temperatures up to 700 oC. The dry ashed bone samples should be stored for at least
2 y to allow build-up of 210Po (Fisenne, 1994).
Lead, bismuth, polonium and calcium are separat ed from phosphate and radium as the
oxalates. Lead, bismuth and polonium are separated from calcium as the sulfides.
Polonium and bismuth are spontaneously deposited on a nickel disc from a weakly acid
solution. The 210Po is measured by alpha spectrometry and the chemical yield is
determined with the alpha emitting tracer 209Po.
Radium-226 is separated from the reserved oxalate supernat e as the sulfate. The
Ra.BaSO4 is dissolved in alkaline EDTA and the chemical yield is determined with the
gamma-emitting tracer 133Ba. The 226Ra is determined by the radon emanation method
(see Procedure Ra-03-RC).
The total and unsupported 210Pb activities are calculated from the 210Po and 226Ra
measurements by application of the Bateman equations for the decay of this subseries of
the Uranium Series (see Procedure 5.6).

SPECIAL APPARATUS
1. Nickel discs - 1.74 cm diameter by 0.06 cm thick, "commercial" pure nickel. Prior to
use, degrease the disc. [Note: Silver or platinum discs may be used but must be
cleaned and recycled. The nickel discs are discarded after measurement of the
sample.]
2. Deposition cells - see Specification 7.16.
3. Mechanical stirrers.
4. Teflon stirring rods.
5. Alpha spectrometry system.
6. Radon bubblers - see Specification 7.7.
7. Polyethylene transfer pipettes - see Specification 7.11.
SPECIAL REAGENTS
1. Polonium-209 tracer solution - 1 Bq g-1 of 1N HNO3 solution.
2. Lead carrier: 20 mg Pb mL -1 - 32 g Pb(NO3)2 L-1 of 1N HNO3.
3. Calcium carrier - solid calcium propionate. [Note: Calcium carrier is added only to
the reagent blank. The 210Po and 226Ra blank value must be established for each lot of
calcium propionate salt prior to its use.]
4. Thioacetamide solution - 100 g CH3CSNH2 L-1 of water.
5. Barium-133 tracer solution - 1x104 Bq g-1 of 1N HCl.
6. Barium carrier: 20 mg mL-1 - 30.4 g BaCl2 L-1 of 1N HCl.
7. Ammonium acetate solution - 15 g NH4OAc L-1 of water.

8. Acetic acid solution - 20 mL glacial HOAc L-1 of water.
9. Ammonium sulfate solution - 100 g (NH4)2SO4 L-1 of water.
10. Aerosol OT solution - 0.1%.
11. EDTA solution - 300 g tetrasodium salt L-1 of water. Filter the solution through a
glass fiber filter prior to use.
12. Monoethanolamine - 1:1 solution with water.
SAMPLE PREPARATION
1. Weigh 5 g of bone ash and transfer to a graduated 1500-mL beaker.
2. Add a weighed aliquot of 209Po (about 0.05 g) and 133Ba (about 0.1 g) tracer solutions
and 1 mL of Pb carrier solution to the beaker. [Note: Add 2.5 g of calcium
propionate to the reagent blank beaker. DO NOT ADD CALCIUM PROPIONATE
TO THE BONE ASH SAMPLES.]
LEAD SEPARATION
1. Add 25 mL of HNO3 and 1 mL of HClO4 to the samples and reagent blank beakers.
[Note: HClO4 is not required for samples dry ashed at $ 500oC.]
2. Place the covered beakers on a medium hotplate. Swirl the beakers to dissolve the
bone ash.
3. Evaporate the solution to dense HClO 4 fumes. Do not allow the sample to reach
dryness.
4. Convert the sample to chloride form with five successive additions of 25 mL of HCl.
Evaporate the solution to near dryness between additions.

5. Add 25 mL of HCl and swirl the beaker to dissolve most of the solids. Remove the
beaker from the hotplate.
6. Dilute the solution to 1 L with water. Stir the solution with a stirring rod to dissolve
any remaining solids.
7. Return the beaker to t he hotplate and heat the solution for 10 min.
8. Using NH4OH in a wash bottle, and stirring constantly, adjust the pH to about
1.5 to 2. At this point no permanent hydroxide flock should be present. Any
hydroxide flock is dissolved with the addition of 6N HCL. [Note: The pH of the
reagent blank is determined with pH paper.]
9. Weigh 5 g of solid oxalic acid and add to t he sample with stirring. Continue heating
the solution for 10 min.
10. Adjust the pH to 2.0 using NH4OH and pH paper for bo th the sample and t he reagent
blank. Stir continuously.
11. Remove the sample from the hotplate. Remove and rinse the stirring rod with water.
Allow the oxalate precipitate to settle overnight.
12. Decant the supernate into a 3-L beaker and reserve for Radium Separation.
13. Destroy the oxalates by evaporating with two successive 25-mL portions of HNO3.
Do not allow the sample to reach dryness.
14. Convert the sample to the chloride form with five successive 25-mL portions of HCl.
15. Add 25 mL of HCl and swirl the beaker to dissolve most of the solids. Add a
minimum amount of water to reach complete solution.
16. Remove the beaker from the hotplate and cool.

17. Transfer the solution with water to a 250-mL centrifuge bottle. Wash the beaker with
water and transfer the washings to the centrifuge bott le. Stir the solution. The
solution volume should be about 200 mL.
18. Place the centrifuge bottle in a 90oC hot water bath. Heat for 10 min.

19. Add 5 mL of thioacetamide solution to the sample. Stir and heat in the water bath for
1 or 2 min.
20. Remove the sample from the water bath. While stirring continuously, add NH4OH to
the sample until the black precipitate just persists.
21. Return the sample to the water bath for 1 h.
22. Remove the sample from the water bath. Remove the stirring rod and rinse with
water.
23. Dry the outside of the centrifuge bottle. Place the bottle in a centrifuge cup. Tare a
pair of samples on a double pan balance.
24. Place the tared samples in the centrifuge. Centrifuge the samples at 1800 rpm for
1 h.
25. Remove the samples from the centrifuge. Add 1 drop of Aerosol OT and decant the
sample. Discard the supernate.
26. Add 2 mL of HCl to t he sample and stir to break up the PbS precipitate. Place the
sample in the water bath. Heat for 5 min.
27. Wash the walls of the bottle with 10 mL of water and heat for an additional 10 min.
28. Gravity filter the sample through a 12.5-cm diameter Whatman No. 42 paper into a
prepared deposition cell.
29. Wash the centrifuge bottle with water and add the washing to the filter. Wash the
filter with water. Discard the filter.
30. Place a cylindrical metal weight over the deposition cell. [Note: A 4-cm diameter by
4-cm height length of galvanized pipe will do.]
31. Place the weighted cell in an 80oC water bath. Lower the stirring motor with the
Teflon rod in its chuck so that the rod is within 1 cm of the nickel disc.

32. Turn on the motor and stir for 4 h at maximum agitation without splashing. Add small
quantities of 0.5N HCl to the cell, and water to the water bath to replace evaporative
losses.
33. Turn off the motor and raise it to clear the stirring rod from the top of the cell.
Remove the cell from the water bath.
34. Pour off the solution and discard. Rinse the cell successively with 0.5N HCl and
water. Discard the rinsing.
35. Dismantle the cell and discard the bottle. Remove the nickel sample disc from the cap
and rinse with ethanol.
36. Place the disc on a warm hot plate to dry.
37. Measure the disc in an alpha spectrometry system to determine the 209Po yield and t he
210
Po content of the sample. [Note: Record the deposition date so that decay
corrections for the unsupported 210Po can be made from separation date to
measurement date.]
RADIUM SEPARATION
1. Evaporate the radium-bearing oxalate solution to dryness on a medium hotplate.
2. Remove the beaker from the hotplate and cool slightly. Add t wo successive 25-mL
portions of HNO3. Heat to destroy the oxalate.
3. Convert the sample to the chloride form with five successive 25-mL portions of HCl.
4. Add 25 mL of HCl to the beaker and warm to dissolve most of the solids. Add about
50 mL of water and stir to dissolve the remaining solids.
5. Transfer the warm solution to a 250-mL centrifuge bottle. Wash the beaker with
water, police and transfer the washing to the centrifuge bottle.

6. Dilute 1 mL of barium carrier to about 5 mL with wat er. Stir the sample thoroughly
and continuously while adding the diluted carrier solution dropwise.
7. Place the centrifuge bottle in a hot water bath and warm the solution for about 5 min.
8. With constant stirring, slowly add NH4OH until a dense white permanent hydroxide
flock forms.
9. Dissolve the flock in a minimum of HCl. [Note: For the blank, adjust the pH from 1.5
to 2.0 using pH paper.
10. Add 2 mL of NH4OAc solution and 1 mL of dilute HOAc solution to the centrifuge
bott le. Stir thoroughly and cool the bot tle to room temperature in a water bath.
11. Add 1 mL of (NH4)2SO4 solution to the bottle. Stir, remove the rod and rinse with
water. Let the bottle stand at room temperature for 1 h.
12. Dry the outside of the centrifuge bottle. Place the bottle in a centrifuge cup. Tare a
pair of samples on a double pan balance.
13. Place the tared samples in the centrifuge. Centrifuge the samples at 1800 rpm for 1 h.
14. Remove the samples from the centrifuge. Add one drop of Aerosol OT to the bottle.
Carefully decant and discard the supernate.
15. Heat 5 mL of EDTA solution (300 g L-1) for each sample in a hot water bath.
16. Break up the BaSO4 precipitate with the stirring rod. Add 5 mL of warm EDTA
solution and 1 mL of 1:1 monoethanolamine. Stir and heat for about 5 min.
17. Wash down the sides of the centrifuge bottle with about 10 mL of water. Continue
heating the bottle for 15 min, stirring occasionally.
18. Gravity filter the solution through a 12.5-cm diameter Whatman No. 42 filter paper
into a 30-mL polyethylene bottle.
19. Wash the centrifuge bottle and the filter paper with water. Discard the filter paper.

20. Dilute the sample to the same liquid level as the 133Ba standard. The standard is
prepared by diluting a known aliquot (about 0.1 g) of 133Ba solut ion to 25 mL in a
30 mL polyethylene bottle.
21. Gamma count the standard and samples to determine the chemical yield o f barium.
22. Transfer the solution to a radon bubbler.
23. Proceed with emanation procedure for 226Ra (Ra-03-RC) to determine the radium
content of the sample.
210 226
Po Ra
Counter efficiency (%) 30. 56.

Counter background (cps) 4x10 ±0.7x10 2.8x10-3±0.2x10-3
-5 -5
Yield (%) 85. 85.

Blank (cps) 3.5x10 ±0.6x10 2.0x10-2±0.8x10-2
-4 -4
LLD (1000 min) (mBq) 1.3 1.5

LLD (2500 min) (mBq) 1.0 N/A
*Reagent blanks must be processed with every batch of samples.
REFERENCE
Fisenne, I. M.
"Lead-210 in Animal and Human Bone: A New Analytical Method"
Env. Int. , 20, 627-632 (1994)

Polonium

Po-01-R C, Vol. I Rev. 0
Po-01-RC
POLONIUM IN WATER AND URINE
APPLICATION
This procedure is applicable to water and urine (Hursh, 1958). Organic materials
which can be converted to Cl- solutions should also lend themselves to analysis by the
procedure given. Reagent blanks must be analyzed along with the samples. [Note: It
has been shown (Fellman et al., 1989) that urine samples must be wet ashed to release
polonium from metabolically labeled organic compounds. The procedure has been
modified to incorporate the destruction of organic matter.]
Polonium is quantitatively deposited on a nickel disc from a strong HCl solution. This
is a very specific separation and therefore can be carried out while many other
radionuclides are present in the sample.
The plated disc is " counted on a scintillation counter. It is also possible to use a 208Po
or 209Po tracer and count on an " spectrometer to measure chemical yield and the activity
of the sample.
SPECIAL APPARATUS
1. Nickel discs - made of 0.064-cm thick "commercial pure" nickel sheets. Discs are
2.2 cm in diameter with a 0.16-cm hole set 0.16 cm in from the edge. [Note: Coating
the disc on one side with an acid resistant paint allows counting time to be cut in half.]

SAMPLE PREPARATION
A. Water.
1. To 1000 mL of tap water in a 1500-mL beaker, add 50 mL of HCl.
2. Evaporate to a volume of 20 mL and transfer to a 250-mL beaker. Add 100 mL of

water and 100 mg of ascorbic acid.
3. Proceed to Determination.
B. Urine.
1. If the time between sample collect ion and analysis is much greater than 1 h, the urine
samples should be preserved by adding 1 mg o f sulfamic acid per mL of urine and
storing in a refrigerator at 3oC.
2. Measure 100 mL of urine in a graduated cylinder and transfer to a 250-mL beaker.

Rinse the graduated cylinder with 20 mL of 1:1 HNO3 and add to the urine.
3. Evaporate the solution to near dryness and add 5 mL portions of HNO3 to destroy
organic matter.
4. Convert the sample to the Cl- form by evaporating to near dryness with three
successive 5-mL portions of HCl.
5. Add 20 mL of 1:1 HCl and 100 mg of ascorbic acid to the beaker.
DETERMINATION
1. Place the beaker in a constant temperature bath at 55oC.
2. Degrease a nickel disc by dipping in HNO3, followed by dipping in HCl and rinsing in
water. Repeat until the surfaces of the disc are bright and shiny.

3. Suspend the disc on a glass stirring hook in the solution and stir for 2.5 h at a speed
giving maximum agitation without splashing.
4. Remove the disc, rinse the stirring rod and disc with water and let dry in air.
5. Alpha count each side of the disc. Subtract backgro und from each count and sum the
two net cps.
6. Standardize the counter with a known quantity of any " emitter on a metal disc.
Natural U plated on a similar disc is a convenient standard.
A B C
Counter Efficiency (%) 50 50 25

Counter Background (cps) 1.675x10-5 1.67x10-5 8.33x10-5
Yield (%) 70 70 70
Blank (cps) - - -
LLD (400 min) (mBq) 0.5 0.33 1.5

LLD (1000 min) (mBq) 0.33 0.17 1.0
LLD (5000 min) (mBq) 0.17 0.10 0.5
A = alpha scintillation counter (bot h sides)

B = alpha scintillation counter (one side)
C = solid-state alpha spectrometer (one side)

REFERENCES
Fellman, A., L. Ralston, D. Hickman, L. Ayres, N. Cohen, H. Spitz and B. Robinson

"The Importance Acid Digestion of Urine Prior to Spontaneous Deposition of 210Po"
Health Physics, 57, 615-621 (1989)
Hursh, J. B. (Editor)
USAEC Report AECU-4024, November (1958)

Po-02-RC
POLONIUM IN WATER, VEGETATION,

SOIL, AND AIR FILTERS
APPLICATION
This procedure has been tested for water, vegetation, soil, and Dynaweb filters.
Reagent blanks must be analyzed along with the samples.
Polonium is equilibrated with 208Po or 209Po tracer and isolated from most other
elements by coprecipitation with lead sulfide. The sulfide precipitate is dissolved in weak
HCl solution. Polonium is quant itatively deposited on a nickel disc. The deposition is
very specific and can be carried out in the presence of other radionuclides.
The plated disc is counted on an " spectrometer to measure chemical yield and activity
of the sample. The solution from the deposition may be retained and analyzed for 210Pb.
SPECIAL APPARATUS
1. Nickel discs - 1.75 cm diameter x 0.06 cm thick "commercial pure" nickel. Degrease
in acetone, dip in HCl and rinse with water.
2. Electrolytic cell - see Specification 7.16.
3. Teflon stirring rods.

SPECIAL REAGENTS
1. Standardized 208Po or 209Po tracer solution - about 2 Bq g-1 in a dispensing bottle.
2. Lead carrier solution: 10 mg Pb mL-1 - 15.98 g Pb(NO3)2 L-1 of 1:99 HNO3.
3. Thioacetamide solution - 100 g CH3CSNH2 L-1 of water.
4. Saturated ascorbic acid solution.
SAMPLE PREPARATION
A. Tap water.
1. Transfer 2.5 L of tap water to a 3-L beaker.
2. Add 50 mL of HNO3 and 1 mL of Pb carrier solution. Add a weighed aliquot

(30-80 mBq) of the 208Po or 209Po tracer solution.
3. Evaporate and add additional aliquots of tap water until a 10-L collection has been
obtained. Evapo rate gently to about 25 mL.
4. Transfer the solution to a 90-mL centrifuge tube with H 2O. Continue with
Determination.
B. Vegetation.
1. Weigh 100 g of dried (105-110oC) material into a 400-mL beaker.
2. Add 1 mL of Pb carrier solution and a weighed aliquot (30-80 mBq) o f 208Po or 209Po
tracer solution.
3. Add 100 mL of HNO3 with magnetic stirring using a Teflon-coated bar. Digest with
gentle heat and stirring for 1 h.
4. Reduce the volume of the solution to about 25 mL and transfer the solution to a
90-mL centrifuge tube with water. Continue with Determination.

C. Soil.
1. Weigh 1 to 5 g of soil into a 40-mL platinum dish. Add 1 mL of Pb carrier and a

weighed aliquot (30-80 mBq) o f 208Po or 209Po tracer solution.
2. Add 10 mL of HNO3 and 10 mL of 48% HF. Heat on a medium hot plate. Repeat the
additions of HNO3 and HF until no further dissolution takes place.
3. Add 10 mL of HNO3 and reduce the volume to about 5 mL.
4. If insoluble material remains, filter the slurry by gravity through a Whatman No. 42
filter paper into a 90-mL centrifuge tube. Wash the filter with hot water. Discard the
residue. Cont inue with Determination.
C. Dynaweb filter.
1. To a 8.9 cm diameter or 1/4 of an 20.3 cm diameter Dynaweb filter in a 600-mL

beaker, add 1 mL of lead carrier and a weighed aliquot (30-80 mBq) o f 208Po or 209Po
tracer solution.
2. Add 300 mL of HNO3 and digest on a medium hot plate.
3. Evaporate to about 25 mL. If the solution is not clear, repeat the evaporation with
additional HNO3.
4. Add about 200 mL of water to polymerize the Dynaweb material.
5. Filter with suction through a Millipore filter and wash with water. Discard the filter
and polymerized Dynaweb material.
6. Transfer the filtrate back into the original beaker.
7. Reduce the volume to 25 mL. Repeat Steps 4-6 until the Dynaweb material is
completely removed.
8. Transfer the solution to a 90-mL centrifuge tube. Continue with Determination.

DETERMINATION
1. Reduce the volume to about 5 mL in a steam bath. Add 50 mL of water.
2. Adjust the pH to 3.5-4 with NH4OH. Add 5 mL of thioacetamide solution. Digest in

a steam bath for 1 h.
3. Cool, centrifuge, and decant the supernate. Discard the supernate.
4. Dissolve the precipitate in 2 mL of HCl. Add 50 mL of water.
5. Adjust the pH to 3.5-4 with NH4OH. Add 2 mL of thioacetamide solution. Digest in

a steam bath for 1 h.
6. Cool, centrifuge, and decant the supernate. Discard the supernate.
7. Dissolve the precipitate in 1 mL of HCl. Dilute the solution to 25 mL with water.
8. Filter the solution by gravity through a Whatman No. 41 filter paper into a prepared
deposition cell. Wash the filter with hot 0.5N HCl. Discard the filter.
9. Add 1 mL of saturated ascorbic acid solution to the cell.
10. Place the cell in an 80oC water bath.
11. Stir with a Teflon stirrer for 4 h at a speed giving maximum agitation without
splashing. Occasional small additions of 0.5N HCl are necessary to make up for
evaporation of the solution.
12. Remove the cell from the water bath and pour off the solution into a beaker. Reserve
for 210Pb determination if required.
13. Dismantle the cell, rinse the disc with water, then ethanol. Air dry the disc.
14. Place the disc on a warm hot plate to dry.
15. Count the disc on an " spectrometer to resolve the 208Po or 209Po tracer and 210Po.

A B C D
Counter Efficiency (%) 40 40 40 40

Counter Background (cps) 8.33x10-5 8.33x10-5 8.33x10-5 8.33x10-5
Yield (%) 80 75 60 60
Blank (cps) 0.01 0.01 0.01 0.01
LLD ( 400 min) (mBq) 1.5 2.0 2.0 2.0

LLD (1000 min) (mBq) 1.0 1.3 1.3 1.3
LLD (5000 min) (mBq) 0.4 0.6 0.6 0.6
Solid-state alpha spectrometer:

A = H2O
B = Vegetation
C = Soil
D = Dynaweb filter

Plutonium

Pu-01-RC, Vol. I Rev. 0
Pu-01-RC
PLUTONIUM IN AIR FILTERS
APPLICATION
This procedure is applicable to all types of air filters. However, if the filter is made
of an organic polymer, it is advisable to first decompose the filter in a muffle furnace at
450oC overnight. Samples are then digested in concentrated HNO3, after which the
remaining residue and filter material are treated with HF.
SPECIAL APPARATUS
1. Muffle furnace.
2. Pyrex long stem fluted funnel with an inside diameter of 9.5 cm.
SPECIAL REAGENT
1. Plutonium-236 tracer - a standard solution containing ~0.15 Bq g-1 in a dispensing

bottle.
SAMPLE PREPARATION
1. Place the air filter in a 400-mL (or appropriate size) beaker.
2. Add a known amount (~ 0.05 Bq) of 236Pu tracer.

3. Add 150 mL of concentrated HNO3 and 50 mL of concentrated HCl (or appropriate

amounts based on air filter size), allow sample to react for about 1 h. Place the
sample on a hot plate and cover with a watch glass. Heat the sample overnight on a
low setting. Continue heating until the volume is ~100 mL.
4. Remove the sample from the hot plate, add 100 mL of water and let the sample cool
to room temperature. Filter by gravity using a conical funnel with an 18.5 cm
Whatman No. 42 filter paper. Wash with 50-75 mL of 1:1 HNO3. Collect the filtrate
in a 250-mL beaker, evaporate the filtrate to near dryness, add ~35 mL 1:1 HNO3,
and save. Cover the beaker with parafilm to prevent changes in the concentration of
1:1 HNO3.
5. Transfer the filter and residue to the original beaker and wet ash with 150-200 mL
concentrated HNO3. Allow refluxing to occur on low heat. Do not boil. Evaporate
to ~25-30 mL.
6. Transfer the filtered residue to a platinum dish or Teflon beaker. Add 10 mL of HF,
5 mL of HNO3, and evaporate to near dryness. Add 10 mL of HNO3 and 10 mL of
HF, then evaporate to near dryness again. Repeat the addition of HNO3 and HF two
more times. Wash the sides of the vessel three times with 1:1 HNO3, and evaporate
to dryness after each addition.
7. Add 20 mL of 1:1 HNO3 to sample.
8. Filter the sample into the beaker containing the filtrate from Step 4 by gravity
filtration using a conical funnel with a 18.5 cm Whatman No. 40 or No. 42 filter
paper. Wash with 1:1 HNO3 (~ 20 mL).
9. Adjust sample volume to 100 mL with 1:1 HNO3.
10. Proceed to Plutonium Purification - Ion Exchange Technique, Procedure

Pu-11-RC.

Pu-02-RC, Vol. II Rev. 0
Pu-02-RC
PLUTONIUM IN SOIL SAMPLES

(see Volume II)

Pu-03-RC
PLUTONIUM IN SOIL RESIDUE -

TOTAL DISSOLUTION METHOD
APPLICATION
This procedure is applicable to acid leached soils as well as unleached soils (Krey and
Bogen, 1987).
The silica in the sample is removed by the formation of SiF4 using HF. The remain-
ing residue is fused with KF to decompose the complex silicates, followed by the addition
of H2SO4 to distill the remaining SiF4. This procedure is followed by a pyrosulfate fusion,
and finally, coprecipitation with BaSO4.
SPECIAL REAGENTS
1. Potassium fluoride.
2. Sodium sulfate.
3. Hydroxylamine hydrochloride.
4. 10% BaCl2 solution - 10 g of BaCl2 100 mL-1 of water.
SAMPLE PREPARATION
1. Using 100 mL of concentrated HNO3, wet ash the sample and filter the remaining
sample from the leaching of the soil (Steps 2-6 of Sample Preparation, Procedure
Pu-02-RC).

2. Evaporate the sample on a hot plate making sure the sample is completely dry.
3. Transfer the mixture to a tared plastic zip lock bag. Quantitatively remove the soil
residue from the beaker. Reweigh the bag to determine the mass of the residue.
4. Break apart large aggregates by kneading the residue in the bag so that the mixture is
homogeneous.
5. Weigh out 50 g of the soil residue and transfer to a 250-mL platinum crucible.
6. Add a known amount (~ 0.05 Bq or appropriate amount) of 236Pu tracer.
7. Add 5 mL of 1:1 HNO3 to wet the soil residue. Very slowly add 10 mL of
concentrated HF, it may be necessary to add the HF dropwise. If excessive frothing
occurs, wet the sample with 1:1 HNO3 from a wash bottle.
8. Add an additional 10 mL of HF carefully. Heat the sample at low heat on a hot plate
until no liquid remains.
9. When the sample is dry, add another 10 mL of HF. Heat the sample on a hot plate
until the sample is dry.
10. Repeat Step 9 until at least a total of 100 mL of HF has been added and the sample no
longer fumes. During the heating of the sample, the soil residue may move up the
walls of the platinum crucible. If this occurs wash the walls with HF.
11. To insure the absence of HF, heat the crucible with a Meker burner until the crucible
glows red.
12. Cool the sample and add 20 g of KFA2H2O. Heat the sample on a hot plate, mixing
with a Teflon stirrer.
13. Continue heating the sample until all the water has evaporated (so that no splattering
occurs in the next step). It may be necessary to raise the temperature of the hot plate
to assure drying.
14. Place the sample in a muffle furnace and heat at 950oC for 30 min.

15. Remove the crucible from the furnace and cool to room temperature.
16. Slowly add 35 mL of concentrated H2SO4 to the crucible on a hot plate at low heat.
Heat the sample until the evolution of a small amount of SO3 vapors occurs. After
this step, continue heating for 5 min.
17. Cool and add 20 g of anhydrous Na2SO4.
18. Place the crucible on a clay triangle mounted on a ring stand and heat the crucible
gently with a Meker burner, minimizing bumping and frothing of the sample.
Gradually raise the amount of heat while watching for frothing, until the molten mass
is dissolved (a clear red color), at this point the temperature is ~ 700oC. Remove the
Meker burner and cool the crucible to room temperature. (Caution: This fusion is to
be performed in a hood because SO3 fumes are emitted.)
19. Flex the walls of the crucible to break apart the fused cake. Transfer the fused
material to a 1500-mL beaker and add 200 mL of water to the crucible. Heat the
crucible on a hot plate to dissolve any material in the crucible. Transfer the water
wash to the 1500-mL beaker containing the fused material.
20. Perform three additional 200-mL washes of the crucible, each time transferring the
solution to the 1500-mL beaker.
21. Add 100 mL of concentrated HCl, 1 g of NH2OHAHCl to the 1500-mL beaker, which
contains the fused material and water, and heat the solution to dissolve the fused
material. Cover with a watch glass.
22. Continue to heat the solution until the boiling point is reached. Using a pipette add
5 mL of 10% BaCl2 solution and continue boiling the sample for 5 min.
23. Cool to room temperature and filter the solution mixture by gravity through a 15-cm
Whatman No. 42 filter paper using a conical funnel. Wash the beaker well with four
50-mL portions of H2O. Transfer each H2O wash to the funnel containing the filtered
precipitate. Discard the filtrate.
24. Transfer the filter paper containing the BaSO4 precipitate to a small platinum crucible
(40 mL). Heat the crucible with a Meker burner to decompose the filter paper.

25. Add 5 g of anhydrous Na2CO3 to the crucible and mix the Na2CO3 with the BaSO4
precipitate. Place the crucible in a muffle furnace at 850oC for 30 min.
26. Remove the crucible from the furnace, cool to room temperature, add 5 mL of water,
and heat gently on a hot plate.
27. Transfer the salts and wash the solution into a 40-mL centrifuge tube using a
minimum amount of H2O to effect the transfer.
28. Centrifuge the sample and discard the supernatant.
29. Dissolve the precipitate in the centrifuge tube with 5 mL of 6M HCl. Transfer the
solution mixture to a 100-mL Teflon beaker using 6M HCl. Also, wash the sides of
the platinum crucible with 6M HCl to remove any remaining residue and transfer to
the Teflon beaker.
30. Add 5 mL of concentrated HF, place the beaker on a hot plate and evaporate the
sample to near dryness.
31. Cool, add 5 mL of 1:1 HNO3, and 5 mL of concentrated HF, heat on a hot plate and
evaporate to near dryness.
32. Add 15 mL of 1:1 HNO3 and evaporate to near dryness.
33. Repeat Step 32, three to five times, to remove any traces of HF.
34. Add 20 mL of 1:1 HNO3 and heat gently for a few minutes. Remove the beaker from
heat, filter mixture under reduced pressure using a 25-mm Millipore filter with a
0.45-:m pore size or by gravity filtration through a 15-cm Whatman No. 42 filter
paper using a conical funnel.
35. Wash the Teflon beaker with 15 mL of 1:1 HNO3 and transfer the wash to the filtered
precipitate. Discard the precipitate. Proceed to Plutonium Purification - Ion
Exchange Technique (see Procedure Pu-11-RC).

REFERENCE
Krey, P. W. and D. C. Bogen

"Determination of Acid Leachable and Total Plutonium in Large Samples"
J. of Radioanalytical and Nuclear Chemistry, 115, 335-355, December (1987)

Pu-04-RC
PLUTONIUM IN TISSUE
(see Volume II)

Pu-05-RC
PLUTONIUM IN TISSUE - SOLVENT EXTRACTION

(see Volume II)

Pu-06-RC
PLUTONIUM IN URINE
(see Volume II)

Pu-07-RC
PLUTONIUM IN LARGE URINE SAMPLES

(see Volume II)

Pu-08-RC
PLUTONIUM IN VEGETATION AND TISSUE -

NITRIC/HYDROCHLORIC ACID METHOD
(see Volume II)

Pu-09-RC

NITRIC/SULFURIC ACID METHOD
(see Volume II)

Pu-10-RC
PLUTONIUM IN WATER
APPLICATION
This procedure is used for all types of water samples (i.e., sea water, lake water, tap
water, etc.). If the sample contains suspended particulates, they must be removed by
filtration. Large volume samples are analyzed after evaporation in an acidic medium.
The sample is heated in HNO3 and then in 3:1 HNO3:HCl. The volume is then
reduced to near dryness and finally the volume of the sample is adjusted with
1:1 HNO3. The sample is then ready to be purified by ion exchange separation (see
Procedure Pu-11-RC).
SPECIAL REAGENT
236
1. Pu tracer - a standard solution containing 0.2 Bq g-1 in a dispensing bottle. The
purity of the tracer is measured by " spectrometry.
SAMPLE PREPARATION
1. Transfer 100-1000 mL of a H2O sample to a beaker.
2. To the sample add ~ 0.05 Bq (or appropriate amount) of 236Pu tracer.
3. Add an equal amount of concentrated HNO3, cover the beaker with a watch glass and
place on a hot plate. Reflux the solution for 4-8 h.

4. Replace the watch glass with a ribbed watch glass and evaporate the solution to near
dryness. When the volume is reduced to ~ 100 mL, allow the solution to cool to
room temperature and transfer to an appropriate size beaker.
5. Continue evaporating the sample to near dryness. Cool, add 75 mL of concentrated

HNO3 and 25 mL of concentrated HCl. Cover with a watch glass. Allow to react for
30 min. Then place the sample on a hot plate and bring to a boil. After the solution
has boiled for 30 min, reduce heat and continue heating overnight. Do not allow the
sample to evaporate to dryness.
6. Remove the sample from the hot plate and add 100 mL of H2O to the sample. Allow
the sample to cool to room temperature and filter under reduced pressure using a
Buchner funnel with a Whatman No. 42 filter paper.
7. Wash with 50 mL of 1:1 HNO3 and then 50 mL of H2O.
8. Transfer the filtrate to a 250-mL beaker, cover the beaker with a ribbed watch glass.
9. (Note: If the filter paper contains a moderate amount of precipitate, it must be treated
with HF.) Transfer the filter paper containing the residue from the HNO3/HCl
digestion to a platinum dish. Place the platinum dish in a muffle furnace and heat at
100oC, raise the temperature by increments of 100oC every hour until a final
temperature of 450oC is reached. Continue heating at this temperature overnight.
Turn off the muffle furnace and let the sample in the platinum dish cool sufficiently
to remove it from the furnace. Add 15 mL of 1:1 HNO3 and 15 mL of concentrated
HF. Heat the sample to near dryness.
10. Repeat Step 9 two times.
11. Add 20 mL of 1:1 HNO3 to the sample and heat on a hot plate under a low setting
until near dryness (to remove traces of HF).
13. Add 20 mL of 1:1 HNO3 to sample.

14. Using a conical funnel, filter the sample by gravity through an 18.5 cm Whatman No.
42 filter paper into a beaker containing the filtrate from Step 9. Wash well with 1:1
HNO3.
15. Reduce the volume of the solution to near dryness on a hot plate.
16. Adjust the volume to 100 mL by the addition of 1:1 HNO3.
17. Proceed to Plutonium Purification - Ion Exchange Technique, Procedure Pu-11-RC.

Pu-11-RC
PLUTONIUM PURIFICATION - ION EXCHANGE TECHNIQUE
APPLICATION
This procedure has been applied to the leachates derived from the plutonium sample
preparation methods described in this Manual. Ion exchange chromatography is used to
remove the large amounts of impurities contained in these leachates.
SPECIAL APPARATUS
Ion exchange columns - see Specifications 7.5 and 7.6.
SPECIAL REAGENTS
1. 1:1 HNO3 - 500 mL HNO3 diluted to 1 L.
2. Hydroxylamine hydrochloride - NH2OHAHCl
3. 0.3M hydroxylamine hydrochloride-0.5M HNO3 - 20.85 g of NH2OHAHCl diluted to

1 L with 0.5M HNO3.
4. Anion exchange resin - Bio-Rad AG 1-X8 (100-200 mesh, Cl- form), see
Specification 7.4.

ION EXCHANGE SEPARATION
1. Cool the sample in an ice bath, add 1 g of NH2OHAHCl, stir, and let stand in an ice
bath for 15 min. Remove the sample from the ice bath and heat to boiling on a hot
plate with medium heat for 1-3 min. Cool the sample to room temperature.
2. Prepare the ion exchange resin column (see Note).
3. Pass the sample through the resin bed at a flow of - 1 mL min-1. Wash the beaker
and the column with 30 mL 1:1 HNO3 three times. Allow the liquid to flow until the
level reaches the top of the resin bed prior to each wash. Reserve the sample and
wash the effluent for 241Am determination (or until yield has been determined as
satisfactory).
4. Elute the plutonium with 10 mL of 0.5M HNO3 twice - then with 100 mL of 0.3M
hydroxylamine hydrochloride - 0.5M HNO3 into a 250-mL beaker. Discard the resin.
5. Slowly add 25-30 mL HNO3 until effervescence begins, then place on a hot plate and
evaporate the eluate to dryness.
6. Dissolve the residue in 30 mL of 1:1 HNO3 and cool in an ice bath. Add 500-600 mg
of NH2OHAHCl and repeat Steps 1-3 using a small column (see Specification 7.6) for
all samples.
7. Wash the resin with 100 mL of HCl (two 10-mL portions followed by two 40 mL
portions). Wash the resin with two 10-mL portions, followed by one 40-mL portion
1:1 HNO3. Save the effluent until yield determination.
8. Repeat Steps 4 and 5. Discard the resin.
9. Convert the residue to the Cl- form by adding 5 mL of HCl and evaporating to
dryness three times at a low temperature.
10. See Procedure G-03 for microprecipitation for " spectrometry.

Note: Preparation of Columns
1. When preparing a large soil sample use a large column (Specification 7.5), otherwise
use the column described in Specification 7.6.
2. Position a plug of glass wool in the base of the column so that no resin will drain out.
3. Add sufficient resin to form a resin bed of 10 cm in length. Wash the column with
sufficient 1:1 HNO3 to remove the Cl- ion from the resin. Test the effluent with a
dilute silver nitrate solution.

Pu-12-RC
PLUTONIUM AND/OR AMERICIUM IN SOIL OR SEDIMENTS
APPLICATION
This procedure is applicable to soils which contain plutonium and americium

deposited from worldwide fallout and some nuclear activities. A total dissolution
technique is required for some soil samples for plutonium determination.
Plutonium and americium isotopes are leached and equilibrated with 236Pu and 243Am
tracers with nitric and hydrochloric acids from soil samples of up to 100 g in size.
Plutonium is isolated and purified by ion exchange. Americium is collected with a
calcium oxalate precipitation, isolated and purified by ion exchange. After source
preparation by microprecipitation, the plutonium isotopes and americium are determined
by alpha spectrometry.
SPECIAL APPARATUS
SPECIAL REAGENTS
1. Americium-243 tracer solution, - 0.15 Bq g-1 in a dispensing bottle.
2. Plutonium-236 (242Pu can also be used) tracer solution, -0.20 Bq g-1 in a dispensing
bottle.

5. TEVA resin 2 mL ion extraction columns (Aliquat 336, methyltricapryl-ammonium

chloride, Henkel Corporation, Tucson, AZ 85745-1273, on Amberchrom resin) or
equivalent or can be prepared from TEVA resin, Eichrom Industries, 8205 Cass Ave.
Suite 107, Darien, IL 60561) - place a plug of glass wool in the bottom of a 2 mL
plastic transfer pipette (see Specification 7.7). Add slurried TEVA resin (0.5 g).
Place additional glass wool on the top of the resin.
6. 2M ammonium thiocyanate in 0.1M formic acid solution - dissolve 152 g of NH4SCN

in ASTM Type 2 water, add 4.25 mL formic acid, and dilute to 1 L.
7. 1M ammonium thiocyanate in 0.1M formic acid - dissolve 76 g of NH4SCN in ASTM

Type 2 water, add 4.25 mL formic acid, and dilute to 1 L.
8. Calcium carrier solution, 100 mg mL-1 - dissolve 25 g CaCO3 in a minimal amount of

concentrated HNO3, and dilute to 100 mL.
reaction ceases. Carefully and slowly add 100 mL of HNO3 while stirring. Cool and
dilute to 1 L.
10. Oxalate wash solution - dissolve 10 g of oxalic acid (H2C2O4 A 2H2O) to make 1 L of
solution (~ 1% solution).
11. Hydroxylamine hydrochloride, NH2OH A HCl - solid.

SAMPLE PREPARATION
1. Weigh 1-100 g of soil into an appropriate sized beaker. Add weighed amounts of
243
Am and 236Pu tracers.
2. Slowly add 100 mL (Note: volumes are based on 100 g sample and should be
adjusted if sample size is smaller) of HNO3 to the beaker. Control the foaming with
the addition of a few drops of n-octyl alcohol. Stir sample with a glass stir rod to mix
sample and acid. When the reaction subsides, add 30 mL of HCl, and stir. Allow the
mixture to react at room temperature, rinse and remove stir rod, cover with a watch
glass, then reflux on a low temperature hot plate overnight. Remove from hot plate
and cool.
3. Dilute the solution in the beaker with water to 1:1 HNO3 and filter the solution with
vacuum through 9 or 11 cm Whatman No. 42 filter paper on a Büchner funnel into a
1 L flask. Wash with 1:1 HNO3. Retain the filtrate in a 2-L beaker, evaporate the
filtrate until salting out begins to occur. Return the residue and filter to the original
beaker using HNO3 to complete the transfer.
4. Add HNO3 to the beaker to bring the volume added to 100 mL. Stir with a glass rod
to mix sample and acid. Cover with a watch glass and heat until filter is wet ashed.
Remove from the hotplate and cool. Add 30 mL of HCl to the beaker, cover with the
watch glass, and heat on a low temperature hot plate for about 3 h with occasional
stirring. Remove the beaker from the hot plate, and cool.
5. Repeat Step 3; dilute, filter and wash. Combine the filtrates. Return the residue and
filter to the original beaker.
6. Repeat Step 4; wet ash filter and leach sample.
7. Repeat Step 3; dilute, filter and wash. Combine the three filtrates in a beaker.
Discard the residue and filter paper.
8. Heat the filtrate with repeated 50-mL additions of HNO3, covering the sample with a
watch glass and letting the sample reflux until all organic matter is decomposed.
Evaporate the solution to incipient dryness. Redissolve in 50-200 mL of 1:1 HNO3.

If the solution is not clear, proceed to Step 9, otherwise go to Plutonium

Determination.
9. If any siliceous matter is present, filter into a flask by gravity through a Whatman No.
42 filter paper. Wash the residue with 1:1 HNO3, and reserve the filtrate.
10. Transfer the filter paper with the residue to the original beaker and wet ash the paper
with 100 mL of HNO3. Repeat wet ashing two or three times, then transfer the
residue in the beaker into a 250-mL Teflon beaker, using 1:1 HNO3. Evaporate to
dryness.
11. Add 5-25 mL of HF and 5-25 mL of HNO3 to the beaker and evaporate on a medium
temperature hot plate. Repeat the addition of the HF/HNO3 and the evaporation
process two or three times. Rinse the walls of the Teflon beaker with 1:1 HNO3 and
evaporate, and repeat. Evaporate to dryness. Dissolve with 1:1 HNO3 and evaporate
to dryness.
12. Dissolve the residue in 1:1 HNO3 and filter by gravity through a Whatman No. 42
filter paper. Add the filtrate to the solution from Step 9. Discard the filter and any
residue. Heat the combined solution to incipient dryness. Redissolve in 50-200 mL
1:1 HNO3.
PLUTONIUM DETERMINATION
Proceed to Plutonium Purification Ion Exchange Technique Procedure Pu-11-RC.

Save the column effluents for Americium Determination.
1. Evaporate the americium effluents to incipient dryness. Redissolve in a minimum

amount of 1:1 HNO3, dilute with four volumes of water.
2. Add 5 mL of calcium carrier solution (500 mg of calcium) and 50 g L-1 of oxalic acid
to the sample while stirring with a magnetic stirrer. (Note: The total volume of the

sample solution can be estimated using the markings on the beaker, and the amount of
oxalic acid to be added is calculated using that volume.)
3. Adjust the pH of the solution to 2.0-2.5 with NH4OH using pH paper as an indicator
and continue to stir for 30 min. Remove the magnetic stir bar.
4. Cool the sample and let it stand until precipitate settles and solution clears (for more
than 6 h or overnight ). Check for completeness of precipitation using a drop of
saturated H2C2O4 solution. Aspirate (or decant), using a disposable transfer pipette
and suction, as much liquid as possible without disturbing the precipitate. Transfer
the precipitate to a 250-mL centrifuge bottle using oxalate wash solution (see Note
1). Balance the bottles on a double pan balance and centrifuge for 10 min at 2000
rpm. Decant and discard the supernate.
5. Break up the precipitate with a stirring rod and wash the precipitate with the oxalate
wash solution. Centrifuge, decant and discard the wash. Repeat wash. Redissolve
the precipitate in a minimal amount (50-70 mL) of concentrated HCl (the final
precipitate should be redissolved in ~200 mL of HNO3, then proceed to Step 8
below). (Note: Dissolution is easier if the centrifuge bottle is placed in a hot water
bath and stirred with a glass rod).
6. Transfer the dissolved precipitate to the original 600-mL beaker. Add enough water
to make ~ 1M solution. Add 50 g L-1 of oxalic acid.
7. Repeat Steps 3 through 6 until supernate is colorless.
8. Transfer the dissolved precipitate to the original beaker and heat to destroy the
oxalate ion. Evaporate to near dryness. Dissolve in a minimum of 1:1 HNO3.
Transfer to centrifuge bottle using water to complete the transfer.
and add 0.2 mL iron carrier solution (20 mg iron).
10. With the centrifuge bottle in the hot water bath adjacent to a hood, adjust the pH of
the solution to 8-9 with NH4OH while stirring with a glass rod. Allow the solution to
digest in a hot water bath for 20 min.

11. Cool in a cold water bath, rinse, and remove the glass rod. Balance the bottles on a
12. Decant (or aspirate) and discard the supernate. Add 10 mL concentrated HCl to
dissolve the Fe(OH)3 pellet. Add four drops 30% H2O2 to oxidize any Mn present,
followed by 100 mL of water and heat in the water bath for 30 min to get rid of
excess H2O2.
13. Repeat Steps 10 to 12 three times. Reprecipitate, centrifuge and redissolve. The final
precipitate should be redissolved in HNO3.
14. Transfer to a 250-mL beaker, evaporate to dryness, add 20 mL HNO3, and evaporate
to dryness again.
15. Dissolve the wet-ashed residue in 40 mL 1:1 HNO3. Cool in an ice-water bath. Add
0.6-1.0 g NH2OH A HCl, dissolve, and let react for 15 min. Cover with a watch glass.
Heat on a low temperature hot plate to decompose unreacted NH2OH A HCl, then
bring to gentle boil for 1-2 min. Cool and pass the solution through a 1:1 HNO3 ion-
exchange column (see Note 2). Collect the effluent in a 400-mL beaker. Wash the
column with 150 mL of 1:1 HNO3 and collect in the beaker.
16. Evaporate the sample in the 400-mL beaker to dryness. Convert to HCl by adding
20-30 mL of HCl at a time, heat to almost dryness, and repeat the HCl addition and
evaporation at least three times. Evaporate again and dissolve the final residue in 30
mL of HCl. Pass this solution through a 12N HCl ion exchange column (see Note 3).
Collect the effluent in a 250-mL beaker. Wash the column with 100 mL of HCl and
collect in the 250-mL beaker.
17. Evaporate to dryness. Dissolve the residue in 10 mL 2M NH4SCN in 0.1M formic

acid.
18. Prepare a TEVA column. Equilibrate the resin by adding 3-4 mL 2M NH4SCN in
0.1M formic acid. Drain to the top of the resin.
19. Transfer the sample to the column. Drain to the top of the resin.
20. Wash the column with 10 mL 1M NH4SCN in 0.1M formic acid. Discard wash.

21. Elute the americium with 15 mL 2M HCl into a clean 100-mL beaker.
22. Add approximately 10 mL aqua regia to the sample. Gently decompose the
thiocyanate solution under a heat lamp. Allow the solution to develop a purple color
which will slowly disappear.
23. Heat the sample on a hot plate to near dryness. Dissolve the residue in 3 to 4 mL
HNO3. Evaporate to dryness. Redissolve in HNO3 and evaporate two more times.
24. Convert to HCl by addition of 3-4 mL HCL. Evaporate to dryness. Redissolve in

HCl and evaporate two more times. Proceed to microprecipitation.
Notes:

ashing filter paper and precipitate in HNO3.
2. Preparation of 1:1 HNO3 column. Position a plug of glass wool at the base of an
11-mm o.d. column. Transfer with ASTM Type 2 water, 15 mL of wet settled Bio-
second plug of glass wool on top of the resin, and with the stopcock open allow the
water level to reach the top of the upper plug. Pass 150 mL (or enough so that the
effluent tests free of Cl- ion) of 1:1 HNO3 through the resin bed in three 50-mL
portions, allowing the level of each to reach the top of the upper glass wool plug.
3. Preparation of HCl column. Position a plug of glass wool at the base of an

11-mm o.d. column. Transfer with ASTM Type 2 water, 10 mL of wet settled Bio-
water level to reach the top of the upper plug. Pass two 50-mL volumes of HCl
through the resin bed and allow each to reach the top of the upper glass wool plug.

MICROPRECIPITATION
See Microprecipitation Source Preparation for Alpha Spectrometry, Procedure G-03.
AMERICIUM

Yield (%) 50
Blank (cps) -

LLD (1000 min) (mBq) 0.5
LLD (5000 min) (mBq) 0.3
PLUTONIUM

Counter Background (cps) 2 x10-5
Yield (%) 75
Blank (cps) -
LLD ( 400 min) (mBq) 1

LLD (1000 min) (mBq) 0.5
LLD (5000 min) (mBq) 0.2

Section 4, Vol. II Rev. 0
HASL-300, 28th Edition April 1996
Radium

Ra-01-RC, Vol. I Rev. 0
Ra-01-RC
RADIUM-226 IN BONE ASH
APPLICATION
This procedure is applicable to bone ash only and has been adapted from Hallden et
al. (1963).
The separated sample is measured by radon emanation. Only 226Ra yields a radon
progeny with suitable characteristics, so the method is specific. Most of the calcium, the
alkali metals and phosphates are separated by coprecipitation of the radium as sulfate
with barium carrier in a buffered solution. Further purification is obtained by repeating
this step in the presence of undissolved BaSO4. The sulfate precipitate is dissolved in
alkaline EDTA to prepare the emanating solution. The chemical yield of barium is
determined with the (-emitting tracer 133Ba.
SPECIAL APPARATUS
Radon bubblers - see Specification 7.7.
SPECIAL REAGENTS
1. Barium-133 tracer solution - about 50 counts sec -1 per 0.1-g aliquot, prepared in 1:99
HCl.
2. Barium carrier solution (20 mg mL-1) - 30.4 g BaCl2 L-1 of 1:99 HCl.
3. Ammonium acetate solution - 15 g NH4 C2H3O2 (NH4OAc) L-1 of water.
4. Acetic acid solution - 20 mL glacial CH3 CO2H (HOAC)L-1 of water.

5. Ammonium sulfate solution - 100 g (NH4)2SO4 L-1 of water.
7. EDTA solution - 300 g tetrasodium salt of EDTA L-1 of water.
8. EDTA wash solution - 1:9 dilution of EDTA solution.
9. Monoethanolamine - 1:1 (v/v) with water.
DETERMINATION
1. Weigh 10 g of bone ash into a 90-mL glass or 100-mL polycarbonate centrifuge tube.
Add a weighed aliquot (about 0.1 g) of 133Ba tracer solution, and 1 mL of barium
carrier solution.
2. Add 20 mL of HCl (slowly at first to prevent foaming). Stir and warm in an 85oC
water bath for about 5 min.
3. Add 10 mL of water. Add NH4OH until a dense white permanent hydroxide flock
forms (about 8-10 mL).
4. Dissolve the flock in HCl (about 4 mL is required).
5. Add 2 mL of NH4OAc solution and 1 mL of HOAc solution. Cool in a water bath to

room temperature.
6. Add 1 mL of (NH4)2SO4 solution. Stir and let stand for 0.5 h.
7. Centrifuge at 2000 rpm for 1 h. Add one drop of 0.1% Aerosol OT. Decant carefully
and discard the supernate.
8. Add 5 mL of HCl and warm in an 85oC water bath for 5 min. (Most of the BaSO4
remains as a precipitate.)
9. Add 10 mL of water and then add NH4OH until a permanent flock forms.

10. Dissolve the flock in HCl.
11. Add 2 mL of NH4OAc solution and 1 mL of HOAc solution. Cool in a water bath to
room temperature.
12. Add 1 mL of (NH4)2SO4 solution. Stir and let stand for 0.5 h.
14. Heat a solution of EDTA (300 g L-1) and an EDTA wash solution (30 g L-1) in an
85oC water bath.
15. Break up the BaSO4 precipitate with a stirring rod. Add 1 mL of 1:1 mono-
ethanolamine and 5 mL of the hot EDTA solution and stir. Let stand for 5 min.
16. Wash down the sides of the tube with about 10 mL of the hot EDTA wash solution.
Let the tube remain in the water bath for 15 min, stirring occasionally.
17. Gravity filter the hot solution through a 12.5 cm Whatman No. 41 filter paper into a
30 mL polyethylene bottle.
18. Wash the centrifuge tube and the filter paper with hot EDTA wash solution. Discard
the paper and residue.
19. Dilute the sample to the same liquid level as the 133Ba standard. The standard pre-
pared by diluting a known aliquot (about 0.1 g) of 133Ba solution to 25 mL in a 30 mL
polyethylene bottle. Gamma count on a flat crystal to determine the chemical yield of
barium.

20. Transfer the sample solution to a 222Rn bubbler.
21. De-emanate 222Rn by bubbling with forming gas for about 10 min at 100 cm3 min-1 as
described in Radium - Emanation Procedure (see Ra-02-RC). Record the time as the
starting time for 222Rn buildup. Continue the analysis using the emanation technique.
Counter Efficiency (%) 57.5

Counter Background (cps) 0.0028
Yield (%) 90
Blank (cps) 0.0012
LLD ( 400 min) (mBq) 3.3
LLD (1000 min) (mBq) 1.7
*Reagent blanks must be analyzed with

each set of samples.
REFERENCE
Hallden, N. A., I. M. Fisenne and J. H. Harley

"The Determination of Radium-226 in Human Bone"
Talanta, 10, 1223-1227 (1963)

Ra-02-RC
RADIUM-226 - EMANATION PROCEDURE
APPLICATION
This procedure is specific and may be applied to almost any matrix which can be
converted to a homogeneous solution.
Radium-226 in solution can be determined by de-emanating its 222Rn into an

ionization chamber or scintillation cell for measurement. The 222Rn can be de-emanated
by bubbling an inert gas through the solution, either after equilibrium has been
established or after any known time period. Two half-lives, 7.65 days for example, give
75% of the maximum buildup.
SPECIAL APPARATUS
1. Radon measuring equipment are described in Radon-222 in Air and Breath Samples,
Procedure Rn-01-RC, and in Fisenne and Keller (1985).
SAMPLE PREPARATION
1. The sample with barium carrier should be in homogeneous solution in a volume of

15-25 mL. The solution should be acidic with perchloric acid, neutral or in basic
EDTA solution. Hydrochloric acid, NH3 or other volatile materials must be absent.
2. Detailed preparation procedures for separation of radium from sample matrices are
presented in other radium procedures in this Manual.

3. Almost all types of samples require simultaneous analysis of reagent blanks, since
radium appears in many chemical compounds. Using distilled or organic reagents
reduces possible contamination.
DETERMINATION
1. Transfer the sample solution to a 222Rn bubbler.
2. Clamp the bubbler in place to the 222Rn system.
3. Open the forming gas (85% N2, 15% H2) tank valve and adjust the line pressure to
70 kPa (10 psi) gauge.
4. Bleed the gas line, the rotometer, and 9.5 mm diameter rubber tubing.
5. Adjust the flow through the rotometer to a rate of 20 cm3 min-1.
6. Open both stopcocks on the 222Rn bubbler.
7. Attach the rubber tubing on the exit of the rotometer to the inlet of the 222Rn bubbler.
Adjust the forming gas flow rate through the bubbler to 100 cm3 min-1.
8. Flush the 222Rn from the solution (de-emanate) for 10 min.
9. Close both stopcocks simultaneously. Record the date and time as the beginning of
the 222Rn build-up period.
10. Shut off the forming gas and remove the rubber tubing from the bubbler.
11. Place the 222Rn bubbler in a refrigerator for a suitable build-up period, usually 1 week.
12. To emanate 222Rn into a pulse ionization chamber, repeat Steps 2-4.
13. Attach the rubber tubing from the rotometer to the inlet of the measurement system.

14. Open the valve to the ionization chamber and close the vacuum valves. Partially fill
the chamber with forming gas to a pressure of -2.7 (-50 cm of Hg) gauge. Close the
chamber valve and system entry valve. Open the vacuum valves and detach the
rubber tubing from the measurement system.
15. Attach a small drying tube containing about 5 g of a color indicating drying agent and
4 cm lengths of 9.5 mm diameter rubber tubing at both ends to the outlet of the
bubbler and the inlet of the measurement system.
16. Open the system entry valve to evacuate the drying tube for 3 min.
17. Adjust the forming gas flow rate to 20 cm3 min-1 and attach the tubing outlet of the
rotometer to the inlet of the bubbler.
18. Close the vacuum valves and open the ionization chamber valve.
19. Open the outlet stopcock of the bubbler and allow the bubbling to subside. Record
the date and time as the end of the 222Rn build-up period.
20. Carefully open the bubbler inlet stopcock and adjust the forming gas flow through the
bubbler to about 100 cm3 min-1.
21. When the system gauge indicates that atmospheric pressure has been reached, close
both bubbler stopcocks simultaneously. Close the chamber, system entry and
forming gas valves. Open the vacuum valves.
22. Remove the bubbler and drying tube from the system. Record the date and time of
the end of the emanation as the beginning of the next 222Rn build-up period.
23. Turn on the ionization chamber’s high voltage. A red LED will light when the
chamber is at or above atmospheric pressure.
24. Measure the sample for at least 17 h.

Notes for Proper Operation:
1. If the Teflon stopcocks of the bubbler are snug fitting, it is not necessary to grease
them. If they do leak, however, a silicone stopcock grease may be used.
2. The glass-to-glass ground joint at the top of the bubbler should also be lightly greased
with silicone.
3. During the de-emanation, the gas bubbling should be started slowly to prevent
popping of the bubbler top or stopcocks.
4. A better transfer of 222Rn from acid or neutral solutions is obtained if the bubbler is
first chilled in a refrigerator. This apparently reduces the bubble size and improves
the transfer efficiency. For samples dissolved in alkaline EDTA solution, a drop of
octyl alcohol is added to reduce foaming.
STANDARDIZATION
The chambers are standardized by de-emanating aliquots of a National Institute of

Standards and Technology SRM 226Ra solution contained in 222Rn bubblers.
1. For routine work, discard the first 5 h of counting data (equilibrium for 222Rn and
progeny).
2. Determine the total count over the remaining counting period.
3. Calculate the net counts per hour per sample by determining the total sample counts
per hour and subtracting the background counts per hour.
4. Divide the net counts per hour by the chamber standardization value of net counts per
hour per Bq of 222Rn.
5. Using the midpoint of the counting interval as the time of counting, extrapolate the
value obtained to the time noted for the end of 222Rn buildup. Figure 1 may be used
for this calculation. This correction is only a few percent. The decay during the
counting period is small and is not corrected for.

6. Correct the 222Rn measurement at the end of buildup for the fractional
buildup. The figure in Procedure Rn-01-RC may be used to obtain the build-
up factor.
7. Subtract the value obtained by carrying a blank determination through the

full procedure.
8. Samples are measured twice and the mean and standard deviation of the
duplicate emanation results are reported.
9. A computational data sheet is attached for handling routine calculations on a

step-by-step basis.

Yield (%) 90
Blank (cps) 0.0012
LLD (400 min) (mBq) 3.3
LLD (1000 min) (mBq) 1.7
*
Reagent blank must be analyzed with each set
of samples.

REFERENCE

"The EML Pulse Ionization Chamber Systems for the Measurement of Radon-222"

Figure 1. Correction factor from midpoint to the counting interval to the start of radon
measurement interval.

Date _________________ Sample Number

Operation
1 Chamber number -
BACKGROUND
2 Total count -
3 Count interval (h) -
4 Background (cph) 2/3
STANDARDIZATION
5 Chamber factor cph Bq-1 -
SAMPLE COUNT
6 Total count -
7 Count interval (h) -
8 Sample at count time (cph) 6/7
CORRECTIONS
9 Time for midpoint of count -
10 Time for end of buildup -
11 Difference (days) 9-10
12 Factor (from graph) -
13 Sample at end of buildup 8/12


Operation
14 Time for start of buildup -
15 Time for end of buildup 10
16 Difference 15-14
17 Factor (from graph) -
18 Sample with full buildup 13/17
19 Bq in sample 18/5
20 Bq in blank*
21 Net Bq in sample 19-20
*This sheet is suitable for calculating the blank value.

Ra-03-RC
RADIUM-226 IN SOIL, VEGETATION ASH,

AND ION EXCHANGE RESIN
APPLICATION
This procedure is applicable to 5 g samples of soil and 10 g of vegetation ash or to

ion exchange resin from sampling columns.
Soil, vegetation ash or ion exchange resin are prepared for 222Rn emanation
measurement. The sample is pretreated with HNO3-HF, fused with KF and transposed to
pyrosulfate (Sill, 1961). The cake is dissolved in dilute HCl. RaBaSO4 is precipitated,
filtered, and dissolved in alkaline EDTA. The chemical yield is determined with the
(-emitting tracer 133Ba.
SPECIAL APPARATUS
2. 100 mL platinum dishes or 250 mL platinum crucibles.
3. Millipore filter setup - 47 mm diameter.
4. Millipore filters - 47 mm diameter, 0.45 :m pore size.

SPECIAL REAGENTS
1. Barium-133 tracer solution - about 50 cps per 0.1-g aliquot, prepared in 1:99 HCl.
2. Barium carrier solution (20 mg mL-1) - 30.4 g BaCl2 L-1 in 1:99 HCl.
3. EDTA solution - 300 g tetrasodium salt of EDTA L-1 of water.
4. Triethanolamine - 1:1 in water.
SAMPLE PREPARATION
A. Soil and vegetation.
1. Weigh 5 g of soil or 10 g of vegetation ash into a 100-mL platinum dish. Add a

weighed aliquot (about 0.1 g) of 133Ba tracer solution and 1 mL of Ba carrier solution.
2. Slowly add 10 mL of HNO3 and 10 mL of HF to the sample and evaporate on a hot

plate to near dryness.
3. Continue the analysis as described below.
B. Ion exchange resin.
1. Transfer the resin and paper pulp from the collection column to a 250-mL platinum
crucible. Dry under a heat lamp and ash at 500oC in a muffle furnace for 48 h.
2. To the cooled crucible, add a weighed aliquot (about 0.1 g) of 133Ba tracer solution
and 1 mL of barium carrier solution.
3. Continue the analysis as described below.

DETERMINATION
1. Weigh out 15 g of KF and add to the sample. Press the KF into the sample with a
plastic spatula.
Caution - wear rubber gloves and safety glasses during Steps 2-5.
2. Fuse the sample over an air fed Meker burner, gradually increasing the temperature
until a clear melt is obtained. Cool the melt.
3. Using a burette, slowly add 17.5 mL of H2SO4 to the melt. Heat the dish on a hot
plate until a clear melt accompanied by dense fumes is obtained. Cool the melt.
4. Weigh out 10 g of Na2SO4, add to the dish and fuse over the Meker burner until a
clear melt accompanied by dense fumes is obtained. Cool the melt.
5. Transfer the cake to a 600 mL beaker containing 350 mL of hot water and 25 mL of
HCl. Stir the solution to dissolve the cake. Cool for 1 h.
6. Filter the precipitate onto a 47 mm diameter, 0.45 :m pore size Millipore filter into a
1 L sidearm flask, police the beaker, and wash with water. Add the washing to the
funnel. Discard the filtrate.
7. Using a strong stream of water from a wash bottle, transfer the precipitate from the
filter into a 150 mL beaker. Discard the filter.
8. Add 5 mL of EDTA solution and 1 mL of 1:1 triethanolamine to the beaker. Heat on

a warm hot plate for about 15 min, stirring occasionally. Reduce the sample volume
to ~15 mL.
9. Gravity filter the warm solution through a Whatman No. 41 filter paper into a 30-mL
polyethylene bottle.
10. Wash the beaker dish and filter with hot water. Discard the filter.

11. Dilute the sample to the same liquid level as a known aliquot (about 0.1 g) of the
133
Ba tracer solution and dilute to 25 mL in a 30 mL polyethylene bottle.
12. Gamma count the samples and standard to determine the chemical yield of barium.
13. Transfer the sample to a 222Rn bubbler with water.
14. De-emanate 222Rn by bubbling with forming gas for about 10 min at 100 mL min-1 as
described in 226Radium - Emanation Procedure (see Ra-03-RC). Record the time as
the starting time for 222Rn buildup. Continue the analysis by the emanation technique.

Yield (%) 90
Blank (cps) 0.0020
LLD ( 400 min) (mBq) 3.3

LLD (1000 min) (mBq) 1.7
*
Reagent blanks must be analyzed with each set
of samples.
REFERENCE
Sill, C. W.
"Decomposition of Refractory Silicates in Ultramicro Analysis"
Anal. Chem., 33, 1684 (1961)

*EPA APPROVED*
Ra-04-RC
RADIUM-226 IN TAP WATER, URINE, AND FECES
APPLICATION
The procedure presented has been applied to tap water, ashed urine, and feces
samples. Only 226Ra yields 222Rn progeny that has suitable characteristics for detection
by an emanation technique; therefore, the procedure is specific.
After sample preparation, radium is isolated from most other elements by copre-
cipitation with barium sulfate. Further purification is obtained by the removal of silica
with HF and reprecipitation of the sulfate. The sulfate precipitate is dissolved in alkaline
EDTA to prepare the emanating solution. The chemical yield of barium is determined
with the (-emitting tracer 133Ba.
SPECIAL APPARATUS
Radon bubblers - see Specification 7.7.
SPECIAL REAGENT
1. Barium carrier solution - 20 mg mL-1 - 30.4 g BaC12 L-1 in 1:99 HCl.
2. Ammonium sulfate solution - 100 g (NH4)2SO4 L-1 in water.
*
Environmental Protection Agency - Guidelines Establishing Test Procedures for the Analysis of Pollutants,
Under the Clean Water Act; National Primary Water Regulations and National Secondary Drinking Water
Regulations; Methods Update, tentatively slated for approval, 66FR3466-3497, January 16, 2001.

4. EDTA solution - 300 g tetrasodium salt of EDTA L-1 in water.
5. EDTA wash solution - 1:9 dilution of EDTA solution.
6. Ammonium acetate solution - 15 g L-1 in water.
7. Acetic acid solution - 20 mL glacial acetic L-1 in water.
8. Triethanolamine - 1:1 in water.
SAMPLE PREPARATION
A. Tap water.
1. Transfer two 0.5-L of tap water to a 3 L beaker.
2. Add 25 mL of HCl and 1 mL of barium carrier solution. Add a weighed aliquot

(about 0.1 g) of the 133Ba tracer solution.
3. Evaporate and add an additional two 0.5-L aliquots of tap water until a 10-L
collection has been obtained. Evaporate gently to about 100 mL.
4. Transfer to a 400-mL beaker with water, policing the sides of the 3-L beaker
thoroughly. Evaporate gently to about 100-mL.
5. Adjust the pH to 4 with 1:1 NH4OH and proceed with Determination.
B. Urine.
1. Weigh an aliquot of 133Ba tracer solution (about 0.1 g) into a 2-L beaker containing a
small amount of water and 1 mL of barium carrier solution.
2. Add 1500 mL of urine, then 100 mL of HNO3 and evaporate to about 1-L.

3. Slowly add 100-mL of HNO3.
4. Repeat the evaporation and addition of acid until a total of 500-mL of HNO3 has been
added.
5. Evaporate to about 20 mL. Transfer to a 400-mL beaker with water.
6. Adjust the pH to 4 with 1:1 NH4OH and proceed with Determination.
C. Feces ash.
1. Weigh 1 g of fecal ash into a 150-mL beaker. Add a weighed aliquot (about 0.1 g) of
133
Ba tracer solution and 1 mL of barium carrier solution.
2. Cover the ash with a small quantity of water and slowly add 10 mL of HNO3.
Evaporate to a small volume on a medium hot plate.
3. Add about 25 mL of water. Add NH4OH until a permanent hydroxide flock forms
(3-5 mL).
4. Dissolve the flock in a few drops of HNO3.
5. Add 2 mL of NH4Ac solution and 1 mL of acetic acid solution. Dilute to about

100-mL and proceed with Determination.
DETERMINATION
1. Add 1 mL of (NH4)2SO4 solution and allow the sample to digest for 1 h at room
temperature.
2. Filter by gravity on a 9 cm Whatman No. 42 filter paper. Wash the paper thoroughly
with water. Discard the filtrate and washings.
3. Transfer the paper to a platinum dish. Dry the paper and then ash at 500oC for about
1 h.

4. Add 1 mL of H2SO4 and 2 mL of HF. Evaporate to SO3 fumes.
5. Cool and transfer to a 90 mL centrifuge tube with water.
6. Police the dish and add the washings to the centrifuge tube.
7. Stir and let stand for 0.5 h.
9. Heat a solution of EDTA (300 g L-1 EDTA) in an 85oC water bath.
10. Break up the BaSO4 precipitate with a stirring rod.
11. Add 1 mL of 1:1 triethanolamine and 5 mL of the hot EDTA solution, and stir. Wash
down the sides of the tube with water.
12. Digest in the steam bath for 15 min, stirring occasionally.
13. Transfer the solution to a 30-mL polyethylene bottle.
14. Dilute the sample to the same liquid level as a known aliquot (about 0.1 g) of 133Ba
solution diluted to 25 mL in a 30 mL polyethylene bottle.
15. Gamma count samples and standard on a flat crystal to determine the chemical yield
of barium.
16. Transfer the sample solution to a radon bubbler.
17. De-emanate radon by bubbling with forming gas for about 10 min at 100 mL-1 min as
described in Procedure Ra-03-RC. Record the time as the starting time for the radon
build-up period. Continue the analysis by the emanation technique.

A B C
Counter Efficiency (%) 57.5 57.5 57.5

Counter Background (cps) 0.0028 0.0028 0.0028
Yield (%) 90 80 85
Blank (cps) 0.0012 0.0020 0.0012
LLD (400 min) (mBq) 0.33 0.45 0.39

LLD (1000 min) (mBq) 0.17 0.29 0.15
*Reagent blanks must be analyzed with each set of samples.
Pulse ionization chamber:

A = Tap water
B = Urine
C = Feces

Ra-05-RC, Vol. II Rev. 0
Ra-05-RC
RADIUM-224 IN URINE
(see Volume II)

Ra-06-RC
RADIUM-226 IN URINE AND WATER
APPLICATION
This procedure is applicable to samples of urine and water. Small amounts of

thorium are carried by the BaSO4 and the method fails in the presence of 230Th. Natural
thorium does not interfere. Other "-emitting isotopes of radium also interfere.
Radium is initially separated from untreated water or urine by coprecipitation with

calcium phosphate. Calcium and most other elements are removed by coprecipitation of
radium on barium sulfate. Organic material is removed by ignition, silica is removed by
volatilization with HF, and the radium-barium sulfate is reprecipitated.
Radium-226 in the barium sulfate precipitate is stored to allow the buildup of 222Rn,
218
Po, and 214Po. The equilibrated " activities are then measured with a scintillation
counter. The instrument response is converted to Bq by application of corrections for
counter background and efficiency and for self-absorption. Chemical recovery is
measured gravimetrically and the 226Ra activity is equivalent to one-fourth of the total Bq
measured.
SPECIAL APPARATUS
2. Teflon filter holders and filter funnels and sample mounts - see Specification 7.12.

SPECIAL REAGENTS
1. Barium carrier solution: 5 mg Ba mL-1 - 9.51 g Ba(NO3)2 L-1 of 1:99 HCl.
SAMPLE PREPARATION
A. Water.
1. Transfer 4 L of the sample to a 5 L stainless steel pot.
2. Add 1 mL of barium carrier solution and 4 mL of HNO3.
3. Evaporate to near dryness, add additional aliquots of water and HNO3, and continue
until 50 L of sample have been treated.
4. Evaporate to about 100 mL, add 3-4 g of NH4Ac, and adjust the pH to 5 with
1:1 NH4OH.
B. Urine.
1. Transfer a measured volume of urine to a 250-mL centrifuge bottle and add 1 mL of

barium carrier solution.
2. Add 2 mL of H3PO4. Adjust the pH to 9 with 1:1 NH4OH. Stir, centrifuge, and
3. Dissolve the precipitate with 10 mL of HNO3. Dilute to about 100 mL with water.
5. Dissolve the precipitate in a few mL of acetic acid and dilute to 100 mL with water.
Adjust the pH to 5 with 1:1 NH4OH.

DETERMINATION
1. Add 3-4 g of (NH4)2SO4 with stirring. Digest for 12 h. Cool and filter by gravity on
a 9 cm Whatman No. 42 filter paper. Wash with 0.5% H2SO4. Discard the filtrate
and washings.
2. Transfer the precipitate and filter to a platinum dish. Dry and ignite at 900oC.
3. Cool and add 2 mL of 1:1 H2SO4 and 5 mL of HF. Evaporate on a sand bath until
SO3 fumes appear.
4. Transfer the solution to a 40 mL, heavy walled centrifuge tube with 30 mL of H2O
and digest for 12 h. Centrifuge and discard the supernate.
5. Wash the precipitate with 10 mL of water. Centrifuge and discard the washings.
6. Slurry the precipitate with water and filter on a tared Whatman No. 42 filter paper.
7. Dry in an oven at about 150oC for at least 2 h.
8. Cool, weigh, and mount on a ring and disc with an " phosphor and Mylar.
9. Store for 30 days and count on an "-scintillation counter.
The 226Ra disintegration rate is obtained from the counting rate of the equilibrated
radium fraction through the following calculation:
Bq = Rs YTCE
where Rs is the net counting rate of the sample, Y is the recovery factor, T is the self-
absorption correction, E is the counter efficiency factor, and C is a theoretical conversion
from total " activity to 226Ra " activity.

Chemical recovery, Y, is obtained by weighing the final Ba sulfate precipitate. The

calculation of the recovery factor is:
x
Y=
(w - t ) f
where x is the weight of barium added as carrier, w is the total weight of the final
precipitate and filter paper, t is the weight of the filter paper, and f is the gravimetric
factor which equals 0.588 mg barium per mg of barium sulfate.
Self-absorption correction, T, is used to normalize the self-absorption of the 226Ra,

222
Rn, 218Po, and 214Po " activities in samples and standards to a common thickness
(mg cm-2). T is obtained by counting representative " emitters over the energy range of
4.8-8.8 MeV in precipitates of varying sample thicknesses. The correction is taken as the
ratio of counting rates at an arbitrary minimum thickness to other thicknesses over the
range of probable sample recoveries. Figure 1 is a typical composite plot of the
correction obtained for 230Th, 212Pb, and 226Ra activities for varying thicknesses of their
oxalate, chromate, and sulfate derivatives, respectively.
Theoretical activity conversion factor, C, equals 0.25 after 30 days of buildup, when
the three "-emitting progeny are in secular equilibrium with 226Ra. However, the ratio of
226
Ra to total " activity at any time after the separation of radium may be calculated from
the Bateman equation for buildup of 222Rn.
Efficiency factor, E, is determined by " counting a known quantity of 226Ra under

sample conditions. The correction is taken as the ratio of the theoretical activity to the
observed counting rate. The calculation is expressed as:
A
E=
R S ′ T ′C ′
where A is the theoretical activity of the standard, and Rs' is the net counting rate of the
standard, T' is the self-absorption correction for the standard, and C' is the theoretical
ratio of 226Ra to total " activity in the standard.

An accompanying computational data sheet illustrates a procedure for routine

calculation of 226Ra activity rates. Experimental data are tabulated as they are derived
and the calculations are performed on a step-by-step basis.
Counter efficiency (%) 50

Counter background (cps) 1.67 x 10-5
Yield (%) 85
Blank (cps) 1.67 x 103
*
Reagent blank must be analyzed with each set
of samples.

Figure 1. Self-absorption for " activities (4.8-8.9 MeV).


Operation
1 Counter number -
STANDARD COUNTING
2 Gross background count -
3 Count interval (s) -
4 Background (cps) 2/3
5 Gross standard count -

6 Count time -
7 Standard (cps) 5/6
8 Standard (net cps) 7-4
CORRECTIONS
9 Gross weight (mg) -
10 Tare weight -
11 Net weight 9-10
12 Weight of barium 11x0.59
13 Carrier added -
14 Chemical yield factor (Y) 13/12


Operation
11 Net weight Copy
15 Thickness correction (T) Graph
16 Corrected standard (cps) 8x14x15

17 Added x 4* (Bq) -
18 Efficiency factor (E) 17/16
*To include progenys


Operation
1 Counter number -
3 Count interval (s) Copy
4 Background (cps) Copy
18 Efficiency factor (E) Copy
SAMPLE COUNTING
19 Gross sample count -
20 Count time -
21 Sample (cps) 19/20
22 Sample (net cps) 21-4
23 Sample (Bq) 22x18
CORRECTIONS
25 Tare weight -
26 Net weight 24-25
27 Weight of barium 26x0.59
28 Carrier added -
26 Net weight Copy

30 Thickness correction (T) Graph


Operation
31 Corrected sample (Bq) 23x29x30
STANDARD DEVIATION
32 Background/count interval 4/3
33 Sample/count intervals 21/20
34 S2 32+33
35 S for sample (net cps) %
34
36 Total correction factor 18x29x30
37 S for sample (Bq) 35x36

Radon

Rn-01 -RC , Vol. I Rev. 0
Rn-01-RC
RADON-222 IN AIR AND BREATH SAMPLES
APPLICATION
Procedures are presented which describe EML's method of sampling, counting, and
calculating 222Rn concentration in air and breath samples. When radium is present in the
body, the gaseous progeny, 222Rn (t1/2 = 3.825 d), will collect in the lungs and will be
eliminated with exhaled breath.
One liter glass sampling flasks are provided to field personnel by EML for collecting
breath or atmospheric 222Rn samples. The 222Rn sample is transferred to a pulse type
ionization chamber, and after it is allowed to come into equilibrium with its progeny
products, the sample is " counted. Two of the progeny, 218Po and 214Po, are " emitters
and contribute to the total count.
SPECIAL APPARATUS
A. Sampling.
1. 1-L glass flasks with two large bore stopcocks per flask.
2. Tank of compressed, aged air with two-stage regulator.
3. Face mask - No. CS-6772 inhalator, modified to block the emergency intake and with
the outlet modified to accept 9.5 mm ID rubber tubing (Mine Safety Appliance Co.,
Pittsburgh, PA).

4. Demand regulator - No. CS-46516 single stage or equivalent (Mine Safety Appliance
Co., Pittsburgh, PA).
B. Analysis.
1. Platinum black catalyst (Baker and Co., Deoxo Units).
2. Drying tube with Drierite.
3. Flame arresters.
4. Capillary orifice.
5. Vacuum pump.
6. Tank of H 2 with two-stage regulator.
7. Tank of forming gas (85% N2, 15% H2) with two-stage regulator.
8. Sample introduction system including valves and piping.
9. Pulse type ionization chamber and associated electronic equipment.
SAMPLE COLLECTION
A. Radon in breath*
1. Set up the equipment as described in the above reference using 9.5 mm (3/8 in) rubber
tubing on the inhalator outlet. Do not attach to sampling flask.
2. Clean facepiece with cotton and alcohol.
3. Set air pressure on two-stage regulator to 4.5 kg (10 lb).
*
Taken from Harley et al., 1951.

4. Have the subject hold the face piece in place while you check for leaks, particularly
around the bridge of the nose.
5. Have the subject breathe with the respirator for 5 min to flush the environmental air
from his or her lungs. (This should be regular breathing. Do not ask for deep
breaths.)
6. While the subject continues regular breathing, attach the sampling flask (with both
stopcocks open) for a 1-min period, remove, and close stopcocks.
7. Repeat Step 6 for a duplicate sample.
B. Radon in the atmosphere.
1. Open both flask stopcocks.
2. Connect about 0.6 m of 9.5 mm (3/8 in) rubber tubing to one stopcock.
3. Inhale through the tubing and flask 20 times. Do not exhale through the flask. If
convenient, a suction pump may be used.
4. Close both stopcocks.
MEASUREMENT EQUIPMENT PREPARATION
A. Sample oxidation.
Before transfer to the counting system, enough H 2 is added to the sample flask to
completely remove O2 (as H2O) in the platinum catalyst. Because O2 acts to quench the
ionization produced by each " disintegration, even small amounts of it in the chamber will
seriously affect the counting rate of a sample. Environmental air contains about 20% O2
and the addition of 40 kPa (6 psi) of H2 is theoretically sufficient for all samples. It has
been our practice to add an excess of H2 and therefore 70 kPa (10 psi) is usually added to
each sample.

B. Flame arresters.
The removal of O 2 from the sample takes place in the platinum black catalyst where O2
and H2 combine to form H 2O. This combustion reaction generates a considerable amount
of heat, and if allowed to strike back, the sample flask may explode. To prevent such
explosions, flame arresters are placed bet ween the catalyst and the sample. The flame
arresters consist of a fine mesh copper wire screen and act to dissipat e the heat of the
reaction.
C. Capillary orifice.
A capillary orifice is placed in the line after the catalyst. This slows the passage of gas
through the catalyst and insures complete combustion.
D. Drierite tube.
Water formed in the O2 removal is collected in a Drierite tube. The Drierite is kept
free of H 2O by evacuating the external piping of the system continuously when not
transferring the samples.
E. Counting apparatus.
The 222Rn counting apparatus consists of a sample introduction system, ionization

chamber, preamplifier, amplifier, and count registering device. The ionization chamber
counts almost 100% of the " disintegrations of 222Rn and about 50% of the disintegrations
of its progeny. Each chamber plus its sample introduction system has a capacity of 2 L
and the chamber is operated at a potential of 1000 V. A mixture of H2 (15%) and N2
(85%) is used as a counting gas. The chambers are constructed of a specially selected,
electropolished stainless steel and have a background count of about 10 counts h-1 and an
efficiency of about 6215 counts h-1 for 1 Bq o f 222Rn.
A block diagram of the counting system and external apparatus is shown below.

Forming Platinum
Radon Drierite Ionizatio
gas x black x
sample tube n
(H2+N2) catalyst
chamber
Vacuum
x
Line
x indicates valve or stopcock.
The pulses from the ionization chamber are fed to an EML-built preamplifier,
amplifier, and control unit. Two Tatt letale Clever counters are interfaced to a PC.
DETERMINATION
1. Connect sample flask to H2 tank with 9.5 mm (3/8 in) rubber tubing.
2. Raise gauge pressure to 70 kPa (10 psi) gauge.
3. Open flask stopcock to tank to admit H2 to the flask.
4. Close stopcock and tank valve.
5. Raise the forming gas line pressure to 70 kPa (10 psi) gauge and bleed the line and
rubber tubing leading to sample inlet.
6. Connect one flask stopcock to the forming gas line with t he above rubber tubing, the
other to the counting system with another section of 9.5 mm (3/8 in) rubber tubing.
7. Open the ionization chamber and the vacuum line valve to evacuate the counting
chamber, external piping, and the rubber tubing between the counting system and t he
flask.
8. Close the vacuum line valve when system reaches minus 10.1 kPa of Hg gauge
pressure.

9. Open the flask stopcock to allow the sample to enter the counting system. Allow
pressure equilibration (indicated by pressure gauge).
10. Check plat inum catalyst by touch to assure that combinat ion of H2 and O2 has
occurred.
11. Close the flask stopcock to the counting system.
12. Open the stopcock to the forming gas line. Allow forming gas to come to pressure in
the flask.
13. Repeat Steps 5 and 7 until the gauge indicates atmospheric pressure.
14. Open the stopcock to the forming gas line, then attach the stopcock to the counting
system. Allow forming gas to flow until the gauge pressure reaches 35 kPa (5 psi).
15. Close all valves and remove flask and tubing from system.
16. Turn on ionization chamber high voltage.
17. Count the sample for at least 14 h.
1. Discard the first 5 h of counting data (equilibration period for 222Rn and progeny).
2. Determine the gross count over the remaining counting period.
3. Calculate net counts per hour per sample by determining gross sample counts per hour
and subtracting background counts per hour.
4. Divide net counts per hour by the chamber standardization value of net counts per
hour per Bq of 222Rn.

5. Using the midpoint of the counting interval as the time of co unting, extrapolate the
value obtained to the time of sampling. Figure 1 may be used for this calculation.
STANDARDIZATION
Each unit is standardized several times a year with 222Rn from a radium solution
obtained from the National Inst itute of Standard and Technology (NIST). This solution is
diluted and split into aliquots which are placed in 222Rn bubblers (see Specification 7.8).
The 222Rn is allowed to build up for a known period before the standard is used.
The 222Rn standard is transferred to the chamber by emanation. The bubbler is first
attached to the external feed system. When the ionization chamber and external system
are evacuated, the vacuum line is shut off from the system and the bubbler outlet stopcock
opened. The inlet stopcock is then opened and forming gas flushes the 222Rn into the
chamber until the system is brought to atmospheric pressure.
At equilibrium, there are three " disintegrations per 222Rn disintegration, however, two
of these are from the particulate "-emitting progeny. Since these " disintegrations
deposit on the walls of the ionization chamber, they are counted with a maximum
efficiency of 50%. One becquerel of 222Rn in the ionization chamber thus has a theoretical
counting rate of 7190 counts h-1. Actually, the ionization chambers in this Laboratory
yield a counting rate of 6215 counts h-1 Bq-1 of 222Rn in equilibrium with its progeny or an
overall efficiency of 86%.

Yield (%) -
Blank (cps) -
LLD (400 min) (Bq) 0.01
LLD (1000 min) (Bq) 0.07

REFERENCE
Harley, J. H., E. Jetter and M. Eisenbud

"A Method of Obtaining Reproducible Breath Radon Samples"
Arch. Ind. Hyg. Occ. Med., 4, 1-9 (1951)

Rn-01-RC, Vol. I Rev. 0

Strontium

Sr-01-RC, Vol. II Rev. 0
*EPA APPROVED*
Sr-01-RC
STRONTIUM-89
(see Volume II)

Sr-02-RC. Vol. II Rev. 0
*EPA APPROVED*
Sr-02-RC
STRONTIUM-90
(see Volume II)

Sr-03-RC, Vol. I Rev. 0
Sr-03-RC
STRONTIUM-90 IN ENVIRONMENTAL MATRICES
Contact Person : Marie Lawrence
APPLICATION
This procedure is applicable to the preparation, separation, and analysis of vege-

tation, water, air filters and soil.
Strontium is separated from calcium, other fission products and natural radioactive
elements. Fuming HNO3 separations remove the calcium and most of the other
interfering ions. Radium, lead and barium are removed with barium chromate. Traces of
other fission products are scavenged with iron hydroxide. After the 90Sr + 90Y
equilibrium has been attained, the 90Y is precipitated as the hydroxide and converted to
the oxalate for counting on a low-background gas proportional beta counter. Chemical
yield is determined with 85Sr tracer by counting in a gamma well detector.
SPECIAL APPARATUS
1. Teflon filter holder or filter funnel and sample mount - see Specification 7.12.
3. Magnetic stirrers with Teflon-coated magnet bars.
5. Glass fiber filters - see Specification 7.8.
6. Fisher filtrator, Fisher Chemical Company, Pittsburgh, PA 15219-4785.

7. Polyethylene reference bottles, 30-mL narrow mouth to fit in a gamma well detector.
SPECIAL REAGENTS
1. Strontium carrier, 20 mg Sr mL-1 - dissolve 48.4 g Sr(NO3)2 in 1 L of 1:99 HNO3.
2. Yttrium carrier, 10 mg Y mL-1 - dissolve 12.7 g of highest purity Y2O3 in a minimal

amount of HNO3; use heat if necessary. Filter, if necessary, and add water to make
1 L of solution. See the APPENDIX for the yttrium carrier counting check.
3. Iron carrier, 5 mg Fe mL-1 - dissolve 5 g Fe wire in 1:1 HCl and dilute to 1 L with
1:99 HCl, or dissolve 34.7 g Fe(NO3)3A9H2O in 1 L of 1:99 HNO3.
4. Barium carrier, 10 mg Ba mL-1 - dissolve 9.5 g Ba(NO3)2 in water and dilute to 0.5
L.
5. Barium buffer solution - 500 mL 6M acetic acid (glacial HOAC) plus 1 L of

6M NH4OAc plus 0.5 L Ba carrier (10 mg mL-1).
6. Calcium carrier, 200 mg Ca mL-1 - dissolve 500 g calcium carbonate (CaCO3) in a

minimum of HCl and dilute to 1 L with water.
85
7. Sr tracer, about 7x105 Bq L-1, in a well counter, this tracer should provide about
150 counts sec-1 mL-1.
8. Sodium carbonate solution, 1M - dissolve 106 g Na2CO3 in H2O and dilute to 1L.
9. Sodium carbonate solution, 2M - dissolve 212 g Na2CO3 in H2O and dilute to 1L.
10. Sodium chromate solution, 0.3M - dissolve 50 g Na2CrO4 in H2O and dilute to 1L.
11. 50% sodium hydroxide solution - slowly dissolve 500 g NaOH in 500 mL of H2O in
a plastic liter bottle immersed in a beaker of ice water.

SAMPLE PREPARATION
A. Water
1. Transfer an aliquot of sample water to an appropriate sized beaker (use deionized

water for the blank).
2. Add 1 mL (20 mg) strontium carrier to the blank and the sample.
85
3. Add exactly 1.00 mL of Sr tracer to three 30-mL plastic bottles, the blank and the
sample.
4. Fill the plastic bottles with equal volumes of 1M HCl. Set bottles aside. They will
serve as references when determining the strontium yield.
5. Evaporate the samples to dryness. Add 10-mL volumes of concentrated nitric acid
to the dried residue, and evaporate repeatedly to remove any trace of HCl due to the
reagents added.
6. Dissolve the final residue in 8M HNO3. If the sample is not in a 400-mL beaker,
quantitatively transfer the sample with water to a 400-mL beaker containing a
Teflon-coated magnetic stirring bar. Dilute the sample to 200 mL with additional
water.
7. Place the beaker on a magnetic stirrer/hot plate and stir. Adjust the pH to 5-6 with
50% NaOH. While continuing to stir, add 15 mL of 2M Na2CO3. Heat the sample
to just below boiling and stir for 30 min.
8. Remove the sample from the hot plate and allow the precipitate to settle overnight.
9. Place a small glass fiber filter backed with a Whatman No. 42 filter paper of the
same size into a Büchner funnel. Mount the funnel on a 500 mL filter flask.
10. Filter the sample by vacuum through the funnel. Wash the carbonates retained on
the filter with 1M Na2CO3 solution. Discard the filtrate.

11. Release the vacuum and transfer the funnel to a clean filter flask. Apply the
vacuum. Dissolve the carbonates on the filter with hot 8M HNO3. Wash the filter
with water.
12. Transfer the filtrate to a 400 mL beaker, rinsing with 8M HNO3. Evaporate the
solution to dryness.
13. Proceed to Determination, Fuming HNO3 Separation
B. Air Filters
1. Place the air filter in a 400-mL beaker (use a dry beaker for the blank).
2. Add exactly 1.00 mL of 85Sr to three 30-mL plastic reference bottles, the blank and
the sample.
3. Fill the plastic bottles with equal volumes of 1M HCl. Set bottles aside. (The same
three reference bottles may be used for water and air filters if the analyses are done
simultaneously.)
4. Add 20 mg (1 mL) strontium carrier to the blank and the sample.
5. Add 150 mL HNO3 and 50 mL HCl. Reflux on a hot plate until clear and colorless.
Evaporate to a volume of ~ 100 mL.
6. Add 100 mL of deionized water. Cool the sample to room temperature. Filter by
gravity through a Whatman No. 42 filter. Wash the filter with 8M HNO3.
7. Evaporate the filtrate to dryness. Add 20 mL volumes of concentrated nitric acid to

the dried residue, and evaporate repeatedly to remove HCl. Continue with Step 6,
Section A, Water.

C. Soil (NaOH-HCl method) - see Note 1
1. Weigh out enough soil to generate an activity at least 10 times background (ideally
100 times) into an appropriate sized beaker containing a Teflon-coated magnetic
stirring bar (see chart below). Add water to about a quarter of the beaker’s volume
and add 5-10 mL (100-200 mg) strontium carrier solution. Place the beaker on a
magnetic stirrer.
2. To each of three 30-mL plastic reference bottles and to the sample add 1.00 mL of
85
Sr tracer solution. Fill the reference bottles to the same level with 1M HCl.
3. Stir the sample. While continuing to stir, add a sufficient amount of 50% NaOH to
make the solution 1N NaOH. (see chart below)
4. Cover with a watch glass and stir for 10 min. Reflux overnight on a warm hot plate.
5. Remove the beaker from the hot plate and allow to cool. While stirring, cautiously
add HCl, 1 mL at a time until the reaction slows, to make the solution 6M acidic (see
chart below). If analyzing highly calcareous soils, an additional quantity of HCl
should be added to replace the acid required to decompose the carbonates. If
necessary, add a few drops of n-octyl alcohol to reduce foaming.
Activity Sample size Beaker size Water Carrier 50% NaOH HCl
(Bq kg-1) (g) (mL) (mL) (mL) (mL) (mL)
~500 5-10 250 70 5 4 90
~100 15-20 400 100 5 6 130
~50 30-40 800 200 5 11 260
~10 100 1000 250 5 14 320
6. Digest the sample overnight on a warm hot plate. Remove the beaker from the hot
plate and cool.
7. Filter the sample under vacuum using a Whatman No. 42 filter paper backed by a
glass fiber filter. Wash with approximately 100 mL hot 6M HCl, followed by 60 mL
hot H2O.

8. Turn off the vacuum. Return the soil residue and the filter paper to the original
beaker.
9. Quantitatively transfer the filtrate and washes to an appropriate sized beaker, rinsing
with water, and place on a warm hot plate to reduce the volume.
10. Remove the filtrate from the hot plate. Add 20-50 mL of HNO3. Cover with a watch
glass and place back on the hot plate. Turn the heat up to high. Continue adding
HNO3 until the conversion is complete, as indicated by the absence of brown fumes
after the addition of HNO3.
11. Add water to about a quarter of the beaker’s volume to the beaker containing the
filter paper and soil residue. Repeat Steps 3-7.
12. Transfer the second filtrate to the beaker containing the original filtrate. Convert to
HNO3 as in Step 10.
13. Reduce the volume of the combined filtrates to ~50 mL or until salting out begins to
occur. Add ~100 mL (or twice the volume) of water, stir and cool to room
temperature. If cloudy, filter under vacuum through two glass fiber filters, washing
with hot 1-2M HNO3. Discard the filters.
14. Quantitatively transfer the filtrate to a large (800-1500 mL) beaker containing a
magnetic stirring bar, rinsing with water. Place the beaker on a magnetic stirrer/hot
plate and stir while warming the solution.
15. Add approximately 5 g of H2C2O4 (oxalic acid) L-1 and continue to stir until the salt
completely dissolves.
16. While stirring, adjust the pH to 5.5-6.0 with NH4OH. If the mixture turns brown due
to the presence of FeO(OH), add just enough H2C2O4 to bring back the green color
and readjust the pH. Repeat this process, using decreasing quantities of H2C2O4, until
the last pH adjustment does not result in the brown color. (Note: At this point, there
should be enough H2C2O4 to precipitate the insoluble white oxalates and to complex
the Fe+3 ion, but not enough to cause crystallization of the (NH4)2C2O4 upon cooling.)
Finish by adding several grams of oxalic acid as excess and adjust the pH again. Stir
for 30 min on a warm hot plate.

17. Turn off the stirrer, remove the beaker from the hot plate, and allow the precipitate to
settle overnight.
18. Add 5 mL of Ca carrier solution (1g Ca), stir the supernatant very gently and allow
the fresh precipitate to settle for 15-20 min.
19. Filter the sample by gravity through a large Whatman No. 42 filter paper. Wash the
beaker with H2O, adding the washes to the funnel. Wash the precipitate with water
until the filtrate is colorless.
20. Transfer the filter paper and precipitate to a 600-mL beaker. Add 100 mL of HNO3.
Cover with a watch glass and wet ash the oxalates until clear and colorless or
oxidation seems complete, adding more HNO3 as necessary.
21. Add an equal volume of water and stir on a magnetic stirrer. If cloudy, filter through
two glass fiber filters washing with 8M HNO3, followed by water. Evaporate to
dryness.
22. Proceed to Determination, Fuming HNO3 Separations.
Note: This method was developed at the U.S. Department of Agriculture Soil Survey
Laboratory, Soil Conservation Service, Beltsville, MD. Comparative soil analyses at
EML showed that the 85Sr tracer could be completely equilibrated with 90Sr present in the
soils when consecutively treated with NaOH and HCl. The NaOH-HCl method yielded
results equal to those obtained with the complete dissolution method.
D. Vegetation (dry ashing).
1. Weigh an aliquot of up to 10 g of vegetation into a tared 250-mL porcelain crucible.

(Note: After ashing, several aliquots can be combined to provide the desired sample
size.) Place each crucible in a muffle furnace with the crucible cover slightly ajar.
Increase the temperature of the furnace at a rate of 0.80/C min-1 to 250/C. Maintain
this temperature for 30 minutes. Increase the temperature at a rate of 10/C min-1 to
600/C. Maintain this temperature for 960 min to completely ash the sample. Cool
the crucible and weigh it to determine the percent ash. Ash content for replicate
crucibles should vary by not more than 4%.

2. Transfer the ashed vegetation to a beaker using 8M HNO3 to dissolve the ash and
rinse the crucible. Add 1 mL of Sr carrier (20 mg).
3. Add 1.00 mL of 85Sr tracer to the blank, the sample and each of three 30-mL plastic
reference bottles. Fill the bottles to the same level with 1M HCl.
4. Cover with a watch glass and reflux on a hot plate until there is no evidence of
remaining organic matter, adding HNO3 or H2O2 as necessary.
5. Evaporate to near dryness. Add 50 mL of 8M HNO3. Filter by gravity through a

Whatman No. 42 filter paper into a beaker, washing with 8M HNO3. Continue with
Step 6 below.
E. Vegetation (wet ashing).
1. Weigh an aliquot of vegetation into an appropriate sized beaker. (For 100-300 g, use
a 3000-mL beaker.) Add 1 mL of Sr carrier (20 mg).
2. Add 1.00 mL of 85Sr tracer to the blank, the sample and each of three 30-mL plastic
reference bottles. Fill the bottles to the same level with 1M HCl.
3. Slowly add 500 mL of 8M HNO3. Control the foaming, if necessary, by adding a

few drops of n-octyl alcohol. Cover with a watch glass and place on a low
temperature hot plate overnight to maintain a slow reaction, stirring as necessary to
break up the foam. Gradually increase the temperature of the hot plate, adding
HNO3 and continuing to reflux until the reaction is complete, as indicated by the
absence of brown nitrogen oxide gas.
4. Remove from the hot plate. Slowly add enough HCl to equal one third the volume
of HNO3 still in the beaker. Allow the mixture to react at room temperature for 15
min, then cover with a watch glass and heat on a low temperature hot plate overnight
with occasional stirring.
5. Remove the sample from the hot plate and add an equal volume of water. Allow the
sample to cool to room temperature. Filter by gravity through a large Whatman No.
42 filter paper into a beaker. Wash with 8M HNO3.

6. Evaporate the filtrate to dryness. Dissolve the residue in a minimum of 8M HNO3.

Quantitatively transfer the solution to a 400-mL beaker containing a Teflon-coated
magnetic stirring bar, rinsing with H2O. Dilute the solution to 200 mL with
additional H2O.
7. Place the beaker on a magnetic stirrer/hot plate and stir. Adjust the pH to 5-6 with
50% NaOH. While continuing to stir, add 15 mL of 2M Na2CO3. Heat the sample
to just below boiling and stir for 30 min.
9. Place a small glass fiber filter backed by a Whatman No. 42 filter paper of the same
size into a Büchner funnel. Mount the funnel on a 500 mL filter flask.
10. Filter the sample by vacuum through the funnel. Wash the carbonates retained on
the filter with 1M Na2CO3 solution. Discard the filtrate.
11. Release the vacuum and transfer the funnel to a clean filter flask. Apply the
vacuum. Dissolve the carbonates on the filter with hot 8M HNO3. Wash the filter
with water.
12. Transfer the filtrate to a 400 mL beaker, rinsing with 8M HNO3. Evaporate to
dryness.
13. Proceed to Determination, Fuming HNO3 Separations.

DETERMINATION
A. Fuming HNO3 separations.
1. Dissolve the residual salt in H2O and some fuming HNO3, while stirring on a
magnetic stirrer. When dissolved, add additional fuming HNO3 to precipitate
Sr(NO3)2. The first two separations require concentrations of > 75% HNO3,
subsequent separations require less HNO3 (see chart below). Water and air filters
usually require two separations. Large quantities of soils with a high Ca content may
require up to five or more fuming HNO3 separations.
Separation Water (mL) Fuming HNO3 (mL) % HNO3 final volume (mL)
1st 40 25 + 195 80.1 260
2nd 60 25 + 195 76.0 280
3rd 40 25 + 115 75.4 180
4th 30 105 75.4 135
5th 23 77 74.9 100
2. Place a dry (very important to prevent sample loss) 5.5-cm glass fiber filter (for
smaller volumes a 4.25-cm filter) in a dry Büchner funnel and mount the funnel in a
1 L filter flask.
3. Suction filter the sample into the flask. Turn off the vacuum. Transfer the funnel to a
Fisher filtrator, placing an appropriate sized beaker underneath (for the last filtration,
use a 40-mL heavy-wall conical centrifuge tube (C-tube)). Apply a vacuum while
dissolving the precipitate on the filter with water into the beaker. Use additional
water to complete the transfer of any residue in the original beaker to the funnel and
subsequently into the beaker or C-tube. Proceed with Step 4 or 5.
4. Evaporate the sample solution to dryness if another fuming HNO3 separation is

desired, and repeat Steps 1 to 3 using smaller volumes as indicated in the chart.

5. If the sample solution is now in a C-tube, place the tube in a hot water bath and adjust
the volume to ~20 mL. Proceed with First Milking.
B. First milking.
1. Add 1 mL of iron carrier solution to the separated strontium fraction in the centrifuge
tube. Stir the solution and place the tube in a 90oC water bath to warm.
2. While stirring, adjust the pH of the sample to 8 with NH4OH. Remove the stirring
rod, rinsing with H2O. Remove the centrifuge tube from the water bath and cool to
room temperature in a cold water bath.
3. Centrifuge the sample at 2000 rpm for 5 min. Decant the supernate into a second 40-
mL centrifuge tube. Reserve the supernate for Step 6 and note the hour and date of
this initial OH-1 precipitation as first milk separation time.
4. Dissolve the precipitate in the first centrifuge tube in a few drops of HCl and dilute to
10 mL with H2O. Stir the solution and warm the tube in the hot water bath.
5. While stirring, adjust the pH of the sample to 8 with NH4OH. Remove the stirring
rod, rinsing with H2O. Remove the centrifuge tube from the water bath and cool to
room temperature in a cold water bath.
6. Centrifuge the sample at 2000 rpm for 5 min. Decant and combine the supernate with
the supernate reserved from Step 3. Evaporate to reduce the volume to 20 mL.
Discard the precipitate.
7. While stirring, add 4 mL of barium buffer solution to the sample. If necessary, adjust
the pH of the sample to 5.5 with either 6M HCl or NH4OH (see Note 1).
8. Return the centrifuge tube to the hot water bath. While stirring vigorously, add 1 mL
of 0.3M Na2CrO4 dropwise to the sample (see Note 2). Allow the sample to digest in
the hot water bath for 10 min or longer to allow a good precipitate to form.
9. Remove the stirring rod, rinsing with H2O. Remove the sample tube from the hot
water bath and cool in a cold water bath.

10. Centrifuge the tube at 2000 rpm for 5 min. Decant the supernate into a 30-mL
polyethylene bottle. Discard the precipitate.
11. Add 10-15 drops of HCl and exactly 1.00 mL of yttrium carrier solution to the sample
in the polyethylene bottle and enough water to bring the volume of the solution to the
same level as in the reference bottles.
12. Proceed to Strontium-85 yield determination.
Notes:
1. The pH of the solution is critical at this point. Complete precipitation of BaCrO4 will
not occur in a more acidic solution and strontium will partially precipitate in more
basic solutions.
2. If large quantities of barium are present in the sample, only a partial precipitation of
the Ba as BaCrO4 may occur. The sample is centrifuged and the supernate decanted
into another 40-mL centrifuge tube. The precipitation is completed by the dropwise
addition of 0.3M Na2CrO4 to the supernate and the analysis is continued with Step 10.
C. Strontium-85 yield measurement.
1. Measure the activity of the three reference aliquots, the blank and the sample with a
NaI(Tl) crystal gamma detector, collecting at least 104 counts.
2. After subtracting the background counts, calculate the 85Sr yield of the sample by
dividing the sample counts by the average of the three reference counts.
3. Store the sample for 2 weeks to allow 90Y to reach secular equilibrium with 90Sr (see
Note).
Note: The first milk separation time noted in Step 3, First milking, is the start of the
yttrium ingrowth period. In order to correct for less than complete buildup of 90Y, a
correction factor is included in the calculations.

D. Second milking.
1. Quantitatively transfer the sample from the polyethylene bottle to a 40-mL, heavy-
walled, conical centrifuge tube with a minimum of H2O. Stir the solution and place
the tube in a 90oC water bath to warm.
2. While stirring, adjust the pH of the sample to 8 with NH4OH. Add six drops of H2O2
and heat for 1 h. Remove and rinse the stirring rod. Remove the centrifuge tube from
the water bath and cool to room temperature in a cold water bath.
3. Centrifuge the sample for 5 min at 2000 rpm. Decant the supernate into another
40-mL centrifuge tube. Record the hour and date of the precipitation as second milk
separation time.
4. Dissolve the precipitate in the centrifuge tube with a few drops of HCl and stir.
Dilute the sample to 15 mL with H2O. Stir the solution and warm the tube in the hot
water bath.
5. While stirring, adjust the pH of the sample to 8 with NH4OH. Remove and rinse the
stirring rod. Remove the centrifuge tube from the water bath and cool to room
temperature in a cold water bath.
6. Centrifuge the sample for 5 min. Decant and combine the supernate with the
supernate reserved from Step 3. Return the combined supernates to the hot water
bath and reduce the volume to 20 mL. Transfer to a 30-mL polyethylene bottle and
set aside for possible future milking.
7. Add four drops of HCl to the precipitate and stir until it dissolves. Add 25 mL of
H2O, stir and heat in the hot water bath.
8. Add 1 mL of strontium carrier (20 mg Sr) to serve as a holdback carrier. While

stirring, adjust the pH to 8 with NH4OH.
9. Remove and rinse the stirring rod. Remove the sample tube from the hot water bath
and cool in a cold water bath.
10. Centrifuge the tube at 2000 rpm for 5 min. Decant and discard the supernate.

11. Add three drops of HCl to dissolve the precipitate, and 25 mL of H2O.
12. Stir the sample and place the tube in a hot water bath. Add 1 mL of saturated H2C2O4
(oxalic acid) solution.
13. Adjust the pH to 2-3 by the dropwise addition of NH4OH with vigorous stirring.
Digest the sample in the hot water bath for 1 h.
14. Rinse and remove the stirring rod from the tube, and cool it to room temperature in
cold water.
15. Centrifuge the tube at 2000 rpm for 10 min. Decant and discard most of the
supernate.
16. Dry a 2.8-cm Whatman No. 42 filter paper on a 110oC hot plate or in an 110oC oven,
cool and weigh to the nearest 0.1 mg.
17. Using a Teflon filter funnel assembly, filter the precipitate by suction through the
weighed 2.8-cm Whatman No. 42 filter paper, backed by a 2.8-cm glass fiber filter,
completing the transfer with a minimum amount of water. Wash the precipitate with
95% ethanol.
18. With the suction on, remove the filter funnel. Carefully separate the Whatman filter
with the precipitate from the glass fiber filter backing. Place the filter paper with the
precipitate on a 110oC hot plate. Turn off the vacuum and discard the glass fiber
filter. Discard the filtrate.
19. Dry the filter with precipitate to a constant weight to determine the gravimetric yield.
20. Carefully mount the filtered precipitate on a nylon disc, cover with Mylar, and fasten
the assembly with a nylon ring.
21. Measure the sample in a low-level gas flow proportional counter, recording the hour
and date of the beginning of the measurement period.
22. Collect at least 10,000 counts, disregarding the first 200 min (2 cycles) of counting to
eliminate possible interference from any 222Rn progeny present due to the filtration
process. Proceed to calculations.

E. Gravimetric yttrium yield measurement.
1. Standardize triplicate 10-mL aliquots of the original yttrium carrier solution each
time a fresh batch is made by precipitating the oxalate as described above and
filtering through a fine (grade F), tared, sintered, glass filter crucible that has been
dried to a constant weight.
2. Determine the weight of the yttrium oxalate precipitated from the sample as described
in Steps 15-19 of Second Milking. The yttrium yield is the ratio of the weight of the
sample oxalate to the standardized weight of the oxalate precipitated from the carrier
solution.
CALCULATIONS
The ß counting data obtained from the 90Y precipitate must be corrected to give the
activity of the 90Sr in the sample. The corrections include those for ingrowth of 90Y,
counter background, 90Y efficiency, strontium yield, yttrium yield, and 90Y decay. 90Y
beta emissions are very energetic and are always counted with approximately the same
mass of precipitate, so no correction for self-absorption is necessary.
The strontium yield is ordinarily determined by measuring the recovery of 85Sr tracer
added to the sample. Since the ratio of sample counts to counts from an aliquot of the
original 85Sr tracer solution is used to determine yield, there is no need to know the
radioactivity rate of the tracer or to apply decay corrections for 85Sr.
The activity of a sample of 90Sr over a time interval, t, is
' ' '

∫0 Adt = ∫0A 0e−λt'dt'
where A0 is the initial activity of the sample. Integrating and rearranging to solve for A0
yields:
λ
( '
A 0 = ∫0 Adt' ⋅ )
1 − e − λt

The half-life of 90Sr is quite large (29 y), so A0 is essentially constant throughout the
period of chemical separation and analysis. After 2 weeks, a sample of 90Sr will be in
secular equlibrium with its daughter, 90Y, and the activities of the two nuclides will be
equal. The quantity under the integral sign in the last equation above is the (corrected)
measured activity of the separated 90Y over the time period from separation to end of
counting:
t N y − B ⋅ dt c
∫ Adt ′ =
0 R y ⋅ R Sr ⋅ I y ⋅ D y ⋅ E c
To obtain A0 , this quantity is multiplied by the factor
λY
1− e λY ⋅dtc
−
where:
8Y = decay constant of 90Y (0.0108 h-1)
dtc = total count time minus two 100-minute cycles (see Note)
Ny = total counts from all cycles except the first two (see Note)
B = counter background for the matrix used (90Y-oxalate)
Ry = yttrium yield fraction
Rsr = strontium yield fraction
90
Iy = Y ingrowth fraction = 1-e-0.0108 A dt162 = fraction of 90Y produced during the
time from extraction of 90Sr ("1st milk") to separation of 90Y from 90Sr ("2nd
milk")
90
Dy = Y decay fraction = e-0.0108 A dt26c0
Ec = counter efficiency for 90Y-oxalate (counts min-1 dpm-1)

dt162 = 1st milk to 2nd milk time
dt26c0 = 2nd milk time to start of counting plus two 100-min cycles (see Note)
Note: The first two cycles are ignored to allow for the decay of short-lived beta-emitting
daughters from any radon-222 that may have attached to the Y-oxalate mount during
preparation.
The calculated activity of the blank is subtracted from the calculated activity of the
sample. The result is converted to appropriate units and divided by the sample size to
obtain the activity concentration of the sample.
To check the radiochemical purity of the 90Y-oxalate precipitate, a weighted linear

regression analysis is done on the counting data, with Ln (counts-background counts)
plotted against time. The weighting factor is the variance of the dependent variable:
( )
2
c + σ c bkg
(
Weighting factor = Var In(c − cbkg ) = )
(c − c )
2
bkg

where:
C = sample counts
Cbkg = background counts
F Cbkg = standard deviation of background counts
The slope of the weighted regression line is equal to 8Y, the decay constant of 90Y.
The value for 8Y obtained from the regression analysis is compared to the known value of
0.0108 h -1.
All calculations are done by computer.

Yield (Sr) (%) 80
Yield (Y) (%) 95
Blank (cps)
LLD (400 min) (Bq) 0.007

LLD (1000 min) (Bq) 0.004

APPENDIX
YTTRIUM CARRIER COUNTING CHECK
To varify that the carrier solution contains only stable yttrium, complete the
following procedure:
1. Pipette 1 mL of ytttrium carrier into each of three 40-mL centrifuge tubes. Dilute to
20 mL with H2O.
2. Heat in a water bath to about 90oC. While stirring, adjust the pH to 8 with NH4OH.
Digest for 10 min and cool in a cold water bath.
3. Centrifuge for 5 min. Decant and discard the supernate. Proceed with Steps 11-22 of
Second Milking.

Sr-04-RC
STRONTIUM-90 IN WATER CONTAINING OTHER

RADIOISOTOPES BY CERENKOV COUNTING
Contact Person(s) : Salvatore C. Scarpitta
APPLICATION
The following procedure is used in the EML Quality Assessment Program (QAP;
Sanderson and Greenlaw, 1996) for water or gross alpha/beta samples containing 90Sr.
This procedure was developed by Jimmy Chang, Institute of Nuclear Energy Research,
Taiwan, and was tested at EML using NIST 90Sr/Y reference materials and 90Sr contained
in QAP water samples. It allows for the rapid determination of 90Sr ($max = 0.546 MeV)
via its progeny, 90Y ($max = 2.27 MeV) in aqueous solutions by Cerenkov counting (see
Procedure Ba-01-R; Scarpitta and Fisenne, 1996).
Cerenkov counting is applicable for $ particles with maximum energies > 0.263
MeV. Alpha and gamma emitting nuclides are not detected. Immediately following
separation of 90Y from 90Sr, a baseline count rate, Cb, is obtained to quantify any
Cerenkov contribution by other nuclides that may be present in the sample.
Yield recovery is determined by adding 30 mg of Sr+2 carrier to the sample or by

gamma counting the added 85Sr tracer. The sample is Cerenkov counted at any two time
intervals, t1 and t2, to measure the ingrowth of 90Y above Cb. Strontium-90 is calculated
from the ingrowth of 90Y. The Cerenkov counting efficiency for 90Y in water is about 65-
70%, whereas that of 90Sr is < 0.3% for a 0-15 keV Cerenkov counting window. For a
20-min count time, the detection limit is about 6 mBq mL-1 (0.16 pCi mL-1) or 0.35 dpm
mL-1 with a relative standard deviation < 3%.

SPECIAL APPARATUS
Packard Tri-Carb 2250-CA liquid scintillation spectrometer
SPECIAL REAGENTS
1. NIST traceable 90Sr/Y reference standard of known activity (about 1000 dpm g-1) to
determine the 90Y Cerenkov counting efficiency.
2. TRU Resin - Eichrom Industries, 8205 Cass Ave., Suite 107, Darien, IL 606651.
DETERMINATION
1. Dispense about 8-16 Bq of 90Sr gravimetrically into either a 20 mL low 40K

borosilicate glass or plastic scintillation vial (see Note 1).
2. Add 10 mL of deionized water.
3. Prepare a blank using 10 mL of water.
4. Count both samples three times for 10-min each using the net average count rate to
determine the 90Y counting efficiency, E 90Y (counts min-1 dpm-1).
5. Preset the Packard Tri-Carb to Protocol 4 for Cerenkov determinations (Scarpitta and
Fisenne, 1996). (Note: The Cerenkov counting window is typically 0-15 keV,
although the full window, 0-2000 keV, may be used with a 50% increase in
background.)
6. Obtain a sample containing an unknown amount of 90Sr.
7. Add 30 mg of Sr++ carrier (as nitrate) to the sample for yield recovery.
8. Prepare an identical vial containing water as a Sr++ reference standard.
9. Reduce a premeasured amount, Mg (g), of sample to be tested to 10 mL to improve

counting statistics.

Note :
1. A wavelength shifter, ANSA (7-Amino 1,3 Naphthalene di-Sulfonic Acid) can be

used to enhance the Cerenkov counting efficiency but is not recommended if
strontium yield recovery is to be determined gravimetrically. Nuclides that produce a
Cerenkov signal in 25 mM ANSA are shown in Figure 1 (see Scarpitta and Fisenne,
1996).
SEPARATION
1. Separate the 90Y from the 90Sr by either oxalate precipitation (see Procedure Sr-03-
RC) or EiChrom’s TRU Spec extraction chromatographic resin. Record the
separation date and time, to.
2. Obtain a net baseline count rate for Cb immediately following 90Y separation, using
Protocol No. 4 on the Packard Tri-Carb 2250 CA counter and the Cerenkov counting
window (0-15 keV).
CALCULATIONS
1. Recount the 90Sr fraction three times a day over a 2-day period using the count rates
(counts min-1) CT1, CT2 and CT3 to calculate the 90Sr activity in Step 2. The times t1,
t2 and t3 are the number of hours after 90Y separation in Step 1 of Separation.
2. Use the 90Sr calculation as follows when 89Sr is not present in the sample. (Note: A
Basic computer program is provided in the Appendix to perform the 90Sr
calculations.)
(CT − CT1 ) − C b
Sr (Bq kg -1 ) =
2
A1 90 (1)
60 x M S x E 90
[ { } {
Y x exp -λ (t 1 - t 0 ) − exp -λ (t 2 - t 0 ) }]
(CT - CT1 ) - C b
A2 90
(
Sr Bq kg -1 = ) 3
(2)
60 x M S x E 90
[ { } {
Y x exp -λ(t 1 - t 0 ) - exp -λ(t 3 - t 0 )}]
where:
90
8 = Y decay constant - 0.01083 h-1
E 90Y = 90Y Cerenkov counting efficiency (counts min-1 dpm-1)
Ms = mass of sample (kg)
3. Obtain the average of the two 90Sr activity concentrations, A1 and A2 from Step 2.
(Note: A third count could be obtained with Equation 2 if modified accordingly.)
4. Using the sample vial and the Sr+2 reference standard, precipitate the strontium as the
carbonate, filter, dry and weigh each to obtain the yield recovery. Correct the value
obtained in Step 3, dividing by the yield recovery factor. (Note: Gamma emitting
85
Sr can be added to the sample in Step 7 of Determination instead of Sr+2.)
REFERENCES
Sanderson, C. G. and P. Greenlaw

“Semi-Annual Report of the Department of Energy, Office of Environmental
Management, Quality Assessment Program”

“Cerenkov Counting as a Complement to Liquid Scintillation Counting”
Appl. Radiat. Isot., 47, 795-800 (1996)


Cerenkov Efficiency in 10 ml of 25 mM ANSA

(Plastic Vials)
Figure 1. Cerenkov efficiency in 10 mL of 25 mM ANSA (plastic vials).

APPENDIX
Basic Computer Program
10 REM "SR90CER.BAS" BY J.CHANG METHOD

20 REM CALCUlaTE 90SR ACTIVITY(DPM) FOR A SAMPLE USING CERENKOV COUNTING
50 TITLE$--"Test of Cerenkov Method Using 895 dpm of NIST 90-Sr Standard"
60 COUNTIME$="10 min"
100 REM ENTER TIME DATA HERE
120 DELTl=.75 ' HRS
122 DELT2=19.22
124 DELT3=111.6
130 REM ENTER COUNT RATES HERE
132 CT1=36.5
134 CT2 = 159.1
136 CT3=514. 4001
150 LAMBD2 = .01083 ' HR-1
160 EFFY90=.82 ' CPM/DPM
200 REM CALCULATE SR90 ACTIVITY(DPM) HERE
205 DF1 = EXP ((-LAMBD2*DELT1)) - EXP ((-LAMBD2*DELT2))
210 A1SR90 = (CT2-CT1) / (DF1*EFFY90)
255 DF2 = EXP ((-LAMBD2*DELT1)) - EXP ((-LAMBD2*DELT3))
260 A2SR90 = (CT3-CT1)/(DF2*EFFY90)
500 REM PRINT RESULTS
510 CLS : SCREEN 2 : KEY OFF
520 PRINT DATES;" ";
525 PRINT "STRONTIUM-90 RESULTS BY Sr-SPEC and CERENKOV COUNTING" : PRINT
530 PRINT TAB(10);TITLE$ : PRINT
535 PRINT TAB (15); "Count Time = ";COUNTIME$; TAB (40) ;"Y-90 Effiency = ";EFFY90:
PRINT : PRINT
540 PRINT "Data" : PRINT
550 PRINT TAB (1); "Del Ti" ;TAB (10); "Cnt Ti" ;TAB (30); "Del T2" ;TAB (40); "Cnt T2" ;TA (60) ;"Del T3" ;TAB (70);
"Cnt T3"
555 PRINT TAB (1);" (hr) ";TAB (10);" (cpm) ";TAB (30);" (hr) ";TAB (40);" (cpm) ";TAB (60); (hr) ";TAB(70);" (cpm)":
PRINT
557 PRINT TAB(l) ;DELT1;TAB(10) ;CT1;TAB(30) ;DELT2;TAB(40) ;CT2;TAB(60) ;DELT3;TAB( 0) ;CT3
560 PRINT : PRINT : PRINT :PRINT "Sr-90 Results";
570 PRINT TAB (30) ;A1SR90;" dpm" ;TAB(60) ;A2SR90;" dpm"
575 PRINT TAB(l) ;"Obs/Exp";TAB(30) ;A1SR90/895;" ";TAB(60) ;A2SR90/895;
580 PRINT : PRINT : PRINT
02-21-1995 STRONTIUM-90 RESULTS BY Sr-SPEC and CERENKOV COUNTING
Test of. Cerenkov Method Using 895 dpm of NIST 90-Sr Standard
Count Time -- 10 min Y-90 Effiency -- .82
Data
Del T1 Cnt T1 Del T2 Cnt T2 Del T3 Cnt T3

(hr) (cpm) (hr) (cpm) (hr) (cpm)
.75 36.5 19.22 159.1 111.6 514.4001
Sr-90 Results 831.421 dpm 840.6198 dpm

Obs/Exp .928962 .9392401
Ok

HASL-300, 28th Edition September 2001
Sr-05-RC
STRONTIUM-90 IN ENVIRONMENTAL WATER SAMPLES
APPLICATION
This procedure is applicable to the radiochemical analysis of 90Sr in tap water,

surface water, and rain water samples.
After addition of strontium carrier and 85Sr tracer, strontium is separated from 137Cs
and other base soluble fission products by carbonate precipitation. The 90Y and traces of
activation and other fission products are scavenged with iron hydroxide. Radium, lead
and barium are removed with barium chromate. The excess chromate from the barium
precipitation is removed by a second strontium carbonate precipitation. Yttrium carrier is
then added. After 90Sr + 90Y equilibrium has been attained, the 90Y is precipitated as the
hydroxide and converted to the oxalate for counting in a low-background gas
proportional beta counter. Strontium recovery is determined by counting the 85Sr tracer
in a NaI(Tl) gamma well detector.
The procedure provides strontium yields of > 80%. Gravimetric yields of yttrium
oxalate are > 90%.
SPECIAL APPARATUS
1. Teflon filter holder or filter funnel and sample mount - see Specification 7.12.
4. Polyethylene bottles, 30 mL narrow mouth to fit in the gamma well detector

(Wheaton No. 209045SP or equivalent).

5. Petri dish, glass, 4 quadrant (VWR, Bridgewater, NJ 08014 or equivalent).
6. Ionizing unit with positioner (static remover, VWR, Bridgewater, NJ 08014 or

equivalent).
SPECIAL REAGENTS
1. Strontium carrier, 20 mg Sr+2 mL-1 - dissolve 48.4 g Sr(NO3)2 in 1 L of 1:99 HNO3.
2 Yttrium carrier, 10 mg Y+3 mL-1 (see Procedure Y-01-RC, Standardization of

Yttrium Carrier).
3. Iron carrier, 5 mg Fe+3 mL-1 - dissolve 5 g of iron wire in 1:1 HCl and dilute to 1 L
with 1:99 HCl, or dissolve 34.7 g Fe(NO3)3C9H2O in 1 L of 1:99 HNO3.
4. Barium carrier, 10 mg Ba+2 mL-1 - dissolve 9.5 g Ba(NO3)2 in water and dilute to
0.5 L.
5. Barium buffer solution - mixture of 0.5 L 6M acetic acid (HOAc) plus 1 L of

6M NH4OAc plus 0.5 L Ba carrier (10 mg mL-1).
85
7. Sr tracer, about 7 x 104 Bq L-1 - this tracer should provide about 25 counts sec-1
mL-1 in a NaI(Tl) gamma well detector with a 85Sr efficiency of ~ 35.0%.
8. Sodium chromate solution, 0.3M - dissolve 50 g Na2CrO4 in water and dilute to 1 L.
9. Sodium carbonate solution, saturated.
10. Ammonium oxalate solution, saturated.
11. Meta cresol purple indicator solution.

SAMPLE PREPARATION
A. Initial preparation and purification.
1. Transfer a measured quantity of water sample to an appropriate sized and labeled

beaker. Prepare an equal volume of blank using deionized water (see Note 1).
2. Add 1.0 mL (20 mg) strontium carrier to the blank and each water sample.
3. Add 1.0 mL of 85Sr tracer to three 30-mL plastic bottles, the blank and each sample.
4. Fill the plastic bottles with equal volumes of 1M HCl. Cap, shake to mix and set
aside. They will serve as references when determining the strontium yield.
5. Place a speedy-vap watch glass on the beakers, place the beakers on a hot plate and
evaporate to reduce the volume to ~ 20 mL. Transfer each solution to a labeled
40-mL centrifuge tube using deionized water as a rinsing agent.
6. Adjust the pH of the solution to >8.5 with NH4OH, while stirring with a glass rod.
7. Warm the tubes in a hot water bath and slowly add 10 mL of saturated Na2CO3 with
stirring.
8. Digest the precipitate for ~ 20 min and cool to room temperature. Add several drops
of 1.0 % Aerosol OT solution and centrifuge at 2000 rpm for ~ 5 min.
9. Decant and discard the supernate in an appropriate manner.
10. Add 10 mL of 3M HNO3 to dissolve the SrCO3 precipitate in the centrifuge tube (stir
well to break up the precipitate).
11. Boil the solution over a flame while stirring with a glass rod for ~ 1 min to evolve all
CO2, cool the tube, and proceed to First Milking.

B. First milking.
1. Add 1 mL (5 mg mL-1) of iron carrier solution to the separated strontium fraction in

the centrifuge tube.
2. While stirring with a glass stirring rod, adjust the pH of the sample to > 8.5 with
NH4OH. Digest the hydroxide precipitate in a hot water bath with occasional
stirring for ~ 15 min. Remove the centrifuge tube from the hot water bath and cool
to room temperature. Remove and rinse the stirring rod with water.
3. Add several drops of 1.0% Aerosol OT solution, and centrifuge the sample at 2000
rpm for ~ 5 min. Decant the supernate into a second 40 mL centrifuge tube. (Note:
Record the time and date of the decantation as the first milk separation time.)
4. Dissolve the Fe(OH)3 precipitate in a few drops of HCl and dilute to 10 mL with
water.
5. Repeat Step 2 of First Milking.
6. Add several drops of 1.0% Aerosol OT solution and centrifuge the sample at 2000
rpm for ~ 5 min.
7. Decant and combine the supernate with the supernate from Step 3; discard the
precipitate.
8. Evaporate the combined supernates in a hot air bath to reduce the volume to
~ 20 mL.
9. Add 4 mL of barium buffer solution to the combined supernates from Step 6.
10. Adjust the pH of the sample to 5.5 with either 6M HCl or NH4OH, if necessary (see
Note 2).
11. Heat the centrifuge tube in a hot water bath.
12. Add 1 mL of 0.3M Na2CrO4 dropwise to the sample, while stirring vigorously (see
Note 3).

13. Allow the precipitate to digest in the hot water bath for ~10 minutes.
14. Remove the sample tube from the hot water bath and cool to room temperature.
15. Remove and rinse the stirring rod with water.
16. Add several drops of 1.0% Aerosol OT solution, and centrifuge the sample tube at
2000 rpm for ~ 5 min.
17. Decant the supernate into a labeled 40 mL centrifuge tube and discard the
precipitate.
18. Adjust the pH of the supernate to >8.5 with NH4OH, heat in a hot water bath and
slowly add 10 mL of saturated Na2CO3 solution with stirring.
19. Digest, with occasional stirring with a glass rod, in a hot water bath for ~ 15 min.
20. Remove the centrifuge tube from the hot water bath and cool to room temperature.
21. Remove and rinse the stirring rod with water.
22. Add several drops of 1% Aerosol OT solution, centrifuge at 2000 rpm for ~ 5 min,
decant and discard the supernate in an appropriate manner.
23. Wash the precipitate with 10 mL of water, add several drops of 1.0% Aerosol OT
solution, centrifuge at 2000 rpm for ~ 5 min and discard the wash.
24. Add 5 mL of 3M HNO3, boil the solution over a flame while stirring with a glass rod
for about 1 min to evolve all the CO2. Cool the solution to room temperature.
25. Add 1 mL of standardized yttrium carrier solution (10 mg Y+3 mL-1) using a Class A
pipette. Transfer the solution to a 30 mL polyethylene bottle using water as a rinsing
agent.
26. Add enough water to bring the volume of the solution to the same liquid level as the
85
Sr reference bottles.
27. Cap the bottle and shake well.

28. Proceed to Strontium-85 yield determination.
C. Strontium-85 yield determination.
1. Measure the activity of the three reference aliquots, the blank and the sample with a
NaI(Tl) gamma well detector. Count each bottle for total of 104 counts.
2. Calculate the 85Sr yield (strontium recovery) of the sample by dividing the sample
counts by the average of the three reference counts, after subtracting the background
counts.
3. Store the sample for 2 weeks to allow 90Y to reach secular equilibrium with 90Sr
(see Note 4).
D. Second milking.
1. Transfer the sample from the polyethylene bottle to a 40 mL centrifuge tube.
2. Rinse the bottle with water and combine with the sample in the centrifuge tube.
3. Add 3 to 4 drops of meta-cresol purple indicator solution.
4. Precipitate Y(OH)3 by the drop-wise addition of 6N NH4OH until the indicator color
changes from yellow to purple at pH 7.8 (see Note 5).
5. Digest the precipitate in a hot water bath with occasional stirring for 15 min, cool to
room temperature, add 3 to 4 drops 1.0% Aerosol OT solution and centrifuge at
2000 rpm for ~ 5 min.
6. Decant the supernate containing the strontium fraction into a clean 40 mL centrifuge
tube and reserve for remilk.
7. Record the date and time of the decantation as the second milk separation time.
8. Dissolve the Y(OH)3 precipitate in the centrifuge tube by adding a few drops of
HCl, stir and dilute to 10 mL with water.

9. Add approximately 1 mL of strontium holdback carrier (20 mg Sr) and 3 to 4 drops

of meta-cresol purple indicator solution and reprecipitate Y(OH)3 with 6M NH4OH
(as in Step 4).
10. Heat the tube in a hot water bath with occasional stirring using a glass rod for ~ 10
min. Cool, add 3 to 4 drops of 1% Aerosol OT solution, centrifuge at 2000 rpm for
~ 5 min and combine the supernate with the strontium supernate from Step 6.
11. Repeat Steps 8 to 10 for a third time.
12. Acidify the combined supernates containing the strontium fraction with HCl and
reduce to a volume of ~ 20 mL in a hot air bath. Transfer the solution to a 30 mL
polyethylene bottle and set aside for possible remilking.
13. Add 2 mL of 1M HCl and 1.5 mL of 6M HNO3 to the Y(OH)3 and stir with a glass
rod to completely dissolve the precipitate.
14. Heat to boiling over a flame while stirring and add 5 mL of saturated (NH4)2C204
solution with stirring.
15. Stir for ~ 1/2 minute and gradually add an additional 10 mL of saturated (NH4)2C204.
16. Digest in a hot water bath for 20 min with intermittent stirring.
17. Remove the centrifuge tube from the hot water bath and cool to room temperature.
18. Condition a 2.8 cm Whatman No. 42 filter paper by washing with ~ 10 mL of water
and ~ 15 mL of 95% ethanol, using a Teflon filter funnel assembly.
19. Place the filter paper in a labeled quadrant of the Petri dish, dry in an oven at 105oC
for ½ hour and cool in a desiccator for ½ h.
20. Weigh the filter paper and record the weight to the nearest 0.1 mg.
21. Filter the yttrium oxalate precipitate onto the previously washed, dried and weighed
Whatman No. 42 filter paper using ~ 10 mL of water and and ~ 10 mL of 95%
ethanol as transfer agents.

22. Place the filter paper and precipitate in a quadrant of a Petri dish, dry in an oven at
105oC for ½ hour and cool to room temperature in a desiccator (½ h).
23. Weigh the filtered precipitate and record the weight to the nearest 0.1 mg.
24. Carefully mount the filtered precipitate on a nylon disc, cover with Mylar (after
removing any static electricity from the Mylar with an ionizing unit), fasten the
assembly with a nylon ring, trim the excess Mylar, and beta count.
25. Determine the yttrium yield from the ratio of the weight of the sample yttrium
oxalate to the expected weight of yttrium oxalate as determined from the yttrium
carrier standardization. [Note: The gravimetric factor for conversion of yttrium to
yttrium oxalate is 3.397].
26. Calculate the sample 90Y activity as in Procedure Sr-03-RC.
Notes:
1. The quantity of deionized water for the blank determination should be equivalent to
the largest sample volume used.
2. The pH of the solution is critical at this point. Complete precipitation of BaCrO4

will not occur in a more acidic solution and strontium will partially precipitate in
more basic solutions.
3. If large quantities of barium are present in the sample, only a partial precipitation of
the Ba as BaCrO4 may occur. The sample is centrifuged and the supernate decanted
into another 40 mL centrifuge tube. The precipitation is completed by the dropwise
addition of 0.3 M Na2CrO4 to the supernate until no additional precipitate forms and
the analysis is continued with Step16.
4. The first milk separation time noted in Step 3, First milking, is the start of the
yttrium ingrowth period. A correction factor for the time between the first milk and
second milk is applied in the calculation to correct for the ingrowth of 90Y.
5. The indicator changes from red to yellow at pH 7.0 and from yellow to purple at
pH 7.8.


Yield (Sr) (%) 80
Yield (Y) (%) 95
Blank (cps) -
LLD (400 min) (Bq) 0.007

LLD (1000 min) (Bq) 0.004

HASL-300, 28th Edition January 1997
Technetium

Tc-01-RC, Vol. II Rev. 0
Tc-01-RC
TECHNETIUM-99 IN WATER AND VEGETATION

(see Volume II)

Tc-02-RC, Vol. I Rev. 0
Tc-02-RC
TECHNETIUM-99 IN WATER - TEVA Resin
Contact Person(s): Salvatore C. Scarpitta*
APPLICATION
This procedure has been applied to the analysis of water.
The sample containing 99Tc is equilibrated with 95mTc, a gamma-emitting tracer. The
technetium is separated from other elements by ferric and ferrous hydroxide precipitation
from ammoniacal solutions. The sample is then passed through a commercially available
column that selectively extracts Tc(VII) from a 0.1M HNO3 solution. Technetium is
purified, eluted from the column and counted directly in a suitable liquid scintillation
cocktail. Typically, the sample is counted for 1 h to simultaneously determine 99Tc
activity and the 95mTc recovery.
Quench/efficiency calibration curves need to be established for the liquid scintillation

spectrometer for both 95mTc and 99Tc.
SPECIAL APPARATUS
1. Packard Tri-Carb 2250CA using Insta-Gel liquid scintillation cocktail - Packard

Instrument Co., 1 State St., Meriden, CT 06540 or equivalent.
_______________________________________
*Currently at Brookhaven National Laboratory, BSA, Upton, NY 11973.

2. Column reservoir - 25 mL capacity (Part No. AC-120) - Eichrom Industries, Inc.,

8205 Cass Ave., Suite 107, Darien, IL 60561 or equivalent.
SPECIAL REAGENTS
1. TEVA extraction chromatographic columns - (Part # TE-C50, 80-160 micron size) -

Eichrom Industries, Inc. or equivalent.
99
2. Tc standard solution - available from NIST.
95m
3. Tc tracer solution (free from 97mTc) - prepare a solution containing about
8 Bq mL-1 in 0.1M NH4OH - Brookhaven National Laboratory, BSA, Upton, NY
11973.
4. 6M sodium hydroxide solution - 240 g NaOH L-1 of water.
5. 2M sodium carbonate solution - 212 g Na2CO3 L-1 of water.
6. Calcium carrier solution, 200 mg of calcium mL-1 - dissolve 500 g of CaCO3 in a

minimum of 6M HCl and dilute to 1 L with 0.1M HCl.
7. Barium carrier solution, 20 mg of barium mL-1 - 30.4 g BaCl2 L-1 in 1 L of 0.1M

HCl.
8. Iron carrier solution, 5 mg of iron mL-1 - dissolve 36 g Fe(NO3)3A9 H2O in 1 L of

0.1M HNO3.
9. Fe(II)SO4 reductant solution, 0.14 mg mL-1 - dissolve 0.7 g of Fe(II)SO4A7 H2O in 1

L of water.
10. 0.1M HNO3 TEVA column wash solution - 6.5 mL HNO3 L-1 of water.
11. Methyl red indicator solution - dissolve 100 mg of the dye in 65 mL of ethyl alcohol
and dilute to 100 mL with water.
12. Nitromethane - Aldrich Chemical Co., Milwaukee, WI 53233.

SAMPLE PREPARATION
A. Water.
1. Evaporate a measured volume of sample containing 95mTc tracer (~8 Bq) to about
200 mL in an appropriate size beaker.
2. Prepare a reagent blank containing 95mTc tracer solution.
3. Add 10 mL of 30% H2O2, cover beaker and heat without boiling.
4. Cool and vacuum filter though a 15-cm glass fiber filter. Wash the filter and beaker
with a minimum of water.
5. Transfer the supernate to a 400-mL beaker and discard filters.
SEPARATION
1. Place a magnetic stirring bar in the sample beaker.
2. Add 1 mL of 200 mg mL-1 calcium carrier solution, 5 mL of 20 mg mL-1 of barium

carrier solution, and 10 mL of 5 mg mL-1 of iron carrier solution to the sample
solution.
3. Without heating, add 6M NaOH with continuous mechanical stirring until the
solution is alkaline (use pH paper). Then add 20 mL of 2M Na2CO3 and stir for
15 min.
4. Filter the sample using suction through two 15-cm glass fiber filters. Wash the
precipitate with 2M Na2CO3 solution. Discard the precipitate that contains any
alkaline earth metals, transition metals, rare earths, strontium, lead, CrO4-2, PO4-3,
and SO4-2. Transfer the sample solution to the original beaker.
5. Slowly add concentrated HCl to the filtrate until the solution is acidic to pH paper.
Add 2 mL of 0.14 mg mL-1 Fe(II) reductant solution and heat to 75°C for 1 h. This
reduces Tc(VII) to Tc(IV).

6. Coprecipitate Tc(IV) with iron hydroxide by the addition of 50% ammonia solution
to pH 9 and allow to stand, covered, for 1 h.
7. Centrifuge the solution in a conical 250-mL tube for 10 min at 2,000 rpm and
8. Dissolve the precipitate in 1 mL of 16M HNO3, which oxidizes Tc(IV) to Tc(VII).
9. Add a sufficient amount of NH4OH to precipitate Fe(OH)3, about pH 8.
10. Adjust the alkaline supernate solution (10 - 15 mL) for Sample Purification by
adding one drop of 0.1% methyl red indicator.
11. Add 8M HNO3 dropwise until the solution is yellow (pH 6.2).
12. Add 7.5M NH4OH until the solution is red (pH 4.2). Then add two drops of 1.6M
HNO3.
SAMPLE PURIFICATION
1. Condition the TEVA extraction columns by passing 8 mL of 0.1M HNO3 wash

solution at full flow (about 20 mL h-1).
2. Apply the entire sample to the 25-mL capacity reservoir. Collect the column effluent
in a 100 mL beaker.
3. Wash the column with 8 mL of 0.1M HNO3. Discard the column effluent and wash
solutions.
4. Cut the column body with a sharp blade and carefully extrude the resin into a 20-mL
low potassium borosilicate glass liquid scintillation counting (LSC) vial, using a
rubber pipetting bulb applied to the exit port of the column.
5. Wash the column body with exactly 2.0 mL of deionized water and add to the LSC
vial.

6. Pipette 15 mL of Insta-Gel cocktail into the vial, cap, and shake vigorously for
several minutes.
7. Wipe the external surface clean with ethyl alcohol.
8. Count the sample along with the reagent blank for 1 h with a window setting of
1-500 keV.
9. Record the gross counts per minute (gcpm), quench index parameter (QIP), and
spectral index of sample (SIS) on attached Technetium Worksheet, Section 1.
SAMPLE MEASUREMENT
A. Technetium-99 quench/efficiency calibration curve.
1. Prepare six labeled LSC vials, each containing 1.0 g of NIST 99Tc standard (about
8 Bq g-1).
2. Evaporate the 99Tc standard solution in the LSC vials to dryness under a heat lamp.
3. Add 15 mL of Insta-Gel to each vial.
4. Into each of the six labeled LSC vials, add successively increasing amounts of
nitromethane in 10 µL increments.
5. Prepare a separate vial containing 15 mL of Insta-Gel, plus 2 mL of deionized water

without 99Tc or nitromethane.
6. Shake capped vials for 1 min and count in the LSC for 1 h with a window setting of
1-500 keV.
7. Record the gcpm, QIP, and SIS on the Technetium Worksheet, Section 2.
B. Technetium-95m quench efficiency calibration curve.
1. Repeat Steps 1-6 above in Section A above with 95mTc tracer in separate vials.

2. Record the gcpm, QIP, and SIS on Technetium Worksheet, Section 3.
3. Also record the SIS value of the “zero” 95mTc vial in the Technetium Worksheet,
Section 1, LSA Ref. Std.
SAMPLE CALCULATION
1. Calculate the efficiency for 99Tc and 95mTc using the Technetium Worksheet,
Sections 2 and 3, Step 6.
2. Plot % efficiency vs. QIP, which should be linear over a wide range of QIP values
(see Figure 1).
3. Calculate the 99Tc activity (Bq kg-1) in a sample containing a mixture of 95mTc and
99
Tc using the following equation (see Technetium Worksheet, Section 1,
Steps 1-10).
( Net Total cpm) × (SIS − SIS )

99
(
Tc Bq kg -1 =) ( E ) × ( R) × 60 sec min × SIS − SIS
Mix 95m Tc
×W (1)
99 ( ) (-1
99 TC 95m TC )
where
E99 = 99Tc counting efficiency (cps Bq-1) at the QIP value of the sample
R = fractional 95mTc yield recovery (see Eqn 3 below)
W = weight of sample (kg)
SIS 99 Tc = SIS component of dual labeled sample due to 99Tc, calculated using
Eqn 2, unitless
SISMix = spectral index of dual-labeled sample, unitless
SIS 95m Tc = spectral index of the sample containing ONLY 95mTc (an LSA reference
vial), unitless
The 99Tc contribution to the SIS of a dual-labeled sample, SIS 99 Tc , is calculated from
the following relationship by taking the anti-log (i.e., the exp(ln SIS):

ln SIS 99 Tc =
(ln SIS 95mTC ) × (ln SIS ) Bl
(2)
ln SIS MIX
where
SISBl = spectral index of water blank sample (see Sample Measurement,

Section 1, Step 5, Column-A), unitless.
The results of these calculations are recorded on the Technetium Worksheet,

Section 1. A computer program can be used for data reduction using the full spectrum
analysis.
The fractional yield recovery, R, is determined directly from the LSA data using
R =
Net cpm of sample
×
(SIS 99 Tc − SIS MIX ) ×
1
Net cpm 95m Tc Ref. vial (SIS 99 Tc − SIS 95m Tc ) E 95 (3)
where
95m
E95 = Tc efficiency as a function of the QIP, determined from the Technetium
Worksheet, Section 3, Step 6.

120
100
99Tc ( 95% )
80
% Efficiency
95mTc (83%)
60
40
20
N o W a te r W a te r 0 .1 M H N O 3 1 .0 M H N O 3
2 .0 M H N O 3 4 .0 M H N O 3 8 .0 M H N O 3
0
0 100 200 300 400 500 600
Q IP
Figure 1. Counting efficiency for 99Tc and 95mTc in Insta-Gel cocktail

[Insta-Gel (50/50 mix); ROI = 1-500 keV].

TECHNETIUM WORKSHEET
1. UNKNOWN SAMPLE DATA
Matrix ____________ Lab. I.D. ______________________

95m
Date ____________ Tc Added ______ Bq g-1 ______
95m
Net cpm Tc: LSA Ref. Std. (1) ______ (2) ______
SIS 95mTc (1) ______ (2) ______
Net gamma counts of Ref. Std. ___________ in ______ min
(A) (B) (C) (D)

1. Sample ID No. H2O Blank Reagent Blank Sample Sample
2. Sample Mass (kg) xxxxx 1.0 ______ ______
3a. Total Gross cpm _________ ____________ ______ ______
3b. Total Net cpm (Bkg) _________ ____________ ______ ______
4. 2 sigma uncertainty _________ ____________ ______ ______
5. SIS _________ ____________ ______ ______
6. QIP _________ ____________ ______ ______
---------------------------------------------------------------------------------------------------------
Calculated Values:
7. SIS-99Tc xxxxx ____________ ______ ______

(use Eqn. 2 and Section 1.5
data)
8. LSA Yield Rec (R) xxxxx ____________ ______ ______

(use Eqn. 3 and Ref. Std.
Data)
9a. E99 @ QIP of Sample xxxxx ____________ ______ ______

(use Calibration Curve-I)
9b. E95 @ QIP of Sample xxxxx ____________ ______ ______

(use Calibration Curve-II)
10. 99Tc (Bq kg-1) xxxxx ____________ ______ ______

(use Eqn. 1)

TECHNETIUM WORKSHEET (Cont'd)
Results:
Net Average 99Tc (Bq kg-1) = ________ ± _______
Average Yield Recovery = _______%
Instrument Calibration Date _______ Code _______
Count Time (h) _______ : Region of Interest (keV) _______ to ________
---------------------------------------------------------------------------------------------------------------------------
99 99
2. Tc QUENCH/EFFICIENCY DATA Tc (Bq) Added _______
Quencher is Nitromethane in 10 :L Amounts

A B C D E F G
1. Sample (:L) 0 10 20 30 40 50 60
2a. Gross cpm ____ ____ ____ ____ ____ ____ ____
2b. Net 99Tc cpm ____ ____ ____ ____ ____ ____ ____
3. 2 sigma uncertainty ____ ____ ____ ____ ____ ____ ____
4. SIS ____ ____ ____ ____ ____ ____ ____
5. QIP ____ ____ ____ ____ ____ ____ ____
6. E99 ____ ____ ____ ____ ____ ____ ____
(Step 2b ÷ Bq 99Tc Added)
Plot E99 vs. QIP for 99Tc Efficiency Calibration Curve

95m 95m
3. Tc QUENCH/EFFICIENCY DATA Tc (Bq) Added _______
Quencher is Nitromethane in 10 :L Amounts

A B C D E F G
1. Sample (:L) 0 10 20 30 40 50 60
2a. Gross cpm ____ ____ ____ ____ ____ ____ ____
2b. Net 99Tc cpm ____ ____ ____ ____ ____ ____ ____
3. 2 sigma uncertainty ____ ____ ____ ____ ____ ____ ____
4. SIS ____ ____ ____ ____ ____ ____ ____
5. QIP ____ ____ ____ ____ ____ ____ ____
6. E95 ____ ____ ____ ____ ____ ____ ____
(Step 2b ÷ Bq 95mTc Added)
Plot E95 vs. QIP for 95mTc Efficiency Calibration Curve

Thorium

Th-01-RC, Vol. II Rev. 0
Th-01-RC
THORIUM IN URINE
(see Volume II)

HASL-300, 28th Edition April 1996
Uranium

U-01-RC, Vol. II Rev. 0
U-01-RC
ENRICHED URANIUM IN URINE

(see Volume II)

U-02-RC, Vol. I Rev. 1
*EPA APPROVED*
U-02-RC
ISOTOPIC URANIUM IN BIOLOGICAL

AND ENVIRONMENTAL MATERIALS
APPLICATION
This procedure has been used to analyze soft tissue, vegetation, water, and air filter
samples (Hindman, 1983; Sill and Williams, 1981; Welford et al., 1960).
Uranium from acid leached, dry-ashed and wet-ashed materials is equilibrated with
232
U tracer, and is isolated by anion exchange chromatography. The separated U isotopes
are microprecipitated for " spectrometry.
SPECIAL APPARATUS
1. Ion exchange columns (see Specification 7.5).
2. Polyethylene dispensing bottles (see Specification 7.11).
3. Special apparatus for the microprecipitation of U are listed under the generic
procedure, G-03.
*

SPECIAL REAGENTS
1. Uranium-232 tracer solution - about 0.3 Bq g-1 of solution in a dispensing bottle.
2. Bio Rad AG 1-X4 (100-200 mesh), anion exchange resin (see Specification 7.4).
SAMPLE PREPARATION
A. Vegetation and soft tissue.
1. Dry ash the sample according to the method described in Procedure Sr-02-RC
(see Note 1).
2. Weigh out 10 g of ash and transfer to a 400-mL beaker.
3. Add a weighed amount of 232U tracer solution (~ 0.03 Bq) from the dispensing bottle
(see Note 2).
4. Add 200 mL of HNO3 to the beaker and evaporate slowly to dryness.
5. Add 25 mL of HNO3 to the beaker. Repeat the acid addition and evaporation until a
white residue is obtained. (Note: If silicious material is present, transfer the sample
to a 100 mL platinum dish or a 100 mL Teflon beaker with HNO3. Add 10 mL of HF
to the vessel and evaporate to dryness. Repeat additions of 25 mL HNO3 - 10 mL HF
as necessary to volatilize the silica. Remove the HF by adding three successive
10-mL volumes of HNO3 to the vessel and evaporate to dryness.)
6. Add 25 mL of HCl and evaporate to dryness. Repeat the acid addition and
evaporation twice more.
7. Heat to dissolve the residue in 50-100 mL of 7N HCl.
8. Continue with Determination.

B. Water.
1. Evaporate the H2O sample to a small volume.
2. Add a weighed amount of 232U tracer solution (~ 0.017 Bq) from a dispensing bottle
and evaporate slowly to dryness (see Note 2).
3. Add 50 mL of HNO3 and evaporate to dryness. Add 25 mL of HNO3 and evaporate

twice more.
4. Dissolve the residue in 25 mL of HCl and evaporate to dryness. Repeat the HCl
addition and evaporation.
5. Heat to dissolve the residue in # 50 mL of 7N HCl.
C. Air filters.
Cellulose filters:
1. Add a weighed amount of 232U tracer solution (~ 0.017 Bq) from a dispensing bottle
to the filter in a platinum dish and dry ash in an electric muffle at 550oC (see Note 2).
2. Dissolve the residue in HNO3 and transfer to a 250-mL beaker.
3. Add 25 mL of HNO3 and evaporate to dryness. Repeat the acid addition and
addition and evaporation twice more.
5. Heat and dissolve the residue in # 50 mL of 7N HCl.

Glass fiber filters:
1. Place the filter and a magnetic stirring bar in a 400-mL Teflon beaker. Add a
weighed amount of 232U tracer solution (~ 0.033 Bq) from a dispensing bottle.
2. Add 100 mL of HNO3, mechancially stir while heating for 1 h. Reduce the solution
volume to ~ 25 mL. Remove the stirring bar and rinse with H2O.
3. Add 10 mL of HF and evaporate to dryness.
4. Repeat the 25 mL HNO3 - 10 mL HF additions and evaporations as necessary to

volatilize the silica.
5. Add 25 mL of HNO3 to the beaker and evaporate to dryness. Repeat twice more.
6. Heat and dissolve the residue in 25 mL of HCl and evaporate to dryness. Repeat the
HCl addition and evaporation twice more.
7. Dissolve the residue in #50 mL of 7N HCl.
DETERMINATION
1. Pass the 7N HCl sample solution obtained during sample preparation through a
prepared anion exchange column (see Note 3). Discard the column effluent.
2. Wash the column with 400 mL of 7N HCl. Discard the washings.
3. Elute the uranium with 200 mL of 1N HCl, collecting the eluate in a 250-mL beaker.
Discard the resin.
4. Evaporate the eluate to near dryness.
5. Destroy any residual organic material with dropwise additions of HNO3.

6. Evaporate the solution to dryness. Dissolve the residue in a few drops of HCl.
7. Convert the solution to the chloride with three 5-mL additions of HCl.
8. Add 1-2 mL of 1N HCl, prepared with filtered water (see Procedure G-03,
Microprecipitation Source Preparation for Alpha Spectrometry). Cool to room
temperature.
9. Continue the analysis under Procedure G-03, Microprecipitation Source Preparation

for Alpha Spectrometry.
Notes:
1. Freeze-dried or wet tissue may be wet ashed directly in HNO3. Proceed with Step 3
of Vegetation and Soft Tissue.
2. It is necessary to analyze reagent blanks with each batch of samples to correct the U
results.
3. 20 mL of Bio-Rad AG1-X4, prepared according to Specification 7.4 are conditioned

with 500 mL of 7N HCl.

Uranium Isotopes

Counter Background (cps) 3.33x10-6 for 238U
3.33x10-6 for 234U
Yield (%) 85
Blank (cps) 3.33x10-6 for 238U
3.33x10-5 for 234U
LLD (400 min) (mBq) 0.23 for 238U
0.53 for 234U
LLD (1000 min) (mBq) 0.21 for 238U
0.48 for 234U
LLD (5000 min) (mBq) 0.065 for 238U
0.15 for 234U

REFERENCES
Hindman, F. D.
"Neodymium Fluoride Mounting for Alpha Spectrometric Determination of Uranium,
Anal. Chem., 55, 2460-2461 (1983)

Anal. Chem., 53, 412-415 (1981)
Welford, B. A. , R. S. Morse and J. S. Alercio

"Urinary Uranium Levels in Non-Exposed Individuals"
Am. Ind. Hyg. Asso. J., 21 (1960)

U-03-RC
ISOTOPIC URANIUM IN BONE ASH
APPLICATION
This procedure has been used to analyze 50 g human bone ash samples (Fisenne
et al., 1980; Hindman, 1983; Sill and Williams, 1981).
Bone ash is dissolved in acid, and the U is equilibrated with 232U tracer and isolated
by solvent extraction. The purified U isotopes are microprecipitated for " spectrometry.
SPECIAL APPARATUS
1. Mechanical shaker.
2. Polyethylene dispensing bottle - see Specification 7.10.
procedure, G-03.
SPECIAL REAGENTS
2. Alamine-336, tertiary tricaprylyl amine (Henkel Corporation, 2430 N. Huachuca Dr.,

Tucson, AZ 85745-1273) 3:7 in toluene. Wash twice with an equal volume of 1:1
HCl. Prepare 100 mL of acid-washed 3:7 Alamine-336 for each sample.

3. Standardized sodium hydroxide 0.1N - dissolve 4 g of NaOH in H2O and dilute to

1 L. Standardize the solution against potassium acid phthalate.
4. Phenolphthalein indicator - dissolve 0.5 g of reagent in 100 mL of 95% ethanol.
SAMPLE PREPARATION
1. Weigh 50 g of ground, dry-ashed bone and transfer to a 400-mL beaker.
2. Add a weighed amount of 232U tracer (~ 0.01 Bq per sample) from the dispensing
bottle. (Note: It is necessary to analyze reagent blanks with each batch of samples to
correct the U results.)
3. Add 100 mL of HCl and heat gently on a hot plate for 10 min with occasional
stirring.
4. Add 70 mL of H2O and stir to obtain a clear solution. If insoluble material is present,
filter the sample through a glass fiber filter. Wash the filter with 1:1 HCl and discard
the residue.
5. Cool the solution. Transfer a 100-:L aliquot of the sample into a 150-mL beaker
containing 25 mL of H2O. Add two to three drops of 0.5% phenolphthalein indicator.
Stir and titrate the solution with 0.1N NaOH to the pink endpoint. Calculate the
normality of the sample solution.
6. If the normality is >5.8N in HCl, proceed directly to the extraction. If the normality
is <5.8N, transfer the sample to a 250-mL graduated cylinder and record the volume.
Return the sample to the beaker and add an appropriate volume of HCl to the cylinder
to increase the sample acid concentration to 6N. Transfer the acid to the sample
beaker and proceed with the extraction.

DETERMINATION
1. Transfer 50 mL of acid-washed Alamine-336 into each of two 500-mL separatory

funnels.
2. Transfer the sample to the first separatory funnel. Wash the beaker with 1:1 HCl and
add the washings to the funnel.
3. Shake the separatory funnel for 5 min. Allow the phases to separate and draw off the
aqueous (lower) phase into the second separatory funnel. Retain the organic phase in
the first funnel.
4. Shake the second separatory funnel for 5 min. Allow the phases to separate, draw
off, and then discard the aqueous (lower) phase.
5. Combine the two organic phases in one of the separatory funnels.
6. Wash the organic phase four times for 5 min with equal volumes of 1:1 HCl. Discard
the washings.
7. Strip the U from the organic phase by shaking twice for 5 min with 100-mL portions
of 0.1N HCl. Combine the strip solutions in a 400-mL beaker.
8 Evaporate the solution to near dryness.
Microprecipitation Source Preparation for Alpha Spectrometry). Cool to room
temperature.

Counter Background (cps) 3.33 x 10-6 for 238U

6.67 x 10-6 for 234U
Yield (%) 90
Blank (cps) 3.33 x 10-6 for 238U

3.30 x 10-5 for 234U
LLD (400 min) (mBq) 0.2 for 238U

0.5 for 234U
LLD (1000 min) (mBq) 0.1 for 238U

0.3 for 234U
LLD (5000 min) (mBq) 0.05 for 238U

0.1 for 234U

REFERENCES
Fisenne, I. M., P. M. Perry, and G. A. Welford

"Determination of Uranium Isotopes in Human Bone Ash"
Anal. Chem., 52, 777-779 (1980)
Hindman, F. D.
Anal. Chem., 55, 2460-2461 (1983)

Anal. Chem., 53, 412-415 (1981)

*EPA APPROVED*
U-04-RC
URANIUM IN BIOLOGICAL AND ENVIRONMENTAL MATERIALS

(see Volume II)

Y-01-RC, Vol. I Rev. 0
Y-01-RC
STANDARDIZATION OF YTTRIUM CARRIER
______________________________
APPLICATION
This procedure is applicable for the standardization of yttrium carrier solution. The
carrier is standardized, in triplicate, by the direct precipitation of yttrium oxalate,
Y2(C2O4)3C9H2O, from a measured quantity of carrier solution. The precipitate is then
filtered through a tared filtering funnel and the weight of the yttrium oxalate is
determined.
SPECIAL APPARATUS
1. Gooch type filtering funnels (30 mL, tall type) with fritted disc, fine or medium
porosity.
2. Filter funnel holders.
3. Flask, side arm vacuum, 500 mL.
4. Volumetric pipette, 10 mL, Class A.
5. Teflon filter holder or filter funnel and sample mount - see Specification 7.12
6. Ring and discs - see Specification 7.2
7. Mylar film - see Specification 7.5

SPECIAL REAGENTS
1. Yttrium carrier, 10 mg Y+3 mL-1:
a) dissolve 12.7 g of highest purity Y2O3 in a minimal amount of HNO3; use heat if
necessary. Gravity filter through Whatman No. 42 filter paper to remove any
insolubles (if necessary). Transfer the solution to a 1 L volumetric flask and
make up to volume with water.
b) or obtain a commercially prepared yttrium standard, e.g., 10000 :g Y+3 mL-1 in

5% HNO3 (SPEX CertiPrep, Metuchen, NJ 08840 or equivalent).
c) see the Appendix to determine any activity in the carrier.
2. Ammonium oxalate solution, saturated.
3. Ethyl alcohol, 95%.
SAMPLE PREPARATION
1. Condition each of three fritted disc glass filtering funnels with 25 mL of water and
25 mL of ethyl alcolhol.
2. Dry the funnels in an oven at 105oC for ½ hour, cool in a desiccator for ½ hour and
weigh to the nearest 0.1 mg. Record the tare weight of each funnel.
3. Pipette 10 mL quantities of yttrium carrier solution into each of three 100-mL

beakers.
4. Dilute to the carrier solutions to ~ 25 mL with water and heat to boiling on a hot
plate.
5. Slowly add 25 mL of saturated ammonium oxalate solution to the beakers with

stirring. Continue to heat the mixture on the hot plate with occasional stirring, using
a glass rod, for ~ 10 min.

6. Cool the beakers to room temperature and filter each precipitate, with vacuum,
through one of the tared filter funnels. Rinse each beaker with water and pass the
rinse through the filter funnels.
7. Wash the yttrium oxalate precipitate with ~ 25 mL of water, followed by 25 mL of

95% ethyl alcohol.
8. Dry the filter funnels in an oven at 105oC for ½ hour, cool in a desiccator for ½ hour.
Weigh the funnels containing the precipitates to the nearest 0.1 mg.
9. Record the total weight of each funnel and precipitate.
10. Calculate the weight of the yttrium oxalate precipitate.
11. Average the weights of the precipitates obtained from the replicate determination
and calculate the precision (standard deviation).
12. Repeat the carrier standardization if the precision from the standardization is > 0.5%.
13. Determine the yttrium yield for each sample analyzed from the ratio of the weight of
the sample yttrium oxalate to the expected weight of the yttrium oxalate, as
determined from the standardization. [Note: The gravimetric factor for conversion
of yttrium to yttrium oxalate is 3.397.]
APPENDIX
DETERMINATION OF THE ACTIVITY OF THE YTTRIUM CARRIER
The carrier is initially screened for activity by radioassay of the directly precipitated
yttrium oxalate (Section A). If the beta counting results are not within plus or minus
1 standard deviation of the mean of the counter background, proceed to Section B to
determine if the activity is attributed to 90Sr.

A. Initial screening.
1. Pipette 1 mL (10 mg mL-1) of yttrium carrier solution into each of three 40-mL
centrifuge tubes. Dilute to 20 mL with water.
2. Heat the tubes in a hot water bath to about 90°C, and, with stirring, add 10 mL of
saturated ammonium oxalate solution.
3. Digest the precipitates in the hot water bath for ~ 20 min or until the precipitate
settles.
4. Cool the tubes to room temperature.
5. Vacuum filter the precipitate, using a Teflon filter assembly, onto a 2.8-cm
Whatman No. 42 filter. Wash the tubes and precipitates with ~ 10 mL of water and
10 mL of 95% ethyl alcohol. Place the precipitates on a glass plate or cover glass.
6. Dry the precipitate in an oven at 105oC for ~ ½ hour, cool to room temperature.
Mount the Whatman disk containing the precipitate on a nylon disc, cover with
Mylar and beta count.
B. Specific determination.
1. If the beta counting results are not within the ± 1 standard deviation of the mean of
the counter background, pipette 1 mL of yttrium carrier into each of three 40-mL
centrifuge tubes and dilute to 20 mL with water.
2. Heat the tubes in a hot water bath to ~ 90oC, and, while stirring, adjust the pH to 8.0
(pH paper) with NH4OH.
3. Digest the precipitates for 10 min and cool to room temperature.
4. Centrifuge for the tubes for 5 min, decant and discard the supernate in an appropriate
manner.
5. Proceed with Steps 8 to 24, Paragraph D, Second Milking, Procedure Sr-05-RC

and beta count for the 90Y half-life.

Sectio n 4.5.5 , Vol. I Rev. 0
4.5.5 Generic Procedures
Environ menta l Measu remen ts Labora tory

G-01 , Vol. I Rev. 0
*EPA A PPROVED*
G-01
ELECTRODEPOSITION OF THE ACTINIDES: MITCHELL METHOD
APPLICATION
This method describes the preparation of separated actinide fractions for "-spectrom-
etry measurement (Mitchell, 1960). It is applicable to any of the actinides that can be
dissolved in HCl solution. The actinide fractions would be either the final elution from
an ion exchange separation or the final strip from a solvent extraction separation.
SPECIAL APPARATUS
1. Electrodeposition apparatus - see Specification 7.15.
2. Electrolytic cells - see Specification 7.16.
3. Platinum - iridium stirrer - see Specification 7.15.
4. Virgin platinum discs - 17.6 mm x 0.006 mm; mirrored finish on one side.
5. Ring and discs - Specification 7.2.
*

SPECIAL REAGENTS
Methyl red indicator solution 0.1% in ethanol - Fisher Chemical Co.
ELECTRODEPOSITION
1. Add 5 mL of concentrated HNO3 to the separated actinide fraction. Evaporate the

solution to dryness but do not bake.
2. Dissolve the residue in 2 mL of HCl and evaporate to near dryness. Repeat the HCl
and evaporate to near dryness. Repeat the HCl addition and evaporation twice more.
3. Add 1 mL of HCl and heat the solution gently. Transfer the solution to an
electrodeposition cell.
4. Rinse and police the beaker with two successive 1-mL portions of water. Add the
rinsing to the cell.
5. Add one drop of methyl red indicator solution to the cell and swirl the solution to
mix.
6. While swirling the solution in the cell, add 7.5N NH4OH until the pink color just
disappears.
7. Adjust the solution to a persistent pink color by dropwise additions of 2N HCl with
swirling to mix. Add two drops of 2N HCl in excess.
8. Dilute the solution in the cell to 5 mL with water.
9. With the platinum anode in the chuck of the stirring motor, lower the anode to about
1 cm above the platinum disc in the electrodeposition cell. Turn on the stirring motor
and adjust the speed to prevent splattering.
10. Turn on the current and adjust the flow to 1.2 A. Electrodeposit with the rotating
anode for 1 h. (Note: At EML the electrodeposition cell is supported on a lucite

pedestal which is immersed in an ice water bath to minimize evaporation of the

sample solution.)
11. Add 1 mL of NH4OH to the cell to quench the electrolyte.
12. Turn off the stirring motor. Raise the stirring motor and anode assembly, and turn off
the power supply. Pour off and discard the electrolyte solution. Rinse the cell with
water and discard the rinse.
13. Disassemble the cell and rinse the disc with ethyl alcohol solution. Touch the edge of
the disc with a tissue to absorb the excess alcohol.
14. Place the disc on a 200 to 250oC hot plate to dry.
15. Submit the sample for alpha spectrometry measurement.
INTERFERENCES
Any element present in the separated fraction that is able to be electrodeposited will
be present on the metal disc. In particular, 210Pb (5.30 MeV) deposited on the disc would
interfere with the yield determination of 232U (5.32 MeV) or 243Am (5.28 MeV) tracers
used in the determination of isotopic U and 241Am, respectively.
Incomplete separation of rare earth elements or incomplete wet ashing for the
removal of organic materials will decrease the efficiency of the electrodeposition and
may result in a thick deposit unsuitable for "-spectrometry measurement.
Samples containing more than 20 :g of U are unsuitable for measurement by

" spectrometry due to the thickness of the deposit.

REFERENCE
Mitchell, R. F.
"Electrodeposition of Actinide Elements at Tracer Concentrations"
Anal. Chem., 32, 326-328 (1960)

G-02
ELECTRODEPOSITION OF THE ACTINIDES: TALVITIE METHOD
Contact Person(s) : Isabel M. Fisenne and Pamela M. Perry
APPLICATION
This method describes the preparation of separated actinide fractions "-spectrometry

measurement (Talvitie, 1972). It is applicable to any of the actinides that can be
dissolved in dilute ammonium sulfate solution. Examples of applicable actinide fractions
would be the final elution from an ion exchange separation or the final strip from a
solvent extraction separation.
SPECIAL APPARATUS
1. Electrodeposition apparatus - see Specification 7.15.
2. Electrolytic cells - see Specification 7.16.
3. Platinum - iridium stirrer - see Specification 7.15.
4. Virgin platinum discs - 17.6 mm x 0.006 mm; mirrored finish on one side.
SPECIAL REAGENTS
Thymol blue indicator, sodium salt solution (0.04%) - dissolve 0.04 g of the salt in
100 mL of H2O.

ELECTRODEPOSITION
1. Add 2 mL of 0.36M NaHSO4 to the separated actinide fraction. Add 5 mL of

concentrated HNO3, swirl to mix, and evaporate the solution to dryness but do not
bake.
2. Dissolve the residue in 5 mL of electrolyte solution and warm the solution.
3. Transfer the sample solution to the electrodeposition cell. Rinse the beaker with
5 to 10 mL of electrolyte solution and add the rinsing to the electrodeposition cell.
4. Add three to four drops of thymol blue indicator to the sample and adjust the pH with
1.8M H2SO4 or concentrated NH4OH, or both, until a salmon pink color persists.
5. With the platinum anode in the chuck of the stirring motor, lower the anode to about
1 cm above the stainless steel disc in the electrodeposition cell. Turn on the stirring
motor and adjust the speed to prevent spattering.
6. Turn on the current and adjust the flow to 1.2 A. Electrodeposit with the rotating
anode for 1 hour. (Note: At EML the electrodeposition cell is supported on a lucite
pedestal which is immersed in an ice water bath to minimize evaporation of the
sample solution.)
7. After 1 h, add 1 mL of NH4OH to the cell to quench the electrolyte.
8. Turn off the stirring motor. Raise the stirring motor and anode assembly and turn off
the power supply. Pour off and discard the electrolyte solution. Rinse the cell with
three successive portions of 0.15M HN4OH. Discard the rinsings.
9. Disassemble the cell and rinse the disc with ethyl alcohol. Touch the edge of the disc
with a tissue to absorb the excess alcohol.
10. Place the disc on a 200 to 250oC hot plate to dry.
11. Submit the sample for "-spectrometry measurement.

INTERFERENCES
1. Any element present in the separated fraction that is able to be electrodeposited will
be present on the metal disc. In particular, 210Pb (5.30 MeV) deposited on the disc
would interfere with the yield determination of 232U (5.32 MeV) or 243Am (5.28 MeV)
tracers used in the determination of isotopic U and 241Am, respectively.
2. Incomplete separation of rare earth elements or incomplete wet ashing for the
removal of organic material will decrease the efficiency of the electrodeposition and
may result in a thick deposit unsuitable for "-spectrometry measurement.
3. Samples containing more than 20 :g of U are unsuitable for measurement by

" spectrometry due to the thickness of the deposit.
REFERENCE
Talvitie, N. A.
"Electrodeposition of Actinides for Alpha Spectrometric Determination"
Anal. Chem., 44, 280-283 (1972)

G-03
MICROPRECIPITATION SOURCE PREPARATION

FOR ALPHA SPECTROMETRY
APPLICATION
Microprecipitates of Th, U, Pu, Am, and Cm, suitable for "-spectrometry

measurements, are prepared by coprecipitation with Nd as the F-. [Adapted from Sill and
Williams (1981) and Hindman (1983).]
SPECIAL APPARATUS
1. Ultrasonic bath.
2. Millipore 47 mm diameter Pyrex glass filtration chimney, fitted glass support and
metal clamp.
3. Millipore 47 mm diameter filters, 0.45 :m pore size.
4. Gelman 25 mm diameter polysulfone filtration chimney, stem support and stainless

steel screen.
5. Gelman 25 mm Metricel filter, 0.1 :m pore size.
6. Eppendorf 100 :L pipette or equivalent.
7. 100 :L disposable pipette tips.
8. 10 mL plastic pipette.

9. 10 mL plastic culture tubes.
10. Pipetting bulb.
11. 50 mL plastic graduated cylinder.
12. 10 mL plastic graduated cylinder.
13. 20 L plastic carboy with spigot.
14. 2 L vacuum filtration flask.
15. 250 mL vacuum filtration flask.
Special Precautions - Due to the use of HF in the preparation of the reagents and in
the precipitation procedure, rubber gloves must be worn and plasticware must be used as
noted above.
SPECIAL REAGENTS
1. Filtered deionized water - filter 20 L of deionized water through 0.45 :m pore size
Millipore filters. Store the filtered water in a 20-L capacity plastic carboy with a
spigot (see Note 1).
2. 1N HCl - add 83 mL of concentrated HCl to 917 mL of filtered deionized water and

store in a plastic bottle.
3. Neodymium carrier solution, 1000 :g mL-1 (Spex Industries, Wayne, NJ), or

equivalent (see Note 2).
4. Neodymium carrier solution, 0.5 mg mL -1. Dilute 10 mL of the 1000 :g mL-1 Nd

carrier solution to 20 mL with filtered deionized water.
5. 48% HF.

6. Neodymium fluoride substrate solution - 10 :g mL-1 - pipette 5 mL of Nd carrier

(1000 :g mL-1) into a 500-mL plastic bottle. Add 460 mL of 1N HCl to the plastic
bottle. Cap the bottle and shake to mix. Measure 40 mL of 48% HF in a plastic
graduated cylinder. Uncap the bottle and add the HF. Recap the bottle and shake to
mix thoroughly.
7. 0.58 N HF - pour 980 mL of filtered deionized water into a 1 L pastic bottle.

Measure 20 mL of 48% HF in a plastic graduated cylinder. Uncap the bottle and add
the HF. Recap the bottle tightly and shake to mix.
8. Ethyl alcohol, 100%.
9. Ethyl alcohol, 80% - mix 800 mL of 100% ethyl alcohol and 200 mL of filtered
deionized water. Store in a 1 L plastic bottle.
10. Titanium trichloride, 20% solution (see Note 3).
Notes:
1. Deionized water may contain a sufficient quantity of solid material to adversely effect
the resolution of the final filtered sample.
2. Neodymium is preferred as a carrier for the determination of thorium. Cerium

compounds tend to contain variable and measurable quantities of thorium.
3. Titanium trichloride is an extremely powerful reducing agent, which should be used

in a well-ventilated hood.
PRECIPITATION OF Th, Pu, Am, AND Cm
1. The separated Th, Pu, Am or Cm solution for precipitation should be in a 1-2 mL

volume of 1N HCI or 1N HNO3 solution. (The conditions for the precipitation of U
are noted separately.)

2. Transfer the solution to a 10-mL plastic culture tube. Wash the original sample
vessel twice with 1-mL washes of the same concentration acid as the sample.
Transfer the washings to the culture tube. Mix by gently shaking the tube.
3. Add 100 :L of the 0.5 mg mL -1 Nd carrier solution to the tube with an Eppendorf
pipette. Gently shake the tube to mix the solution.
4. Add 10 drops (0.5 mL) of 48% HF to the tube and mix well by gentle shaking.
5. Place the tube in a cold-water ice bath for at least 30 min.
6. Insert the polysulfone filter stem in the 250-mL vacuum flask. Place the stainless
steel screen on top of the fitted plastic filter stem.
7. Place a 25-mm Metricel filter on the stainless steel screen. Caution - place the less
glossy side of the Metricel filter face up. The filters are usually shipped in the box in
this manner, but the analyst should check each filter visually.
8. Wet the filter with 100% ethyl alcohol. Center the filter on the stainless steel screen
support and apply a vacuum.
9. Lock the filter chimney firmly in place on the filter stem. Open the system to full
vacuum.
10. Wash the filter with 100% ethyl alcohol, followed by a filtered deionized water wash.
11. Draw 5000 :L (5 mL) of Nd substrate solution into a plastic pipette.
12. Add 5 mL of the Nd substrate solution down the side of the filter chimney. Apply a
vacuum to the filter for at least 15 sec.
13. Repeat Steps 11 and 12 with an additional 5000 :L of the substrate solution.
14. Place the sample to be filtered in a 150 mL beaker containing 25 mL of H2O. Set the
beaker in an ultrasonic unit containing about a 2.54 cm depth of H2O.

15. Ultrasonicate the sample tube for about 1 min to suspend the NdF3 precipitate.
16. Pour the sample down the side of the filter chimney and apply a vacuum.
17. Add about 2 mL of 0.58N HF to the tube and ultrasonicate briefly. Pour the wash
down the side of the filter chimney.
18. Repeat Step 17.
19. Add about 2 mL of filtered deionized water to the tube and ultrasonicate briefly.
Pour the wash down the side of the filter chimney.
20. Repeat Step 19.
21. Add about 2 mL of 80% ethyl alcohol to the tube and ultrasonicate briefly. Pour the
wash down the side of the filter chimney.
22. Repeat Step 21.
23. Wash any drops remaining on the sides of the chimney down toward the filter with
80% ethyl alcohol. Caution - Directing of a stream of liquid onto the filter will
disturb the distribution of the precipitate on the filter and render the sample
unsuitable for "-spectrometry resolution.
24. Without turning off the vacuum, remove the filter chimney.
25. Reduce or turn off the vacuum to remove the filter. Discard the filtrate. (Caution - If
the filtrate is to be retained, it should be placed in a plastic container to avoid
dissolution of the glass vessel by dilute HF.)
26. Place the filter directly on a suitable mounting disc. Secure with a mounting ring.
27. Place the mounted sample under a heat lamp (sample to lamp distance should be
about 10 cm) for 10 min prior to "-spectrometry measurement.

PRECIPITATION OF U
1. The U bearing solution must be in HCl solution.
2. Transfer 1-2 mL of the U bearing solution (1N HCl) to a 10-mL plastic culture tube.
Wash the original sample vessel twice with 1-mL portions of 1N HCl. Transfer the
washings to the culture tube. Mix by gently shaking the tube.
3. Add 100 :L of the 0.5 mg mL -1 Nd carrier with an Eppendorf pipette. Gently shake
the tube to mix the solution.
4. Add four drops of 20% Ti trichloride to the tube and gently shake the tube. A strong
permanent violet color should appear. If the color fails to appear, add a few more
drops of Ti trichloride.
5. Continue the precipitation from Step 4, Precipitation of Th, Pu, Am, and Cm.
REFERENCES
Hindman, F. D.
Plutonium, and Americium"
Anal. Chem., 55, 2460-2461 (1983)

"Preparation of Actinides for Alpha Spectrometry Without Electrodeposition"
Anal. Chem., 53, 421-415 (1981)

HASL-300, 28th Edition March 1999
G-04
PREPARATION OF MIC ROPR ECIPITA TION SO URCE S FOR R EANA LYSIS
Contact Person(s): Michele L. DeGennaro
APPLICATION
This procedure is applicable for the reanalysis of microprecipitation sources on

Metricel filters (see Procedure G-03).
A 25 mm Metricel filter is removed from the sample mount and dry ashed in a
temperature programmed oven that is held at a final temperature of 475°C for 6 h. The
residue is redissolved in preparation for additional treatment.
SPECIAL APPARATUS
1. Temperature programmed oven.
2. Sample mounts.
SPECIAL REAGENTS
Analytical grade concentrated nitric acid.
Env ironm ental M easu rem ents L abora tory

U . S . D e p a r tm e n t o f E n e r g y Page 1 of 2
HASL-300, 28th Edition March 1999
SAMPLE PREPARATION
1. Remove the 25 mm Metricel filter from the mount using a pair of tweezers and place
it in a small Pyrex beaker.
2. Place the beaker in a programmable oven.
3. Program the oven to ramp at 1.5°C min-1 to a final temperature of 475°C. Hold that
temperature for 6 h.
4. Allow the sample to cool to room temperature before treating it any further.
5. Treat the residue with several additions of concentrated nitric acid (~5-10 mL),
evaporating each addition (1-2 mL).
6. Redissolve the residue in the appropriate solution (based on the nuclide of interest).
7. The sample is now ready for further treatment or analysis (based on the nuclide of
interest).
Env ironm ental M easu rem ents L abora tory

U . S . D e p a r tm e n t o f E n e r g y Page 2 of 2
Section 4.5.6 Rev. 0
4.5.6 Sequential Analyses

Se-01, Vol. I Rev. 0
Se-01
ISOTOPIC URANIUM AND RADIUM-226
APPLICATION
This procedure is applicable to 5 g soil samples, 10 g vegetation and fecal ash

samples and ion exchange resin from sampling columns. [Adapted from Fisenne et al.
(1980), Hindman (1983), Sill (1961), and Sill and Williams (1981).]
Tracers and carriers are added to the sample which is pretreated with HNO3-HF,
fused with KF, and transposed to pyrosulfate. The cake is dissolved in HCl. Radium/
barium sulfate is precipitated, filtered, and dissolved in alkaline EDTA. The chemical
yield for Ra is determined with the (-emitting tracer 133Ba. Radium-226 is determined
by 222Rn emanation.
Uranium is isolated by solvent extraction. The U isotopes are coprecipitated with

Nd as the F- for measurement by " spectrometry.
SPECIAL APPARATUS
1. 100-mL platinum dishes or 250-mL platinum crucibles.
2. Millipore glass filtration chimney, fritted glass support, and metal clamp - 47 mm
diameter.
4. Polyethylene dispensing bottle or similar - see Specification 7-11.
5. Mechanical shaker.

procedure, G-03.
SPECIAL REAGENTS
133
1. Ba tracer solution - about 50 cps per 0.1 g aliquot, prepared in 1:99 HCl.
2. Barium carrier solution (20 mg mL-1) - 30.4 g BaCl2 L-1 in 1:99 HCl.
3. EDTA solution - 300 g tetrasodium salt of EDTA L-1 in H2O.
4. Triethanolamine - 1:1 in H2O.
232
5. U tracer solution - about 0.17 Bq g-1 of solution in a dispensing bottle.
6. Alamine-336, tertiary tricaprylyl amine (Henkel Company, 2430 N. Huachuca Dr.,

SAMPLE PREPARATION
A. Soil and vegetation.
1. Weigh 5 g of soil or 10 g of fecal or vegetation ash into a 100-mL platinum dish.

Add a weighed aliquot (about 0.1 g) of 133Ba tracer solution and 1 mL of Ba carrier
solution. Add a weighed aliquot of 232U tracer solution (about 1 g for soil and about
0.5 g for fecal or vegetation ash).
2. Slowly add 10 mL of HNO3 and 10 mL of HF to the sample and evaporate on a hot

3. Continue the analysis as described under Determination.

B. Ion exchange resin.
1. Transfer the resin and paper pulp from the collection column (see Specification 7.4)
to a 250-mL platinum crucible. Dry under a heat lamp and ash at 500oC in a muffle
furnace for 48 h.
2. To the cooled crucible, add a weighed aliquot (about 0.1 g) of 133Ba tracer solution
and 1 mL of Ba carrier solution. Add a weighed aliquot (about 0.1 g) of 232U tracer
solution.
3. Continue the analysis as described under Determination.
DETERMINATION
A. Radium separation.
1. Weigh out 15 g of KF and add to the sample. Press the KF into the sample with a
plastic spatula.
Caution: Wear rubber gloves and safety glasses during Steps 2-5.
2. Fuse the sample over an air-fed Meker burner, gradually increasing the temperature
until a clear melt is obtained. Cool the melt.
3. Using a burette, slowly add 17.5 mL of H2SO4 to the melt. Heat the dish on a hot
plate until the cake dissolves and evaporate until SO3 fumes appear.
4. Weigh out 10 g of Na2SO4, add to the dish and fuse over a blast burner until a clear
melt accompanied by dense fumes is obtained. Cool the melt.
5. Transfer the cake to a 600-mL beaker containing 350 mL of hot water and 25 mL of
HCl. Stir the solution to dissolve the cake. Cool for 1 h.
6. Filter the precipitate onto a 47 mm diameter 0.45 :m pore size Millipore filter,
police the beaker and wash with H2O. Reserve the filtrate for U separation.

7. Using a strong stream of H2O from a wash bottle, transfer the precipitate to a 150-mL
beaker. Discard the filter.
8. Add 5 mL of EDTA solution and 1 mL of 1:1 triethanolamine to the beaker. Heat on

a warm hot plate for about 15 min, adding 10 mL of H2O and stirring occasionally.
Reduce the sample volume to about 15 mL.
9. Filter the warm solution by gravity through a Whatman No. 42 filter paper into a
30-mL polyethylene bottle.
10. Wash the beaker and filter with hot water. Discard the filter.
11. Dilute the sample to the same liquid level as a known aliquot (about 0.1 g) of the
133
Ba tracer solution diluted to 25 mL in a 30-mL polyethylene bottle.
12. Gamma count the samples and standard to determine the chemical yield of Ba.
13. Transfer the sample to a 222Rn bubbler with H2O.
14. De-emanate 222Rn by bubbling with forming gas for about 10 min at 100 mL min-1 as
described in the Emanation Procedure for 226Ra, Ra-03. Record the time as the
starting time for 222Rn buildup. Continue the analysis by the emanation technique.
B. Uranium separation.
1. Evaporate the reserved filtrate (Radium Separation, Step 6) to a 150-mL volume.
2. Add 150 mL of HCl to the sample solution and stir.
3. Remove the sample from the hot plate and cool to room temperature.
4. Transfer 100 mL of acid washed Alamine-336 into a 500-mL separatory funnel.
5. Transfer the sample solution into the separatory funnel. Wash the beaker with 1:1
HCl and add the washings to the funnel.
6. Shake the separatory funnel for 5 min. Allow the phases to separate. Draw off the
aqueous (lower) phase and discard.

7. Wash the organic phase four times for 5 min with equal volumes of 1:1 HCl. Discard
the washings.
8. Strip the U from the organic phase by shaking twice for 5 min with 100-mL portions
of 0.1N HCl. Combine the strip solutions in a 400-mL beaker. Place the organic
phase in a suitable container for disposal.
9. Evaporate the strip solution to near dryness.
11. Evaporate the solution to dryness. Dissolve the residue in a few drops of HNO3.
Microprecipitation Source Preparation for Alpha Spectrometry).

226
Ra
Counter Efficiency (2%) 57.5

Yield (%) 90
Blank (cps) 0.0020
LLD (400 min) (mBq) 3.3
LLD (1000 min) (mBq) 1.7
Uranium Isotopes

3.33x10-6 for 234U
Yield (%) 85
3.00x10-5 for 234U
LLD (400 min) (mBq) 0.3 for 238U
0.8 for 234U
LLD (1000 min) (mBq) 0.2 for 238U
0.5 for 234U
(5000 min) (mBq) 0.1 for 238U
0.2 for 234U
*
It is necessary to analyze the reagents used with each batch of samples so that
blank corrections can be made for U and 226Ra.
REFERENCES
Fisenne, I. M., P. M. Perry, and G. A. Welford

Anal. Chem., 52, 777-779 (1980)
Hindman, F. D.
Anal. Chem., 55, 2460-2461 (1983)

Sill, C. W.
Anal. Chem., 33, 1684 (1961)

Anal. Chem., 53, 412-415 (1981)

Se-02. Vol. I Rev. 0
Se-02
ISOTOPIC URANIUM, ISOTOPIC THORIUM AND RADIUM-226
__________________________
APPLICATION
The method is applicable to 5 g soil samples, 20 g vegetation ash samples and 50 g

bone ash samples.
Soil, vegetation ash and bone ash samples are spiked with 229Th, 232U and 133Ba
tracer solutions. The soil and vegetation ash samples are pretreated with HNO3-HF
fused with potassium fluoride and transposed to pyrosulfate. The cake is dissolved in
HCl. Bone ash samples are dissolved directly in HCl. Uranium isotopes are isolated by
solvent extraction and are coprecipitated with neodymium as the fluoride for alpha
spectrometry measurement. Thorium is coprecipitated with calcium as the acidic
oxalate. The thorium is separated by solvent extraction and coprecipitated with
neodymium as the fluoride for alpha spectrometry measurement. Barium carrier is
added and Ra@BaS04 is precipitated, filtered and dissolved in alkaline EDTA. The
chemical yield is determined with the (-emitting tracer 133Ba and 226Ra is determined by
radon emanation.
SPECIAL APPARATUS*
1. 100-mL platinum dishes.
2. Polyethylene transfer pipettes.
3. Separatory funnels - 125, 250, 500 and 1000 mL.
*
Special apparatus and special reagents for the microprecipitation of uranium and thorium
with neodymium as the fluoride are listed in Microprecipitation of the Actinides, G-03.

4. Wrist action separatory funnel shaker unit.
5. Millipore filtration unit - 47 mm diameter Pyrex glass filtration chimney, fritted

glass support and metal clamp.
SPECIAL REAGENTS
1. Uranium-232 tracer solution - about 0.2 Bq g-1 of solution in a polyethylene transfer

pipette (see Note 1).
2. Thorium-229 tracer solution - about 0.2 Bq g-1 of solution in a polyethylene transfer

pipette.
3. Barium-133 tracer solution - about 10 kBq g-1 of solution in a polyethylene transfer

pipette. Add 0.1 g of tracer to each sample.
4. Alamine-336, tertiary tricapryl amine (Henkel Corp., 2430 N. Huachuca Dr.,

5. Aliquat-336, methyltricapryl-ammonium chloride (Henkel Corp., 2430 N. Huachuca

Dr., Tucson, AZ 85745-1273) 4:6 in toluene. Wash four times with an equal
volume of 2N HN03 and once with an equal volume of 1:1 HN03. Prepare 50 mL of
acid-washed 4:6 Aliquat-336 for each soil and vegetation ash sample and 100 mL for
each bone ash sample.
6. Calcium propionate ((CH3CH2COO)2Ca) - solid (see Note 2).
7. Oxalic acid (CHO2COOH) - solid (see Note 2).
8. Barium carrier solution (20 mg Ba mL-1) - 30.4 g of BaCl2 L-1 of 1:99 HCl.
9. Ammonium sulfate solution (100 mg mL-1) - 100 g of (NH4)2SO4 L-1 of H20.

10. EDTA solution - 500 g tetrasodium salt of EDTA L-1 of H20.
11. Triethanolamine - 1:1 with H20.
SAMPLE PREPARATION
A. Soil, milk, and vegetation ash.
1. Weigh 5 g of soil or up to 20 g of milk or vegetation ash into a 100-mL platinum

dish. Add weighed aliquots of 133Ba, 229Th and 232U tracer solutions (see Note 3).
2. Slowly add 10 mL of HN03 and 10 mL of HF to the sample and evaporate on a hot

3. Continue the analysis as described under Sample Dissolution.
B. Bone ash.
1. Weigh 50 g of ground, dry ashed bone into a 400-mL beaker. Add weighed aliquots
of 133Ba, 229Th and 232U tracer solutions (see Note 3).
2. Continue the analysis as described under Sample Dissolution.
SAMPLE DISSOLUTION*
A. Soil, milk, and vegetation ash.
1. Weigh 15 g of KF and sprinkle over the surface of the sample.
2. Fuse the sample over a Meker burner, gradually increasing the temperature until a
clear melt is obtained. Cool the melt.
*
Based upon Sill (1981).

3. Slowly add 17.5 mL of H2S04 to the melt. Heat the dish on a high temperature hot
plate until the cake dissolves and heat until sulfur trioxide fumes appear.
4. Weigh 10 g of Na2S04, add to the dish and fuse over the Meker burner until a clear
melt, accompanied by dense fumes, is obtained. Cool the melt.
5. Transfer the cake to a 600-mL beaker containing 250 mL of hot 1:1 HCl. Stir the
solution to dissolve the cake. If necessary, add additional HCl to completely
dissolve the cake. Cool for 1 h.
6. Continue the analysis as described under Uranium Separation.
B. Bone ash.
1. Add 100 mL of HCl and heat gently on a hot plate for 10 min with occasional
stirring.
2. Add 70 mL of water and stir to obtain a clear solution. Cool the solution for 1 h.
3. Continue the analysis as described under Uranium Separation.
URANIUM SEPARATION*
1. Transfer 50 mL of acid-washed Alamine-336 into each of two 500-mL separatory

funnels.
2. Transfer the sample to the first separatory funnel. Wash the beaker with 1:1 HCl
and add the washings to the funnel.
3. Shake the separatory funnel for 5 min. Allow the phases to separate and draw off
the aqueous (lower) phase into the second separatory funnel. Retain the organic
phase in the first funnel.
*
Based on Fisenne et al. (1980)

off the aqueous phase into a 2000-mL beaker for subsequent analyses of thorium
and radium.
6. Wash the organic phase four times for 5 min with an equal volumes of 1:1 HCl.
Combine the washings in the 2000-mL beaker (Step 4).
7. Strip the uranium from the organic phase by shaking twice for 5 min with
100-mL portions of 0.1N HCl. Combine the strip solutions in a 400-mL beaker.
The organic phase is placed and retrained in a suitable disposal container (see
Note 4).
8. Add 1 mL of H2S04 to the strip solution and evaporate the solution to sulfur trioxide
fumes.
9. Destroy any residual organic material with dropwise additions of HN03.
12. Add 1-2 mL of 1N HCl, prepared with filtered water (see Microprecipitation). Cool
to room temperature.
13. Continue the analysis under Microprecipitation of the Actinides, G-03.
THORIUM SEPARATION*
A. Calcium oxalate collections.
1. Add 0.5 g of calcium carrier (2.5 g of calcium propionate) to the sample waste and
wash solutions reserved from Steps 4 and 6 in Uranium Separation.
*
Based upon Fisenne and Perry (1978).

Note: DO NOT ADD CALCIUM CARRIER TO BONE ASH OR MILK SAMPLES.
2. Evaporate the solution volume to 100-200 mL.
3. Dilute the solution to 1400 mL with deionized water. Heat the solution to near
boiling.
4. Adjust the pH to 2.5 with NH40H.
5. Add 10 g of oxalic acid to soil, milk, and vegetation ash samples. Add 25 g of oxalic
acid to bone ash samples.
6. Stir and heat the solution to a gentle boil. Continue heating for 5 min.
7. Adjust the pH to 2.5 with NH40H. Gently boil the solution for 10 min.
8. Remove the sample from the hot plate, check the pH and allow the sample to stand
overnight at room temperature.
9. Decant the supernate into a 3000-mL beaker and reserve for radium analysis.
Reduce the volume of the decanted solution to 500 mL or less.
10. Add 100 mL of HN03 to the calcium oxalate precipitate and heat to destroy the
oxalate. Repeat the HN03 addition, if necessary.
11. Convert the sample solution to the chloride with three successive additions of
50 mL of HCl.
12. Repeat Steps 5-10 for soil, milk, and vegetation ash samples. Bone ash samples
require four calcium oxalate collections to remove most of the phosphate ions.
13. Wet ash the oxalate precipitate with repeated additions of 50-100 mL of HN03 for
soil and vegetation samples. Bone samples initially require 200 mL of HN03.
14. Reduce the sample solution to near dryness and add 25 mL of 1:1 HNO3 to the soil
and vegetation ash samples. Add 100 mL of 1:1 HNO3 to the bone ash sample.

15. Warm to dissolve the calcium salts. Cool the solution to room temperature.
B. Solvent extraction separation.
1. For soil and vegetation ash samples, transfer 25 mL of acid-washed Aliquat-336 into
each of two 125-mL separatory funnels. For bone ash samples, add 50 mL of
acid-washed Aliquat-336 into each of two 250-mL separatory funnels.
2. Transfer the sample to the first separatory funnel. Wash the beaker with 1:1 HN03
and add the washings to the funnel.
3. Shake the separatory funnel for 5 min. Allow the phases to separate and draw off the
aqueous (lower) phrase into the second separatory funnel. Retain the organic phase
in the first funnel.
off the aqueous phase into the beaker with the reserved radium fraction.
6. Wash the combined organic phases twice for 5 min with half volumes of
1:1 HNO3. Add the washings to the reserved radium fraction.
7. Strip the thorium from the organic phase by shaking for 5 min with 25 mL of
concentrated HCl. Allow the phases to separate and draw off the aqueous phase into
the empty separatory funnel.
8. Repeat Step 7, combining the thorium bearing aqueous phases. The organic phase
should be placed and retained in a suitable disposal container (see Note 4).
9. Add 25 mL of toluene to the separatory funnel and shake for 5 min.
10. Allow the phases to separate and draw off the aqueous phase into a 150-mL beaker.
Discard the organic phase.
11. Heat the solution gently to drive off organic vapors.

12. Reduce the sample solution volume to 10 mL. Wet ash the solution with repeated
10-mL additions of HNO3 to remove organics. Caution - Do not allow the solution
to reach dryness.
13. Convert the solution to the chloride with three 5-mL additions of HCl. Reduce the
acid volume to near dryness.
14. Add 1-2 mL of 1N HCl, prepared with filtered water (see Microprecipitation of the
Actinides, G-03). Cool to room temperature.
15. Continue the analysis under Microprecipitation of the Actinides, G-03.
RADIUM SEPARATION*
1. Add 1 mL of barium carrier (20 mg barium mL-1) to the reserved radium fraction.
2. Reduce the sample solution to dryness and wet ash with repeated 50-100 mL
additions of HN03 to remove organics.
3. Convert the sample to the chloride with repeated 50-100 mL additions of HCl.
4. Dilute the sample solution to 1000 mL with water. Heat and stir to dissolve the salts.
Add additional water, if necessary.
5. Adjust the solution pH to 2.5 with NH40H. Cool the beaker to room temperature in a
water bath.
6. Add 5 mL of (NH4)2S04 solution (100 mg (NH4)2SO4 mL-1). Stir and let stand at
room temperature overnight.
7. Filter the solution through 47 mm diameter, 0.45 :m pore size Millipore filter.
8. Police and wash the beaker with water. Add the washings to the filter chimney.
Wash the filter with water.
*
Based upon Hallden et al. (1963).

9. Place the filter with the Ra.BaS04 in a 150-mL beaker. Discard the filtrate.
10. Add 5 mL of warm EDTA solution and 1 mL of 1:1 triethanolamine to the beaker.
Heat on a warm hot plate for about 5 min. Add 10 mL of water and stir occasionally.
Continue to heat for 15 min.
11. Gravity filter the warm solution through Whatman No. 42 filter paper into a 30-mL
(1 oz) polyethylene bottle.
12. Wash the beaker and filter with hot water. Discard the filter paper.
13. Dilute the sample solution to the same liquid level as a known aliquot of the 133Ba
tracer solution diluted to 25 mL in a 30-mL (1 oz) polyethylene bottle.
14. Gamma count the samples and standard to determine the chemical yield of barium.
15. Transfer the sample to a radon bubbler with water.
16. Determine the 226Ra content of the sample as described in Emanation Procedure for
Radium-226, Ra-03.
Notes:
1. The 232U decays to 228Th and its daughters. Therefore the activity of the thorium
subseries increases with time in the 232U spike. Thus, a blank correction for 228Th
from the added 232U tracer is required, resulting in an increasing lower limit of
detection (LLD) for 228Th.
2. Calcium compounds and oxalic acid contain variable and measurable quantities of
226
Ra. Each lot of these reagents should be checked prior to use to obtain the lowest
possible reagent blank value.
3. It is necessary to analyze reagent blank samples along with each batch of samples to
determine the proper blank corrections.
4. The organic phase is washed twice for 5 min with an equal volume of water and
placed in a suitable disposal container.

Based upon Fisenne et al. (1987) and Harley and Fisenne (1990).
REFERENCES
Fisenne, I. M. and P. M. Perry

"Determination of Plutonium in Tissue by Aliquat-336 Extraction"
Radiochemical and Radioanalytical Letters, 33, 259 (1978)
Fisenne, I. M., P. M. Perry and G. A. Welford

Analytical Chemistry, 52, 777 (1980)
Fisenne, I. M., P. M. Perry, K. M. Decker and H. W. Keller

"The Daily Intake of 234,235,238U, 228,230,232Th and 226,228Ra by New York City
Residents"
Hallden, N. A., I. M. Fisenne and J. H. Harley

"Determination of Radium-226 in Human Bone"
Talanta, 10, 1223 (1963)
Harley, N. H. and I. M. Fisenne

"Distribution and " Radiation Dose from Naturally Occurring, U, Th and Ra in the
Human Skeleton"
Sill, C. W.
Analytical Chemistry, 33, 1684 (1981)

Se-03
AMERICIUM, PLUTONIUM AND URANIUM IN WATER
APPLICATION
This procedure describes a method for the separation and measurement of

americium, plutonium and uranium in water (adapted from Eichrom Industries, Inc.,
Procedure ACW03, Rev. 1.5). Americium, plutonium and uranium are separated by
Eichrom resins prior to measurements by alpha spectrometry. Tracers are used to
monitor chemical recoveries and to correct the results to improve precision and
accuracy. This is a rapid, reliable method for the measurement of actinides in water
samples that is more cost-effective and efficient than traditional ion exchange, solvent
extraction and precipitation techniques.
INTERFERENCES
Actinides with unresolvable alpha energies such as 241Am and 238Pu or 237Np and 234U
must be chemically separated to enable measurement. This method effectively separates
these isotopes.
SPECIAL APPARATUS
1. Column rack
2. Filter - 0.45 micron
SPECIAL REAGENTS

1. Ammonium hydrogen oxalate (0.1M) - dissolve 6.31 g of H2C2O4@2H2O and 7.11 g

of (NH4)2C2O4@H2O in 900 mL of water, filter (Whatman No. 4 suggested) and dilute
to
1 L with water.
2. Ammonium hydroxide (5 wt %) - dissolve 50 g ammonium hydroxide in 950 g of

water.
3. Appropriate tracers or standards.
4. Ascorbic acid.
5. Ferrous sulfamate solution (0.6M) - add 57 g of NH2SO3H to 150 mL of water, heat

to 70oC, add 7 g of iron, in small increments until dissolved, filter (Whatman No. 4
suggested), transfer to flask and dilute to 200 mL with water. Prepare fresh weekly.
6. Hydrochloric acid (0.01M HCl) - add 0.8 mL of HCl to 900 mL of water and dilute
to 1 L with water.
7. Hydrochloric acid (4M HCl) - add 333 mL of HCl to 500 mL of water and dilute to
1 L with water.
8. Hydrochloric acid (5M), oxalic acid (0.05M) solution - Dissolve 6.3 g oxalic acid
dihydrate in 400 mL of water. Add 417 mL HCl. Cool to room temperature and
dilute to 1 L with water.
9. Hydrochloric acid (9M HCl) - add 750 mL of HCl to 100 mL of water and dilute to
1 L with water.
10. Iron powder - a fine mesh powder dissolves faster in sulfamic acid.
11. Nitric acid (2M) - sodium nitrite (0.1M solution) - add 32 mL of HNO3 to 200 mL of
water, dissolve 1.72 g of sodium nitrite in the solution and dilute to 250 mL with
water. Prepare fresh daily.
12. Nitric acid solution (0.5M) - add 32 mL of HNO3 to 900 mL of water and dilute to
1 L with water.

13. Nitric acid solution (2M) - add 127 mL of HNO3 to 800 mL of water and dilute to
1 L with water.
14. Nitric acid solution (3M) - add 191 mL of HNO3 to 700 mL of water and dilute to
1 L with water.
15. Nitric acid (3M) - Aluminum nitrate (1M) solution -dissolve 212 g of anhydrous
aluminum nitrate in 700 mL of water, add 191 mL of HNO3 and dilute to 1 L with
water.
16. Hydrochloric acid (4M HCl) - hydrofluoric acid (0.1M) - add 333 mL of HCl and
3.6 mL HF to 500 mL of water and dilute to 1 L with water. Prepare fresh daily.
23. TRU Resin - prepacked column, 0.7 g 100-150 micron particle size resin.
24. U/TEVA Resin - prepacked column, 0.7 g 100-150 micron particle size resin.
SAMPLE PREPARATION
1. If not already prefiltered, filter the sample through a 0.45 micron filter.
2. If samples larger than 1 L are analyzed, evaporate the sample to ~1 L.
3. Aliquot 500 to 1000 mL of the filtered sample (or enough to meet the required
detection limit) into an appropriate size beaker.
4. Add 5 mL of HCl per liter of sample (0.5 mL per 100 mL) to acidify each sample.
5. Add the appropriate tracers.
6. Evaporate sample to <50 mL and transfer to a 100-mL beaker. (Note: For some
water samples, calcium sulfate formation may occur during evaporation.) Gently
evaporate the sample to dryness and redissolve in approximately 5 mL of HNO3.
Evaporate to dryness and redissolve in HNO3 two more times, evaporate to dryness
and go to Actinide Separation Using Eichrom’s Resins.

SEPARATION
1. Dissolve each precipitate from Step 6, Sample Preparation, in 10 mL of 3M HNO3-

1.0M Al(NO3)3. (Note: An additional 5 mL may be necessary if the volume of
precipitate is large.)
2. Add 2 mL of 0.6M ferrous sulfamate to each solution. Swirl to mix. (Note: If the
additional 5 mL was used to dissolve the sample in Step 1, add a total of 3 mL of
ferrous sulfamate solution.)
3. Add 200 mg of ascorbic acid to each solution, swirling to mix. Wait for 2-3 min.
(Note: If particles are observed to be suspended in the solution, centrifuge the
sample. The supernatant will be transferred to the column in Step 5, Uranium
separation from plutonium, americium using U/TEVA resin. The precipitates
will be discarded.)
A. Uranium separation from plutonium, americium using U/TEVA resin
1. For each sample solution, place a U/TEVA Resin column in the column rack.
2. Place a beaker below each column, remove the bottom plug from each column and
allow to drain.
3. Pipette 5 mL of 3M HNO3 into each column to condition the resin and allow to
drain.
4. Place a clean, labeled 50-mL beaker below each column.
5. Transfer each solution from Step 3 into the appropriate U/TEVA Resin column by
pouring or by using a plastic transfer pipette and collect the eluate.
6. Add 5 mL of 3M HNO3 to rinse to each beaker and transfer each solution into the
appropriate U/TEVA Resin column and collect eluate.
7. Add 5 mL of 3M HNO3 into each column and collect eluate.

8. Set aside the solutions collected in Steps 5, 6 and 7 for americium and plutonium
separations.
9. Pipette 4 mL of 9M HCl into each column and allow to drain. Discard this rinse.
(Note: The rinse converts the resin to the chloride system. Some neptunium may be
removed here.)
10. Pipette 20 mL of 5M HCl - 0.05M oxalic acid into each column and allow it to drain.
Discard eluate. (Note: This rinse removes neptunium and thorium form the column.
The 9M HCl and 5M HCl-0.05M oxalic acid rinses also removes any residual
ferrous ion that might interfere.)
11. Place a clean, labeled beaker below each column.
12. Pipette 15 mL of 0.01M HCl into each column to strip the uranium. Allow to drain.
13. Evaporate to dryness. Treat with 5 mL of HNO3 several times to remove traces of
oxalic acid. Convert to HCl.
14. Set beakers aside for Procedure G-03, Microprecipitation Source Preparation for
Alpha Spectrometry.
B. Plutonium and americium separation using TRU resin
1. Place a TRU Resin column in the column rack for each sample dissolved.
2. Remove the bottom plug from each column and allow each column to drain.
3. Pipette 5 mL of 2M HNO3 into each column to condition resin and allow to drain
(just prior to sample loading).
4. Transfer each solution from Step 8 of Uranium Separation into the appropriate
TRU Resin column by pouring and/or using a plastic transfer pipette.
5. Allow the load solution to drain through the column.

6. Pipette 5 mL of 2M HNO3 into the sample beaker and transfer this rinse to the
appropriate column using the same plastic pipette.
7. Allow the initial rinse solution to drain through each column.
8. Pipette 5 mL of 2M HNO3 - 0.1M NaNO2 directly into each column, rinsing each
column reservoir while adding the 2M HNO3 - 0.1M NaNO2. (Note: Sodium nitrite
is used to oxidize Pu+3 to Pu+4 and to enhance the plutonium/americium separation).
9. Allow the rinse solution to drain through each column.
10. Add 5 mL of 0.5M HNO3 to each column and allow to drain. (Note: 0.5M HNO3 is
used to lower the nitrate concentration prior to conversion to the chloride system.)
11. Discard the load and rinse solutions.
12. Ensure that clean, labeled beakers or vials are below each column.
13. Add 3 mL of 9M HCl to each column to convert to HCl. Collect the eluate.
14. Add 20 mL of 4M HCl to elute americium. Collect the eluate in the same beaker.
Evaporate to dryness. Treat with 5 mL HNO3 several times until wet-ashing of the
residue is complete. Convert to HCl. Set beakers aside for Procedure G-03,
Microprecipitation Source Preparation for Alpha Spectrometry.
15. Rinse the columns with 25 mL of 4M HCl-0.1M HF. Discard eluate.
16. Ensure the clean, labeled beakers or vials are below each column. Add 10 mL of
0.1M NH4HC2O4 to elute plutonium from each column.
17. Evaporate to dryness. Treat with 5 mL HNO3 several times until wet-ashing of the
residue is complete. Convert to HCl. Set beakers aside for Procedure G-03,
Microprecipitation Source Preparation for Alpha Spectrometry.

PRECISION AND BIAS
1. Precision - A relative standard deviation of 4.2% at the 0.42 Bq level has been
reported for uranium. A relative standard deviation of 3.2% at the 1 Bq level has
been reported for plutonium.
2. Bias - Mean chemical recoveries of 95% for americium, 93% for plutonium and 86%
for uranium have been reported. Since results are corrected based on spike recovery,
no significant bias exists for the method.

NATURAL URANIUM
Counter Background (cps) 3.33 x 10-6 for 238U
6.67 x 10-6 for 234U
Recovery : (%) 85
LLD (400 min) (m Bq) 0.2 for 238U
0.3 for 234U
LLD (1000 min) (m Bq) 0.1 for 238U
0.2 for 234U
LLD (5000 min) (m Bq) 0.06 for 238U
0.09 for 234U

PLUTONIUM

Counter Background (cps) 2 x 10-5
Recovery (%) 75
Blank (cps) -
LLD (400 min) (mBq) 0.6
LLD (1000 min) (mBq) 0.4
LLD (5000 min) (mBq) 0.2
AMERICIUM

Counter Background (cps) 1.6 X 10-5
Recovery (%) 80
LLD (400 min) (mBq) 0.5
LLD (1000 min) (mBq) 0.3
LLD (5000 min) (mBq) 0.1

5. RADIONUCLIDE DATA

New York, NY 10014-4811

Page
5. Radionuclide Data . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1-1
5.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1-1
5.2 Alpha . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2-1
5.2.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2-1
5.3 Beta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3-1
5.3.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3-1
5.4 Gamma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4-1
5.4.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4-1
5.5 X-Ray . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5-1
5.5.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5-1
5.6 Natural Decay Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.6-1
5.6.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.6-1

5. RADIONUCLIDE DATA
5.1 OVERVIEW
This section describes current radionuclide measurement techniques in use at EML and
their associated data. A radionuclide is identified by its three principal characteristics:
half-life, type of emission, and energy of the emission. Sometimes overlooked in the
process are progeny radionuclides with their own particular characteristics.
In the 1960s, routine measurements were being performed at EML for ", $, and
( radionuclides. Measurements in both the Frisch grid ion chamber and the solid-state
surface barrier detection systems were used to identify " energies in sources in
properly calibrated systems. Contained in this section is a table of " emitters by
energy, especially linked to the charts of the naturally occurring radionuclides, which
assists in radionuclide identification in separated samples and in radionuclide purity
checks.
Routine measurement of $ emitters is performed on counters designed at EML. These

counters have a very low background count rate due to anticoincidence counting tech-
niques. The overall counting efficiencies are comparable to proportional counters.
Radiochemical purity is typically assessed by decay measurements.
Use of NaI(T1) ( spectrometry detection systems provides poorly resolved spectra

compared with the Ge(Li) and intrinsic Ge systems presently in use. The resolution of
these present systems require sophisticated computer algorithms to identify energies
associated with particular radionuclides. It is most important that the energies and the
branching ratios used at any facility be documented and a table of ( emitters in the
environment is included.
Contained in the natural decay series are charts of three natural radionuclide series and
the man-made americium series. Pertinent data are included in these charts.

5.2 ALPHA
5.2.1 SCOPE
The tables on " emitters by atomic number and by energy have been developed for
internal use at EML. The present tables are revisions compiled from the data given in
Table of Radioactive Isotopes by Browne et al. (1986).
REFERENCE
Browne, E., R. B. Firestone and V. S. Shirley (Editors)

Table of Radioactive Isotopes
John Wiley and Sons, Inc., New York (1986)

ALPHA EMITTERS BY ATOMIC NUMBER
Most short-lived nuclides are included as principal members of

the natural decay series (see Section 5.6)
Isotopic " Emission

Abundance (when not
Radionuclide t1/2 (%) 100%) EMeV
60 144Nd 2.1 x 1015 y 23.8 1.83

62 147Sm 1.03 x 108 y 2.46
147 11
62 Sm 1.06 x 10 y 15.0 2.233
64 148Gd 75.3 y 3.183
64 152Gd 1.79 x 106 y 2.726
64 152Gd 1.08 x 1014 y 0.20 2.14
66 154Dy 2.9 x 106 y 2.872
174 15
72 Hf 2.0 x 10 y 0.162 2.50
76 186Os 2.0 x 1015 y 1.58 2.80
78 190Pt 6.0 x 1011 y <0.02 3.175
83 210mBi 3.00 x 106 y 4.946(55.5%), 4.908(38.8%),
4.569(3.8%)
83 211Bi(AcC) 2.14 m 6.623(84%), 6.279(16%)
83 212Bi(ThC') 1.0092 h 39.54% 6.090(26.8%), 6.051(70.2%),
5.768(1.7%), 5.707(1.1%)
84 206Po 8.83 d 5.45% 5.223
84 208Po 2.898 y 5.116
84 209Po 102.0 y 4.866
210
84 Po (RaF) 138.376 d 5.305
84 212Po (ThC)' 298.0 ns 8.784
84 213Po 4.28 µs 8.375
84 214Po(RaC)' 163.69 µs 7.687
84 215Po(AcC) 1.780 ms 7.386
216
84 Po(ThA) 150.0 ms 6.779
84 218Po(RaA) 3.05 m 6.003

ALPHA EMITTERS BY ATOMIC NUMBER (Cont'd)
Isotopic " Emission

Abundance (when not
85 211At 7.215 h 41.7% 5.868

217
85 At 32.3 ms 7.067
86 219Rn(219Em) 3.96 s 6.819(80.9%), 6.553(12.2%),
6.425(7.5%)
86 220Rn(220Em, Tn) 55.6 s 6.288
86 222Rn(222Em, Rn) 3.825 d 5.490
87 221Fr 4.9 m 6.341(83.4%), 6.243(1.3%),
6.127(15.1%)
88 223Ra(AcX) 11.43 d 5.747(9.5%), 5.716(52.5%),
5.607(24.2%), 5.540(9.2%),
others
88 224Ra(ThX) 3.66 d 5.686(95.1%), 5.449(4.9%)
88 226Ra 1600.0 y 4.784(94.5%), 4.601(5.6%)
225
89 Ac 10.0 d 5.829(51.6%), 5.793(18.1%),
5.791(8.6%), 5.731(10%),
5.637(4.5%), others
90 227Th(Rd Ac) 18.718 d 6.038%(24.5%),
5.978(23.4%),
5.757(20.3%), 5.714(4.9%),
5.710(8.2%), others
90 228Th(Rd Th) 1.913 y 5.423(72.7%), 5.341(26.7%)
90 229Th 7340.0 y 5.050(5.2%), 4.968(6.0%),
4.901(10.2%), 4.845(56.2%),
4.814(9.3%), others
90 230Th(Io) 7.54 x 104 y 4.688(76.3%), 4.621(23.4%)
90 232Th(Th) 1.405 x 1010 y 100. 4.010(77%), 3.952(23%)
91 231Pa(Pa) 3.276 x 104 y 5.059(11%), 5.029(20%),
5.013(25.4%), 4.951(22.8%),
4.734(8.4%), others
92 230U 20.8 d 5.889(67.4%), 5.818(32%),
others
92 232U 68.9 y 5.320(68.6%), 5.264(31.2%)
92 233U 1.592 x 105 y 4.825(84.4%), 4.783(13.2%),
others
234 5
92 U(UII) 2.454 x 10 y 0.0055 4.776(72.5%), 4.724(27.5%)

Isotopic " Emission

Abundance (when not
92 235U(AcU) 7.037 x 108 y 0.7200 4.597(5%), 4.556(4.2%),

4.395(55%), 4.364(~11%),
4.218(5.7%), others
92 236U 2.342 x 107 y 4.494(74%), 4.445(26%)
238 9
92 U(UI) 4.468 x 10 y 99.2745 4.196(77%), 4.147(23%)
93 237Np 2.14 x 106 y 4.873(2.6%), 4.988(47%),
4.772(25%), 4.766(8%),
4.640(6.2%), others
94 236Pu 2.851 y 5.768(68.1%), 5.721(31.7%)
94 238Pu 87.74 y 5.499(71.6%), 5.456(28.3%)
239 4
94 Pu 2.411 x 10 y 5.156(73.2%), 5.143(15.1%),
5.105(10.6%)
94 240Pu 6563.0 y 5.168(73.5%), 5.124(26.4%)
242 5
94 Pu 3.763 x 10 y 4.901(78%), 4.856(22.4%)
244
94 Pu 8.26 x 107 y 4.589(80.5%),4.546(19.4%)
95 241Am 432.7 y 5.486(85.2%), 5.443(12.8%),
5.388(1.4%)
95 243Am 7380.0 y 5.277(88%), 5.234(11%),
5.180(1.1%)
96 240Cm 27.0 d 6.291(70.6%), 6.248(28.8%)
96 242Cm 162.94 d 6.113(74%), 6.070(25%)
96 243Cm 28.5 y 6.067(1.5%), 6.059(5%),
5.992(6.5%), 5.786(73.3%),
5.742(10.6%), others
96 244Cm 18.11 y 5.805(76.4%), 5.763(23.6%),
others
96 245Cm 8500.0 y 5.362(93.2%), 5.304(5.0%),
others
96 246Cm 4730.0 y 5.386(79%), 5.343(21%)
96 247Cm 1.56 x 107 y 5.266(13.8%), 5.210(5.7%),
4.869(71%), 4.818(4.7%),
others

Isotopic " Emission

Abundance (when not
96 248Cm* 3.40 x 105 y 91.7% 5.078(81.9%), 5.035(18%)

247
97 Bk 1380.0 y 5.795(5.5%), 5.712(17%),
5.687(13%), 5.532(45%),
5.501(7%), others
98 246Cf 1.487 d 6.750(78.0%), 6.709(21.8%)
98 248Cf 334.0 d 6.262(83.0%), 6.220(17.0%)
98 249Cf 350.6 y 6.194(2.2%), 6.140(1.1%),
5.945(4%), 5.903(2.8%),
5.812(84.4%), others
98 250Cf 13.09 y 6.031(84.5%), 5.989(15.1%)
98 251Cf 898.0 y 6.074(2.7%), 6.014(11.6%),
5.851(27%), 5.812(4.2%),
5.677(35%), others
98 252Cf* 2.646 y 96.9% 6.118(84%), 6.076(15.8%)
252
99 Es* 1.291 y 76.4% 6.632(79.8%), 6.562(13.5%),
6.483(2.2%), others
99 253Es 20.4 d 6.633(89.8%), 6.592(6.6%),
others
99 254Es 275.7 d 6.427(93.1%), 6.416(1.8%),
6.357(2.6%)
99 255Es* 39.8 d 8.0% 6.300(87.5%), 6.260(10.0%),
6.213(2.5%)
100 52Fm 1.058 d 7.04(~85%), 6.999(~15%)
100 253Fm* 3.00 d 12.0% 7.024(6.7%), 6.943(42.7%),
6.901(9.8%), 6.847(8.5%),
6.674(23.3%), others
255
100 Fm 20.07 h 7.022(93.4%), 6.963(5.0%),
others
100 257Fm 100.5 d 6.696(3.4%), 6.519(93.5%),
6.441(2.0%)
101 258Md 55.4 d 6.790(28%), 6.716(72%)
*Relative "-intensity normalized to 100 "-decays.

ALPHA EMITTERS BY ENERGY (MeV)*
3.8-4.0 4.0-4.2 4.2-4.4 4.4-4.6 4.6-4.8 4.8-5.0 5.0-5.2 5.2-5.4 5.4-5.6 5.6-5.8 5.8-6.0 6.0-6.2 6.2-6.4
Uranium Series:
238 234 210 222 218
U U Po Rn Po
230
Th
226
Ra
Thorium Series:
232 232 228 228 212 212 220
Th Th Th Th Bi Bi Rn
224 224
Ra Ra
Actinium Series:
235 235 231 231 231 223
U U Pa Pa Pa Ra
227 227 227
Th Th Th
Americium Series:
237 241 241 225 225 221 221
Np Am Am Ac Ac Fr Fr
233 233
U U
229 229
Th Th
All Emitters:
232 232 235 210m 226 209 208 206 222 212 211 212 211
Th Th U Bi Ra Po Po Po Rn Bi At Bi Bi
238 235 230 210m 229 210 223 223 225 218 220
U U Th Bi Th Po Ra Ra Ac Po Rn
236 231 229 231 228 224 224 227 221 221
U Pa Th Pa Th Ra Ra Th Fr Fr
244 233 231 239 232 228 225 230 227 240
Pu U Pa Pu U Th Ac U Th Cm
234 233 240 241 238 227 243 242 248
U U Pu Am Pu Th Cm Cm Cf
237 237 243 243 241 236 244 243 254
Np Np Am Am Am Pu Cm Cm Es
242 248 245 247 243 249 249 255
Pu Cm Cm Bk Cm Cf Cf Es
247 246 244 250 250
Cm Cm Cm Cf Cf
247 247 251 251
Cm Bk Cf Cf
251 252
Cf Cf
*A listing may denote more than one energy.

U5.S. Department of Energy 5.2 - 6
5
ALPHA EMITTERS BY ENERGY (MeV) -- (Cont'd)
6.4-6.6 6.6-.68 6.8-7.0 7.0-7.2 7.2-7.4 7.4-7.6 7.6-7.8 7.8-8.0 8.0-8.2 8.2-8.4 8.4-.86 8.6-8.8
Uranium Series::
214
Po
Thorium Series:
216 212
Po Po
Actinium Series:
219 211 219 215
Rn Bi Rn Po
Americium Series:
217 213
At Po
All Emmitters:
219 211 219 217 215 214 213 212
Rn Bi Rn At Po Po Po Po
252 216 252 252
Es Po Fm Fm
253 246 253 253
Es Cf Fm Fm
254 252 255 255
Es Es Fm Fm
257 253
Fm Es
253
Fm
257
Fm
258
Md

Section 5, Vol. I
SPECIFIC ACTIVITY OF SELECTED ALPHA EMITTERS

(in order of ascending atomic numbers)
Nuclide t1/2 (y) mCi mg-1 MBq mg-1
210m
Bi 3.00 x 106 5.7 x 10-4 2.11 x 10-2
208
Po 2.898 593.1 2.19 x 104
209
Po 102 16.8 6.22 x 102
226
Ra 1600 0.989 3.66 x 101
228
Th 1.913 819.6 3.03 x 104
229
Th 7340 0.213 7.88
230
Th 7.54 x 104 2.062 x 10-2 7.63 x 10-1
232
Th 1.405 x 1010 1.0969 x 10-7 4.06 x 10-6
231
Pa 3.276 x 104 4.724 x 10-2 1.75
232
U 68.9 22.4 8.29 x 102
233
U 1.592 x 105 9.64 x 10-3 3.57 x 10-1
234
U 2.454 x 105 6.225 x 10-3 2.30 x 10-1
235
U 7.037 x 108 1.922 x 10-6 7.11 x 10-5
236
U 2.342 x 107 6.508 x 10-5 2.41 x 10-3
238
U 4.468 x 109 3.36237 x 10-7 1.24 x 10-5
237
Np 2.140 x 106 7.05 x 10-4 2.61 x 10-2
236
Pu 2.851 531.3 1.97 x 104
238
Pu 87.74 17.119 6.33 x 102
239
Pu 2.411 x 104 6.204 x 10-2 2.30
240
Pu 6563 0.22696 8.40

Section 5, Vol. I
SPECIFIC ACTIVITY OF SELECTED ALPHA EMITTERS (Cont'd)

(in order of ascending atomic numbers)
Nuclide t1/2 (y) mCi mg-1 MBq mg-1
242
Pu 3.763 x 105 3.962 x 10-3 1.45 x 10-1
241
Am 432.7 3.428 1.27 x 102
243
Am 7380 0.1993 7.37
242
Cm 4.461 x 10-1 3311.4 1.23 x 105
243
Cm 28.5 51.6 1.91 x 103
244
Cm 18.11 80.90 2.99 x 103
245
Cm 8500 0.1717 6.35
248
Cm 3.40 x 105 4.24 x 10-3 1.57 x 10-1
247
Bk 1380 1.05 3.89 x 101
248
Cf 9.1444 x 10-1 1579 5.84 x 104
249
Cf 350.6 4.095 1.52 x 102
250
Cf 13.08 109.3 4.04 x 103
251
Cf 898 1.59 5.88 x 101
252
Cf 2.645 536.3 1.98 x 104
252
Es 1.291 1098 4.06 x 104
254
Es 7.54825 x 10-1 1865 6.90 x 104

5.3 BETA
5.3.1 SCOPE
The table of $ emitters presented here is useful in identifying unknown $ emitters

whose energies and possibly half-lives have been determined by standard laboratory
techniques, including the Harley-Hallden method (see Procedure A-01-R). It is also a
handy guide to $ emitting isotopes for applications requiring specific half-lives and/or
energies.
The original table was developed by Hallden (1955). Since that time there have been
three revisions based on "current" published compilations. The present table was com-
piled from the Table of Isotopes (Lederer and Shirley, 1978).
The emitter energy listings are the maximum $ energy (Emax). Isotopes decaying
the emission of $ particles of different energies are listed in the energy group
corresponding to each Emax, provided that the branch contributes > 5% of the total $
emission. Isotopes with longer-lived parents are also listed under the parent half-life.
In the case of multiple long-lived parents, the nuclide is listed under the half-life of the
nearest long-lived parent, as well as its own half-life.
REFERENCES
Hallden, N. A.
"Beta Emitters by Energy and Half-life"
Nucleonics, 13, 78-79 (1955)
Lederer, C. and V. S. Shirley (Editors)

Table of Isotopes - Seventh Edition
John Wiley and Sons, New York, NY (1978)

BETA EMITTERS BY HALF-LIFE AND ENERGY (EMAX IN MeV)
T1/2 <0.1 0.1-0.3 0.3-0.5 0.5-0.7 0.7-0.9 09.-1.1 1.1-1.3 1.3-1.5 1.5-1.7 1.7-1.9 1.9-2.1 2.1-2.3 2.3-2.5 2.5-2.7 2.7-2.9 2.9-3.1 >3.1
234 156 62 52 91 163 73 208 152m 77 128 91 93 62 66

6-12 h Pa Sm Zn Fe Sr Tb Se Tl Eu Ge Sb Sr Y Cu Ga
212 91 77 135 184 77 212 208 212
Pb Sr Ge I Ta Ge Bi Tl Bi
228 135 82m 135 208 91 228 228
Ac I Rb Xe Tl Sr Ac Ac
244 152m 101 171 228 135 228
Am Eu Pd Er Ac I Ac
171 127 245 163
Er Te Pu Tb
212 156 245 184
Pb Sm Am Ta
228 173
Ac Tm
234 173
Pa Tm
234 180m
Pa Ta
112 28 64 43 55 86 24 55 76 42 142 72 28 42
12 h-1 d Pd Mg Cu K Co Y Na Co Br K Pr Ga Al K
43 64 69 109 97 133 72 97 188 152 72
K Cu Zn Pd Nb I Ga Zr Re Tb Ga
96 119 90 130 157 86 112 194 76
Nb Te Nb I Eu Y Ag Ir Br
197 130 96 150 187 90 152 240m 112
Pt I Nb Eu W Nb Tb Np Ag
236 159 157 157 240m 240m 188 112
Np Gd Eu Eu Np Np Re Ag
240 187 159 159 194
U W Gd Gd Ir
187 197
W Pt
187 240m
W Np
197
Pt
200m
Au
236
Np
240m
Np
242
Am
242
Am
248
Bk

BETA EMITTERS BY HALF-LIFE AND ENERGY (EMAX IN MeV) - (Cont’d)
T1/2 <0.1 0.1-0.3 0.3-0.5 0.5-0.7 0.7-0.9 0.9-1.1 1.1-1.3 1.3-1.5 1.5-1.7 1.7-1.9 1.9-2.1 2.1-2.3 2.3-2.5 2.5-2.7 2.7-2.9 2.9-3.1 >3.1
231 66 67 48 57 143 69 122 66 76 122 90 76 66 76 72

1-3 d Th Ni Cu Sc Ni Ce Ge Sb Cu As Sb Y As Cu As Ga
72 67 67 71 149 83 131 72
Zn Cu Cu As Pm Sr Te Ga 166
Ho 131
Te 72
Ga 72
As
105 72 77 143 151 131
Rh Zn As Ce Pm 99
Mo 140
La Te 140 72
166 La As
140
Ho
172
Er 82
Br 79
Kr 149
Pm 189
Re 115 143
La
Cd Ce 172
172 99 105 151 198 Tm
Tm Mo Rh Pm Au 140
La 172
231
Th 121
Sn 115
Cd 151
Pm Tm
143
231
Th 131m
Te 131m
Te 151
Pm Ce
231 151 140 153 151
Th Pm La Sm Pm
238 172 143 153
Np Er Ce Sm 151
Pm
238 172 151 172
Np Tm Pm Tm 193
Os
238 232 153 189
Np Pa Sm Re 226
Ac
239 193 193
Np Os Os
238
239 193 226
Np
Np Os Ac
245m
239 239 Es
Np Np
245m
Es
Note: Where the symbol for a nuclide appears more than once in any grouping it indicates emission of more than one energy.

T1/2 <0.1 0.1-0.3 0.3-0.5 0.5-0.7 0.7-0.9 0.9-1.1 1.1-1.3 1.3-1.5 1.5-1.7 1.7-1.9 1.9-2.1 2.1-2.3 2.3-2.5 2.5-2.7 2.7-2.9 2.9-3.1 >3.1
175 132 47 47 89 132 127 127 124 166 47 124 140 134 214
3-5 d Yb Te Sc Ca Zr I Sb Sb I Ho Ca I Pr La Bi
199 166 47 127 186 132 127 166 132
Au Dy Sc Sb Re I Sb Ho I
199 166 127 132 186 132 214
Au Dy Te I Re I Bi
175 214 214 214 214
Yb Pb Pb Bi Bi
199
Au
214
Bi
237 177 131 52 111 210 148 125 72 72

5-10 d U Lu I Mn Ag Bi Pm Sn As As
196 133 111 148 148
Au Xe Ag Pm Pm
237 161 131
U Tb I
169 161
Er Tb
177 161
Lu Tb
183
Ta
246 140 140 140 140 140 140 140 126 140
10-13 d Pu Ba La Ba Ba La La La Sb La
147 209 147 207 246 246
Nd Pb Nd Tl Am Am
246 211 211
Pu Pb Pb
213
Bi
246
Am
126 136 126 143 126 32

13-15 d I Cs I Pr I P
136
Cs
225
Ra

T1/2 <0.1 0.1- 0.3-0.5 0.5-0.7 0.7-0.9 0.9- 1.1-1.3 1.3-1.5 1.5-1.7 1.7-1.9 1.9-2.1 2.1-2.3 2.3-2.5 2.5-2.7 2.7-2.9 2.9-3.1 >3.1
0.3 1.1
191 156 48 74 74 156 74 86 156

15-20 d Os Eu V As As Eu As Rb Eu
253 156 230 86
Cf Eu Pa Rb
33 233 234 82
20-30 d P Pa Pa Rb
233 234
Pa Pa
233 234
Pa Pa
234
Th
234
Th
234
Pa
95 141 141 84 129 129 84

30-40 d Nb Ce Ce Rb Te Te Rb
103 129m
Ru Te
103
Ru

BETA EMITTERS BY HALF-LIFE AND ENERGY (EMAX IN MeV) - (Cont'd)
T1/2 <0.1 0.1-0.3 0.3-0.5 0.5-0.7 0.7-0.9 0.9-1.1 1.1-1.3 1.3-1.5 1.5-1.7 1.7-1.9 1.9-2.1 2.1-2.3 2.3-2.5 2.5.-2.7 2.7-2.9 2.9-3.1 >3.1
59 59 148m 115m
40-50 d Fe Fe Pm Cd
203 148m 148m
Hg Pm Pm
181
Hf
35 46 124 160 124 56 91 114 188 124

50-100 d S Sc Sb Tb Sb Co Y In Re Sb
95 58 160 89 124 188
Nb Co Tb Sr Sb Re
124 95 192
Sb Zr Ir
160 95 192
Tb Zr Ir
192 160
Ir Tb
253 185
Cf W
188
W
182 127 170 170 123

100-150 d Ta Te Tm Tm Sn
182
Ta
45 177
150-200 d Ca Lu
177
Lu
102
200-250 d Rh
110m 144 144 110m 250 68 144

250 d-1 y Ag Ce Ce Ag Bk Ga Pr
249 250
Bk Bk
106 106 106

1-2 y Rh Rh Rh
171 106
Tm Rh

T1/2 <0.1 0.1-0.3 0.3-0.5 0.5-0.7 0.7-0.9 0.9-1.1 1.1-1.3 1.3-1.5 1.5-1.7 1.7-1.9 1.9-2.1 2.1-2.3 2.3-2.5 2.5-2.7 2.7-2.9 2.9-3.1 >3.1
134 125 125 22

2-3 y Cs Sb Sb Na
147 125 125
Pm Sb Sb
134
Cs
155
3-5 y Eu
155 204
Eu Tl
194 154 60 154 146 228 154 194 194

5-10 y Os Eu Co Eu Pm Ac Eu Ir Ir
228 228 228 154 228 228
Ra Ac Ac Eu Ac Ac
228 228
Ra Ac

T1/2 <0.1 0.1-0.3 0.3-0.5 0.5-0.7 0.7-0.9 0.9-1.1 1.1-1.3 1.3-1.5 1.5-1.7 1.7-1.9 1.9-2.1 2.1-2.3 2.3-2.5 2.5-2.7 2.7-2.9 2.9-3.1 >3.1
3 85 152 154
10-20 y H Kr Eu Eu
241 113
Pu Cd
152
Eu
154
Eu
210 90 210 90
20-30 y Pb Sr Bi Y
210
Pb
227
Ac
137 137 44
30-50 y Cs Cs Sc
151 121m
50-100 y Sm Sn
63 14 94 10 36 26 40 32 126 234m
>100 y Ni C Nb Be Cl Al K P Sb Pa
93 32 98 39 158 238
Zr Si Tc Ar Tb Np
107 79 115 176
Pd Se In Lu
166m 87 182 182
Ho Rb Ta Ta
187 99 225 233
Re Tc Ra Pa
227 126 242
Ac Sn Am
228 129 242
Ra I Am
228 135
Ra Cs
231 138
Th La
231
Th
231
Th

T1/2 <0.1 0.1-0.3 0.3-0.5 0.5-0.7 0.7-0.9 0.9-1.1 1.1-1.3 1.3-1.5 1.5-1.7 1.7-1.9 1.9-2.1 2.1-2.3 2.3-2.5 2.5-2.7 2.7-2.9 2.9-3.1 >3.1
231
Th
233
Pa
233
Pa
234
Th
234
Th

5.4 GAMMA
5.4.1 SCOPE
Presented here is a tabulation of ( rays and nuclides that are common to environmental
analyses. These data may be useful for interpreting either field or laboratory measurements.
As an aid in verifying nuclide identifications, two additional (-ray lines are included
when possible as E2 and E3.
The following special notations are used in the table:
Symbol Meaning
% ratio of (-rays to disintegrations.
X indicates X-ray.
KX, LX sum of K or L X-rays.
D indicates a doublet.
T indicates a triplet.
* indicates annihilation radiation.
Long in half-life column is used for all members of

the primordial series, % refers to U or Th
decays
REFERENCE
Browne, E., R. B. Firestone and V. S. Shirley (Editors)


TABLE OF ( RAYS AND NUCLIDES COMMON TO ENVIRONMENTAL ANALYSES
Energy Nuclide % T1/2 E2 % E3 % Origin
57
14.4 Co 9.5 272D 122.1 85.5 136.5 10.7 Activation
241 241
26.3 Am 2.4 433Y 59.5 35.7 17.0LX 38.7 Pu
140
30.0 Ba 13.6 12.8D 162.7 6.2 304.9 4.3 Fallout
129
39.6 I 7.5 1.6E7 30.0KX 70.8 Fission
212 232
39.9 Bi 1.1 Long 727.3 6.7 1620.7 1.5 Th
99
40.6 Mo 1.1 65.9H 18.3X 3.2 140.5 3.5 Fallout
210 238
46.5 Pb 4.1 22.3Y U
132
49.8 Te 14.4 78.2H 30.0KX 70.9 111.9 1.9 Fallout
133
53.2 Ba 2.2 10.5Y 81.0 34.2 31.0KX 101.3 Activation
237
59.5 U 32.8 6.75D 101.1 26.0 208.0 22.0 Fallout
241 241
59.5 Am 35.7 433Y 26.3 2.4 17.0LX 38.7 Pu
155
60.0 Eu 1.1 4.96Y 86.5 30.4 105.3 20.6 Fallout
239
61.5 Np 1.0 2.36D 14.3LX 56.1 101.0KX 38.9 Fallout
234 238
63.3 Th 3.8 Long 92.6D 5.4 U
136
66.9 Cs 12.5 13.2D 34.0KX 17.6 86.4 6.3 Fission
214 238
74.8X Pb 6.5 Long 77.1X 11.0 87.3X 3.9 U
212 232
74.8X Pb 10.5 Long 77.1X 17.7 87.2X 6.3 Th
208 232
75.0X Tl 3.6 Long 72.8X 2.1 84.8X 1.3 Th
214 238
77.1X Pb 11.0 Long 74.8X 6.5 87.2X 3.9 U
212 232
77.1X Pb 17.7 Long 74.8X 10.5 87.2X 6.3 Th
133
79.6 Ba 3.2 10.5Y 53.2 2.2 Activation
144
80.1 Ce 1.1 285D 133.5 11.1 696.5 1.3 Fallout
131
80.2 I 2.6 8.04D 364.5 81.2 284.3 6.1 Fission
133
81.0 Ba 34.2 10.5Y 276.4 7.3 79.6 3.2 Activation
133
81.0 Xe 37.0 5.25D 79.6 0.2 31.0KX 40.1 Fission
228 232
84.3X Th 1.2 1.91Y 12.3X 3.1 Th
136
86.4 Cs 6.3 13.2D 66.9 12.5 153.3 7.5 Fission
155
86.5 Eu 34.0 4.96Y 105.3 20.6 60.0 1.1 Fallout
214 238
87.2X Pb 3.9 Long 77.1X 11.0 241.9 7.5 U
212 232
87.2X Pb 6.3 Long 238.6 43.6 77.1X 17.7 Th
109
88.0 Cd 3.6 463D 23.0KX 99.8 Activation
228 232
90.0X Ac 3.4 Long 93.4X 5.6 99.6 1.3 Th
147
91.1 Nd 28.0 11.0D 38.5KX 37.4 319.4 2.0 Fallout
234 238
92.6D Th 5.4 Long 63.3 3.8 U
228 232
93.4X Ac 5.6 Long 90.0X 3.4 99.6 1.3 Th
237
97.1 U 16.0 6.75D 101.0 26.0 208.0 22.0 Fallout
228 232
99.6 Ac 1.3 Long 129.0 2.9 209.4 4.1 Th

TABLE OF ( RAYS AND NUCLIDES COMMON TO ENVIRONMENTAL ANALYSES (Cont'd)
237
101.1 U 26.0 6.75D 59.5 32.8 208.0 22.0 Fallout
155
105.3 Eu 20.6 4.96Y 86.5 34.0 60.0 1.1 Fallout
228 232
105.4X Ac 2.0 Long 99.6 1.3 129.0 2.9 Th
239
106.1 Np 22.7 2.36D 61.5 1.0 117.0KX 11.6 Fallout
235
109.2 U 1.5 70E7Y 93.4KX 5.5 143.8 10.5 Natural
132
111.9 Te 1.9 78.2H 49.8 14.4 116.4 1.9 Fallout
237
113.9 U 25.0 6.75D 101.1 26.0 208.0 22.0 Fallout
132
116.3 Te 1.9 78.2H 111.9 1.9 228.3 88.2 Fallout
152
121.8 Eu 28.4 13.3Y 344.3 26.6 244.7 7.5 Fallout
57
122.1 Co 85.5 273D 136.5 10.7 14.4 9.5 Activation
154
123.1 Eu 40.5 8.8Y 248.0 6.6 591.8 4.8 Fallout
101
127.2 Rh 73.0 3.3Y 198.0 70.8 325.2 13.4 Fallout
228 232
129.0 Ac 2.9 Long 99.6 1.3 209.4 4.1 Th
144
133.5 Ce 11.1 285D 696.5 1.3 80.1 1.1 Fallout
57
136.5 Co 10.7 272D 122.1 85.5 14.4 9.5 Activation
138 138
138.0 Cs 1.5 32.2M 227.7 1.5 462.8 30.7 Xe
99
140.5 Mo 3.5 65.9H 40.6 1.1 181.1 6.1 Fallout
99m 99
140.5 Tc 87.2 6.01H 18.4X 6.1 20.6X 1.2 Mo
235
143.8 U 10.5 70E7Y 109.2 1.5 163.4 4.7 Natural
141
145.4 C 48.4 32.5D 37.0KX 17.4 Fission
85m
151.2 Kr 75.2 4.48H 304.9 13.7 Fission
136
153.3 Cs 7.5 13.2D 86.4 6.3 164.0 4.6 Fission
138
153.9 Xe 6.0 14.1M 242.7 3.5 258.4 31.5 Fission
140
162.7 Ba 6.2 12.8D 304.9 4.3 30.0 13.6 Fallout
235
163.4 U 4.7 70E7Y 143.8 10.5 185.7 53.0 Natural
136
164.0 Cs 4.6 13.2D 153.3 7.5 176.6 13.6 Fission
139
165.9 Ce 79.9 138D 34.0KX 79.5 Activation
88
166.0 Kr 3.1 2.84H 196.3 26.0 362.3 2.3 Fission
125
176.3 Sb 6.8 2.73Y 427.9 29.4 380.4 1.5 Fallout
136
176.6 Cs 13.6 13.2D 164.0 4.6 273.7 12.7 Fission
99
181.1 Mo 6.1 65.9H 140.5 3.5 366.4 1.2 Fallout
235
185.7 U 53.0 70E7Y 143.8 10.5 205.3 4.7 Natural
226
186.1 Ra 3.3 1600Y Natural
59
192.3 Fe 3.1 44.5D 1099.3 56.5 1291.6 43.2 Activation
88
196.3 Kr 26.0 2.84H 362.3 2.3 166.0 3.1 Fission
101
198.0 Rh 70.8 3.3Y 127.2 73.0 325.2 13.4 Fallout
235
205.3 U 4.7 70E7Y 185.7 53.0 143.8 10.5 Natural
237
208.0 U 22.0 6.75D 59.5 32.8 101.1 26.0 Fallout

228 232
209.4 Ac 4.1 Long 129.0 2.9 270.3 3.8 Th
138 138
227.7 Cs 1.5 32.2M 138.0 1.5 409.0 4.7 Xe
239
228.2 Np 10.7 2.36D 106.1 22.7 277.6 14.2 Fallout
132
228.3 Te 88.2 78.2H 116.4 1.9 111.9 1.9 Fallout
133m
233.2 Xe 10.3 2.19D 30.0KX 56.3 Fission
212 232
238.6 Pb 43.6 Long 300.0 3.3 Th
224 232
240.8 Ra 3.9 Long Th
214 238
241.9 Pb 7.5 Long 295.1 19.2 352.0 37.1 U
138
242.7 Xe 3.5 14.1M 153.9 6.0 258.4 31.5 Fission
152
244.7 Eu 7.5 13.3Y 121.8 28.4 344.3 26.6 Fallout
154
248.0 Eu 6.6 8.8Y 123.1 40.5 591.8 4.8 Fallout
135
249.8 Xe 90.0 9.10H 608.2 2.9 31.0KX 5.2 Fission
138
258.4 Xe 31.5 14.1M 242.7 3.5 396.6 6.3 Fission
132 132
262.8 I 1.4 2.28H 505.9 5.0 522.7 16.1 Te
228 232
270.3 Ac 3.8 Long 209.4 4.1 328.0 3.5 Th
136
273.7 Cs 12.7 13.2D 176.6 13.6 340.6 48.6 Fission
133
276.4 Ba 7.1 10.5Y 302.9 18.4 81.0 34.2 Activation
208 232
277.3 Tl 2.4 Long 510.6 7.8 583.0 30.9 Th
239
277.6 Np 14.2 2.36D 228.2 10.7 315.9 1.6 Fallout
203
279.2 Hg 81.5 46.6D 74.6X 12.9 Fallout
131
284.3 I 6.1 8.04D 364.5 81.2 80.2 2.6 Fission
214 238
295.1 Pb 19.2 Long 351.9 37.1 241.9 7.5 U
212 232
300.0 Pb 3.3 Long 238.6 43.6 Th
133
302.9 Ba 18.4 10.5Y 276.4 7.1 356.0 62.2 Activation
140
304.9 Ba 4.3 12.8D 162.7 6.2 423.7 3.1 Fallout
85m
304.9 Kr 13.7 4.48H 151.2 75.1 Fission
239
315.9 Np 1.6 2.36D 277.6 14.2 334.3 2.1 Fallout
147
319.4 Nd 2.0 11.0D 439.9 1.2 91.1 28.0 Fallout
51
320.1 Cr 9.8 27.7D Activation
101
325.2 Rh 13.4 3.3Y 127.2 73.0 198.0 70.8 Fallout
228 232
328.0 Ac 3.5 Long 270.3 3.8 338.4 12.4 Th
140
328.8 La 20.7 40.3H 432.5 3.0 487.0 45.9 Fallout
239
334.3 Np 2.1 2.36D 315.9 1.6 61.5 1.0 Fallout
228
338.4 Ac 12.4 Long 328.0 3.5 409.6 2.2 232Th
136
340.6 Cs 48.6 13.2D 273.7 12.7 818.6 99.8 Fission
152
344.3 Eu 26.6 13.3Y 244.7 7.5 411.1 2.2 Fallout
214 238
352.0 Pb 37.1 Long 241.9 7.5 295.1 19.2 U
133
356.0 Ba 62.2 10.5Y 302.9 18.4 383.8 8.9 Activation

88
362.3 Kr 2.3 2.84H 196.3 26.0 834.9 13.0 Fission
131
364.5 I 81.2 8.04D 637.0 7.3 284.3 6.1 Fission
99
366.4 Mo 1.2 65.9H 181.1 6.1 739.5 12.1 Fallout
125
380.4 Sb 1.5 2.73Y 176.3 6.8 427.9 29.4 Fallout
133
383.8 Ba 8.9 10.5Y 356.0 62.2 302.9 18.4 Activation
138
396.6 Xe 6.3 14.1M 258.4 31.5 401.5 2.2 Fission
138
401.5 Xe 2.2 14.1M 434.6 20.3 396.6 6.3 Fission
87
402.6 Kr 49.6 76.3M 845.5 7.3 673.9 1.9 Fission
138 138
409.0 Cs 4.7 32.2M 227.7 1.5 462.8 30.7 Xe
228 232
409.6 Ac 2.2 Long 338.4 12.4 463.1 4.6 Th
152
411.1 Eu 2.2 13.3Y 344.3 26.6 444.0D 3.1 Fallout
102
415.3 Rh 2.1 2.89Y 418.5 10.6 420.4 3.2 Fallout
102
418.5 Rh 10.6 2.89Y 415.3 2.1 420.4 3.2 Fallout
102
420.4 Rh 3.2 2.89Y 418.5 10.6 475.1 95.0 Fallout
140
423.7 Ba 3.1 12.8D 437.6 1.9 304.9 4.3 Fallout
125
427.9 Sb 29.4 2.73Y 380.4 1.5 463.4 10.5 Fallout
140
432.5 La 3.0 40.3H 487.0 45.9 328.8 20.7 Fallout
138
434.6 Xe 20.3 14.1M 401.5 2.2 1114.3 1.5 Fission
140
437.6 Ba 1.9 12.8D 537.3 24.4 423.7 3.1 Fallout
147
439.9 Nd 1.2 11.0D 319.4 2.0 531.0 13.1 Fallout
152
444.0D Eu 3.1 13.3Y 411.1 2.2 778.9 13.0 Fallout
110m
446.8 Ag 3.8 250D 657.8 94.6 620.4 2.8 Activation
138 138
462.8 Cs 30.7 32.2M 547.0 10.8 409.0 4.7 Xe
228 232
463.1 Ac 4.6 Long 409.6 2.2 755.3 1.3 Th
125
463.4 Sb 10.5 2.73Y 427.9 29.4 600.5 17.8 Fallout
102m
468.7 Rh 2.9 207D 475.1 46.0 556.6 1.9 Fallout
102m
475.1 Rh 46.0 207D 468.7 2.9 556.6 1.9 Fallout
102
475.1 Rh 95.0 2.89Y 628.1 8.5 420.5 3.2 Fallout
134
475.4 Cs 1.5 2.06Y 563.2 8.4 569.3 15.4 Fission
7
477.6 Be 10.3 53.2D Cosmic
140
487.1 La 45.5 40.2H 751.9 4.3 432.6 2.9 Fallout
103
497.1 Ru 89.5 39.6D 610.3 5.6 Fallout
132 132
505.9 I 5.0 2.28H 262.8 1.4 522.7 16.1 Te
208 232
510.6 Tl 7.8 Long 277.3 2.4 583.0 30.9 Th
65
511.0 Zn 2.9 244D 1115.5 50.8 Activation
58
511.0 Co 30.0 70.9D 810.8 99.5 Activation

22
511.0 Na 180.8 2.60Y 1274.5 99.9 Cosmic
106
511.9 Ru 20.7 372D 1050.4 1.5 621.9 9.8 Fallout
85
514.0 Sr 99.3 64.8D 13.4KX 50.6 15.0KX 8.7 Activation
132 132
522.7 I 16.1 2.28H 505.9 5.0 547.0 1.3 Te
135m
526.6 Xe 81.2 15.7M 30.0KX 14.0 Fission
147
531.0 Nd 13.1 11.0D 439.9 1.2 319.4 2.0 Fallout
140
537.3 Ba 24.4 12.8D 437.6 1.9 423.7 3.1 Fallout
138 138
547.0 Cs 10.8 32.2M 462.8 30.7 871.7 5.1 Xe
132
547.0 I 1.3 2.28H 522.7 16.1 621.2 ~2.0 132Te
102m
556.6 Rh 1.9 207D 475.1 46.0 628.1 5.5 Fallout
134
563.2 Cs 8.4 2.06Y 475.4 1.5 569.3 15.4 Fission
134
569.3 Cs 15.4 2.06Y 563.2 8.4 604.7 97.6 Fission
207
569.2 Bi 97.8 32.2Y 1063.1 74.9 1769.7 6.9 Fallout
208 232
583.0 Tl 30.9 Long 510.6 7.8 860.3 4.3 Th
154
591.8 Eu 4.8 8.8Y 248.0 6.6 692.5 1.7 Fallout
125
600.5 Sb 17.8 2.73Y 463.4 10.5 606.6 5.0 Fallout
124
602.7 Sb 97.8 60.2D 645.9 7.4 709.3 1.4 Fallout
134
604.7 Cs 97.6 2.06Y 795.9 85.4 569.3 15.4 Fission
125
606.6 Sb 5.0 2.73Y 600.5 17.8 635.9 11.3 Fallout
135
608.2 Xe 2.9 9.10H 249.8 90.0 31.6KX 5.2 Fission
214 238
609.3 Bi 46.1 Long 665.4 1.6 768.4 4.9 U
103
610.3 Ru 5.6 39.3D 497.1 88.7 Fallout
110m
620.4 Ag 2.8 250D 657.8 94.6 446.8 3.8 Activation
132 132
621.2 I ~2.0 2.28H 547.1 1.3 630.3 13.8 Te
106
621.9 Ru 9.8 372D 511.9 20.7 1050.4 1.5 Fallout
102m
628.1 Rh 5.5 207D 556.6 1.9 1103.2 2.9 Fallout
102
628.1 Rh 8.5 ~2.9Y 475.1 95.0 631.3 56.0 Fallout
132 132
630.3 I 13.8 2.28H 621.2 ~2.0 650.6 2.7 Te
102
631.3 Rh 56.0 ~2.9Y 628.1 8.5 692.4 1.8 Fallout
125
635.9 Sb 11.3 2.73Y 606.6 5.0 671.4 1.8 Fallout
131
637.0 I 7.3 8.04D 364.5 81.2 722.9 1.8 Fission
124
645.9 Sb 7.4 60.2D 602.7 97.8 709.3 1.4 Fallout
132 132
650.6 I 2.7 2.28H 630.3 13.8 667.7 98.7 Te
110m
657.8 Ag 94.6 250D 620.4 2.8 677.6 10.4 Activation
137
661.7 Cs 85.2 30.0Y 33.0KX 7.1 Fallout
214 238
665.4 Bi 1.6 Long 609.3 46.1 768.4 4.9 U
132 132
667.7 I 98.7 2.28H 650.6 2.7 669.9 4.9 Te

132 132
669.9 I 4.9 2.28H 667.7 98.7 671.6 5.2 Te
125
671.4 Sb 1.8 2.73Y 635.9 11.3 606.6 5.0 Fallout
132 132
671.6 I 5.2 2.28H 669.9 4.9 727.D 5.4 Te
87
673.9 Kr 1.9 76.3M 845.5 7.3 402.6 49.6 Fission
110m
677.6 Ag 10.4 250D 657.8 94.6 687.0 6.4 Activation
110m
687.0 Ag 6.4 250D 677.6 10.4 706.7 16.4 Activation
102
692.4 Rh 1.8 ~2.9Y 631.3 56.0 695.6 2.7 Fallout
154
692.5 Eu 1.7 8.8Y 591.8 4.8 723.4 19.7 Fallout
102
695.6 Rh 2.7 ~2.9Y 692.4 1.8 697.6 45.7 Fallout
144
696.5 Ce 1.3 285D 133.5 11.1 80.1 1.1 Fallout
102
697.6 Rh 45.7 ~2.9Y 766.9 34.0 695.6 2.7 Fallout
110m
706.7 Ag 16.4 250D 687.0 6.4 744.3 4.7 Activation
124
709.3 Sb 1.4 60.2D 645.9 7.4 713.8 2.3 Fallout
124
713.8 Sb 2.3 60.2D 709.3 1.4 722.8 10.9 Fallout
124
722.8 Sb 10.9 60.2D 713.8 2.3 968.2 1.9 Fallout
131
722.9 I 1.8 8.04D 364.5 81.2 637.0 7.3 Fission
154
723.4 Eu 19.7 8.8Y 692.5 1.7 756.8 4.3 Fallout
95
724.2 Zr 44.1 64.0D 756.7 54.5 Fallout
132 132
727.0D I 5.4 2.28H 671.6 5.2 728.7 1.1 Te
212 232
727.3 Bi 6.7 Long 39.9 1.1 1620.7 1.5 Th
132 132
728.7 I 1.1 2.28H 727.0D 5.4 772.7 76.2 Te
99
739.5 Mo 12.1 65.9H 366.4 1.2 777.9 4.4 Fallout
110m
744.3 Ag 4.7 250D 706.7 16.4 763.9 22.3 Activation
140
751.7 La 4.3 40.3H 487.0 45.9 815.8 23.6 Fallout
228 232
755.3 Ac 1.3 Long 463.1 4.6 772.3 1.1 Th
95
756.7 Zr 54.5 64.0D 724.2 44.1 Fallout
154
756.8 Eu 4.3 8.8Y 723.4 19.7 873.2 11.5 Fallout
208 232
763.1 Tl 0.6 Long 583.0 30.9 860.3 4.3 Th
110m
763.9 Ag 22.3 250D 744.3 4.7 818.0 7.3 Activation
95
765.8 Nb 99.8 35.0D Fallout
102
766.9 Rh 34.0 ~2.9Y 697.6 45.7 1046.6 34.0 Fallout
214 238
768.4 Bi 5.0 Long 665.6 1.6 786.4D 0.3 U
228 232
772.3 Ac 1.1 Long 755.3 1.3 794.8 4.6 Th
132 132
772.7 I 76.2 2.28H 728.7 1.1 780.1 1.2 Te
99
777.9 Mo 4.4 65.9H 739.5 12.1 366.4 1.2 Fallout
152
778.9 Eu 13.0 13.3Y 444.0D 3.1 867.4 4.2 Fallout
132 132
780.1 I 1.2 2.28H 772.7 76.2 809.8 2.9 Te

212 232
785.5 Bi 1.1 Long 727.3 6.7 1620.7 1.5 Th
214 238
786.4 Bi 0.3 Long 768.4 4.9 806.2 1.2 U
228 232
794.8 Ac 4.6 Long 772.3 1.1 830.6 0.6 Th
134
795.8 Cs 85.4 2.06Y 604.7 97.8 801.9 8.7 Fission
134
802.0 Cs 8.7 2.06Y 795.9 85.4 1038.6 1.0 Fission
214 238
806.2 Bi 1.2 Long 786.4 0.3 934.0 3.2 U
132 132
809.8 I 2.9 2.28H 780.1 1.2 812.3 5.6 Te
58
810.8 Co 99.5 70.9D 511.0 30.0 Activation
132 132
812.3 I 5.6 2.28H 809.8 2.9 877.2 1.1 Te
140
815.8 La 23.6 40.3H 751.7 4.3 867.8 5.6 Fallout
110m
818.0 Ag 7.3 250D 763.9 22.3 884.7 72.7 Activation
136
818.6 Cs 99.8 13.2D 340.6 48.6 1048.1 79.7 Fission
228 232
830.6 Ac 0.6 Long 794.8 4.6 835.6 1.7 Th
54
834.8 Mn 100.0 312.2D Fallout
88
834.9 Kr 13.0 2.84H 362.3 2.3 985.8D 1.3 Fission
228 232
835.6 Ac 1.7 Long 830.6 0.6 840.4 0.9 Th
228 232
840.4 Ac 0.9 Long 835.6 1.7 904.3 0.9 Th
87
845.5 Kr 7.3 76.3M 673.9 1.9 1175.5 1.1 Fission
208 232
860.3 Tl 4.3 Long 2614.4 35.8 583.0 30.9 Th
152
867.4 Eu 4.2 13.3Y 778.9 13.0 964.1 14.5 Fallout
140
867.8 La 5.6 40.3H 815.8 23.6 919.6 2.7 Fallout
138 138
871.7 Cs 5.1 32.2M 547.0 10.8 1009.8 29.8 Xe
154
873.2 Eu 11.5 8.8Y 756.8 4.3 996.3 10.3 Fallout
132 132
877.2 I 1.1 2.28H 812.3 5.6 954.6 18.1 Te
110m
884.7 Ag 72.7 250D 818.0 7.3 937.5 34.4 Activation
88
898.1 Y 92.7 107D 1836.1 99.4 Activation
88 88
898.0 Rb 14.1 17.8M 1836.1 21.4 2677.9 2.0 Kr
228 232
904.3 Ac 0.9 Long 840.4 0.9 911.2 29.0 Th
228 232
911.2 Ac 29.0 Long 966.0D 23.2 840.4 0.9 Th
140
919.6 La 2.7 40.3H 867.8 5.6 925.2 7.0 Fallout
140
925.2 La 7.1 40.3H 487.0 45.9 919.6 2.7 Fallout
214 238
934.0 Bi 3.2 Long 1120.3 15.0 806.2 1.2 U
110m
937.5 Ag 34.4 250D 1384.3 24.3 884.7 72.7 Activation
132 132
954.6 I 18.1 2.28H 877.2 1.1 1136.2 3.0 Te
152
964.1 Eu 14.5 13.3Y 1085.9 9.9 867.4 4.2 Fallout
228 232
964.6 Ac 5.8 Long 969.0 17.4 911.2 29.0 Th
124
968.2 Sb 1.9 60.2D 1045.1 1.9 722.8 10.9 Fallout

228 232
969.0 Ac 17.4 Long 911.2 29.0 1459.2 1.1 Th
88
985.8 Kr 1.3 2.84H 1141.4 1.3 834.9 13.0 Fission
154
996.3 Eu 10.3 8.8Y 1004.8 17.9 873.2 11.5 Fallout
234m 238
1001.0 Pa 0.7 Long 766.4 0.2 742.8 0.1 U
154
1004.8 Eu 17.9 8.8Y 1274.5 35.5 996.3 10.3 Fallout
138 138
1009.8 Cs 29.8 32.2M 1147.3 1.2 871.7 5.1 Xe
134
1038.6 Cs 1.0 2.06Y 1167.9 1.8 802.0 8.7 Fission
124
1045.1 Sb 1.9 60.2D 1325.5 1.6 968.2 1.9 Fallout
102
1046.6 Rh 33.0 2.9Y 1103.2 4.4 766.9 34.0 Fallout
136
1048.1 Cs 79.7 13.2D 818.6 99.8 1235.4 19.8 Fission
106
1050.4 Ru 1.5 372D 511.9 20.7 621.9 9.8 Fallout
207
1063.1 Bi 74.9 32.2Y 569.2 97.8 1769.7 6.9 Fallout
152
1085.9 Eu 9.9 13.3Y 1112.1 13.6 964.1 14. Fallout
59
1099.3 Fe 56.5 44.5D 1291.6 43.2 192.3 3.1 Fallout
102m
1103.2 Rh 2.9 207D 556.6 1.9 628.1 5.5 Fallout
102
1103.2 Rh 4.4 2.9Y 1046.6 33.0 1112.9 18.9 Fallout
152
1112.1 Eu 13.6 13.3Y 1085.9 9.9 1212.9 1.4 Fallout
102
1112.9 Rh 18. 2.9Y 1046.6 33.0 1103.2 4.4 Fallout
138
1114.3 Xe 1.5 14.1M 1768.4 16.7 434.6 20.3 Fission
65
1115.5 Zn 50.8 244D 511.0 2.9 Activation
214 238
1120.3 Bi 15.0 Long 1155.2 1.7 934.0 3.2 U
132 132
1136.2 I 3.0 2.28H 954.6 18.1 1143.6 1.4 Te
88
1141.4 Kr 1.3 2.84H 1369.4 1.5 985.8D 1.3 Fission
132 132
1143.6 I 1.4 2.28H 1136.2 3.0 1173.3 1.1 Te
138 138
1147.3 Cs 1.2 32.2M 1009.8 29.8 1343.6 1.1 Xe
214 238
1155.2 Bi 1.7 Long 1238.1 5.9 1120.3 15.0 U
134
1167.9 Cs 1.8 2.06Y 1038.6 1.0 1365.2 3.0 Fission
60
1173.2 Co 99.9 5.27Y 1332.5 100.0 Activation
132 132
1173.3 I 1.1 2.28H 1143.6 1.4 1290.8 1.1 Te
87
1175.5 Kr 1.1 76.3M 1740.6 2.0 845.5 7.3 Fission
152
1212.9 Eu 1.4 13.3Y 1112.1 13.6 1299.2 1.6 Fallout
136
1235.4 Cs 19.8 13.2D 818.6 99.8 1048.1 79.7 Fission
214 238
1238.1 Bi 5.9 Long 1155.2 1.7 1281.0 1.5 U
22
1274.5 Na 99.9 2.60Y 511.0 181.0 Cosmic
154
1274.5 Eu 35.5 8.8Y 1004.8 17.9 1596.6 1.8 Fallout
214 238
1281.0 Bi 1.5 Long 1238.1 5.9 1377.7 4.0 U
132 132
1290.8 I 1.1 2.28H 1173.3 1.1 1295.4 2.0 Te
59
1291.6 Fe 43.2 44.5D 1099.3 56.5 192.3 3.1 Activation

41
1293.6 Ar 99.2 1.83H Activation
132 132
1295.4 I 2.0 2.28H 1290.8 1.1 1372.1 2.5 Te
152
1299.2 Eu 1.6 13.3Y 1212.9 1.4 1408.0 20.8 Fallout
124
1325.5 Sb 1.6 60.2D 1045.1 1.9 1368.2 2.7 Fallout
60
1332.5 Co 100.0 5.27Y 1173.2 99.9 Activation
138 138
1343.6 Cs 1.1 32.2M 1147.3 1.2 1435.8 76.3 Xe
134
1365.2 Cs 3.0 2.06Y 1167.9 1.8 1038.6 1.0 Fission
124
1368.2 Sb 2.7 60.2D 1325.5 1.6 1436.7 1.3 Fallout
24
1368.6 Na 100.0 14.7H 2754.1 99.9 Activation
88
1369.4 Kr 1.5 2.84H 1141.4 1.3 1518.4 2.2 Fission
132 132
1372.1 I 2.5 2.28H 1295.4 2.0 1398.6 7.1 Te
214 238
1377.7 Bi 4.0 Long 1281.0 1.5 1401.5 1.4 U
110m
1384.3 Ag 24.3 250D 1475.8 4.0 937.5 34.4 Activation
132 132
1398.6 I 7.1 2.28H 1372.1 2.5 1442.5 1.4 Te
214 238
1401.5 Bi 1.4 Long 1377.7 4.0 1408.0 2.5 U
214 238
1408.0 Bi 2.5 Long 1401.5 1.4 1509.2 2.2 U
152
1408.0 Eu 20.8 13.3Y 1299.2 1.6 1212.9 1.4 Fallout
138 138
1435.8 Cs 76.3 32.2M 1343.6 1.1 2218.0 15.2 Xe
124
1436.6 Sb 1.3 60.2D 1368.2 2.7 1691.0 47.1 Fallout
132 132
1442.5 I 1.4 2.28H 1398.6 7.1 1921.1 1.2 Te
228 232
1459.2 Ac 1.1 Long 1499.0D 1.6 969.0 17.4 Th
40
1460.8 K 10.7 1.3E9 Natural
110m
1475.8 Ag 4.0 250D 1384.3 24.3 1505.0 13.0 Activation
228 232
1499.0D Ac 1.6 Long 1459.2 1.1 1588.2 3.6 Th
110m
1505.0 Ag 13.0 250D 1475.8 4.0 1562.3 1.0 Activation
214 238
1509.2 Bi 2.2 Long 1408.0 2.5 1661.3 1.2 U
88
1518.4 Kr 2.2 2.84H 1369.4 1.5 1529.8 10.9 Fission
88
1529.8 Kr 10.9 2.84H 1518.4 2.2 2029.9 4.5 Fission
228 232
1588.2 Ac 3.6 Long 1499.0D 1.6 1630.5 2.0 Th
140
1596.5 La 95.4 40.3H 487.0 45.9 2521.7 3.4 Fallout
154
1596.6 Eu 1.7 8.8Y 1274.5 35.5 1004.8 17.9 Fallout
212 232
1620.7 Bi 1.5 Long 727.3 6.7 785.5 1.1 Th
228 232
1630.5 Ac 2.0 Long 1588.2 3.6 1499.0D 1.6 Th
214 238
1661.3 Bi 1.2 Long 1509.2 2.2 1729.6 3.1 U
124
1691.0 Sb 47.1 60.2D 2090.9 5.5 1436.7 1.3 Fallout

214 238
1729.6 Bi 3.1 Long 1764.5 15.9 1661.3 1.2 U
87
1740.6 Kr 2.0 76.3M 1175.5 1.1 2011.9 2.9 Fission
214 238
1764.5 Bi 15.9 Long 1729.6 3.1 1847.4 2.1 U
138
1768.4 Xe 16.7 14.1M 1114.3 1.5 1850.9 1.4 Fission
1769.7 207Bi 6.9 32.2Y 1063.1 74.9 569.2 97.8 Fallout
88 88
1836.1 Rb 21.4 17.8M 2677.9 2.0 898.1 14.1 Kr
88
1836.1 Y 99.4 107D 898.1 92.7 Other
214 238
1847.4 Bi 2.1 Long 1764.5 15.9 2118.5 1.2 U
138
1850.9 Xe 1.4 14.1M 1768.4 16.7 2004.8 5.4 Fission
132 132
1921.1 I 1.2 2.28H 1442.5 1.4 2002.4 1.1 Te
132 132
2002.4 I 1.1 2.28H 1921.1 1.2 1442.5 1.4 Te
138
2004.8 Xe 5.4 14.1M 1850.9 1.4 2015.9 12.3 Fission
87
2011.9 Kr 2.9 76.3M 1740.6 2.0 2556.0D 13.1 Fission
138
2015.9 Xe 12.3 14.1M 2004.8 5.4 2079.3 1.4 Fission
88
2029.9 Kr 4.5 2.84H 1529.8 10.9 2035.5 3.7 Fission
88
2035.5 Kr 3.7 2.84H 2029.9 4.5 2195.8 13.2 Fission
138
2079.3 Xe 1.4 14.1M 2015.9 12.3 2252.3 2.3 Fission
124
2090.9 Sb 5.5 60.2D 1436.6 1.3 1691.0 47.1 Fallout
214 238
2118.5 Bi 1.2 Long 1847.4 2.1 2204.1 5.0 U
88
2195.8 Kr 13.2 2.84H 2035.5 3.7 2231.8 3.4 Fission
214 238
2204.1 Bi 5.0 Long 2447.7 1.6 2118.5 1.2 U
138 138
2217.8 Cs 15.2 32.2M 1435.8 76.3 2639.4 7.6 Xe
88
2231.8 Kr 3.4 2.84H 2195.8 13.2 2392.1 34.6 Fission
138
2252.3 Xe 2.3 14.1M 2079.3 1.4 2015.9 12.3 Fission
88
2392.1 Kr 34.6 2.84H 2231.8 3.4 2195.8 13.2 Fission
214 238
2447.7 Bi 1.6 Long 2204.1 5.0 2118.5 1.2 U
140
2521.7 La 3.4 40.3H 1596.5 96.4 487.0 45.9 Fallout
87
2556D Kr 13.1 76.3M 2011.9 2.9 1740.6 2.0 Fission
208 232
2614.4 Tl 35.8 Long 860.3 4.3 583.0 30.9 Th
138 138
2639.4 Cs 7.6 32.2M 2217.8 15.2 1435.8 76. Xe

88 88
2677.9 Rb 2.0 17.8M 1836.1 21.4 898.1 14.1 Kr
24
2754.0 Na 99.9 14.7H 1368.6 100.0 Activation
16
6129.2 N 68.8 7.13S 7115.2 4.7 Other
16
7115.2 N 4.7 7.13S 6129.2 68.8 Other

U. S. Department of Energy 5.4 - 12
5.5 X-RAY
5.5.1 SCOPE
This section presents a table of X-ray energies which are useful for radiochemical
analyses.
A number of nuclides emit X-rays as part of their decay scheme. These X-rays may be
counted with Ar proportional counters with Ge planar or n-type Ge co-axial detectors or
with thin crystal NaI(Tl) scintillation counters. In both cases, spectral measurements can
be made and both qualitative and quantitative information obtained on the sample.
K Shell vacancies are filled by a higher shell election. In the process an energy
Ek - Ex is liberated either as an X-ray or an Auger electron. The most important X-ray
transitions are designated as,
K"1 = K - LIII
K"2 = K - LII
Kß1 = K - MIII
Kß2 = K - NIII
Kß3 = K - MII
Kß4 = K - NII
Kß5 = K - MIV

With moderate resolution only Kß1' and Kß2' can be resolved,
Kß1' = Kß1 + Kß3 + Kß5
Kß2' = Kß2 + Kß4
The same is true for K"
K" = K"1 + K"2
The present table lists the values for K", Kß1' and Kß2'. Electron binding energies used
in this table were based on the tabulations of Wapstra et al. (1959) and Siegbahn (1965).
REFERENCES
Browne, E. and R. B. Firestone

Shirley, V. S. (Editor)
Siegbahn, K.
Alpha, Beta, and Gamma Ray Spectroscopy
North-Holland Publishing, Co., Amsterdam (1965)
Wapstra, A. H., G. J. Nijgh and R. Van Lieshout

Nuclear Spectroscopy Tables
North-Holland Publishing, Co., Amsterdam (1959)

Energy
(keV)
Z Element K"- Kß1' Kß2'
3 Li 0.05
4 Be 0.11
5 B 0.18
6 C 0.28
7 N 0.40
8 O 0.53
9 F 0.68
10 Ne 0.85
11 Na 1.04
12 Mg 1.25
13 Al 1.49
14 Si 1.74
15 P 2.01
16 S 2.31
17 C1 2.62
18 Ar 2.96 3.19
19 K 3.31 3.59
20 Ca 3.69 4.01
21 Sc 4.09 4.46
22 Ti 4.51 4.93
23 V 4.95 5.43
24 Cr 5.42 5.95
25 Mn 5.90 6.49
26 Fe 6.40 7.06
27 Co 6.93 7.65
28 Ni 7.47 8.26
29 Cu 8.03 8.91
30 Zn 8.63 9.57
31 Ga 9.24 10.3
32 Ge 9.88 11.1

Energy
(keV)
Z Element K"- Kß1- Kß2'
33 As 10.5 11.7
34 Si 11.2 12.5
35 Br 11.9 13.3
36 Kr 12.6 14.1
37 Rb 13.4 15.0
38 Sr 14.1 15.8 16.1
39 Y 14.9 16.7 17.0

40 Zr 15.7 17.7 18.0
41 Nb 16.6 18.6 19.0
42 Mo 17.4 19.6 20.0

43 Te 18.3 20.6 21.0
44 Ru 19.2 21.6 22.1
45 Rh 20.2 22.7 23.2

46 Pd 21.1 23.8 24.3
47 Ag 22.1 24.9 25.5
48 Cd 23.1 26.1 26.6

49 In 24.1 27.3 27.9
50 Sn 25.1 28.4 29.1
51 Sb 26.3 29.7 30.4

52 Te 27.3 31.0 31.7
53 I 28.5 32.3 33.0
54 Xe 29.6 33.6 34.4

55 Cs 30.8 34.9 35.8
56 Ba 32.0 36.4 37.2
57 La 33.3 37.8 38.7

58 Ce 34.5 39.3 40.2
59 Pr 35.9 40.7 41.8
60 Nd 37.2 42.3 43.3

61 Pm 38.5 43.8 44.9
62 Sm 39.8 45.4 46.6

Energy
(keV)
63 Eu 41.3 47.0 48.2

64 Cd 42.7 48.7 49.9
65 Tb 44.1 50.4 51.7
66 Dy 45.6 52.1 53.4

67 Ho 47.1 53.8 55.3
68 Er 48.7 55.6 57.1
69 Tm 50.3 57.5 59.0

70 Yb 51.9 59.4 60.9
71 Lu 53.5 61.3 62.9
72 Hf 55.2 63.2 64.9

73 Ta 57.1 65.2 67.0
74 W 58.8 67.2 69.1
75 Re 60.6 69.3 71.2

76 Os 62.4 71.4 73.4
77 Ir 64.3 73.6 75.6
78 Pt 66.2 75.7 77.8

79 Au 68.2 78.0 80.1
80 Hg 70.1 80.1 82.5
81 Tl 72.1 82.4 84.9

82 Pb 74.2 84.7 87.3
83 Bi 76.3 87.1 89.8
84 Po 78.4 89.6 92.3

85 At 80.5 92.7 95.0
86 Rn 82.8 94.7 97.5
87 Fr 85.0 97.3 100.2

88 Ra 87.3 99.9 103.0
89 Ac 89.7 102.6 105.7

Energy
(keV)
90 Th 92.1 105.3 108.6

91 Pa 94.5 108.1 111.4
92 U 97.0 111.0 114.5
93 Np 99.5 113.9 117.5

94 Pu 102.1 116.9 120.5
95 Am 104.7 119.9 123.6
96 Cm 107.5 123.0 126.9

97 Bk 110.2 126.2 130.2
98 Cf 113.0 129.4 133.5
99 Es 115.9 132.7 136.9

100 Fm 118.8 136.0 140.4
101 Md 122.8 139.4 144.9
102 No 124.8 142.7 147.5

103 Lw 127.9 146.2 151.2
104 130.5 149.7 154.5

5.6 NATURAL DECAY SERIES
5.6.1 SCOPE
Charts of the four heavy element series are given in this section. These are the three
natural series and the artificial Am series.
Data for half-lives and energies have been taken from Browne et al. (1986). Energies
are given in order of abundance and include only the major emissions. Branching in the
chains that amount to one percent or less are also omitted.
REFERENCE
Browne, E. and R. B. Firestone

Shirley, V. S. (Editor)
John Wiley and Sons, Inc. (1986)

Principal Members of the Uranium Series
238 234
U (UI) U (UII)
4.47 x 109 y
4.2 MeV
234
_ 2.45 x 105 y
4.7 MeV
9 9
Pa (UX2)
1.17 min
234
Th (UX1)
_ 2.3 MeV
230
Th (Io)
24.1 d 7.54 x 104
0.2, 0.1 MeV 4.6 MeV
9
226
Ra (Ra)
1600 y
4.8 MeV
9
222
Rn (Rn)
3.825 d
5.5 MeV
9
218
Po (RaA) Po (RaCN)
214 210
Pb (RaF)
1.64 x 10-4 s
_
3.05 m 138.376 d
6.0 MeV
_ 7.7 MeV 5.3 MeV
9
214 210
Bi (RaC) Bi (RaE)
Alpha Decay
_ 9
19.9 m
9
5.013 d
9
_ _
0.4-3.3 MeV 1.2 MeV
Beta Deca
214 210 206
Pb (RaB) Pb (RaD) Pb (RaG)
26.8 m 22.3 y
0.7, 1.0 MeV 0.02, 0.06 MeV Stable

Principal Members of the Thorium Series
232 228
Th (Th) Th (Rd Th)
1.405 x 1010 y 1.91 y
_
4.0 MeV 5.3, 5.4 MeV
228
9 9
Ac (Ms Th II)
_
6.13 h
0.4-2.2 MeV
228 224
Ra (Ms Th I) Ra (ThX)
5.75 y 3.66 d
0.01, 0.04 MeV 5.4, 5.7 MeV
9
220
Rn (Tn)
55.6 s
6.3 MeV
9
216
Po (ThA)
0.15 s
6.8 MeV
9
218 212
Pb (ThB) Po (ThCN)
10.64 h 2.98 x 10-7
0.3, 0.6 MeV
212 _ 8.8 MeV
9 9
Bi (ThC)
60.6 min
6.1 MeV ", 2.2 MeV $
9
212
Pb (ThB) _ 208
Pb (ThD)
9
_
Alpha Decay 10.64 h
1/3
0.3, 0.6 MeV Stable
_
Beta Decay
208
TI (ThCO)
3.053 min
1.0-1.8 MeV

Principal Members of the Actinium Series
235
U (AcU)
7.037 x 108 y
4.4-4.6 MeV
231
9
Pa
3.276 x 104 y
_
4.7-5.1 MeV
231 227
9
Th (UY) Th (Rd Ac)
1.063 d 18.718 d
0.09-0.30 MeV
227 _
5.7-6.0 MeV
9
Ac
21.77 y
0.05 MeV
223
Ra (AcX)
11.43 d
5.5-5.7 MeV
9
219
Rn (An)
3.96 s
6.4-6.8 MeV
9
215
Po (AcA)
1.78 x 10-3 s
7.4 MeV
211
9
Bi (AcC)
2.14 min
_
6.3, 6.6 MeV
211 207
9
Pb (AcB) Pb
9
36.1 min
_
Alpha Decay
0.5-1.4 MeV Stable
Beta Decay
207
Ti (AcC'')
_
4.77 m
1.43 MeV

Principal Members of the Americium Series
241
Am
432.7 y
5.4-5.5 MeV
241
9
Pu
14.4 y
0.02 MeV
237
9
Np
2.14 x 106 y
237 _ 4.6-4.8 MeV

233
9
U U
_
6.75 d 1.592 x 105 y
0.09, 0.25 MeV 4.8 MeV
233
9 9
Pa
27.0 d
233
Th
22.3 min
_ 0.15-0.57 MeV
229
Th
7340 y
1.23 MeV 4.8-5.1 MeV
225
9
Ac
_
10.0 d
5.8 MeV
225
9
Ra
14.8 d
0.32 MeV
221
Fr
4.9 min
6.1-6.3 MeV
9
217
At
0.032 s
7.1 MeV
213
9
Po
4.2 x 10-6 s
213 _ 8.4 MeV
9 9
Bi
_
209
45.59 min Bi
Alpha Decay Stable
1.0-1.4 MeV
Beta Decay
209
Pb
3.253 h
_
0.64 MeV

HASL-300, 28th Edition October 1999
Page
6. Special Facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1-1
6.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1-1
6.2 Radon Gas and Radon/Thoron Progeny

Facilities for Testing and Research . . . . . . . . . . . . . . . . . . . . . 6.2-1
6.2.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2-1

6.2.2 The EML Pulse Ionization Chamber Facility for Radon-222
Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2-1
6.2.2.1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2-1
6.2.2.2
Principle of Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2-2
6.2.2.3
Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2-2
6.2.2.4
Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2-2
6.2.2.5
Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2-3
6.2.2.6
Routine Chamber Checks and Maintenance . . . . . . . . . . . . . . . 6.2-3
6.2.3 Radon, Thoron, and Progeny Exposure Facility . . . . . . . . . . . . . . . 6.2-4
6.2.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2-4
6.2.3.2 Description of the Exposure Facility . . . . . . . . . . . . . . . . . . . . 6.2-5
6.3 Scanning Electron Microscope Facility . . . . . . . . . . . . . . . . . 6.3-1
6.3.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3-1

6.3.2 Sample Preparation Room . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3-1
6.3.3 Microscope Room . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3-1
6.3.3.1 Scanning Electron Microscope . . . . . . . . . . . . . . . . . . . . . . . . 6.3-2
6.3.3.2 Microanalysis System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3-2
6.3.3.3 Sample Critical Point Drying and Coating Equipment . . . . . . 6.3-3
6.3.4 Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3-4

6. SPECIAL FACILITIES
6.1 OVERVIEW
Two facilities that are used in research programs at EML are described in this section:
Radon Gas and Radon/Thoron Progeny Facilities for Testing and Research, and the
Scanning Electron Microscope Facility. These facilities are stationary and are located in
EML's quarters in New York City.

6.2 RADON GAS AND RADON/THORON PROGENY

FACILITIES FOR TESTING AND RESEARCH
Contact Person(s) : Isabel M. Fisenne and Alfred J. Cavallo
6.2.1 SCOPE
Two major on-site EML facilities that are used for research on Rn gas measurements,
instruments, and methods are described here (the pulse ionization chamber facility and
the Rn, Th, and progeny exposure facilities).
6.2.2 THE EML PULSE IONIZATION CHAMBER FACILITY

FOR RADON-222 MEASUREMENTS
6.2.2.1
INTRODUCTION
The pulse ionization chamber facility is used for the direct measurement of
environmental levels of 222Rn in air and breath samples. The chambers are calibrated
periodically by de-emanating Rn gas from Ra solutions certified by the National Institute
of Standards and Technology (NIST). Thus, the facility also serves as the EML reference
for Rn gas measurements, and values so obtained are considered to be EML's best
estimate of the Rn activity in a sample.
The following discussion will be confined to the direct measurement of 222Rn in air
samples as part of an integrated calibration facility. A fuller description of the EML
pulse ionization chamber facility can be found in Fisenne and Keller (1985).

6.2.2.2
PRINCIPLE OF OPERATION
The EML pulse ionization chamber is operated on the principle of fast pulse counting
(Curtiss and Davis, 1943). Fast pulse counting is based on direct detection of the
" ionization produced in a single ionization chamber. To accomplish fast pulse counting,
it is mandatory that O2 and water vapor be removed before a sample is introduced into the
chamber.
6.2.2.3
DESIGN
The EML pulse ionization chambers, which are shown in Figure 6.1, are constructed
of stainless steel. The interior surface is electropolished to remove surface contamination
and to lower the background count rate, which is the limiting factor for measurement
sensitivity. Clean chambers have a background of about 10 counts h-1.
The EML chambers are constructed with a plug in the baseplate to accommodate an
electrodeposited standard source for the determination of the " counting plateau. The
" detection efficiency of the chambers with such a source is 52%.
The transfer systems for the removal of O2 and water vapor are designed to meet
three criteria: simplicity; a small ratio of dead space to chamber volume; and dichotomy,
that is, access to one or two ionization chambers.
6.2.2.4
PROCEDURE
For direct transfer and measurement to a single chamber, the air or breath sample
volume is restricted to 1 L or less. Sample transfer is accomplished by evacuating the
entire system, including the ionization chambers. Pure H2 gas is added to the sample
container (35 kPa of H2). The sample is transferred through the system with forming gas
(85% N2, 15% H2). The gas flow rate through the system is regulated by a capillary

orifice and small particles are removed by a filter paper. The added excess H2 and the O2
in the sample react in the platinum black catalyst cartridges to produce H2O and excess
heat. The H2O formed in the catalytic reaction is removed in a Drierite column. The gas
is collected in a single ionization chamber which is pressurized to 35 kPa with forming
gas. A block diagram of the ionization chamber and external transfer apparatus is shown
in Section 4, Procedure Rn-01-RC in which the details of the procedure for the
measurement of air samples are described.
6.2.2.5
CALIBRATION
The EML pulse ionization chambers are calibrated with NIST standard reference
material (SRM) 226Ra solutions using the Rn emanation technique (see Section 4,
Procedure Ra-07-RC). In April 1984, NIST issued a new series of SRM 226Ra solutions
for Rn emanation measurements. As part of EML's internal quality control program, a
major effort was undertaken to determine the calibration factor for the nine ionization
chambers currently in use. The overall mean and standard deviation of 81 emanations
into the nine chambers was 6245 ± 135 counts h-1 per Bq of 222Rn in equilibrium with its
short-lived progeny. This value was in excellent agreement with previous calibrations.
6.2.2.6
ROUTINE CHAMBER CHECKS AND MAINTENANCE
The backgrounds of the nine pulse ionization chambers are measured with forming
gas each weekend and occasionally during the work week to ensure against temporal
biases. The backgrounds for the nine chambers in service range from 8-16 counts h-1. A
control chart of the weekend background count rates is maintained for each chamber. At
the beginning of the calendar year, the yearly average and running average background
rates from previous years are calculated and control limits are established for the year.

Over a period of years, the background of any chamber increases due to the buildup
of long-lived Rn progeny on the interior surfaces. The background increase is a function
of exposure in terms of 222Rn Bq h-1 in the chamber, that is, 0.037 Bq of 222Rn in a
chamber for 17 h will produce 2.2 x 10-6 Bq of 210Pb. After 1 y, the 210Po will have
reached 82% of the 210Pb activity and will contribute an additional 3 x 10-3 counts h-1 to
the chamber background. Fractions or multiples of the .037 Bq of 222Rn example are
additive in the total temporal increase of the chamber background count rate. The
background count rate is reduced by dismantling and electropolishing the chamber.
The platinum black catalyst and Drierite are kept free of water vapor by maintaining
these cartridges under vacuum, except during sample introduction into a chamber.
The chamber systems are checked occasionally for electrically generated noise by
filling the chambers with room air. The O2 in the air effectively reduces the pulse sizes
below the 0.75 V tripping level of the electronic system and only electrically generated
pulses are registered during the overnight measurement period. The electrical noise in
the chamber system is < 0.25 counts h-1.
Throughout the year the calibration factor of each chamber is checked by emanating
Rn from a standard Ra emanation flask.
6.2.3 RADON, THORON, AND PROGENY EXPOSURE FACILITY
6.2.3.1
INTRODUCTION
The EML radon, thoron, and progeny exposure facility consists of a walk-in chamber
that is used for research, testing, calibration, and for the evaluation of measuring
instruments.
The 30 m3 chamber, installed in 1993, provides for a well-controlled, clean, airtight,

and uniform test environment. Research with inert aerosols and other pollutants can also
be carried out. Figure 6.2 shows the major features of the exposure facility.

6.2.3.2
DESCRIPTION OF THE EXPOSURE FACILITY
A. Radon and thoron gas sources.
Radon is generated from a Pylon (Model RN-1025, Ottawa, Ontario, Canada) 226Ra
source with 3810 kBq of radium. The source is sealed hermetically inside a container
located on top of the chamber. The injection of radon into the mixing chamber is
computer controlled to obtain the desired concentrations of radon inside the main
chamber.
Thoron is generated from a Pylon (Model TH-1025) 228Th source. The strength of
the source was 1960 kBq at the time of acquisition. The source has to be recharged every
5 yr because of its short half-life. The thoron generator can be installed in different
locations inside the main chamber in order to achieve the desired airborne thoron
concentrations.
B. Design characteristics of the chamber.
A schematic diagram of the chamber is shown in Figure 6.2. The interior dimensions
of the main exposure room are 3.3 m x 3.83 m x 2.59 m with a total volume of 30.75 m3.
The wall panels are made of enameled aluminum on the exterior, and 22 gauge stainless
steel on the inside. The floor is constructed of 16 gauge stainless steel. The floors, walls,
and ceiling are insulated to ensure minimum heating and cooling requirements.
The mixing room has a volume of 3.5 m3. The anteroom, which has a volume of
5.8 m3, serves as a means to transfer instruments in and out of the main chamber and as a
buffer between the main chamber and the adjacent laboratory space. Two viewing
windows, with triple panes, are located on the west wall. On the same wall there are 10
sampling ports that are 10 cm in diameter at a height of 1 m off the floor. A two-way
audio system is provided for communication purposes.

C. Environmental control characteristics.
The environmental conditioning system (Fidelity Engineering, Hunt Valley, MD)

consists of the following systems: refrigeration, heating, humidification,
dehumidification, air delivery, control, and pressurization air.
The refrigeration system consists of a single air-cooled condensing unit, two

refrigeration evaporator coils, and a refrigerant piping network. The cooling coils are
made of copper with aluminum fins; the refrigerant is HCFC-22. All of the elements of
the air conditioning system are constructed to minimize contamination. The compressor,
condenser coils receiver, and filter dryer are located outside the chamber, adjacent to the
mixing room (see Figure 6.2). The evaporator coils are inside the mixing room. The
temperature in the main test chamber can be controlled from 5oC - 40oC. The difference
in temperature anywhere within the chamber is no more than 1oC.
For humidification of the environment, water vapor is generated by an evaporative

type system which is installed inside the mixing room. The system runs hot water across
a screen-like surface and allows the water to evaporate into the air. The temperature of
the water is kept below boiling. Dehumidification is accomplished by a refrigeration coil
that becomes active only on call. It is isolated by a damper for the defrost cycle to avoid
reintroduction of humidity during defrosting. The humidity is variable between a
minimum that is determined by a -10oC dew point temperature and a maximum of 95%.
The humidity inside the chamber is controlled to within 2 units of the set point during
steady conditions.
The environmental conditioning system also has a hydronic hot water system located
outside the test chamber. It consists of a small glass electric hot water heater of about
2000 W, a water circulation pump, a diaphragm expansion tank, and a filter. The hot
water system is used to heat the test chamber air as needed.
The air delivery system, located in the mixing room, uses an in-line axial fan that can
deliver a maximum of 30 m3 min-1. A typical operating range is 3-10 m3 min-1. In
addition, a filtered pressurization air system is used to create a slight positive pressure in
the main chamber to prevent uncontrolled infiltration.

D. Aerosol generator systems.
A TSI Model 3470 condensation monodisperse aerosol generator (TSI, St. Paul, MI)
located outside the main chamber, is used to produce particles of the desired
concentration and size. Vaporized Carnauba wax condenses on NaCl nuclei to produce
monodisperse aerosols with a geometric standard deviation (Fg) of around 1.1 or less.
The concentration of the aerosols inside the test chamber can be controlled from 1,000 to
30,000 cm3. If polydisperse aerosols are desired, the concentration can be increased to
more than 100,000 cm-3. The generated aerosols are injected through a sampling port
hole into the main chamber. Aerosols from a burning candle, an electric heater, a
kerosene lamp, or from cigarette smoke, can be generated individually or in combination
by placing the generators inside the test chamber. The particle concentration inside the
main chamber without any generated aerosol is < 200 cm3.
E. Aerosol and vapor monitoring systems.
The aerosol concentration inside the main chamber is measured with an Environment
One Rich Model 200 condensation nucleus counter, or a TSI Model 3025 ultra-fine
particle counter. The size distribution of the test aerosol is measured with a TSI scanning
mobility particle sizer. A Bruel & Kjaer Multi-gas Monitor Type 1302 is used to
measure key organic pollutants. The detection limit depends on the type of pollutant and
ranges from 0.001 - 1.0 ppm.
F. Radon control and monitoring systems.
The concentration of radon and progeny is regulated by adjusting the output from the
radon generator. Radon is measured with two continuous scintillation cell monitors (cell
volume = 0.096 and 3.3 L). The monitors are interfaced to a computer located at the
control panel outside the chamber. The calibration and the accuracy of the radon
monitors are based on intercomparisons made with pulse ionization chambers (see
Section 6.2.2). The data are logged to a computer at 15-min intervals, and may be
recalled at any time. Radon and thoron concentrations in the main chamber are adjustable
in the range from 100 - 5000 Bq m-3, and 50 - 5000 Bq m-3, respectively.

The radon and thoron progeny concentrations are regulated by the dilution of the
parent gases and by the presence of aerosols. The progeny concentrations are measured
inside the main chamber by grab, integrating, and continuous monitoring devices. The
standard monitoring instruments for radon and thoron progeny are the AlphaSmart-760
(Alpha Nuclear, Missisauga, Ontario, Canada) and the GRI-1100 monitor. The analyses
for the individual radon and thoron progeny and the potential alpha energy concentrations
are performed using the methods of Thomas (1972), Nazaroff (1983), and Raabe and
Wrenn (1969). All three methods are computerized and the data are available on an
hourly basis. The concentrations in the main chamber range from 5.6 x 10-9 J m-3 to 1.4 x
10-5 J m-3 for radon progeny, and 1 x 10-5 to 7 x 10-5 J m-3 for thoron progeny.
Because of the capability to maintain the test chamber at less than 200 particle cm-3,
the equilibrium factor as low 0.01 is achievable. At very high particle concentrations, an
equilibrium factor of 0.5 is obtainable.
The sensors for temperature and humidity are located in the main test chamber and in
the mixing room. The static pressure in the main chamber and the speed of the
conditioned air exiting from the mixing room are monitored continuously. The data are
automatically logged on the control computer.
G. Radon progeny particle size distribution measurements.
The test chamber particle size conditions can be measured with the micro-orifice
uniform deposit impactor (MOUDI - see Section 2.2.2.5), EML developed screen
diffusion batteries (see Section 2.2.2.6), and graded screen array (see Section 2.2.2.7).
When used in combination, these instruments can measure radon and thoron progeny
particle sizes ranging from 0.5 to 5000 nm (Tu and Knutson, 1994).

REFERENCES
Curtiss, L. F. and F. J. Davis

"A Counting Method for the Determination of Small Amounts of Radium and Radon"
J. Res. Nat. Bur. Stand., 31, 181-195 (1943)

"The EML Pulse Ionization Chamber System for 222Rn Measurements"
Nazaroff, W. W.
“Optimizing the Total Alpha Three Count Technique for Measuring Concentrations of
Radon Progeny in Residences”
Health Phys., 46, 395-405 (1983)
Raabe, O. G. and M. E. Wrenn

“Analyses of the Activity of Radon Daughter Sampler by Weighted Least Squares”
Health Phys., 17, 593-605 (1969)
Thomas, J. W.
“Measurements of Radon Daughters in Air”
Health Phys., 23, 783-789 (1972)
Tu, K. W. and E. O. Knutson

“Measurements of Radon Progeny Size Distribution with a MOUDI and a Graded Screen
Array”
Richard C. Flagan (Editor)
in: Proceedings of the 4th International Aerosol Conference, Vol. 2, p. 767 (1994)

Figure 6.1 Photograph of pulse ionization chamber facility.

Figure 6.2 Schematic drawing of radon/thoron and progeny exposure facility.

6.3 SCANNING ELECTRON MICROSCOPE FACILITY
Contact Person(s) : Robert Leifer
6.3.1 SCOPE
This section describes EML's scanning electron microscope (SEM) facility. The
physical layout of this facility is shown in Figure 6.4. The SEM is used to: 1) analyze
aerosols collected from the troposphere and the stratosphere (Kromidas et al., 1996);
2) characterize laboratory-generated aerosol; and 3) analyze biological samples.
6.3.2 SAMPLE PREPARATION ROOM
The sample preparation room is maintained under clean-room conditions using high
efficiency particulate air (HEPA) ceiling filters. The air is recirculated and controlled
with a system that is independent of the building air delivery system. There are two
Class-100 benches to provide additional cleanliness for sample preparation and for the
preparation of sampling equipment. The first, an exhausting laminar bench (Advanced
Purification Inc., Hauppauge, NY 11788; Model G68-PD) allows the use of various
solvents and provides a Class 100 environment for equipment setup and preparation of
biological samples. The second bench (Laminar Flow Inc., Ivyland, PA 18974; special
order) is a recirculating vertical laminar flow system with two cartridges that contain
molecular sieve 5A and activated charcoal. These cartridges remove substances from the
airstream that may interfere with aerosols. Such interfering substances include ammonia,
water vapor, and organics.
6.3.3 MICROSCOPE ROOM
The microscope room is also maintained under clean-room conditions using HEPA
ceiling filters.

6.3.3.1
SCANNING ELECTRON MICROSCOPE
The SEM is an AMRAY-1820 (AMRAY, Bedford, MA 01730) and has a 150-mm

specimen chamber and a resolution of 5 nm. The SEM may be operated at low voltages
(~1 kV), thus allowing imaging of samples without prior preparation. Microprocessor
controlled operations permit automatic image focusing and stigmation and provides push
button digital magnification from 25X- 400,000X at a 12 mm working distance.
However, just how much of this magnification is usable depends heavily on the contrast
characteristics of the sample. The SEM is supplied with a solid-state backscatter
detector. This detector produces images which emphasize maximum atomic number
differences. The resulting image shows contrast differences that can be related to
differences in trace element composition. The SEM is also supplied with an X-
ray/imaging system (described below). This system controls the sample stage
automatically and thus allows for unattended X-ray analyses, imaging, and sample
characterization of more than 100 different fields.
The whole microscope assembly is isolated on a Micro-g vibration isolation table

(TMC, Peabody, MA 01960).
6.3.3.2
MICROANALYSIS SYSTEM
The microanalysis system used in conjunction with the AMRAY 1820 SEM is the
PGT IMIX system with a two position light element Si(Li) energy dispersive
spectrometer (Model 4200 EDS, Princeton Gamma-Tech, Princeton, NJ 08540). The
PGT IMIX system is equipped with:
1. An ultrahigh resolution 19-in color display.
2. Dec 11/73 high performance processor with floating point.
3. SPARC station 1+ (SUN Microsystems) with a built-in, 3 1/2" floppy disk drive,
external CD ROM drive, and a 1.27 gigabyte Fujitsu drive.

4. Two thousand channel data collection system.
5. Pulse processing electronics.
6. EDS X-ray analysis software.
7. Qualitative and quantitative analysis software.
8. Chemical classification software.
9. PGT beam control package.
10. Advanced feature analysis package.
11. Mega plane option (800 x 1040 pixel image).
The microanalysis system allows detailed chemical and size classifications of

samples. In the windowless mode, the model 4200 EDS allows the analysis of X-rays
with energies down to 700 eV. In this position, detection of B, C, N, and O is possible, as
well as enhanced detection of F, Na, Mg, and Al. The PGT beam control package allows
automated analysis of specific points on a collection surface by controlling the scan coils
of the microscope column. Up to 300 points can be automatically stored for later use.
The PGT imaging system is connected to the Tissue Culture Facility via a video cable
that is attached to a CCD video camera and can capture images from the optical
microscopes.
6.3.3.3
SAMPLE CRITICAL POINT DRYING AND COATING EQUIPMENT
The sample coating equipment consists of a Denton high vacuum evaporator (Denton
Vacuum, Inc., Cherry Hill, NJ 08003), an EFFA Carbon Coater (Ernest E. Fullam Co.,
Latham, NY 12110; Model No. 12560), and a sputter coater (Polaron, Warrington, PA;
Model E5000). The sputter coater is supplied with platinum, gold, and silver targets.
The carbon coater and sputter coater, plus an optical microscope are housed in a vertical
flow class 100 laminar clean bench (Laminaire Corp., Rahway, NJ 07065; Model DWS-
630).

Critical point drying of biological samples is accomplished via the Balzers CPD 030
using acetone as the transfer medium and liquid CO2 as the transition liquid. The CPD
030 is located in the Sample Preparation Room with access to the exhaust laminar flow
bench.
6.3.4 QUALITY CONTROL
When using an SEM, several things should be kept in mind. The sampling process
must be conducted very carefully to provide the microscopist with a representative
sample of the material of interest. Many methods of sampling introduce bias in that their
collection efficiency varies with particle size. The internal environment of the
microscope should also be taken into account. In order to function, the column is kept at
a high vacuum (10-5 Torr) and there can be large amounts of heat generated in the sample
by electron bombardment. These conditions can alter or destroy susceptible samples.
Contamination is always a concern. Considering the size of the particles of interest,
unless strict sample handling procedures are followed, contributions from contaminating
sources may outweigh the sample material.
REFERENCE
Kromidas, L., and R. Leifer

"An Innovative Application of a Commercially Available Double-sided Adhesive for
the Collection of Aerosols by Impaction"
Atmospheric Environment, 30, 1177-1180 (1996)

Figure 6.3 SEM facility: A) clothing change room; B) sample preparation room; C) SEM
room. Areas in rooms: 1) sticky floor mat; 2) exhaust laminar flow bench;
3) recirculating laminar flow bench; 4) HEPA ceiling filters with blowers; 5a) column
and stage; 5b) SEM electronic console; 5c) SEM vacuum, air and water support module
(equipment placed outside microscope room); 6a) Micro-g vibration table; 6b) air supply
for Micro-g table; 7) PGT microanalysis system; 8) vertical laminar flow bench; 9)
particle coating devices; 10) optical microscope; 11) tank of Argon; 12a) Denton high
vacuum evaporator; 12b) evaporator and coating device vacuum, air and water module.

7. SPECIFICATIONS*
*Section 7 has been updated to reflect changes in Vendors, e.g., Phoenix

Custom Molders, Inc., GA-MA and Associates, Inc. (March 2002)

New York, NY 10014-4811

Table of Contents, Vol. I Rev.0
Page
6SHFLILFDWLRQV 7.1-1
7.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.1-1
7.2 Ring and Disc Mounts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2-1
7.2.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2-1

7.2.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2-1
7.2.3 Costs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2-2
7.3 Mylar Film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3-1
7.3.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3-1

7.3.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3-1
7.4 Ion Exchange Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.4-1
7.4.1 Description and Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.4-1
7.5 Large Ion-exchange Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.5-1
7.5.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.5-1

7.5.2 Supplier and Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.5-1
7.6 Small Ion-exchange Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.6-1
7.6.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.6-1

7.6.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.6-1
7.7 Radon Bubblers - Pyrex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.7-1
7.7.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.7-1

7.8 Glass Fiber Filter Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.8-1

7.8.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.8-1

Page
7.9 Beta Phosphors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.9-1
7.9.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.9-1

7.10 Alpha Phosphor on Mylar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.10-1
7.10.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.10-1

7.10.2 Supplier and Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.10-1
7.11 Polyethylene Dispensing Bottles . . . . . . . . . . . . . . . . . . . . . . . 7.11-1
7.11.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.11-1

7.11.2 Supplier and Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.11-3
7.12 Filter Funnels and Sample Mounts . . . . . . . . . . . . . . . . . . . . 7.12-1
7.12.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.12-1

7.12.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.12-1
7.13 Filter Stoppers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.13-1
7.13.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.13-1

7.13.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.13-1
7.14 Ion-exchange Fallout Collectors . . . . . . . . . . . . . . . . . . . . . . . 7.14-1
7.14.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.14-1

7.14.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.14-1
7.15 Electrolysis Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.15-1
7.15.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.15-1

7.15.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.15-1

Page
7.16 Plating Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.16-1
7.16.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.16-1

7.16.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.16-2
7.17 Air Sampling Filters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.17.1
7.17.1 Dynaweb DW7301L Filters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.17-1
7.18 Air Samplers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.18-1
7.18.1 Roots System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.18-1

7.18.2 Fuji System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.18-2
7.19 Gamma Planchets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.19-1
7.19.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.19-1

7.19.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.19-1
7.20 Electrolysis Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.20-1
7.20.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.20-1
7.21 Aluminium Sample Cans for Gamma Counting . . . . . 7.21-1
7.21.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.21-1

7.21.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.21-1
7.22 Molded Marinelli Beakers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.22-1
7.22.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.22-1

7.22.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.22-1
7.23 Radon Sampling and Counting Flasks . . . . . . . . . . . . . . . . 7.23-1
7.23.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.23-1

7.23.2 Coating Flasks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.23-1

U.S. Department of Energy 7 - iv
Page
7.24 Containers for the Collection of Fallout and

Atmospheric Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.24-1
7.24.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.24-1
7.25 Fallout Collection and Shipping Container . . . . . . . . . . . 7.25-1
7.25.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.25-1

7.25.2 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.25-1
7.26 Disposable Chromatographic Column . . . . . . . . . . . . . . . . . 7.26-1
7.26.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.26-1

7.26.1 Supplier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.26-1

U.S. Department of Energy 7-v
Section 7 Rev. 0
63(&,),&$7,216
7.1 OVERVIEW
This section describes materials used in some of the procedures. These materials are
unique in that they are not necessarily available from the usual scientific vendors.
Consequently, an attempt was made to provide all pertinent information in order to enable
the user of this Manual to obtain the items referred to.
Special attention is drawn to Section 7.2 since it provides information on several

items from a single vendor.

Section 7 Rev. 0
7.2 RING AND DISC MOUNTS
7.2.1 DESCRIPTION
Plastic rings and discs in nominal 1 in (2.54 cm) and 2 in (5.08 cm) diameters are
molded of nylon. The 1-in units are made according to dimensions given in Figure 7.1,
and the 2-in units follow the same form with an overall diameter of 2.03 in (5.16 cm).
The discs are molded as cups to allow use of the discs either for mounting solid
samples using the ring or to evaporate liquid samples in the cup.
Figure 7.1. Plastic ring and disc mounts.
7.2.2 SUPPLIER
The present source of supply is:
Phoenix Custom Molders, Inc.

Five Wickers Drive
Wolfeboro, NH 03894
Phone: (603) 569-5100
Fax: (603) 569-6041
an example of the price list is reproduced and included as Specification 7.2.3.

Section 7 Rev. 0
7.2.3 COSTS
RINGS AND DISCS: Prices are per set (one set = one ring and disc) in lots of:
500 1000 2500 5000 10000 25000
1 in dia. plain* .70 .57 .42 .34 .32 .22

2 in dia. plain** .70 .64 .50 .40 .36 .26
1 in dia. funnel 1.20 1.13 .67 .55 .42 .37
disc and ring***
Minimum Order $350.00
*EML Manual, Specification 7.2, PCMI 5230-01. Color Natural

**EML Manual, Specification 7.2, PCMI 5236-01. Color Natural
***EML Manual, Specification 7.12, PCMI 5229-01. Color Black
FILTERS: Prices are cents per each in lots of:
100 250 1000
Polyethylene 4.50 2.25 1.03

filter chimney*
Geon filter stopper** 4.50 2.25 1.03
*EML Manual, Specification 7.12, PCMI 5231-01

**EML Manual, Specification 7.13, PCMI 5232-01

Section 7 Rev. 0
PLATING CEL CAP: (20-mm thread to fit Polyethylene bottles, with brass bushing for
mounting and electrical connection)
Dollars each in lot of: 25 50 100 500
18.50 11.10 6.65 3.46
EML Manual, Specification 7.16, PCMI 5227-01
GAMMA PLANCHETS: Prices are per set in lots of:
100 250 500 1000 2500 5000
2 in dia. x 1 in deep 5.00 3.00 1.50 1.15 .91 .68

with .030 in disc
EML Manual, Specification 7.19, PCMI 5226-01
MARINELLI BEAKER AND COVER: Unit price in lots of:
100 250 500 1000 2500 5000
Black Butyrate 4.07 3.19 2.88 2.73 2.65 2.61
EML Manual, Specification 7.22, PCMI 5237-01. Other materials and colors quoted on
request.
Prices are in U.S. dollars, F.O.B. Franklin, NH. For shipments outside the U.S., add 5% to prices
listed and $45.00 for bank transferral charges. Unless otherwise specified, all items are bulk
packed in poly bags. All orders are subject to $350.00 minimum. Blanket orders welcome.
Discounts available for volume buyers.

Section 7 Rev. 0
7.3 MYLAR* FILM
7.3.1 DESCRIPTION
Mylar film is used to cover precipitates to protect them during counting and storage.
The film is obtained in 38.1 mm width rolls. The most useful films are .013 mm thick,
weighing about 1.8 mg cm-2 and .006 mm thick, weighing about 0.9 mg cm-2.
7.3.2 SUPPLIER
Retail quantities may be obtained from:
Spex Sample Preparation

203 Norcross Ave.
Metuchen, NJ 08840
1-800-LAB-SPEX
*
Mylar is the registered trademark of E.I. du Pont de Nemours & Co. for its polyester film.

Section 7 Rev. 0
7.4 ION EXCHANGE RESINS
7.4.1 DESCRIPTION AND SUPPLIER
Analytical grade anion and cation exchange resins are required to concentrate trace
amounts of radionuclides from environmental samples. They are available from:
Bio-Rad Laboratories
2000 Alfred Nobel Drive
Hercules, CA 94547
(510) 741-1000
FAX: (510) 741-1060
or
Eichrom Industries, Inc.

8205 S. Cass Ave., Suite 107
Darien, IL 60561
(800) 422-6693
FAX: (708) 963-1928
and may be used as received.

Section 7 Rev. 0
7.5 LARGE ION-EXCHANGE COLUMNS
7.5.1 DESCRIPTION
Fabricated from borosilicate glass tubing.
7.5.2 SUPPLIER AND COST
Ace Glass, Inc.

1430 Northwest Boulevard
P.O. Box 688
Vineland, NJ 08360
(609) 692-3333
Ace Glass, Inc., supplies large ion-exchange columns as specialty items. Costs will
be quoted by the supplier.

Section 7 Rev. 0
Figure 7.2 Large ion-exchange column.

Section 7 Rev. 0
7.6 SMALL ION-EXCHANGE COLUMNS
7.6.1 DESCRIPTION
Fabricated from borosilicate glass tubing.
7.6.2 SUPPLIER
Ace Glass, Inc.

P.O. Box 688
Vineland, NJ 08360
(609) 692-3333
Ace Glass, Inc., supplies small ion-exchange columns as a specialty item. Costs will
be quoted by the supplier.

Section 7 Rev. 0
Figure 7.3 Small ion-exchange columns.

Section 7 Rev. 0
7.7 RADON BUBBLERS - PYREX
7.7.1 DESCRIPTION
1. Main chamber about 150-mm long, base to neck, with capacity about 50 mL.
2. Top of chamber to have 19/38 standard taper joint.
3. Stopcocks 2-mm bore with tapered Teflon plug - side arms 7 mm O.D.
4. All side tubing to be 7 mm (not as shown).
5. Glass rod structural support between main chamber and side tube, 15 mm in length,
4-mm diameter.
6. Medium porosity glass frit in bottom of chamber.
7. Glass tubing from stopcocks 25-mm long.
Ace Glass, Inc.

P.O. Box 688
Vineland, NJ 08360
(609) 692-3333
Cost: ~ $69.00

Section 7 Rev. 0
Figure 7.4 Radon bubbler.

Section 7 Rev. 0
7.8 GLASS FIBER FILTER PAPER*
7.8.1 DESCRIPTION
Two equivalent materials are available. One is No. X-934-AH made by Hurlburt
Paper Company, the other is Whatman glass fiber paper GF/C. These are available from
laboratory supply houses. Gelman Instrument Company sells a "Spectro Grade Type A"
filter with the following typical analyses.
µg per 203 mm x 254 mm

Sheet Less Than:
Antimony Sb 50
Arsenic As 50
Beryllium Be 10
Bismuth Bi 50
Cadmium Cd 15
Chromium Cr 50
Cobalt Co 15
Copper Cu 10
Iron Fe 400
Lead Pb 25
Manganese Mn 50
Mercury Hg 100
Molybdenum Mo 15
Nickel Ni 100
Selenium Se 2000
Tin Sn 50
Titanium Ti 15
Vanadium V 15
Zinc Zn 60
Water Extractable
Ions SO4- 150
NO3- 10
NH4+ 10
F- 120
Cl- 1650
*
Most glass fiber filters contain traces of alpha and beta activity. Any procedure where the final sample is
mounted on a glass filter for counting should be carefully checked for possible interference.

Section 7 Rev. 0
7.9 BETA PHOSPHORS
7.9.1 DESCRIPTION
This technique has been described by Harley et al. (1962). Phosphor discs
.2540-mm thick and 23.8 mm in diameter and other sizes are available in lots of 1000, as
NE-102 clear to as NE-102A, at about $1.50 each.
Bicron Corp.
12345 Kinsman Rd.
Newbury, OH 44065
(216) 564-2251
Approximate cost: $1,600/1000 sq. in.
REFERENCE
Harley, J. H., N. A. Hallden and I. M. Fisenne

"Beta Scintillation Counting with Thin Plastic Phosphors"
Nucleonics, Vol. 20, 1, 59-61, January (1962)

Section 7 Rev. 0
7.10 ALPHA PHOSPHOR ON MYLAR
7.10.1 DESCRIPTION
The phosphor is the standard silver-activated zinc sulfide (Sylvania Type 130 [7] or
DuPont 1101 phosphor) coated on one side of a Mylar film. The material is sprayed onto
the backing using the zinc sulfide as a pigment in a paint vehicle.
A fresh die-cut phosphor disc, 23.8 mm in diameter, is used for each sample. The
sample filter paper is laid on a nylon disc, the phosphor is placed against the sample, a
strip of .0076-mm Mylar is overlaid, and the assembly is locked together with a nylon
ring.
Counting is performed with a bare phototube on either manual or automatic counters.
7.10.2 SUPPLIER AND COSTS
The phosphor is available in strips or discs from:
William B. Johnson & Associates, Inc.

P.O. Box 472
Ronceverte, WV 24970
(304) 645-6568
FAX: (304) 645-2182
The zinc sulfide is sprayed on .076-mm Mylar. The catalog numbers are:
Price
ASP-3, 305 mm wide strip $27/sheet

ASP-4, 23.8 mm discs $32/C

Section 7 Rev. 0
7.11 POLYETHYLENE DISPENSING BOTTLES
7.11.1 DESCRIPTION
Commercially available disposable plastic transfer pipettes (DPTP), made from low
density polyethylene (LDPE) are used for weighing and dispensing small aliquots of
radionuclide solutions.
The DPTPs may be purchased in capacities of 1 to 10 mL. All are pre-drawn with
capillary tips of various diameters. The DPTP may be completely or partially filled by
squeezing the pipette to expel the air, inserting the tip under the surface of the solution
and releasing the vacuum in the pipette. The pipette tip is wiped with a disposable tissue.
Single drops or a larger volume may be dispensed by squeezing the pipette with the tip
down. Depending on the size of the capillary tip, individual drops may range from 0.10
to 0.05 g.
A radioactive solution may be sealed in the DPTP by heating the tip of the capillary
and squeezing it with forceps. The tip may then be cut below the seal when it is desired
to deliver another portion of the solution.
Similar polyethylene dispensing bottles (5 cm3 ampules) were tested for loss of liquid
over a storage period up to 6 months. The loss from 5.5 g of distilled water was 0.042 g.
The loss from 4.0 g of ethyl alcohol was 0.136 g and the loss from 6.7 g of concentrated
HCl was 0.188 g. Intermediate measurements showed a roughly linear rate of weight
loss.
In general, it appears that the losses from the sealed dispensing bottles are small for
short-time periods, but that they must be taken into consideration if long-time storage is
required.
The stability of nuclide solutions in polyethylene bottles and possible losses through
absorption on the walls have been questioned many times. A series of tests were
performed to determine if appreciable losses occurred in the normal use of these bottles

Section 7 Rev. 0
for solution storage and handling. The data obtained should be considered as a guide and
appropriate tests carried out as needed.
Six isotopes (137Cs, 144Ce, 95Zr, 131I, 106Ru, 140Ba) were obtained from Oak Ridge
National Laboratory, split, diluted, and stored in sealed polyethylene dispensing bottles
for a period of from 10-63 days.
In each case, duplicate samples were prepared in water, carrier (1 mg mL-1 ) or HCl
(1N) solution, except in the case of 131I where Na2SO3 (pH at 8) was used, and 95Zr where
oxalic acid was used.
The samples were gamma counted in a NaI well-crystal so that a counting error of at
least 1% was maintained. After the initial count, the drawn stems were cut off, the bottles
rinsed four times with warm water, and then recounted. In the case of residual activity,
the bottles were rewashed four times in a 1N HCl solution and recounted. The data are
shown in Table 7.1. Ruthenium adsorbed appreciably on polyethylene, but the other
nuclides were kept in solution with carrier or acid (Harley et al., 1963).
Testing of additional nuclides and various solution/carrier combinations were carried

out in subsequent years. These results are shown in Table 7.2, where even ruthenium is
kept is solution with both carrier and acid.
REFERENCE
Harley, J. H., N. A. Hallden and I. M. Fisenne

"Storage of Standardized Radioactive Solutions"
Nature, 197, 1230 (1963)

Section 7 Rev. 0
The DPTPs are available from several supply houses, including:
Bio-Rad Chemical Division

Hercules, CA 94547
(510) 741-1000
FAX: (510) 741-1060
The most useful sizes are sold in boxes of 400 to 500/box at prices ranging from $18
to $30/box.

Section 7 Rev. 0
TABLE 7.1
STORAGE CONDITIONS FOR NUCLIDES IN POLYETHYLENE AMPOULES*
% Retained after Rinse
Nuclide Carrier Acid Water Acid
137
Cs - - 0
x - 0
- x 0
144
Ce - - 5 0.6
x - 0
- x 0
95
Zr - - 48 33
x - 0**
- x 1.2 0.8
131
I - - 25 25
x - 17 17
- x 26 26
131
I with Na2SO3 0
at pH 8
106
Ru - - 35 15
x - 25 26
- x 29 28
140
Ba - - 0
x - 0
- x -
*
Taken from Harley et al., 1963.
**
With either Zr or Nb or with both as carriers.

Section 7 Rev. 0
TABLE 7.2
ADDITIONAL NUCLIDES SUCCESSFULLY STORED

IN POLYETHYLENE
Nuclide Conditions
125
Sb 5 µg Sb g-1 4N HCl
241
Am 0.1N HNO3
7
Be 0.1N HCl
109
Cd 1N HCl
45
Ca 0.1N HCl
51
Cr 1N HCl
60
Co 0.1N HCl
244
Cm 3N HCl
198
Au 4N HCl
59
Fe 0.1N HCl
210
Pb + Progeny 3N HNO3
54
Mn 1N HCl
63
Ni 0.1N HCl
32
P 0.1N HCl
239
Pu 0.1N HNO3
210
Po 1N HNO3
147
Pm 1N HCl
226
Ra 0.1N HCl
106
Ru 25 µg Ru g-1 1N HCl
22
Na 0.1N HCl
90
Sr 0.1N HCl
204
Tl 1N HNO3
228
Th 3N HNO3
232
U 1N HCl
88
Y 0.1N HCl
65
Zn 0.1N HCl

Section 7 Rev. 0
7.12 FILTER FUNNELS AND SAMPLE MOUNTS
7.12.1 DESCRIPTION
A simple and inexpensive combined filter funnel and sample mount is shown in
Figure 7.5. The funnel chimney is molded of polyethylene and may be reused. It is
sufficiently inexpensive that it could be discarded after each use, but the smooth surface
should not retain any material to cross-contaminate the samples. The nylon funnel base is
designed to be used as a sample mounting disc.
In the filtration, a double paper or glass fiber filter is used with a diameter of
23.5-24 mm. A short piece of 3.1750 mm I.D. plastic tubing is attached to the base tube
and the base is put in place on a rubber stopper mounted on a standard filter flask. The
rubber stopper can be bored out to about 1 cm. No seal is required between the plastic
tubing and the stopper as the suction is maintained between the funnel base and the
stopper. After filtration, the funnel chimney is removed and the base mounted as with the
standard disc.
7.12.2 SUPPLIER
The present source of supply is:
Phoenix Custom Molders, Inc.

Five Wickers Drive
Wolfeboro, NJ 03894
Phone: (603) 569-5100
Fax: (603) 569-6041

Section 7 Rev. 0
This vendor is retaining the molds for EML. They have been instructed to accept
orders from any source. They may be ordered as:
1. Polyethylene funnel chimney, and
2. Funnel disc and ring.
Figure 7.5 Filter funnels and sample mounts.

Section 7 Rev. 0
7.13 FILTER STOPPERS
7.13.1 DESCRIPTION
The stopper sketched below is molded from "Geon" which is reasonably inert to
common chemicals. It is intended for use in supporting the filter discs described in
Section 7.12.
If the filtrate is not to be saved, the stopper may be used as is with a filter flask. If the
filtrate is to be saved, a length of thin plastic tubing may be attached to the bottom of the
filter disc and passed through the stopper hole for use with a Fisher filtrator.
7.13.2 SUPPLIER
These stoppers are available from the supplier who furnishes the filter discs (Phoenix
Custom Molders, Inc., see Specification 7.2).
Figure 7.6 Filter stopper, twice full size (corresponds to a No. 6 rubber stopper).

Section 7 Rev. 0
7.14 ION-EXCHANGE FALLOUT COLLECTORS
7.14.1 DESCRIPTION
A schematic diagram of the ion exchange fallout collector is shown in Figure 7.7.
This unit consists of a funnel, ion-exchange column, leveling device, wooden housing
with a clamp, and electric heater (optional). The funnel is welded to a threaded cap
which may be attached to the top of the ion exchange column. The bottom of the column
is also threaded for a tapered fitting to attach the leveling tube. The device consists of a
polyethylene tube extending from the bottom of the column to a T-connector above the
height of the paper pulp in the column. This prevents the column from running dry
during the collection period. Water flows out of the T-connector and is directed out of
the wooden housing through a flexible hose. The tapered fitting and the funnel are
replaced with standard bottle caps prior to shipment.
7.14.2 SUPPLIER
Aside from the housing unit and electric heater, the various components of the ion-
exchange fallout collector can be obtained from
Bel-Art Products
Pequannock, NJ 07440
(201) 694-0500
Figure 7.8 is a schematic diagram showing the dimensions of the funnel, column, and
tapered cap which EML uses.
We at EML assemble all of the components before placing the unit in the field.

Section 7 Rev. 0
Figure 7.7 Ion-exchange fallout collector unit.

Section 7 Rev. 0
Figure 7.8 Schematic diagram of funnel, column, and tapered cap.

Section 7 Rev. 0
7.15 ELECTROLYSIS ELECTRODE
7.15.1 DESCRIPTION
The platinum electrolysis electrode is used in the electrodeposition procedure

(see Figure 7.9). It is attached to a rotary motor and intended for use in the plating cell
described in Specification 7.16. It is separated from the platinum electrodeposition disk
by 1 cm.
7.15.2 SUPPLIER
Johnson-Matthey, Inc.
2001 Nolte Drive
West Deptford, NJ 08066
(609) 853-8000

Section 7 Rev. 0
Figure 7.9 Platinum anode for electrolysis (drawn twice actual size).

Section 7 Rev. 0
7.16 PLATING CELLS
7.16.1 DESCRIPTION
The plating cell used at EML for electroplating on platinum discs is based on
numerous other designs, chiefly the one used at the Laboratory of Radiation Biology,
University of Washington (see Figure 7.10).
Figure 7.10 Plating cell.

Section 7 Rev. 0
The major feature of the cell is an elongated 20-mm cap for either a 30 mL (1 oz) or a
60 mL (2 oz) polyethylene bottle. This cap has space for an 18-mm diameter plating disc
and has a threaded brass bushing for making electrical connection.
In use, the bottom is cut off either a 30-mL or 60-mL bottle (20-mm cap size), and
any flashing or other roughness on the top of the bottle is smoothed by rubbing once or
twice over a piece of sandpaper if necessary. The plating disc is placed on the cap and the
bottle is screwed in firmly.
Electrical connection may be made by a clip, or by threading the bushing into a metal
plate which then also acts as a support for the cell.
7.16.2 SUPPLIER
Phoenix Custom Molders, Inc.*

Five Wickers Drive
Wolfeboro, NH 03894
Phone: (603) 569-5100
Fax: (603) 569-6041
*
See Specification 7.2.3.

Section 7 Rev. 0
7.17 AIR SAMPLING FILTERS
7.17.1 DYNAWEB DW7301L FILTERS
Since the end of 1992, all sites in SASP and RAMP have been supplied with
Dynaweb filters. The filter is composed of a 100% polypropylene web that is 100%
binderless. Three layers of this web are collated and sandwiched between two sheets of a
protective DuPont Reeme (100% polyester) scrim. The top scrim is removed prior to
sampling at RAMP sites because after their return to EML for analysis these samples are
compressed into a pellet and the scrim hinders compression. At all other sites, the filter
can be used in sampling with both the top and bottom scrim in place. The filter medium
weighs about 20 mg cm-2, has an ash weight ranging from 0.1-1% of the total weight, and
about 65 cm2 of the filter can be compressed to 1.3 cm3 at 5 tons pressure. Radio-
chemical analyses of blank filters for 90Sr, 238Pu, and 239Pu indicate values that are near or
below the lower limits of detection for these analyses. Gamma-ray spectrometry on blank
filters indicates the absence of the gamma-ray emitting isotopes that we routinely report.
The collection efficiency of the Dynaweb filter media was determined using
electrically classified monodisperse aerosols of dioctyl sebacate (DOS) liquid and sodium
chloride (NaCl) solid particles. The test aerosol particle sizes and face velocities ranged
from 0.015 to 0.5 µm at 30 and 100 cm sec-1 NaCl, and from 0.05 to 0.5 µm at 50 to
100 cm sec-1 for DOS. The submicron particle penetration data are summarized in Figure
7.11. The most penetrating particle size is in the 0.07 to 0.1 µm range. The minimum
collection efficiency, using a test aerosol of NaCl at a face velocity in the vicinity of 100
cm sec-1 was about 87%. The average pressure drops at face velocities of 50 and 100 cm
were 2.26 and 3.92 kPa, respectively.
Filter intercomparisons are conducted using Microdon LM2020 and Dynaweb

DW7301L materials at EML’s Regional Baseline Station at Chester, NJ, and in Barbados
by the University of Miami. The filter samples collected at Chester, NJ, were measured
for 7Be and 210Pb, while those from Barbados were measured for dust loading, sodium,
chloride, nitrate, and non-sea salt sulfate. Statistical t-tests and Sign tests were performed
on the paired data to determine if the measured differences were significant. At the 95%

Section 7 Rev. 0
probability level, in all but one case (210Pb), no t-test or Sign test indicated a significant
difference between the two filters.
Dynaweb DW7301L is manufactured and distributed by:
WEB Dynamics
1 Forge Road
East Stroudsburg, PA 18301

Section 7 Rev. 0
Figure 7.11 Submicron particle penetration data.

Section 7 Rev. 0
REFERENCES
Cambray, R. S. and K. Playford

Unpublished data
AERE Harwell, Oxfordshire, England, December (1985)
Lockhart, L., R. Patterson and W. Anderson

"Characteristics of Air Filter Media Used for Monitoring Airborne Radioactivity"
Naval Research Laboratory Report NRL-6054, June (1964)

Section 7 Rev. 0
7.18 AIR SAMPLERS
7.18.1 ROOTS SYSTEM
The SASP sites are equipped with a Roots Rotary Lobe Blower Type 24 AF
connected to a 1 HP electric motor by a fan belt. Roots lobe pumps fall into a category of
pumps where volumetric displacement is the means by which flow is induced. Lobe
pumps use two counter-rotating impellers to provide flow. As each impeller passes over
the inlet, a volume of air is trapped, carried through the blower to the discharge and is
expelled against the discharge pressure. Figure 7.12 shows a sketch of the Roots pump
and motor. Figures 7.13 and 7.14 show a detailed and field view of the Roots system.
The Roots rotary is manufactured by:
Dresser Industries Incorporated

Roots Blower and Vacuum Pump Division
Connersville, IN 47331
The local distributor is:
Hayes Machine Co.

11-03 43rd Road
Long Island City, NY 11101
The electric motor which is used to drive the blower is purchased from:
Harry Lumb and Associates, Inc.

39 Golden Star
Irvine, CA 92714

Section 7 Rev. 0
The specifications on the electric motor are:
60/50 Hz, 115/230 V, 15/7.5 Amps

Single Phase, 1 HP, 1725 RPM
TEFC, Frame ELX-182T, Design B
Code J, Ambient 40oC, Insulation Class B
SF1.2, Continuous Duty
The Roots system, composed of blower, motor, frame, plumbing, and accessories
costs ~ $2500 including labor. The wooden shelter and metal stand both cost about $500
each.
7.18.2 FUJI SYSTEM
The RAMP sites are equipped with a Fuji ring compressor Model 302P which is
directly connected to a 0.5 HP electric motor. Fuji ring compressors induce flow through
momentum transfer. Air enters through an inlet port and is accelerated by the impeller.
Through centrifugal force, energy is imparted to the inlet air which is discharged out of
the pump outlet. Figure 7.15 presents a sketch of the Fuji system. Figures 7.16 and 7.17
show a detailed and field view of the Fuji system. The Fuji Ring Compressors are
manufactured by:
Fuji Electric Corp. of America

Frassetto Industrial Park
6A Frassetto Way
Lincoln Park, NJ 07035
These compressors are distributed by:
The Knotts Company, Inc.

350 Snyder Avenue
Berkeley Heights, NJ 07922

Section 7 Rev. 0
The Fuji Compressor motor has the following specifications:
50/60 Hz, 115/230V

5.0/2.5 Amp, Single Phase
0.51 HP
The Fuji system containing the ring compressor, aluminum housing, sampling
manifold and accessory equipment is purchased from:
Dr. Joseph Prospero

University of Miami
Rosenstiel School of Marine and Atmospheric Science
Miami, FL 33181
The cost is ~ $2500 per system.

Section 7 Rev. 0
Figure 7.12 Sketch of the Roots system.
Figure 7.13 Detailed presentation of the Roots system.

Section 7 Rev. 0
Figure 7.14 The Roots system at a field site.

Section 7 Rev. 0
Figure 7.15 Sketch of the Fuji system.

Section 7 Rev. 0
Figure 7.16 Detailed presentation of the Fuji system.
Figure 7.17 The Fuji system at a field site.

Section 7 Rev. 0
7.19 GAMMA PLANCHETS
7.19.1 DESCRIPTION
This is a planchet molded of nylon. The inside diameter is 50.8 mm, the depth is 25.4
mm, and the mean wall thickness is 0.64 mm. A flat circular cover is also provided.
These planchets are used to provide a uniform geometry for gamma counting air
particulate filter samples and other similar materials. The filters are pressed into the
planchet with a hand-operated hydraulic press using a steel die. When used in this way, a
6.35-mm hole is cut in the bottom of the planchet to allow the filter to be punched out for
radiochemical analyses after counting.
7.19.2 SUPPLIER
The planchets are available from:

Five Wickers Drive
Wolfeboro, NH 03894
Phone: (603) 569-5100
Fax: (603) 569-6041
*

Section 7 Rev. 0
7.20 ELECTROLYSIS CELLS*
7.20.1 DESCRIPTION
A. This electrolysis cell was developed at New York University for the electrolytic
enrichment of tritium in acid solution. The electrodes were subsequently modified at
EML by replacing a coiled platinum wire with platinum sheet.
The cells that were used at EML were made by a commercial glass blower from the
drawing shown in Figure 7.18, using standard glass tubing and standard taper joints.
B. This electrolysis cell (Figure 7.19) was developed at the University of Miami by
Dr. Gote Ostlund for the electrolytic enrichment of tritium in alkaline solution. The
cell is also used for the final distillation of the enriched sample.
For distillation, an adapter and receiver were substituted for the funnel top.
*
No longer used at EML.

Section 7 Rev. 0
Figure 7.18 Electrolysis cell.

Section 7 Rev. 0
Figure 7.19 Alkaline electrolysis cell.

Section 7 Rev. 0
7.21 ALUMINUM SAMPLE CANS FOR GAMMA COUNTING
7.21.1 DESCRIPTION
The sample containers for gamma counting and gamma spectrometry measurements
are drawn, straight-walled, "step shoulder" aluminum can bodies and accompanying "full
panel pull out" lids. The body and lid are fabricated from .254 mm and .305 mm
thickness, respectively, of various alloy-temper combinations of aluminum, and their
inside surfaces are enameled.
One size is in current use. It holds about 100 mL and is about 60.325 mm by
31.8 mm. It is described as:
208 x 107 can body

209.5 lid
7.21.2 SUPPLIER
They are available from:
The Central States Can Corporation

P.O. Box 642
Massillon, OH 44648-0642
(330) 833-1011
FAX: (330) 833-9932
The device for sealing the lid to the can is the Automatic Portable Electric Can Sealer,
No. EL-12253-120V available from:
Wisconsin Aluminum Foundry Co., Inc.

P.O. Box 246
838 South 16th Street
Manitowac, WI 54220
(414) 682-8627
FAX: (414) 682-4090

Section 7 Rev. 0
7.22 MOLDED MARINELLI BEAKERS
7.22.1 DESCRIPTION
The annular sample containers for gamma counting and gamma spectrometry of soil
samples are molded from black Butyrate (see Figure 7.20). They are fitted with a snap
cap and the wall thickness is ~ 0.18 cm. The capacity of the beaker is about
600 mL.
7.22.2 SUPPLIER

Five Wickers Drive
Wolfeboro, NH 03894
Phone: (603) 569-5100
Fax: (603) 569-6041
in lots of 100 or more.
Similar molded sample containers with 1 L and 4 L capacities (see Figure 7.21),
having a 7.6 cm deep well to fit standard 7.6 cm x 7.6 cm NaI crystals are available from:
GA-MA AND ASSOCIATES, INC.

P.O. Box 2918
Ocala, FL 34478-2918
Phone: (352) 687-8840 or gama@atlantic.net
in lots of 25 or more.
These containers were specifically designed to fit the current Ge(Li) detectors. They
will also fit some integral line NaI(T1) detectors, but will not fit most of the standard
crystals.
*

Section 7 Rev. 0
Figure 7.20 Molded Marinelli beaker.

Section 7 Rev. 0
Wall
thickness
0.18 cm
D H
Figure 7.21. Molded Marinelli beaker.
Well Well Beaker Beaker

Part* Capacity Dia. Depth Dia. Height
No. (mL) A-mm D-mm B-mm H-mm Detectors
J762A 500 77.5 70.0 116.0 104 Most Ge(Li0; old NaI(Tl)
J762B 500 86.0 70.0 116.0 104 Newer NaI(Tl)-dia.>2 7/8
J1155 650 98.5 92.8 125.2 122 Ge(Li); NaI(Tl)
*Phoenix Custom Molders, Inc.

Section 7 Rev. 0
7.23 RADON SAMPLING AND COUNTING FLASKS
7.23.1 DESCRIPTION
Scintillation flasks are made up of methyl-methacrylate tubing and sheet. They are
fitted with simple valves for flow-through samplings. The bottoms of the flasks are
cemented in, while the tops slide in with O-ring seals. They range in size from
165-2.0 L. A schematic drawing and photograph of the 415-mL scintillation flask are
shown in Figures 7.22 and 7.23.
7.23.2 COATING FLASKS
Materials
1. DuPont 1101 silver-activated zinc sulfide phosphor.
2. Bonding solution (caution - flammable). Dissolve 30 mL of Dow Corning 200

silicone fluid (200,000 cs) in 285 mL of reagent benzene plus 285 mL of reagent
cyclohexane. This is enough for about 100 flasks.
Procedure (Use a Hood)
1. Clean the flask with a nonabrasive cleaner. A plastic cleaning foam (Ren RP-70
cleaner) has been found to be excellent.
2. Remove cover, add 50 mL of the bonding solution, close both valves, replace cover
and rotate the flask slowly until all surfaces are coated. Open valves and remove
cover.
3. Pour out bonding mixture into a second clean flask or return to the stock bottle. Air
dry the flask for a few minutes.
4. Add 15-20 g of phosphor, close both valves and replace cover.

Section 7 Rev. 0
5. Shake gently until all surfaces are coated. Open valves and remove cover.
6. Pour the loose powder into a second flask or a clean container. Blow off excess
phosphor from flask.
7. Replace cover and purge the flask with aged air or nitrogen for a few minutes. Close
the valves and store the flask for use.
8. When background becomes excessive through use, wipe out phosphor with tissues,
clean, and rephosphor.

Section 7 Rev. 0
Figure 7.22 Schematic drawing of scintillation flask.
Figure 7.23 Photograph of

scintillation flask.

Section 7 Rev. 0
7.24 CONTAINERS FOR THE COLLECTION OF FALLOUT

AND ATMOSPHERIC DEPOSITION
7.24.1 DESCRIPTION
Samples of atmospheric deposition that are obtained using a wet/dry collector (see
Section 2.3.4) and that are to be measured for radioactive fallout or for the chemical
composition of the deposited material are usually collected using a polyethylene bucket of
the type that has been used by the National Atmospheric Deposition Program/National
Trends Network (NADP/NTN).
These (3.5 gallon) buckets, which will hold about 13 kg of water, are constructed of
high density polyethylene. The ears for the wire bail are integrally molded near the top of
the container. The bucket is molded in one piece and with two reinforcing rings around
the outside diameter above the ears to provide additional container strength. The body of
the bucket is tapered to permit one pail to nest inside another for economical shipping and
storage of empty buckets. The inner rim of the plastic cover interlocks with the upper rim
of the bucket. An O-ring seal in a groove just inside of the rim of the cover presses down
against the bucket rim and prevents leakage after the cover has been hammered into
place, using a rubber mallet. The covers must be discarded after one use because their
rims need to be cut in order to remove them from the buckets. The buckets may be
cleaned and reused for most purposes. We obtain the buckets and covers from:
Southcorp Packaging Bennett Industries

Peotone, IL 60468
(708) 258-3211
We use custom made cubic fiber boxes for mailing the buckets to and from distant
sampling sites. For mailing the boxes, we use a reversible, plastic covered address card,
with the site address on one side and our address on the other side. We commonly glue a
return address label to the box within the frame that holds the reversible address label so
that the box can be returned to us even if the reversible label is lost during shipment.

Section 7 Rev. 0
There are a few problems that have been encountered in the use of these sample
buckets. When the buckets are cleaned routinely for reuse, some contamination may
remain in them. The cleaning process has to be designed and monitored to prevent cross
contamination of samples. When the rims of the lids are cut to facilitate their removal
from the buckets, care must be taken not to cut the surface of the bucket also, if the
buckets are to be reused. During the NADP/NTN it has been shown that the O-rings are a
potential source of contamination even if they have been cleaned before use. If the
buckets are upside down or lying on their sides for some period during shipment, the
water sample may dissolve small amounts of sulfate and other materials from the O-rings.
For most uses to which the buckets may be put, this should not be a major problem.

Section 7 Rev. 0
7.25 FALLOUT COLLECTION AND SHIPPING CONTAINER
7.25.1 DESCRIPTION
The sampling containers for the EML wet/dry collectors are polyethylene pails (see
Section 2.3.4) particularly well suited for shipping because of the design of the lip and
cover. On the underside rim of the cover there is a groove with an O-ring seal. When the
cover is securely hammered onto the pot with a rubber mallet, no leakage will occur. In
most cases when the cover is removed back at the laboratory, it is destroyed.
The samples are shipped in fiber mailing boxes.
7.25.2 SUPPLIER
FIBERBILT
601 West 26th Street, 15th Floor
New York, NY 10001
(212) 675-5820

Section 7 Rev. 0
7.26 DISPOSABLE CHROMATOGRAPHIC COLUMN
7.26.1 DESCRIPTION
The column is prepared from a disposable polyethylene transfer pipette. The pipette
used here (Bio-Rad Cat #223-9527, Style EE) has a working capacity of ~4.5 mL and a
barrel ~100 mm long and 6.5 mL O.D.
7.26.2 SUPPLIER
Bio-Rad Laboratories
Hercules, CA 94547
(510) 741-1000
FAX: (510) 741-1060

2. SAMPLING

New York, NY 10014-4811

Table of Contents, Vol. II Rev. 0
Page
2. Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1-1
2.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1-1
2.7 Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7-1
2.7.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7-1

2.7.2 Protocols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7-1
2.7.2.1 Point of Production Sampling . . . . . . . . . . . . . . . . . . . . . . . 2.7-1
2.7.2.2 Mixed Diet Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7-2
2.7.2.3 Consumption Statistics Sampling . . . . . . . . . . . . . . . . . . . . 2.7-2
2.7.3 EML Diet Sampling Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7-3

2. SAMPLING
2.1 OVERVIEW
The purpose of environmental sampling and analysis is to obtain data that describe a
particular site at a specific point in time from which an evaluation can be made as a basis
for possible action. In this process, the collection of valid samples is the vital first step.
Sampling should be done with the same care as the analysis, and both should be done
with a rigor that is appropriate for the project at hand. In order for the data to be mea-
ningful, sampling must be carried out with a clear purpose and with an understanding of
the problem to be solved and the physical conditions that exist.
At EML, environmental sampling is carried out for purposes such as inventorying a

pollutant at a specific point in time, calculating the pollutant transfer coefficients, and
reconstructing deposition chronologies. Through these long-term studies, experience has
been gained in sampling radioactive fallout, air particulates and gases, and total and rate
of deposition. In this section, we describe procedures developed by EML for
environmental sampling, that are currently not used at EML but are still valid and are
used at other laboratories.
General guidance on collecting valid samples is given in Section 1.6.2, Volume I.

Unlike chemical or radiometric analyses, it is not possible to set down step-by-step
procedures for sampling. For example, a variety of samples may be required for the
purpose of establishing relationships between concentrations in different matrices to
further the understanding of dynamic processes. Also, the concentration of a particular
pollutant in an environmental matrix will change with time and location.
Usually, the crucial decisions in planning a sampling program are how many sites
should be sampled and how often they should be sampled. These decisions can only be
made based on a knowledge of the degree of variability due to these two factors (see
Section 1.6.2, Volume I). Most sampling programs require exploratory sampling so that
the varia-bility with time and location can be assessed in comparison with the required
uncertainty. Experience has shown that statistical approaches based on these exploratory

samples usually lead to the taking of a smaller number of samples than would have
otherwise been predicted. Another important consideration is that the number of samples
must be consistent with the available analytical facilities.
Many times, the samples received in the laboratory may be representative of the
particular conditions to be evaluated, but are not in the proper physical form for analysis.
The samples may require reduction in size, drying or some form of homogenizing before
subsamples can be taken for analysis. Some general considerations concerning sample
preparation are discussed in Section 1.6.3, Volume I of this Manual.
The philosophy at EML is usually to collect a sufficient amount of sample so that

there is not only enough to measure the constituent of interest, but also enough for
reanalysis at a later time (see Section 1.6.3, Volume I). Storage of samples for later
analyses requires judgment in order to avoid loss of constituents to be measured or to
avoid undesirable decomposition. EML maintains an extensive library of samples
associated with its research programs, in some cases going back over 30 years (Klusek,
1989).
REFERENCE
Klusek, C. S.
"The EML Soil Inventory and Archive"

2.7 FOOD
Contact Person(s) : Catherine S. Klusek
2.7.1 SCOPE
The determination of the radionuclide concentration in the diet or individual food

items constitutes an important element of an integrated program of radiological
surveillance and assessment. An overview of EML's sampling protocols will be
presented here.
2.7.2 PROTOCOLS
Food is analyzed to determine: 1) the level of contamination at the point of

production, or 2) the level of intake of the contaminant for the consumer or a particular
population group. Several factors must be considered in determining the sampling
protocol for diet intake studies. These include the number of samples that can be
handled, the effect of the lag time between production and consumption on the level of
the contaminant, the importance of the relative contribution of a single food or food
group, and the effect of processing of the food for consumption on the level of the
contaminant. There is no single method that is entirely satisfactory for estimating human
dietary intake of contaminants in foods. Several approaches will be discussed in the
following section. More detailed information can be found in World Health Organization
(1986).
2.7.2.1
POINT OF PRODUCTION SAMPLING
One method of food monitoring is to sample individual foods at the point of

production. This is most useful for relating contaminations to local conditions of fallout,
soil content, or farming practice. The geographic area to be sampled is generally
relatively small. This sampling system is used, for example, by the Food and Drug

Administration (FDA) in their program of food monitoring near power reactors (Stroube
and Jelinek, 1985). It is very difficult however to correlate the concentration level of a
contaminant in samples collected at the point of production to the dietary intake of any
specific group of people.
2.7.2.2
MIXED DIET SAMPLING
Another sampling procedure often used is to duplicate the actual foods consumed by
an individual during a day, a week or some specified time period ("duplicate plate"
sampling). This type of sampling is used in metabolic balance studies where the intake
and the retention of the contaminant are monitored on an individual basis (e.g., Spencer
et al., 1973). This procedure has also been used in the U.S. Environmental Protection
Agency's Institutional Diet Sampling Program (USEPA, 1974) and the California
(Hospital Standard) Diet Study (USEPA, 1973). The advantage of collecting meals over
a week period, and duplicating meals as consumed is that the resulting sample is a better
estimate of the average dietary intake. However, since the analyses are performed on the
composite of the diet, only the total intake can be estimated. Information on the
contribution of the component parts of the diet is not obtained.
2.7.2.3
CONSUMPTION STATISTICS SAMPLING
A third diet sampling procedure is based on analysis of representative food items

purchased locally and on food consumption statistics. The intake estimates are then
calculated by multiplying the concentration estimate of each food by the respective
consumption estimates per day or per year. This approach is used by EML in our 90Sr in
Diet Program (Klusek, 1984), Argonne's 137Cs in Chicago Foods Program (Karttunen,
1982), and FDA's Total Diet Studies Program (Stroube and Jelinek, 1985).
This sampling method allows a considerable degree of flexibility for consideration of

special diet types or differences in consumption by region, age, sex, income or
urbanization. It is possible to reduce the number of foods or to consider more general
categories of foods to reduce cost or effort in particular cases. It is recommended that the

sampling take place at the retail level, however, if appropriate (i.e., rural farm intake) the
sampling can take place at the consumption level.
The advantage of this method is that the analysis of a number of foods or food groups
gives more information than the analysis of a single composite diet sample. It is also
useful in indicating the primary sources of intake for a particular contaminant. However,
the intake estimates are limited by the accuracy of the consumption statistics. A
comparison of estimates of dietary intake of 90Sr by mixed diet sampling and
consumption estimates is presented in Kramer et al. (1973).
Food consumption statistics are available through national food sheets (e.g., FAO,
1984) or local specialists. Food consumption statistics for U.S. population groups have
been published by the U.S. Department of Agriculture (USDA) in a series of surveys
conducted since 1936. The "Household Food Consumption Survey" presents data on the
consumption of 200 food types by income group, by region in the U.S. and by degree of
urbanization (USDA, 1982). Food intake summaries for 22 sex-age categories, by racial
group and by season are also available through the USDA (1983). In cases where it is
necessary to compile other surveys of consumptions statistics, several reviews of the
methods of measuring dietary intake are available (Block, 1982; Marr, 1971; Morgan et
al., 1987).
2.7.3 EML DIET SAMPLING PROGRAM
The EML diet sampling program was developed to provide estimates of the intake of
90
Sr by man. These dietary intake estimates are then correlated with fallout measure-
ments and the 90Sr content of human bone. The sampling protocol or archived samples
from the diet sampling program have been used by other researchers in studies of the
dietary intake of other natural (Fisenne and Keller, 1970; Fisenne et al., 1987; Petrow et
al., 1965; Welford and Baird, 1967) and artificial radionuclides (Bennett, 1976; Rivera,
1967) and some stable elements (Bogen, 1972; Rivera, 1962).
At EML, the diet sampling is grouped into 19 food categories representing the five
basic food groups. On a quarterly basis, 42 food items are purchased in New York City
markets. The foods purchased within each category approximate the distribution of food
consumption within that category. The food items sampled are shown in Table 2.8. The

quantities purchased for an individual item allow for duplicate 90Sr analyses and
sufficient archival material. Additional information on % ash of certain foods and the
amount of wet sample needed for a 10 g sample of ash is discussed in Procedure Sr-02-
RC, Section 4 of this volume. It is recommended that the purchases be made in several
chain supermarkets or that a variety of brands of packaged goods be purchased.
Three categories of food intake are not sampled: fats and oils, sugars and sweets, and
beverages. The total liquid intake estimate and the concentration in water can be used to
obtain an estimate of the intake from the beverage category. Omission of these
categories is valid for most radionuclides and for metallic contaminants. Studies of
tritium intake or pesticides would probably require their inclusion.
Milk is a particularly important diet component and often a prime contributor to 90Sr
intake. Since it is easily sampled, we routinely obtain daily samples of pasteurized milk
which are then composited and analyzed monthly.
The foods are prepared as for consumption (but are not cooked). Using consumption
estimates from the USDA for all urbanizations (central city, suburban, and non-
metropolitan) of the U.S. (USDA, 1982), the daily intake of each food category is
calculated from the nuclide concentration multiplied by the daily consumption values.
The total intake is calculated from the total of all food categories. Quarterly sampling of
diet items has been sufficient to demonstrate seasonal variations and to provide
satisfactory average yearly intake estimates for typical Northern Hemisphere population
regions.

REFERENCES
Bennett, B. G.
"Fallout Pu-239+240 in the Diet - Results Through 1975"
USERDA Report HASL-306, pp. 115-125, July (1976)
Block, G.
"A Review of Validations of Dietary Assessment Methods"
Am. J. Epidemiology, 115, 492 (1982)
Bogen, D. C.
"Stable Lead Concentrations in New York City Foodstuffs"

"Radium-226 in the Diet of Two U. S. Cities"
USAEC Report HASL-224, pp. 2-8, April (1970)
Fisenne, I. M., P. M. Perry, K. M. Decker, and H. W. Keller

"The Daily Intake of 234,235,238U, 228,230,232Th, and 226,228Ra by New York City Residents"
Health Physics, 53, 357-64 (1987)
FAO, Food and Agricultural Organization

"Food Balance Sheets"
Food and Agricultural Organization, Rome (1984)
Karttunen, J. O.
"Cesium-137 in Various Chicago Foods"
USDOE Report EML-405, Part III, pp. 3-6, May (1982)
Klusek, C. S.
"Strontium-90 in the U. S. Diet, 1982"

Kramer, L., H. Spencer, and E. P. Hardy

"Dietary Strontium-90 Intake in Chicago"
Health Physics, 25, 445-448 (1973)
Marr, J. W.
"Individual Dietary Surveys: Purposes and Methods"
World Rev. Nutr. Diet, 13, 105 (1971)
Morgan, K. J., S. R. Johnson, R. L. Rizek, R. Reese, and G. L. Stampley

"Collection of Food Intake Data: An Evaluation of Methods"
J. American Dietetic Assoc., 87, 888-896 (1987)
Petrow, H. S., W. J. Schiessle, and A. Clover

"Dietary Intake of Radium-228"
USAEC Report NYO-3086-1, pp. 1-10 (1965)
Rivera, J.
"Stable Strontium in Tri-City Diets"
USAEC Report HASL-131, p. 230, October (1962)
Rivera, J.
"Cesium-137 in Tri-City Diets - Results for 1965"
Spencer, H., L. Kramer, J. Samachson, E. P. Hardy, and J. Rivera

"90Sr - Calcium Interrelationships in Man"
Health Phys, 24, 525-534 (1973)
Stroube, W. B., Jr. and Jelinek, C. F.

"Survey of Radionuclides in Foods, 1978-1982"
Health Physics, 49, 731-35 (1985)

U.S. Department of Agriculture

"Food Consumption: Households in the United States, Spring 1977"
Human Nutrition Information Service NFCS 1977-78, Report H-1 September (1982)
[regional tabulations are available for the Northeast (H-2), North Central (H-3), South
(H-4), and West (H-5)]
U.S. Department of Agriculture

"Food Intakes: Individuals in 48 States, Years 1977-78"
Human Nutrition Information Service NFCS 1977-78, Report I-1, August (1983)
U.S. Environmental Protection Agency

"California Diet Study"
Radiation Data and Reports, 14, 69-73, February (1973)
U.S. Environmental Protection Agency

"Radionuclides in Institutional Total Diet Samples"
Radiation Data and Reports, 15, 126-128, February (1974)
Welford, G. A. and R. Baird

"Uranium Levels in Human Diet and Biological Materials"
Health Physics, 13, 1321-1324 (1967)
World Health Organization

"Guideline for the Study of Dietary Intakes of Chemical Contaminants"
Joint FAO/WHO Food Contamination Monitoring Programme Report WHO-EFT/83.53,
WHO Offset Publication No. 87, World Health Organization, Geneva (1986)

TABLE 2.8
EML DIET SAMPLING PROGRAM FOOD PURCHASE LIST
Food group Food category Food item purchased1
Dairy products Milk Whole milk
Vegetables Fresh vegetables Lettuce, cabbage, spinach, peas,

beans, tomatoes
Canned vegetables Peas, beans, tomatoes
Root vegetables Onions, carrots, turnips
Potatoes White potatoes
Dry beans Navy beans
Fruit Fresh fruit Oranges, apples, bananas, melons,

berries
Canned fruit Peaches, pears, pineapple,
applesauce
Fruit juice Orange, pineapple, tomato,
grapefruit
Grain products Bakery products White bread

Flour White flour
Whole grain products Whole wheat bread
Macaroni Spaghetti, elbow macaroni
Rice White rice
Meat, eggs, and Meat Pork, beef

fish Poultry Chicken legs, chicken breasts
Eggs Fresh white eggs
Fresh fish Halibut, fillet
Shell fish Shrimp, clams or oysters
1
The amount of item is dependent on the food consumption in the district being studied. See text.


New York, NY 10014-4811

U. S. Department of Energy 4-i
Page
4. Analytical Chemistry . . . . . . . . . . . . . . . . . . . . . . 4.1-1
4.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1-1
4.3 Inorganics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3-1
4.3.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3-1

4.3.2 Elemental Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3-2
Procedures:
Anions-01-E
Anions - Ion Chromatography
Ca-01-ECalcium - Atomic Absorption Spectrometry
Ca-02-ECalcium - Permanganate Titration of the Oxalate
F-01-EFlouride in Soil and Sediment - Specific Ion Electrode
Measurements
Hg-01-E Mercury - Atomic Absorption Spectrometry
NH3--01-E Ammonium in Water and Precipitation Samples -
Autocolorimetry
Sr-01-E Strontium - Atomic Absorption Spectrometry
U-01-E Uranium in Urine - Fluorimetry
4.3.3 Multielemental Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3-3
Procedures:
M-01 Cadmium and Lead in Human Excreta and Composite
Diet Samples - Atomic Absorption Spectrometry
M-02 Precipitation and Lake Water Samples - Physical
and Chemical Measurements
M-03 Trace Metals - Atomic Absorption and/or Emission
Spectrometry
4.5 Radiochemical
4.5.1 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5-1

4.5.4 Radiochemical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5-4

U. S. Department of Energy 4 - ii
Page
Procedures:
Am-03-RC Americium in Water, Air Filters, and Tissue
Am-05-RC Americium in Water and Air Filters
3
H-01-RC Tritium in Water - Acid Electrolysis
3
H-02-RC Tritium in Water - Alkaline Electrolysis
3
H-03-RC Organically Labeled Tritium - Combustion Procedure
Pu-02-RC Plutonium in Soil Samples
Pu-04-RC Plutonium in Tissue
Pu-05-RC Plutonium in Tissue - Solvent Extraction
Pu-06-RC Plutonium in Urine
Pu-07-RC Plutonium in Large Urine Samples
Pu-08-RC Plutonium in Vegetation and Tissue - Nitric/Hydrochloric
Acid Method
Pu-09-RC Plutonium in Vegetation and Tissue - Nitric/Sulfuric
Acid Method
Ra-05-RC Radium-224 in Urine
Sr-01-RC Strontium-89
Sr-02-RC Strontium-90
Tc-01-RC Technetium-99 in Water and Vegetation
Th-01-RC Thorium in Urine
U-01-RC Enriched Uranium in Urine
U-04-RC Uranium in Biological and Environmental Materials

U. S. Department of Energy 4 - iii
4.1 OVERVIEW
During the past 40 years, EML has developed analytical procedures for the
determination of specific gases, inorganic and organic constituents, and radionuclides.
The procedures in this section are subdivided into two general categories: inorganics and
radionuclides. All of the procedures have been written in a detailed manner to provide
the user with sufficient information to obtain a quantitative result which is accurate,
precise, free from chemical interference and contamination with specified detection
capabilities. These procedures are currently not used at EML but they are still valid and
are used at other laboratories.
The procedures described in the inorganic subsection have been applied to a variety
of research programs. Most of the analyses for trace metals are performed by atomic
absorption spectrometry and instrument operational conditions are provided. Anions are
routinely determined by ion chromatography for various environmental matrices. Again,
operational conditions, limitations and interferences are provided.
The second subsection is devoted to radionuclide measurements and radiochemical

procedures. Information about background corrections, efficiency determination, and
quality control methods and limits of detection are also included. The radiochemical
procedures described are designed for various environmental matrices. The sample
preparation portion introduces the procedure so that representative, homogeneous, and
equilibrated samples are obtained. Next, separation and purification techniques are
described to obtain a radiochemically pure sample. Measurement techniques, including
limits of detection, quality control or special procedural precautions are also included.

4.3 INORGANICS
4.3.1 SCOPE
Described in this section are the inorganic procedures currently not in use at EML.
These procedures have been adapted for inorganic constituent analyses in air filter
extract, water, rain water, and certain soils and sediments. Atomic absorption
spectrometry is used for determination of metals, ion chromatography for specific anions,
and a specific ion electrode is used for fluoride determination. These procedures have
been thoroughly tested; accuracy, precision, and lower limits of detection have been
established. Effects from interferences and contamination are detailed in each
appropriate procedure.

4.3.2 Elemental Analyses

Anions-01-E
ANIONS - ION CHROMATOGRAPHY
APPLICATION
This procedure has been applied to precipitation and lake water samples and the
aqueous extracts of air filters. Anions are separated and quantitated using an ion
chromatograph.
Ion chromatography (IC) is a form of high pressure liquid chromatography (HPLC)

which utilizes an anion exchange column (separator column), a cation exchange column
(suppressor column), and a conductivity detector to identify and quantitate anions in
solution. Anions analyzed by IC include F -, Cl -, HPO4=, Br-, NO3 -, and SO4 =. Detection
of ng mL-1 anion concentrations is possible since the suppressor column converts the
highly conductive eluent (NaHCO3/Na2CO3) into a slightly conductive acid (H2CO3).
SPECIAL APPARATUS
1. Ion chromatograph - i.e., Dionex Corporation Model 2020 i (Dionex Corp.,

Sunnyvale, CA).
2. HPIC-AG4 anion guard column - No. 35210 (Dionex Corp., Sunnyvale, CA).
3. HPIC-AS4 anion separator column - No. 35311 (Dionex Corp., Sunnyvale, CA).
4. Anion fiber suppressor - No. 35350 (Dionex Corp., Sunnyvale, CA).
5. Strip chart recorder - available from chemical supply houses, i.e., Houston

Omnigraphic-3000, 1 V input.
6. 10-mL plastic syringes - available from chemical supply houses, i.e., Becton-
Dickinson No. 5604.
7. 50-mL disposable plastic beakers - Fisher No. 2-544-38 (Fisher Scientific, Fairlawn,
NJ).
8. 100-:L Eppendorf pipette - available from chemical supply houses.
SPECIAL REAGENTS
1. 0.0027M NaHCO3/0.0022M Na2CO3 eluent - weigh out 4.292 g NaHCO3, and

4 413 g of Na2CO3. Combine and dissolve in 18.925 L (5 gallons) of deionized
water.
2. 0.27M NaHCO3/0.22M Na2CO3 concentrated eluent - weigh out 2.268 g NaHCO3 and
2.332 g of Na2CO3. Combine and dissolve in 100 mL of deionized water.
3. 0.054M H2SO4 regenerant - dilute 14 mL of concentrated H2SO4 in 18.925 L

(5 gallons) of deionized water.
4. Deionized water - water having a specific conductance of <2 :S cm-1 must be used to
prepare all sample dilutions, eluents, and regenerants.
DETERMINATION
A schematic diagram of the ion chromatograph flow system is shown in Figure 1.
1. Prime the eluent and regenerant valves (see Dionex Operator's Manual, Chapter 2,
Section 4.1).
2. Prime the pump (Dionex Operator's Manual, Chapter 2, Section 4.2).

3. Optimize the Temperature Compensation Setting for the eluent and columns used
(Dionex Operator's Manual, Chapter 4, Section 4.4).
4. Connect the leads from the conductivity cell to the recorder. Adjust the recorder's
zero and full scale settings using its Zero and Calibration knobs.
5. Select the analytical pump module's parameters:
a. Choose the low and high pressure limits for each pump (Dionex Operator's
Manual, Chapter 2, Section 4.3).
b. Adjust the flow rate to 2 mL min-1.
c. Turn the eluent switch On and the Local/Remote switch to Local.
6. Select the advanced chromatography module's parameters:
a. Set the Load/Inject switch to Load, the "A" valve to Off, the "B" valve to Off,
and the Local/Remote switch to Local.
7. Select the conductivity detector module's parameters:
a. Turn the cell On, the auto-offset Off, and the Local/Remote switch to Local.
8. To equilibrate the system:
a. Select the 30 :S cm-1 Output Range. This setting will allow the baseline to be
monitored on the recorder.
b. Set the recorder chart speed at 0.5 cm min-1.
c. Pump the eluent through the separator column, suppressor column and
conductivity cell for ~ 15 min.
d. Turn the Auto-Offset On. Adjust the position of the recorder's pen to ~ 20% scale
with the Zero knob of the recorder.

e. Select the 1 :S cm-1 Output Range. Monitor the baseline. When the baseline
drifts <1 chart division in 5 min, the system has equilibrated sufficiently to begin
the analysis of the samples. Change the Output Range setting to
10 :S cm-1.
f. Choose several samples from the group of samples to be analyzed. Scan each
sample for peak height and retention time according to the directions outlined
beginning in Step 9.
9. Sample injection:
a. Draw 10 mL of sample into a 10-mL plastic syringe.
b. Transfer the 10 mL of sample into a 50-mL disposable plastic beaker.
c. Add 100 :L of concentrated eluent to the 10-mL sample.
d. Draw the sample/concentrated eluent solution into the syringe.
e. Attach the syringe to the injection port.
f. Flush the injection loop with at least 1 mL of sample.
g. Inject the solution by setting the Load/Inject switch to Inject. Simultaneously

press the Mark switch on the conductivity detector module so that the recorder's
pen marks the time of injection. A chromatogram for the injected solution is
obtained on the recorder. A typical chromatogram is shown in Figure 2.
h. When the chromatogram is finished, set the Load/Inject switch to Load.
i. If the peak heights are shorter than 15 chart divisions, increase the sensitivity by a
factor of 3; change the Output Range setting to 3 :S cm-1. (Peak height is defined
as the distance between the constructed baseline and the peak maximum.) Repeat
Steps f and h.

j. If the peak heights are >80 chart divisions, decrease the sensitivity by a factor of 3
(change the Output Range setting to 30 :s cm-1). Repeat Steps f and h.
k. Continue adjusting the Output Range setting and keep repeating Steps f and h
until the sample's peak heights are between 15-80 chart divisions high. If it is
necessary to use the 100, 300 or 1000 :S cm-1 setting to keep the recorder's pen on
scale, dilute the sample so that its peak heights are within the recommended limits
when the detector is set on the 3, 10 or 30 :S cm-1 setting.
l. Analyze each sample at least twice with the detector set at the Output Range
setting determined in Steps g-k. If the peak heights differ by more than 5%, inject
the sample a third time. Continue analyzing the sample until the relative standard
deviation of the peak heights is within 5%.
10. Calibration procedure:
a. Prepare at least four standards whose peak heights bracket the peak heights of the
anion samples to be analyzed.
b. Analyze these standards according to the procedures outlined in Determination,

Steps 6-9.
c. Multiply the peak height measured by the Output Range selected for analysis.
(The peak height values calculated in this manner are in units of :S cm-1.)
d. Calculate the mean peak height for each anion.
e. Determine the retention time of each peak. (The retention time is the interval
measured from the point of injection to the maximum point of the peak.)
f. Plot the average peak height value for each anion (y) versus its corresponding
concentration value (x). The plot generated will be a straight line which can be
described by the following function:
y = mx + b (1)

where y is the peak height in :S cm-1, m is the slope of the line, x is the anion
concentration in :g mL-1 and b is the y intercept. The slope and intercept values
will later be used to calculate the concentrations of anion samples.
g. Perform a linear regression analysis of the standard data. The correlation

coefficient should be at least 0.99 or the calibration procedure should be repeated.
11. Determination of sample peak height and retention time:
a. Analyze each sample according to the procedure described in Determination,

Step 9.
b. Identify the peaks by comparing their retention times with the retention times of
the standards determined in Determination, Step 10.
c. Measure the height of each of the peaks in the chromatogram.
d. Calculate the mean peak height value from the duplicate measurements for each
anion.
e. Calculate each sample's anion concentrations (x) using Equation (1), the average
peak height value (y), the slope (m), and intercept values (b) determined in the
Determination, Step 10.

The LLD is defined as the anion concentration which produces a detector response
(peak height) that is twice the mean variation of the background (baseline noise).
The following LLDs were determined using a 50-:L injection loop and the columns,
sensitivity, parameters, eluent, and regenerant listed in this section.
F- 0.01 :g mL-1
Cl- 0.01 :g mL-1
HPO4= 0.02 :g mL-1
Br- 0.02 :g mL-1
NO3- 0.02 :g mL-1
SO4= 0.02 :g mL-1

Injection Value
PUMP ELUENT
S E PARATOR COLUMN - Strong anion exchange resin separates

sample anions in a background of
NaHCO 3 /Na 2 CO3 eluent.
S E P P R E S S O R C O L U M N - Strong cation exchange resin converts

NaHCO 3 /Na 2 CO 3 eluent into H2 CO3 and
sample anions into their acid forms.
CONDUCTIVITY RECORDER
DETECTOR
CONDUCTIVITY DECTECTOR -
Squantitates the anions in a background
WASTE of slightly conductive H 2 CO 3 .
Figure 1. Schematic diagram of the ion chromatograph flow system.

Figure 2. Typical ion chromatogram.

Ca-01-E
CALCIUM - ATOMIC ABSORPTION SPECTROMETRY
APPLICATION
Bone, milk, food, and vegetation ash have been analyzed by this procedure. Stable
Ca is determined by atomic absorption (AA) spectrometry. The sample is dissolved in
HCl. Lanthanum is added as a releasing agent to eliminate chemical interference of
phosphorus, aluminum, silicon and sulfur and their anions in the analysis of Ca.
SPECIAL APPARATUS
1. Double beam AA spectrometer (e.g., Perkin-Elmer Model 603).
2. Boiling burner head recommended (Perkin-Elmer Corp., Norwalk, CT).
3. Recorder readout (optional).
4. Acetylene and filtered compressed air.
SPECIAL REAGENTS
1. Calcium "AA standard" stock solution - 1000 mg L-1 (Aztec Instruments, Inc.,
Westport, CT).
2. Stock La solution: 5% - dissolve 58.65 g of La2O3 (obtained from Lindsay Chemical
Page 1 of 3
Division, American Potash and Chemical Corp., West Chicago, IL) in 250 mL of HCl
and dilute to 1 L with water.
3. Calcium standard solutions - prepare dilutions of the stock Ca solution to contain 0,

1, 2, 5, 8, and 10 mg L-1 Ca, all in 1% La and 1:19 HCl. If other concentrations of Ca
are required, the final standard solutions should contain 1% La in 1:19 HCl.
4. Deionized or doubly-distilled water should be used for sample preparation and

reagents.
SAMPLE PREPARATION
1. Prepare samples by ashing as in the radiochemical procedure for 90Sr (see Section
4.5.4, Sr-02-RC, this volume).
2. Weigh 1 g of ash into a 100-mL beaker (0.1 g is adequate for bone ash). Add
1 mL of 1:1 HCl and evaporate to dryness. Repeat one time.
3. Dissolve the residue in 10 mL of 1:11 HCl and filter by gravity through a 7 cm

Whatman No. 42 filter paper. Collect the filtrate in a 100-mL volumetric flask and
wash the residue with hot water until the total volume is about 50-75 mL.
4. Cool to room temperature and dilute to volume with water.
5. Make a rough estimate of the concentration of Ca in the sample by making an

absorption measurement on the instrument and comparing it with a Ca solution of
known concentration.
6. Make the necessary dilution so that the final concentration of Ca is in the 1-10 mg L-1
range and the solution contains 1% La in 1:19 HCl.
DETERMINATION
Page 2 of 3
1. Measure the Ca standard solutions and a blank with the AA spectrometer. (Detailed
instructions are not given here as they apply only to a specific instrument.)
2. Measure the sample solutions. At least two different sample concentrations should be
analyzed to determine any effect from matrix interferences.
3. Prepare a calibration curve by plotting absorbance versus concentration of the

standard Ca solutions.
4. Read off the Ca concentration of the samples from the calibration curve.
5. Calculate the amount of Ca in the sample by correcting for Ca in the blank, dilutions
and sample weight. The chemical yield is assumed to be 100%.
Page 3 of 3
Ca-02-E
CALCIUM - PERMANGANATE TITRATION OF THE OXALATE
APPLICATION
This procedure is applicable for wet- or dry-ashed biological materials and for
inorganic materials. In soil analyses, the Ca must be separated from interfering elements
before determination.
Calcium oxalate is precipitated by excess ammonium oxalate from an ammonium

acetate solution buffered to a pH of 4.5-5.0. The precipitate is dissolved in dilute H2SO4
and the liberated oxalic acid is determined by permanganate titration.
SPECIAL APPARATUS
1. 40-mL short cone, heavy walled, centrifuge tubes.
2. 5-mL buret - calibrated in 0.01-mL increments.
3. Stand to accommodate automatic volume dispensers.
4. Automatic volume dispensers - 1 mL, 3 mL, 4 mL, and 10 mL.
SPECIAL REAGENTS
1. Standard Ca solution - 2.000 mg Ca mL-1. Dissolve 5.004 g oven-dried reagent grade

CaCO3 in a 1-L volumetric flask by adding distilled water containing 12 mL of HNO3
and diluting to volume. This amount of acid is sufficient to prevent precipitation of

Ca(OH)2. The solution is covered with a layer of toluene to prevent mold formation.
2. Saturated oxalic acid solution - 100 g of oxalic acid (H2C2O4 • 2H2O) crystals per
600 mL of water.
3. Concentrated (stock solution) K permanganate solution - 6.900 g KMnO4 L-1 H2O.
4. Dilute K permanganate (for food, vegetation, and urine samples) - dilute one part of
stock solution with nine parts of water. Dilute one part of stock solution with six
parts of water (for milk and bone samples). Keep all permanganate solutions in the
dark when not in use.
5. Methyl red indicator solution - dissolve 100 mg of the dye in 60 mL of 95% ethanol
and dilute to about 100 mL with water.
6. Ammonia wash solution - 5-10 drops of NH4OH L-1 of water.
SAMPLE PREPARATION
Biological samples are dry ashed at 550oC or wet ashed with concentrated HNO3. In
the latter procedures, hydrogen peroxide is added to obtain a white ash. Since the
quantity of the elements that interfere is at a minimum in these samples, an aliquot of the
final ash solution is used directly for Ca determination.
In the analysis of soil for Ca, it is preferable to prepare a separate sample for Ca
analysis or to remove the aliquot immediately after dissolution of the soil. The Ca
aliquot is purified using the radiochemical procedure for 90Sr (see Section 4.5.4, Sr-02-
RC, this volume), without adding Sr or Y carrier, and is processed through to the Ba
precipitation step. The sample is then ready for Ca determination.
Since HCl interferes with the permanganate titration, it should not be used to dissolve
samples or precipitates. Nitric acid should be used wherever possible.
DETERMINATION

1. Transfer the proper sized aliquot to a 40-mL conical heavy-walled centrifuge tube.
(The aliquot should contain between 0.5 and 2 mg of Ca. This is the preferred range,
however, it is possible to determine Ca from 0.1 to 10 mg.)
2. Add 4 mL of 1:4 acetic acid. Stir.
3. Add 3 mL of saturated oxalic acid. Stir.
4. Add 7-10 drops methyl red (see Note 1). Add 1:4 ammonium hydroxide drop by
drop (see Note 2) until just alkaline to the methyl red, a yellow color.
5. Add 1:4 acetic acid drop by drop until faintly acid to the methyl red, an orange color.
Let stand at room temperature overnight or in a water bath at 75oC for 3 h.
6. Centrifuge. Decant supernate and discard.
7. Wash precipitate with 10 mL of NH3 wash solution, stirring precipitate and rinsing
down the sides of the tube. Place in a hot water bath for 1 h.
8. Cool. Centrifuge. Decant and discard washings. Carefully place a tissue over the
tube while in an inverted position and leave in a tube rack until dry.
9. Add 1 mL of 1:9 H2SO4. Heat in water bath to 70o-80oC until precipitate is

completely dissolved (see Note 3).
10. Titrate with dilute permanganate solution to a faint pink shade that persists at least 30
sec. Rewarm during titration if necessary (see Note 4).
Notes:
1. If methyl red is added before the saturated oxalic acid, an interfering brown
coloration may be produced.
2. If NH4OH is added too rapidly, local concentrations may precipitate hydroxides.

3. Milk and bone samples usually require 2-4 mL of 1:9 H2SO4.
4. Chloride will interfere in the permanganate titration by reducing MnO4 to MnO2.

Samples giving a brownish color during titration should be discarded.
CALIBRATION
One milliliter of the standard Ca solution containing 2 mg Ca is analyzed by the

procedures given under Determination. The volume of permanganate solution that is
needed is then equivalent to 2 mg Ca. At least two standard Ca determinations should be
run with each set of unknowns on each day. A reagent blank will usually require less
than one drop of permanganate and may usually be neglected unless very accurate results
are required or the total Ca is < 0.1 mg.
COMPUTATION
1. Divide the volume of permanganate used to titrate the Ca standard by two to

determine mL of titrant per mg Ca.
2. Divide the volume of permanganate required for the sample by the value obtained in
Step 1 to determine mg of Ca per aliquot used.
3. Apply the proper dilution factor to determine the total Ca in the sample.
Example: an unknown solution of 100-mL volume contains ~1 g of Ca (10 mg mL-1).

In the determination, 5 mL is diluted to 50 (Ca ~1 mg mL-1) and 1 mL is taken for
analysis.
The standard requires 4.84 mL of permanganate for 2 mg of Ca, therefore, 2.42 mL of

permanganate = 1 mg Ca.

The sample requires 2 mL, therefore, it contains
2.0/2.42 = 0.827 mg
The dilution factor is 100/5 x 1 x 50 = 1000, therefore, the total Ca = 1000 x 0.827 =
0.827 g.

F-01-E, Vol II Rev. 0
F-01-E
FLUORIDE IN SOIL AND SEDIMENT - SPECIFIC

ION ELECTRODE MEASUREMENTS
APPLICATION
This procedure is applicable to soils and sediments in the range of 1-1000 :g of F- g-1
of sample.
The sample is fused with sodium hydroxide, extracted with water, adjusted to pH 5,
and measured for F- by specific ion electrode.
SPECIAL APPARATUS
1. Fluoride, specific ion electrode, e.g., Orion Model 96-09 (available from chemical
supply houses).
2. Digital pH/ion meter, e.g., Orion Model 901 (available from chemical supply houses).
3. Standard pH and reference electrodes.
4. 100-mL Teflon beakers.
5. Nickel crucibles (100 mL).
6. 90-mL polyethylene centrifuge tubes.

SPECIAL REAGENTS
1. Sodium hydroxide (17N) - dissolve 670 g of sodium hydroxide pellets in distilled

water and dilute to 1 L.
2. Total ionic strength adjuster buffer - add 84 mL of concentrated HCl, 242 g of Tris
(hydroxymethyl) amino acid, and 230 g of Na tartrate to 500 mL distilled water. Stir
until all the reagents have been dissolved, cool to room temperature and dilute to 1 L
with distilled water.
3. Stock F- solution - dissolve 2.2 g of NaF in distilled water and dilute to 1 L. Store in
a polyethylene container.
SAMPLE PREPARATION
1. Weigh the sample (0.5, 1 or 1.5 g of soil or sediment) and transfer to an oxidized
nickel crucible. (Note: the crucible is oxidized by heating in air.)
2. Add 12 mL of 17N NaOH to the crucible for each gram of sample and tap gently to
disperse the sample in the sodium hydroxide solution.
3. Place the sample under a drying lamp and dry thoroughly (usually overnight).
4. Place the sample in a cold muffle furnace. Slowly raise the temperature to 600oC and
fuse for 30 min.
5. Cool to room temperature and add 10 mL of distilled water.
6. Heat the sample gently on a hot plate to dissolve the fusion cake.
7. Slowly add 16 mL of concentrated HCl for each gram of sample to dissolve the
remainder of the fusion cake.
8. Transfer the sample to a 100-mL Teflon beaker. Wash the crucible with a minimum
amount of distilled water and transfer the washings to the Teflon beaker.
Page 2 of 4
9. Evaporate to about 40-mL volume. Place pH electrodes in the sample and slowly add
concentrated HCl to adjust the pH to 8.5.
10. Allow the sample to stand for several hours and recheck the pH. Adjust to pH 8.5, if
necessary.
11. Transfer the sample to a 90-mL polyethylene centrifuge tube.
12. Centrifuge for 10 min. Decant into a tared polyethylene bottle and adjust pH to 5 by
the addition of concentrated HCl. Reweigh the bottle and record the net sample
weight.
13. Transfer the precipitate remaining from Step 12 back to the 100-mL Teflon beaker
with a minimum amount of distilled water. Repeat Steps 8-12. Decant the wash into
a separate tared polyethylene bottle. Reweigh the bottle and record the wash solution
weight.
14. Retain samples for measurement of F-.
DETERMINATION
1. Prepare 0.01, 0.1, 10, and 100 :g mL-1 F- standards by serial dilution.
2. Combine 25 mL of the standard and 25 mL of total ionic strength adjuster buffer in a

100-mL plastic beaker. Add a small magnetic stirring bar.
3. Immerse the electrode at least 2 cm into the solution. Wait for the response to
stabilize (~ 45-60 sec), mixing continuously using the magnetic stirrer.
4. Prepare a calibration curve plotting mV readings versus concentration of F- on

semilog graph paper. (The curve should be linear with a slope of 59 ± 2 mV.)
5. To analyze the samples, combine 25 mL of sample and 25 mL of the buffer in a

100-mL plastic beaker. Add a magnetic stirring bar. While stirring, add sequentially:
50-:L additions (using a :L dispensing pipette) of distilled water; 10,100, and 1000

:g mL-1 of F- standards corresponding to 0, 0.1, 1 and 10 :g mL-1 of F- additions.

Record the mV response after each addition.
6. Plot the mV response versus added concentration of F- on semilog graph paper. (The
intersection of the curve with the concentration axis corresponds to the concentration
of F- in the diluted sample.)
7. Measure the sample and wash separately using the F- ion selective electrode.
8. Compute the concentration of F- in :g g-1 of sample by correcting for dilution and for
the sample volume. Correct these values for reagent blanks processed in the same
manner.
Notes:
1. Fluoride standard solutions may be prepared in a glass vessel, but must be analyzed
within 4 h or transferred to polyethylene bottles for storage.
2. The total ion strength adjuster buffer must be prepared fresh every 4 weeks, and
should be stored in a refrigerator.
3. The pH of the sample prior to analysis must be buffered to a pH of 5.5 to minimize

the interference of (OH)- ion. Interference with the electrode response occurs when
the concentration of (OH)- is greater than one-tenth the concentration of F-.
4. The technique "Method of Additions" (see Step 5, Determination) is used to

eliminate the effects of sample size and possible matrix problems.
The LLD of this procedure is estimated to be about 5 :g g-1 of the sample.

Hg-01-E
MERCURY - ATOMIC ABSORPTION SPECTROMETRY
APPLICATION
This procedure has been tested with NIST standard reference materials - coal, orchard
leaves, and bovine liver - with sample sizes up to 1 g. The combustion procedure gives
the total - inorganic plus organic - Hg and has been applied to dried samples of foods,
water, urine, and biota.
The volatility of Hg and its compounds is utilized for separation. The sample is
combusted in an atmosphere of O2 and the Hg is collected in a liquid N2 trap (Rook
et al., 1972). The isolated Hg is measured by cold-vapor flameless atomic absorption
(AA) spectrometry (Hatch and Ott, 1968).
SPECIAL APPARATUS
1. Double beam AA spectrometer, e.g., Perkin-Elmer Model 403 with strip chart
recorder.
2. Combustion tube - heavy-walled quartz, ~ 2.0 cm ID x 45.0 cm long, with 19/38

female joint.
3. Condenser - standard wall, quartz, 1.3 cm ID x 20.0 cm long with 19/38 male joint.
4. Liquid N2 trap - The liquid N2 trap is prepared from a 0.95-L polyethylene aspirator
bottle with an outlet tube near the bottom to drain off the liquid N2. Two holes are
cut 3.8 cm from the bottom so that the condenser tube can pass through. In use, the
bottle is filled with liquid N2 to the top. The trap can be conveniently insulated with

material from a styrofoam acid case. When the liquid N2 is added, the contraction of
the polyethylene forms a permanent seal around the condenser.
5. Oxygen-methane hand torch with high temperature fishtail tip.
6. Quartz wool.
7. One-way gas flow valve.
8. Glazed ceramic combustion boat.
9. Reduction cell (see Figure 1).
10. Magnetic stirrer.
11. Drying tube, 2.0 cm ID x 10.0 cm long, filled with silica gel.
12. Absorption cell, 1.0 cm ID x 15.0 cm long with quartz window.
SPECIAL REAGENTS
1. 10% SnCl2 - dissolve 10 g SnCl2 in 1:11 HCl and make up to ~ 100 mL.
2. 0.1N HCl solution.
3. Mercury "AA standard" stock solution, 1000 mg L-1, Fisher Scientific Co., Fairlawn,
NJ. Prepare a working standard of 100 ng mL-1, as required, by dilution with water.
4. Liquid N2.
5. Compressed gases: Ar, O2, methane.
SAMPLE PREPARATION

1. Weigh up to 1 g of dried sample into a glazed ceramic combustion boat.
2. Assemble the combustion train shown in Figure 2.
3. Open the train at the junction of the combustion tube and condenser. Place an ~ 1.3
cm plug of quartz wool at the O2 inlet port of the combustion tube.
4. Place the combustion boat with sample 2.5-5.0 cm from the quartz wool.
5. Place a 7.5-10.0 cm plug of quartz wool 12.5-17.0 cm away from the combustion
boat.
6. Reconnect the combustion tube to the condenser.
7. Fill the liquid N2 trap to the top.
8. Adjust the O2 flow rate to 30 cm3 min-1 and allow O2 to flow through the combustion
train.
9. With the O2-methane torch fitted with a fishtail tip, heat downstream from the 10.0
cm quartz wool plug to red heat (~ 700oC).
10. Place a sheet of Siltemp on top of the combustion tube to maximize heating in the
region. This region is where all pyrolysis products must be completely oxidized.
(Note: Traces of incomplete pyrolysis products will cause extremely low recoveries
of Hg, on the order of 0-10%. These products can be recognized as a yellow to
brown color in the condenser or a distinct odor when the train is opened.)
11. Begin heating the sample slowly with a Meker burner starting near the O2 inlet.
Rapid oxidation must be avoided. Too rapid combustion is indicated by a red glow in
the downstream quartz wool. Carefully remove moisture, carbonize, and finally ash
the entire sample with the Meker burner.
12. With the O2-methane torch, starting at the O2 inlet, flame the entire combustion tube
for 10 min.

13. Cool the combustion train for 15-30 min, then remove the liquid N2 from the trap by
draining through the outlet at the base of the polyethylene bottle.
CALIBRATION OF THE SPECTROMETER
The following instructions relate specifically to the spectrometer used here.
1. Optimize the response for Hg at a wavelength of 253.6 :M on the AA spectrometer.
2. Set the noise suppression at 2 and the scale expansion at 3.
3. Place the reduction cell on a magnetic stirrer and connect the inlet to an Ar gas
cylinder. Connect the outlet to a drying tube containing Drierite which is connected
in turn to the absorption cell.
4. Add 5 mL of 0.1N HCl to the reduction cell and flush the system with Ar at a flow
rate of 2 L min-1.
5. Turn the stopcocks of the reduction cell to bypass the cell.
6. Transfer 50 :L of a freshly prepared 100 ng Hg standard to the reduction cell.
7. Add 50 :L of 10% SnCl2 to the reduction cell and stir for 2 min.
8. Turn both stopcocks simultaneously to pass Ar through the reduction cell. Record the
percent absorption of the standard.
9. Remove the reduction cell and wash several times with 0.1N HCl and finally with
deionized water. Discard the washings.
10. Repeat Steps 6-9 with 100, 200, and 250 :L of the 100 ng Hg standard.
11. Determine blanks before and after Hg standards are measured.
12. Subtract the mean blank value from the measured values and construct the calibration

curve by plotting absorbance versus concentration.
DETERMINATION
1. Separate the combustion tube from the condenser. Wash the Hg from the condenser
with one 3-mL and one 2-mL volume of 0.1N HCl, and transfer the washings to the
reduction cell.
2. Add 50 :L of 10% SnCl2 and stir for 2 min.
3. Turn both stopcocks simultaneously to pass Ar gas through the reduction cell.
Record the percent absorption of the sample.
4. Subtract the blank value and read off the Hg concentration from the calibration curve.
The LLD for this procedure is estimated to be about 0.5 ng Hg.
REFERENCES
Hatch, W. R. and W. L. Ott

Anal. Chem., 40, 2085-87 (1968)
Rook, H. L., T. E. Gillis and P. D. LaFleur

Anal. Chem., 44, 1114-17 (1972)

Figure 1. Reduction cell.
Figure 2. Combustion train for Hg determination.

NH-01-E, Vol. II Rev. 0
NH3--01-E
AMMONIUM IN WATER AND PRECIPITATION SAMPLES -

AUTOCOLORIMETRY
APPLICATION
This procedure has been applied to the analysis of NH4+ in water and precipitation
samples.
Ammonium ions are determined spectrometrically at 630 nm. Alkaline phenol and
hypochlorite react with NH4+ to form indophenol blue which is directly proportional to
the NH4+ concentration. The blue color formed is intensified by the addition of sodium
nitroprusside. Calcium and magnesium ions are interferences but may be eliminated by
the addition of sodium citrate.
SPECIAL APPARATUS
Spectrometer [commercially available, e.g., Spectronic 21/MV].
SPECIAL REAGENTS
1. Phenol reagent - dissolve 76 g of phenol and 400 mg of disodium nitroprusside in

water and dilute to 1 L. Store the reagent solution in a brown glass bottle.
2. Sodium citrate - dissolve 240 g of trisodium citrate dihydrate in 500 mL of water.

Add 20 mL of 0.5M NaOH and gently evaporate the solution to <500 mL. Cool and
dilute to 500 mL.

3. Sodium hypochlorite - commercial bleach, 5.25% active sodium hypochlorite.
4. Ammonium standard solution, 100 mg mL-1 - dissolve 4.4373 g of NH4NO3 in 1 L of

H2O.
SAMPLE PREPARATION
1. Add 47 mL each of the sample, reagent blank and dilutions of NH4+ standard
solutions to individual 50-mL volumetric flasks.
2. Pipette 1 mL of sodium citrate into each flask and mix gently.
3. Pipette 1 mL of phenol reagent into each flask and mix gently.
4. Pipette 1 mL of sodium hypochlorite into each flask, mix thoroughly and store the
samples in the dark for 3 h for color development.
DETERMINATION
1. Adjust the spectrometer operating conditions as predetermined for optimum

sensitivity.
2. Use 1-cm path length cells for NH4+ concentrations >1 :g mL-1 and 10-cm path length
cells for concentrations <1 :g mL-1.
3. Measure the absorbancies for the sample, reagent blank, and NH4+ standard solutions
at 630 nm.

DATA PROCESSING
1. Subtract the reagent blank absorbance reading from the sample and NH4+ standard
readings.
2. Prepare a calibration curve using the NH4+ standard results. Determine the sample
concentration from the calibration curve.
The LLD for this procedure is estimated to be 10 ng mL-1.

Sr-01-E
STRONTIUM - ATOMIC ABSORPTION SPECTROMETRY
APPLICATION
Bone, milk, fresh water, food, vegetation, and excreta have been analyzed by this
technique.
Stable Sr is determined by atomic absorption (AA) spectrometry. The sample ash is

dissolved in HCl and La is added to reduce interferences from phosphate, silicate, and
aluminate that occur in the flame. A preliminary measurement is made to obtain the
range, and the final sample dilution is measured against standard solutions of similar
chemical composition.
SPECIAL APPARATUS
1. Double beam AA spectrometer (e.g., Perkin-Elmer Model 603).
2. Acetylene and filtered compressed air.

SPECIAL REAGENTS
1. Strontium "AA standard" stock solution - 1000 mg L-1 (Aztec Instruments, Inc.,
Westport, CT 06880).
2. Stock La solution, 5% [the La2O3 was obtained from Lindsay Chemical Division,
American Potash and Chemical Corp., West Chicago, IL 60185] - dissolve 58.65 g of
La2O3 in 250 mL of HCl and dilute to 1 L with water.
3. Strontium standard solutions - prepare dilutions of the stock Sr solution to contain

0.2, 0.4, 0.6, 0.8, and 1.0 mg L-1 of Sr all in 1% La and 1:19 HCl solution. If other
concentrations of Sr are required, the final standard solutions should contain 1% La in
1:19 HCl.
4. Deionized or doubly-distilled water should be used throughout for sample preparation

and reagents.
SAMPLE PREPARATION
1. Prepare samples by ashing as in the radiochemical procedure for 90Sr (see Sr-02-RC).
2. Weigh 1 g of ash into a 100-mL beaker. Add 5 mL of 1:1 HCl and evaporate to
dryness. Repeat.
3. Dissolve the residue in 2 mL of 1:9 HCl and filter by gravity through a 7 cm

Whatman No. 41 filter paper. Collect the filtrate in a 25-mL volumetric flask, wash
the residue with water and dilute to volume with water.
4. Make a rough estimate of the concentration of Sr in the sample by making an

absorption measurement on the instrument and comparing it with a solution of known
Sr concentration.
5. Make the necessary dilution so that the final concentration of Sr is in the 0.1-1.0
mg L-1 range and the solution contains 1% La in 1:19 HCl. (Note: The final sample
phosphate concentration should be < 300 mg L-1.)

DETERMINATION
1. Measure the Sr standard solutions and a blank with the AA spectrometer. (Detailed
instructions are not given here as they apply only to a specific instrument.)
2. Measure the sample solutions. At least two different sample concentrations should be
analyzed to determine any effect from matrix interferences.
3. Prepare a calibration curve by plotting absorbance versus concentration of the

standard Sr solutions.
4. Read off the Sr concentration of the samples from the calibration curve.
5. Calculate the amount of Sr in the sample by correcting for Sr in the blank, dilutions
and sample weight. The chemical yield is assumed to be 100%.
The LLD for this procedure is estimated to be about 20 :g L-1.

U-01-E, Vol. II Rev. 0
U-01-E
URANIUM IN URINE - FLUORIMETRY
APPLICATION
The procedure was developed for urine specimens; however, it may be used for other
materials after the U has been sufficiently isolated from the matrix.
Uranium is determined from the fluorescence produced when fused with NaF and
exposed to ultraviolet light. The fluorimeter will measure from 1-10,000 µg of U L-1 of
urine.
SPECIAL APPARATUS
1. A 5-mL hypodermic syringe connected by plastic tubing to an 0.5-mL Mohr

(graduated in 0.01 mL) pipette which is mounted o a ring stand.
2. Platinum fluorimeter dishes fabricated from 0.004-cm thick, 2.5-cm diameter blanks.
A circular depression 1.3-cm in diameter and 0.4-cm deep is formed at the center.
3. A booster pump with a pressure regulator, set for 45 cm (Hg), is required for natural
gas supply to obtain fusion temperatures within 25-30 sec.
4. Uranium fluorimeter (Giovanni et al., 1954).
5. A pellet dispenser made by cutting a 1-mL glass hypodermic syringe to leave the full
bore open. The plunger is fitted with a stop so that the maximum opening will
contain 100 ± 10 mg of NaF.

6. Platinum loop dish holders made of 2-mm platinum rod, mounted on a ring stand so
that the dishes are held in the zone of maximum flame temperature.
7. Low temperature hot plate covered with 0.6-cm transite. The transite has three rows
of 1.3-cm circular cutouts for holding dishes for evaporation.
8. Transite racks to hold nine sample dishes are fitted with legs for stacking.
SPECIAL REAGENTS
1. Reagent grade NaF - several lots from different manufacturers should be tested to
obtain material with a minimum blank reading and high U sensitivity. Sufficient
reagent from the best lot should be obtained to last for several years.
2. Stock solution “A” (500 :g mL-1) - dissolve 58.9 mg of pure of U3O8 in 2 mL of

HNO3 and evaporate to dryness. Take up with water containing 10 drops of HNO3,
transfer to a 100-mL Pyrex volumetric flask and dilute to volume.
3. Standard solution “B” (50 :g mL-1) - transfer 10 mL of solution “A” to a 100-mL

Pyrex volumetric flask. Add 10 drops of HNO3 and dilute to volume.
4. Standard solution “C” (5 :g mL-1) - transfer 1 mL of solution “A” to a 50-mL Pyrex

volumetric flask, add five drops of HNO3 and dilute to volume.
Note:
It is important that the standard solutions be slightly acid to prevent hydrolysis and
absorption of U. They should be stored in polyethylene bottles.
SAMPLE PREPARATION
Properly preserved urine samples are analyzed as received. Samples that are cloudy
are treated with 1% by volume of HCl and allowed to stand overnight before analysis.
Those that do not become clear are wet ashed with HNO3 and 30% H2O2 and made up to

the original volume with water.
The addition of about 1% by volume of HCl at the time of sampling will prevent
deterioration.
INSTRUMENT STANDARDIZATION
Prior to initial use, allow the fluorimeter to warm up for 15 min. A permanent glass
standard is used for daily adjustment of the instrument and for stability checks after
reading each sample. A 0.6 :g U standard is adjusted to 6000 divisions and the prepared
glass standard is read. This reading is recorded and in subsequent use of the instrument
the meter is set at this value by adjusting the phototube voltage. The glass standard
prepared at EML is equivalent to 0.27 :g of U and given an instrument response of 2700
divisions.
DETERMINATION
A. Measurement.
1. Analyze all samples in triplicate.
2. Rinse pipette with water and the sample before taking the aliquots.
3. Pipette 0.1 mL of urine onto each of three platinum dishes.
4. Evaporate to dryness on the low heat hot plate.
5. Ignite the residue over a Meker burner.
6. Cool and add 100 ± 10 mg of NaF.
7. Fuse completely over a Meker burner with gas at 45-cm Hg. The temperature of the
flame should be such that complete fusion takes place within 25-30 sec.

8. Cool by holding dish in air, with platinum tipped forceps, for a few seconds. Place in
a transite rack to cool completely.
9. Read the fluorescence of each sample.
10. Calculate the U from a calibration factor or calibration curve.
B. Cleaning platinum dishes.
Dishes are cleaned daily since there are sufficient platinum dishes available for a full
day of analyses. Samples that read >50 divisions are separated from those that read <50
divisions for special cleaning. After the sample have been read, remove the bead by
washing with hot water. The low reading dishes are allowed to stand in hot 1:1 HNO3 for
at least 15 min and preferable overnight. The high reading dishes are fused with a small
amount of K2S2O7 (potassium pyrosulfate), washed in tap water and then placed in 1:1
HNO3 as above.
When ready to use the dishes, rinse with tap water, then distilled water and dry over a
flame. Select three dishes at random and run blank determinations. If one or more show
a reading above a normal blank, reclean the entries batch.
C. Standardization.
The quantity of U in the samples is determined from a calibration curve. The

standards are prepared by pipetting suitable portions of standard U solutions onto
platinum dishes and treating as described in Determination. A new calibration is run
each time a fresh bottle of NaF is put into use. For calibration, four standards are used in
each instrument range. The dilutions are always made fresh from solutions A, B, and C
described above. The median net meter readings from triplicate aliquots are plotted
against the quantity of U to give the calibration curve or the slope of the straight line
obtained is used as calibration factor for sample analyses.
Background fluorescence reduces the accuracy of the analysis at very low

concentrations (1-10 :g L-1). High concentrations (over 1000 :g) are usually diluted
prior to analysis to prevent saturation of the fluorescence in the bead.

DATA PROCESSING
The net median value of the triplicate results is used to determine the micro grams of
U in the sample. The U values corresponding to the meter reading are calculated using
the standardization factors for the instrument (see Note 4).
The following equation is used for calculating the :g L-1.
(DR - B) F = :g L-1
where
D = the meter deflection of the sample,

R = the meter range (1, 10, or 100),
B = the meter deflection of the blank (always on the 1 scale), and
F = the factor in :g U L-1 per unit deflection for the meter range used.
Since the fluorimeter is set to a fixed value for the glass standard (27 on the 100 scale
for 2700 :g U L-1), F is normally unity. This may vary slightly from time to time on the
1 and 10 scales.
Notes:
1. The NaF should not be allowed to stand open to the air since it is hygroscopic.
2. Tongs should not be used to hold the dishes in the flame as the flux tends to run
toward the cold spot. Using the loop, a uniform bead confined to the depression will
be produced.
3. After fusion, allow the dish to cool for at least 10 min and not more than 30 min
before reading.
4. The whole problem of quenching is one that has not been satisfactorily explained or
investigated particularly at extremely low levels of U concentration. It is known that
colored ions will produce quenching, but the degree must be determined for each
sample. Experimentally, there appears to be no quenching of U fluorescence in urine

samples and quenching in general is minimized when pure NaF flux is used, rather
than mixtures.
REFERENCE
Giovanni, H. J. D., R. T. Graveson, and B. Dwork

“Photofluorimeters for Determination of Uranium and Be Concentration”
New York Operations Office Report NYO-4508, U. S. Atomic Energy Commission
(1954)

Section 4.3.3, Vol. II Rev. 0
4.3.3 Multielemental Analyses

M-01
CADMIUM AND LEAD IN HUMAN EXCRETA AND COMPOSITE DIET SAMPLES -

ATOMIC ABSORPTION SPECTROMETRY
APPLICATION
This procedure is applicable to biological matrices such as: composite diet and
excreta samples and also, orchard leaves, bovine liver, pine needles, tomato leaves,
spinach, and fish homogenate.
The samples are wet ashed using high purity HNO3 or are dry ashed. Cadmium and
Pb are determined by graphite furnace atomic absorption (AA) spectrometry without
extraction or matrix modification.
SPECIAL APPARATUS
1. Atomic absorption spectrometer - Perkin-Elmer Model 603 equipped with a 2100

heated graphite atomizer (HGA), a deuterium-arc background corrector and a strip
chart recorder.
2. Sub-boiling quartz distillation apparatus - Quartz & Silice Societe, Rue D'Anjou,
Paris (Quartz Products Corp., Plainfield, NJ).
3. This procedure was developed and performed in a positive pressure laminar air flow
clean room laboratory.

SPECIAL REAGENTS
1. High purity mineral acids - "Suprapur", EM Laboratories, Inc.
2. Commercially available Cd and Pb AA standards, 1000 :g mL-1 diluted to

appropriate concentrations in the presence 32% HNO3, i.e., Spex Industries, Inc.
SAMPLE PREPARATION
A. General.
1. All glassware and polyethylene containers are cleaned before use as follows: soak in
2% tetrasodium ethylene-diamine tetra-acetate solution for 12 h, thoroughly rinse
with tap water, soak in 1:1 reagent grade HNO3 for 12 h, rinse at least three times
with demineralized water then air dry.
2. Approximately 10% of the total samples prepared should be reagent blank samples
which contain equivalent amounts of the reagents used in the preparation procedure.
B. Urine (wet ashing).
1. Transfer 25 mL of concentrated HNO3 into a 1000-mL heavy walled Pyrex beaker.
2. Slowly, add a 750-mL aliquot of a 2-L urine sample into the beaker (see Note 1).
Caution - sample may effervesce or froth over beaker if acid is added to urine.
3. Evaporate the aliquot on a hot plate at a low heat until the entire sample is added to
the beaker and the volume is reduced to ~ 100-150 mL.
4. Add 25 mL of concentrated HNO3 to the sample, cover with a watch glass, and digest
on low heat; evaporate the sample to dryness.
5. Repeat Step 4 until the residue is completely white.

6. Dissolve the sample residue with 12.5 mL of concentrated HNO3 and 150-200 mL
deionized-distilled water. Heat to boiling on medium heat. Cool to room
temperature.
7. Transfer the sample to a 250-mL volumetric flask, dilute to volume and mix. Discard
the residue.
8. Store the sample in a polyethylene container.
9. Measure the sample for Cd and Pb by graphite furnace AA spectrometry (see

Determination).
C. Composite diet and feces (dry ashing).
1. Transfer a 250-g sample into a 400-mL heavy walled Pyrex beaker (see Note 1).
2. Place sample in a drying oven at 110oC until completely dry, ~ 24 h.
3. Place sample in a cold muffle furnace, slowly increase the temperature from
100-430 ± 20oC (do not exceed 450oC). Ash at 430oC for 24-60 h. Cool to room
temperature.
4. Moisten the ash with deionized-distilled water and 5 mL of concentrated HNO3. Dry
the residue on a low heat.
5. Place the sample in a cold muffle furnace, slowly increase the temperature to 430oC
and maintain for 12 h. Cool to room temperature.
6. Dissolve the sample with 12.5 mL of concentrated HNO3 and 150-200 mL deionized-
distilled water. Heat to boiling for 10 min. Cool to room temperature.
7. If a residue is present, filter the sample through a Whatman No. 42 filter paper, which
has been previously washed with 5% HNO3 and deionized-distilled water. Collect
the filtrate in a 250-mL volumetric flask, dilute to volume and mix. Discard the
residue.

8. Store the sample in a polyethylene container.
9. Measure the sample for Cd and Pb by graphite furnace AA spectrometry (see

Determination).
D. Other biological materials (dry ashing).
The above dry ashing procedure is applicable to the other biological samples. Use
desired amounts and proceed as described in Steps 1-9 above.
DETERMINATION
1. Prepare the AA spectrometer for graphite furnace analyses.
2. The Perkin-Elmer 603 AA spectrometer and the HGA 2100 graphite furnace
instrumental parameters are as follows:

____________________________________________________________________________
Element Cd Pb
____________________________________________________________________________
Light source Hollow Cathode Lamp Hollow Cathode Lamp

Lamp current, mA 6 10
Wavelength, nm 228.8 283.3
217.0*
Slit setting, nm 0.7 0.7
D2 background corrector yes yes
Graphite tube uncoated uncoated
Purge gas/flow Ar/7.5 mL min-1 Ar/7.5 mL min-1
Gas flow mode interrupt interrupt
Dry 100oC/50-100 sec 100oC/50-100 sec
Char 250oC/20 sec 250oC/20 sec
Atomize 2100oC/5 sec 2220oC/5 sec
Working standard range 5-25 pg 100-500 pg
50-250 pg*
Standard and sample
aliquot 25-50 :L 25-50 :L
___________________________________________________________________________
*Most sensitive Pb wavelength.
3. Dilute the sample solutions such that the Cd or Pb concentrations are within the
standard ranges given above. Typical starting dilutions are as follows:
____________________________
Cd Pb
____________________________
Urine (1/50) (1/50)

Diet (1/50) (1/50)
Feces (1/100) (1/200)
____________________________

4. Measure the nonspecific absorption of the sample dilutions in the background only
(bkgd) mode on the AA spectrometer to ensure that the manufacturer's recommended
maximum background absorbance is not exceeded.
5. Determine the Cd and Pb concentrations directly on the AA spectrometer, except for

Pb in urine (see Step 6 below). The following steps apply to each trace metal:
a. Measure the prepared standards in the AA/bkgd mode and establish the linear
response range for Cd or Pb. A minimum of three readings is made for each
standard or sample.
b. Enter the concentration value for the highest standard from the linear response
found in Step a into the S-1 concentration mode on the spectrometer.
c. Set the mean absorbance obtained for this standard as the calibrating standard, S-1.
The instrument is now calibrated for direct concentration readings.
d. Use the other prepared standards and any available reference standards to check
for the accuracy of the calibration.
e. Measure the same size aliquots of the diluted samples as for the standards and the
prepared blank samples to obtain direct Cd and Pb concentrations under optimum
conditions.
f. Check the calibration periodically using the prepared standards; if necessary,

recalibrate as described in Step c.
g. Calculate the Cd and Pb concentrations in the original sample by correcting for

any blank contributions then multiplying by the appropriate dilution factors.
6. Determine the concentration of Pb in urine by the method of standard additions (see

Note 2):
a. Take three aliquots of the sample solution. Dilute one as described in Step 3
above. To the second and third aliquots, respectively, add a known quantity of Pb
equivalent to once and twice the absorbance values found for the diluted sample

alone. (The absorbance responses for the sample plus the additions must be linear.)
b. Measure each solution and obtain mean absorbances.
c. Plot these absorbance readings against the added concentrations.
d. Extrapolate the resulting straight line through zero absorbance (see Figure 1).
e. Obtain the Pb concentration in the diluted sample from the intercept on the
concentration axis.
f. The prepared blank samples are measured as described in Step 5 above.
g. Calculate the Pb concentration in the original sample by correcting for any blank
contributions then multiplying by the appropriate dilution factors.
Notes:
1. Smaller amounts of diet and human excreta may be used for the determination of Cd
and Pb by graphite furnace AA. This procedure was developed for large sample sizes
to accommodate aliquoting for several other investigations of the same sample.
2. The method of standard additions is required to compensate for the matrix

interferences observed for the direct determination of Pb in urine. Figure 1 illustrates
the Pb suppression effects found for several urine samples.
The LLD for this procedure is estimated to be about 10 :g L-1 for Cd and 20 :g L-1
for Pb.

Figure 1. Calibration curve for aqueous lead standards and urine standard-addition.

M-02
PRECIPITATION AND LAKE WATER SAMPLES -

PHYSICAL AND CHEMICAL MEASUREMENTS
INTRODUCTION
The physical and chemical parameters in precipitation and lake water samples are
measured directly with a number of instruments. Some of the measurements are
described here, while the determination of trace metals and anions may be found in other
procedures in this Manual (see Anions-01-E and M-03). The measurements described
here are: conductivity, pH, Na, Mg, K, and Ca. If both pH and conductivity measure-
ments are to be made on the same sample aliquot, the conductivity measurement must be
made first.
Conductivity Measurements
APPLICATION
This procedure has been applied to precipitation and lake water samples. The
specific conductance (reciprocal of the electrical resistance) is measured using a
conductivity cell and conductivity bridge.
SPECIAL APPARATUS
1. Conductivity bridge (available from chemical supply companies, e.g., Barnstead

Model PM-70CB).

2. Conductivity cell (available from chemical supply companies, e.g., Yellow Springs
Institute Model 3417, cell constant 1.0 cm-1).
3. Disposable polystyrene beakers, 50 mL (available from chemical supply companies,

e.g., Fisher 02-544-38).
SPECIAL REAGENTS
1. 0.02M KCl: dissolve 1.4912 g of KCl in 1 L of water. This solution has a specific
conductance of 294 :S.
2. High purity water (2-20 MS resistance).
DETERMINATION
1. Prepare several standards ranging from 10-294 :S by serial dilution of the 0.02M
KCl stock solution.
2. Immerse the conductivity cell for 3-5 min in at least 20 mL of high purity water that
is contained in a 50-mL disposable beaker. The cell should not touch the plastic
beaker. At least 20 mL of solution is necessary for accurate measurement.
3. Remove the cell from the water and dry using a tissue. Care should be taken not to
touch the cell with bare hands, which can adversely affect subsequent measurements.
4. Measure each standard, rinsing with deionized water, and drying the cell after each
reading. Start with the multiplier knob of the conductivity bridge at the :S X1
position. If the reading is off scale, use a higher multiplier scale position until the
meter is on scale. Null the meter using the digital switch. The conductivity reading
is the product of the digital switch valve and the multiplier scale setting.
5. Plot the conductance readings obtained in Step 4 against their expected conductances.
The plot will be a straight line and can be described by the equation:

y = mx + b (1)
where m is the slope of the line, x the expected conductance, y the conductivity meter
reading, and b the y-intercept. The intercept represents the specific conductance of
the deionized water. If m is between 0.9-1.1, proceed to Step 6. If m is outside this
range, the conductivity cell electrode should be replatinized according to the
manufacturer's instructions.
6. Measure each sample, rinsing with deionized water and drying the cell after each
reading.
7. For each conductivity reading (y), compute the specific conductance (x) using
Equation 1, and intercept value (b) calculated in Step 5.
Note:
All solutions must be at room temperature prior to measurement. At least 20 mL of

each solution should be available for each measurement. The conductivity cell should be
stored in deionized water when not in use.
pH Measurements
APPLICATION
This procedure is applicable to precipitation and lake water samples. The low ionic
strength (often <20 :S conductance) and poor buffering capacities of these samples
require precautions in calibration and handling of the electrode to obtain accurate pH
values.
The pH of a solution is measured using either glass sensing and reference electrodes
or a combination electrode coupled to a pH meter.

SPECIAL APPARATUS
1. pH meter (available from chemical supply companies, e.g., Orion Research Model
901).
2. Combination sensing/reference electrode (available from chemical supply companies,

e.g., Orion Research Model 810200).
3. Glass sensing electrode (Orion Research Model 4153-H30; A. H. Thomas).
4. Reference electrode (Orion Research Model 4153-40; A. H. Thomas).
5. Disposable polystyrene beakers, 50 mL (available from chemical supply companies,

e.g., Fisher Scientific 02-544-38).
SPECIAL REAGENTS
1. Buffer solution, 4.00 ± 0.02; potassium acid phthalate (available from chemical
supply companies, e.g., Fisher Scientific SO-B-101).
2. Buffer solution, 5.00 ± 0.02; potassium acid phthalate (available from chemical
supply companies, e.g., Fisher Scientific SO-B-102).
3. Buffer solution, 7.00 ± 0.02; potassium phosphate monobasic (available from

chemical supply companies, e.g., Fisher Scientific SO-B-112).
4. Water, high purity (2-20 MS).
DETERMINATION
1. Rinse the electrode thoroughly with the high purity deionized water. Dry the tip by
gently dabbing it with a tissue. Great care should be taken to prevent scratching the
electrode surface.

2. Check to see that the internal filling solution (3M KCl) is within ~ 1 cm of the fill
hole. If not, remove the band and add additional filling solution.
3. Remove the band covering the fill hole. Immerse the electrode in pH 7.00 buffer so
that the solution completely covers the ceramic frit and the electrode does not touch
the plastic beaker. (Twenty milliliters of sample in a 50-mL disposable plastic beaker
is necessary for accurate measurements.)
4. To calibrate the meter, turn the Mode Switch on the Model 901 meter to pH. Set the
Standard Value Switch to read the value of the buffer. The meter will display the
response in mV. Wait until the reading on the unit stabilizes (the value should not
vary more than 0.1 mV in a 1-min interval). Then press the Set Concentration
button on the right of the meter. The meter will now display the value of the buffer to
four significant figures, 7.000.
5. Carefully rinse the electrode with deionized water and dry.
6. Immerse the electrode in the pH 4.00 buffer solution.
7. Allow the pH reading to stabilize; the reading should vary no more than ± 0.002 pH
units in a 1-min interval. Using the Slope Switch, adjust the pH reading to 4.000.
8. Carefully rinse the electrode with deionized water and dry.
9. Immerse the electrode in the pH 5.00 buffer solution.
10. The pH value that is displayed should be 5.000 ± 0.005 and should be stable for
1 min. If these criteria are not met, the entire calibration procedure should be
repeated. If a second attempt does not provide these results, consult both the
electrode and meter manual for further assistance.
11. Proceed to analyze the samples, carefully rinsing and drying the electrode between
each reading. For samples below pH 5.000, the readings should be stable to ± 0.002
pH units in <5 min. Above pH 5.000 and in solutions of low ionic strength (<20 :S

specific conductance), longer periods may be required to achieve a stable reading.

The pH reading should be stable to ± 0.002 pH units before the value is recorded.
12. Measure the pH 5.00 buffer after every five samples are measured. If the value has
changed by more than 0.01 pH units, return to Step 3 and recalibrate.
Note:
At least 20 mL of solution is required for each pH measurement. Although the Orion

Model 810200 combination electrode is designed to accommodate solutions of varying
temperature without significant changes in pH, it is desirable to maintain all solutions at
room temperature. If electrodes other than the Orion Model 810200 are used, changes in
the temperature of the solutions can affect the pH. Store the electrode in pH 5 buffer
with the band covering the fill hole when not in use.
Sodium
APPLICATION
This procedure is applicable for aqueous solutions containing Na in concentrations

from 0.01 :g mL-1 to brines. Sodium is determined directly by atomic absorption (AA)
or atomic emission (AE) spectrometry. A preliminary sample measurement is made to
estimate the concentration range. Standard solutions of similar chemical composition
bracketing this value are prepared within the linear calibration range. Comparison of the
sample to the standards gives the actual Na concentration.
SPECIAL APPARATUS
1. Atomic absorption spectrometer - Perkin Elmer Model 5000 equipped with a

10.5-cm single slot and an air/acetylene atomizer burner or equivalent.
2. Printer.
3. Sodium hollow cathode lamp (Perkin Elmer).

SPECIAL REAGENTS
1. Sodium stock solution (100 :g mL-1) - weigh out 0.254 g of analytical reagent grade
NaCl, dissolve in deionized water and dilute to 1 L in a volumetric flask.
2. Doubly-deionized water must be used throughout for sample preparation and

analyses.
SAMPLE PREPARATION
1. Clean all glassware by rinsing several times with 1:1 HNO3, followed by copious
rinsing with doubly-deionized water.
2. Prepare a series of standard Na solutions ranging in concentration from 0.01-1.6 :g

mL-1.
3. If sample dilution is required, prepare at least two different dilutions of the sample.
DETERMINATION
1. Set up the spectrometer according to the measurement conditions listed in Table 1

(see Procedure M-03).
2. Measure each standard solution and sample a minimum of three times. (Note: Wear
tinted safety glasses while performing this analysis.)
3. Prepare a calibration curve by plotting mean absorbance versus concentration for the
standard solutions.
4. Read off the Na concentration of the sample from the curve.
5. Calculate the Na concentration in the original sample by correcting for any dilutions.

6. Solutions should be analyzed within 24 h of preparation to minimize changes in Na

concentration due to evaporation, contamination, and other effects.
Atomic absorption: Sensitivity: 20 :g L-1

Detection limit: 0.5 :g L-1
Atomic emission: Sensitivity: 5 :g L-1

Magnesium
APPLICATION
This procedure is applicable for aqueous solutions of varying Mg concentrations.

Magnesium is determined directly by AA spectrometry. A preliminary sample
measurement is made to estimate the concentration range. Standard solutions of similar
chemical composition bracketing this value are prepared within the linear calibration
range. Dilution of the sample may be required. Comparison of the sample to the
standards gives the actual Mg concentration.
SPECIAL APPARATUS
Atomic absorption spectrometer - Perkin Elmer Model 5000 equipped with a

10.5-cm single slot, air/acetylene atomizer burner, and a Mg hollow cathode lamp or
equivalent.

SPECIAL REAGENTS
1. Magnesium stock solution (100 :g mL-1) - weigh out 0.100 g of Mg ribbon, dissolve
in a minimum of HCl (<5 mL) and dilute with deionized water to 1 L in a volumetric
flask.

analyses.
SAMPLE PREPARATION
2. Prepare a series of standard Mg solutions ranging in concentrations from

0.01-0.24 :g mL-1.
DETERMINATION
1. Set up the spectrometer according to the measurement conditions listed in Table 1

(see Procedure M-02).
standard solutions.
4. Read off the Mg concentration in the sample from the curve.
5. Calculate the Mg concentration in the original sample by correcting for any dilutions.

6. Solutions should be analyzed within 24 h of preparation to minimize changes in Mg

concentrations due to evaporation, contamination, and other effects.
Sensitivity: 5 :g L-1
Potassium
APPLICATION
This procedure is applicable for aqueous solutions of varying K concentrations.

Potassium is determined directly by AA spectrometry. To reduce the effect of ionization
of the sample in the flame, a substantial excess of Na is added to all standards and
samples. A preliminary sample measurement is made to estimate the concentration
range. Standard solutions of similar chemical composition bracketing this value are
prepared within the linear calibration range. Dilution of the sample may be required if
the sample concentration exceeds the calibration curve range. Comparison of the sample
to the standards gives the actual K concentration.
SPECIAL APPARATUS
1. Atomic absorption spectrometer - Perkin Elmer Model 5000 equipped with a 10.5-cm
single slot, air/acetylene atomizer burner, and a potassium hollow cathode lamp or
equivalent.
2. Micropipette (available from chemical supply companies, e.g., Epperdorf).

SPECIAL REAGENTS
1. Potassium stock solution (100 :g mL-1) - weigh out 0.191 g of oven-dried analytical
reagent grade KCl, dissolve in water and dilute to 1 L in a volumetric flask.
2. Sodium stock solution (10,000 :g mL-1) - weigh out 25.42 g of oven-dried analytical
reagent grade NaCl, dissolve in water and dilute to 1 L in a volumetric flask.

analyses.
SAMPLE PREPARATION
2. Oven-dry a 10-mL volumetric flask for each sample.
3. Pipette 1.0 mL of the 10,000 :g mL-1 Na solution into each 10-mL volumetric flask
and add a known amount of sample, either by pipette or by adding sample to the
calibration mark. Each sample is now in a 1000 :g mL-1 Na matrix.
4. Prepare a 1000 :g mL-1 Na stock by diluting 100 mL of the 10,000 :g mL-1 Na

solution to volume in a 1-L volumetric flask.
5. Prepare a series of standard K solutions ranging from 0.02-0.80 :g mL-1 using a

micropipette for the standard additions and dilute to volume with the 1000 :g mL-1 Na
solution. This 1000 :g mL-1 Na solution is used as the blank in the determination.
DETERMINATION
1. Set up the spectrometer according to the conditions listed in Table 1 (see Procedure
M-03).

3. Correct all standard and sample absorption values for the blank.
4. Prepare a calibration curve by plotting the corrected mean absorbances versus

concentration for the standard solutions.
5. Read off the K concentration of the sample from the curve.
6. Calculate the K concentration in the original sample by correcting for any dilutions.
7. Solutions should be analyzed within 24 h of preparation to minimize changes in

Detection limit: 10 :g L-1
Calcium
APPLICATION
This procedure is applicable for aqueous solutions of varying Ca concentrations.

Calcium is determined directly by AA or AE spectrometry. To reduce the effect of
chemical suppression of the sample in the flame, a substantial excess of La is added to all
standards and samples. A preliminary sample measurement is made to estimate the
concentration range. Standard solutions of similar chemical composition bracketing this
value are prepared within the linear calibration range. Dilution of the sample may be
required if the sample concentration exceeds the calibration curve range. Comparison of
the sample to the standards gives the actual Ca concentration.

SPECIAL APPARATUS
Atomic absorption spectrometer - Perkin Elmer Model 5000 equipped with a 10.5-cm
single slot, air/acetylene atomizer burner, and a Ca hollow cathode lamp or equivalent.
SPECIAL REAGENTS
1. Calcium stock solution (100 :g mL-1) - weigh out 0.25 g of oven-dried analytical
reagent grade CaCO3, dissolve in a minimum of HCl (<5 mL) and dilute to 1 L in a
volumetric flask.
2. Lanthanum stock solution (10,000 :g mL-1) - commercially available through Spex

Industries, NJ.

analyses.
SAMPLE PREPARATION
2. Pipette 1.0 mL of the 10,000 :g mL-1 La solution into each 10 mL volumetric flash
and add a known amount of sample by adding sample to the calibration mark.
3. Prepare a series of standard Ca solutions ranging from 0.06-1.40 :g mL-1.
DETERMINATION
1. Set up the spectrometer according to the conditions listed in Table 1 (see Procedure
M-03).

standard solutions.
4. Read off the Ca concentration in the sample from the curve.
5. Calculate the Ca concentration in the sample by correcting for any dilutions.
6. Solutions should be analyzed within 24 h of preparation to minimize changes in Ca

Atomic Absorption: Sensitivity: 80 :g L-1

Detection limit: 5 :g L-1
Atomic Emission: Sensitivity: 40 L-1

Detection limit: 5 L-1

M-03
TRACE METALS - ATOMIC ABSORPTION AND/OR

EMISSION SPECTROMETRY
INTRODUCTION
This procedure has been used to calibrate carrier solutions used for radiochemical
procedures.
The instrument operational parameters, sensitivities, and limits of detection for a

spectrometer are provided. The following metals, Cs, Rb, K, and Y are described
separately in this procedure.
Atomic Emission Determination of Cesium
APPLICATION
This procedure has been applied to aqueous solutions of varying Cs concentrations.
Cesium is determined directly by AE spectrometry. A preliminary measurement is

made to indicate the range. A large quantity of another alkali metal (1000 mg L-1 K as
KCl) is added to all samples and standards to correct for the large fraction of Cs atoms
that are ionized in the air/acetylene flame. Comparison of the sample to the standards
gives the Cs concentration in the samples.

SPECIAL APPARATUS
1. Atomic absorption spectrometer - Perkin Elmer Model 5000 equipped with 10.5-cm
single-slot air/acetylene atomizer burner or equivalent.
2. Acetylene source.
SPECIAL REAGENTS
1. Cesium stock solution (1000 :g mL-1) - weigh out 1.2670 g of CsCl. Dilute to 1 L
with water.
2. KCl stock solution (10,000 :g mL-1) - weigh out 19.1 g of KCl and dissolve in 1 L of
water.

analysis.
SAMPLE PREPARATION
2. For each sample, add 5 mL of the 10,000 :g mL-1 KCl stock solution to a 50-mL
volumetric flask.
3. Dilute to 50 mL with the sample solution.
4. If further dilutions are required, prepare each so that the K concentration in the final
dilution is 1000 mg L-1.
5. Prepare a minimum of two final dilutions per sample of different concentrations.

6. In a similar manner, prepare a series of Cs standard solutions that bracket the

concentration range of the samples. All standards and final dilutions now contain at
least 1000 mg L-1 K.
DETERMINATION
1. Set up the spectrometer for the flame emission spectroscopic determination of Cs

according to the conditions listed in Table 1.
2. Measure each standard solution and the final sample dilutions a minimum of two
times.
3. Prepare a calibration curve by plotting the mean emission value versus concentration
for the standard solutions.
4. Read the Cs concentration from the curve.
5. Calculate the Cs concentration in each sample value by correcting for all dilutions.
Sensitivity: 0.10 :g mL-1

Detection Limit: 0.005 :g mL-1
Atomic Emission Determination of Potassium
APPLICATION
This procedure has been applied to aqueous solutions of varying K concentrations.
Potassium is determined directly by AE spectrometry. A preliminary measurement is

made to indicate the range. Comparison of the sample to the standards gives the K
concentration in the samples.

SPECIAL APPARATUS
SPECIAL REAGENTS
1. Potassium stock solution (100 :g mL-1) - weigh out 0.1907 g of KCl and dissolve in
1 L of water.

analysis.
SAMPLE PREPARATION
2. Prepare a series of standard solutions that bracket the range of K concentrations in the
samples.
DETERMINATION
1. Set up the spectrometer for the flame emission spectroscopic determination of K

2. Measure each standard solution and sample dilution a minimum of two times.

for the standard solution.
4. Read the K concentration from the curve.
5. Correct each sample value for dilutions if necessary.
Detection Limit: 0.5 :g L-1
Atomic Emission Determination of Rubidium
APPLICATION
This procedure has been applied to aqueous solutions of varying Rb concentrations.
Rubidium is determined directly by AE spectrometry. A preliminary measurement is

KCl) is added to all samples and standards to correct for the large fraction of Rb atoms
that are ionized in the air/acetylene flame. Comparison of the sample to the standards
gives the Rb concentration in the samples.
SPECIAL APPARATUS
SPECIAL REAGENTS

1. Rubidium stock solution (1000 :g mL-1) - weigh out 1.4150 g of RbCl. Dilute to 1 L
with water.
2. Potassium chloride stock solution (10,000 :g mL-1) - weigh out 19.1 g of KCl and
dissolve in 1 L of water.

analysis.
SAMPLE PREPARATION
2. For each sample, add 5.00 mL of the 10,000 :g mL-1 KCl stock solution to a 50-mL
volumetric flask.
4. If further dilutions are required, prepare each so that the K concentration in the final
dilution is 1000 mg L-1.
6. In a similar manner, prepare a series of Rb standard solutions that bracket the

concentration range of the samples. All standards and final sample dilutions now
contain at least 1000 mg L-1 K.
DETERMINATION
1. Set up the spectrometer for the analysis of Rb by flame emission spectroscopy


times.
from the curve.
4. Read the Rb concentration from the curve.
5. Calculate the Rb concentration in each sample value by correcting for all dilutions.
Detection Limit: 2 :g L-1
Atomic Emission Determination of Yttrium
APPLICATION
This procedure has been applied to aqueous solutions of varying Y concentrations.
Yttrium is determined directly by AA spectrometry. A preliminary measurement is

KCl) is added to all samples and standards to correct for the large fraction of Y atoms
that are ionized in the nitrous oxide/acetylene flame. Comparison of the sample to the
standards gives the Y concentration in the samples.
SPECIAL APPARATUS
single-slot nitrous oxide/acetylene atomizer burner or equivalent.

3. Nitrous oxide source with heating tape around gas regulator.
SPECIAL REAGENTS
1. Yttrium stock solution (1000 :g mL-1) - weigh out 1.27 g of Y2O3. Dissolve in a
minimum volume of HCl and dilute to 1 L with water.
2. KCl stock solution (10,000 :g mL-1) - weigh out 19.1 g of KCl and dissolve in 1 L of
water.

analysis.
SAMPLE PREPARATION
2. For each sample, add 5 mL of the 10,000 :g mL-1 KCl stock solution to a 50-mL
volumetric flask.
4. If further dilutions are required, prepare each sample so that the K concentration in
the final dilution is 1000 mg L-1.
6. In a similar manner, prepare a series of Y standard solutions that bracket the

concentration range of the samples. All standards and final sample dilutions now
contain at least 1000 mg L-1 K.

DETERMINATION
1. Set up the spectrometer for the flame emission spectroscopic determination of Y

using the conditions listed in Table 1.
times.
3. Prepare a calibration curve by plotting the mean absorption value versus

concentration for the standard solutions.
4. Read the Y concentration from the curve.
5. Calculate the Y concentration in each sample value by correcting for all dilutions.

Detection Limit: 200 :g L-1

TABLE 1
TRACE ELEMENT ANALYSIS BY ATOMIC ABSORPTION OR
ATOMIC EMISSION SPECTROMETRY OF TRACE METALS
Source
Mode Flame Gases Wavelength Slit HCl (mA)*, Sensitivity LLD
Element (AA or AE) (Press./Press.) Modifier (nm) (nm) EDL (W)** (:g mL-1) (:g mL-1)
Al AA N+ - 60/40 - 309.3 0.7 HCL:10 0.500 0.100

Ca AA A++ - 30/60 - 422.7 0.7 HCL:20 0.080 0.005
AE A++ - 30/60 - 422.7 0.7 - 0.040 0.005
AA A++ - 30/60 1000 mg L-1 La 422.7 0.7 HCL:20 0.040 0.002
AE A++ - 30/60 1000 mg L-1 La 422.7 0.7 - 0.020 0.002
AA N+ - 60/40 - 422.7 0.7 HCL:20 0.060 0.005
AE N+ - 60/40 - 422.7 0.7 - 0.030 0.005
Co AA A++ - 35/60 - 240.7 0.2 HCL:20 0.200 0.040
Cd AA A++ - 35/60 - 228.8 0.7 HCL:10 0.020 0.002
Cu AA A++ - 30/60 - 324.7 0.7 HCL:15 0.050 0.005
Cs AE A++ - 35/60 1000 mg L-1 K 852.1 4.0 - 0.100 0.005
Fe AA A++ - 35/60 - 248.3 0.2 HCL:20 0.100 0.020
K AA A++ - 35/60 1000 mg L-1 Na 766.5 4.0 HCL:12 0.040 0.010
AE A++ - 35/60 - 766.5 4.0 - 0.002 0.0005
Mg AA A++ - 35/60 - 285.2 0.7 HCL:10 0.005 0.0005
Mn AA A++ - 35/60 - 279.5 0.2 HCL:10 0.040 0.004
Na AA A++ - 35/60 - 589.0 1.4 HCL:8 0.020 0.0005
AE A++ - 35/60 - 589.0 1.4 - 0.005 0.0005
Ni AA A++ - 35/60 - 232.0 0.2 HCL:20 0.100 0.020
Pb AA A++ - 35/60 - 217.0 0.7 HCL:10 0.200 0.040
AA A++ - 35/60 - 217.0 0.7 HCL:10 0.200 0.040
AA A++ - 35/60 - 283.3 0.7 HCL:10 0.400 0.060
AA A++ - 35/60 - 283.3 0.7 HCL:10 0.400 0.060
Rb AE A++ - 35/60 1000 mg L-1 K 780.0 4.0 - 0.030 0.002
Se AA A++ - 35/60 1000 mg L-1 Ni 196.0 2.0 ELD:5W 0.400 0.100
Sr AA A++ - 35/60 1000 mg L-1 La 460.7 0.14 HCL:20 0.200 0.040
V AA N+ - 60/40 - 318.4 0.7 HCL:35 0.400 0.100
Zn AA A++ - 30/60 - 213.9 0.7 HCL:15 0.020 0.002
Y AA N+ - 60/40 1000 mg L-1 K 410.9 0.2 HCL:30 2.00 0.200
*HCL = hollow cathode lamp

**EDL = electrodeless discharge lamp
Notes:
N+ = N2O/C2H2
A++ = Air/C2H2
Sensitivity: The concentration of the element being analyzed in :g mL-1 that generates 1% absorption (0.0044
absorbance units).
Detection Limit: The concentration of the element being analyzed in :g mL-1 that generates a signal equal to twice the
instrument background noise level.

4.5 RADIOCHEMICAL
4.5.1 SCOPE
Described in this section are the radiochemical procedures currently not in use at EML.
These procedures have been constantly updated for the past 40 years to reflect current
separation technology and measurement techniques. The radiochemical procedures are
usually written for a distinct environmental matrix since chemical interferences and
contamination levels vary according to sample type.

4.5.4 Radiochemical

Americium

Am-03-RC
AMERICIUM IN WATER, AIR FILTERS, AND TISSUE
APPLICATION
This procedure is applicable to the determination of americium in tissues, air filters

and water samples.
Americium is leached from the sample and simultaneously equilibrated with 243Am
tracer. Americium is collected with a calcium oxalate coprecipitation and isolated and
purified by organic extraction and ion exchange. The americium is electrodeposited on a
platinum disc and the 241Am plus tracer 243Am are resolved by " spectrometry.
SPECIAL APPARATUS
1. Virgin platinum discs - 17.6 mm ID x 0.00127 mm mirror finish on one side.
2. Plating cells - see Specification 7.16, Vol. I.
3. Electrolysis electrode - see Specification 7.15, Vol. I.
4. Electrodeposition apparatus - see Specification 7.16, Vol. I.
5. Ion exchange columns - see Specification 7.5 and Procedure Pu-11-RC, Vol. I.
6. Solid-state " spectrometer - see Procedure A-01-R, Vol. I.

SPECIAL REAGENTS
243
1. Am tracer solution, about 0.2 Bq g-1 in dispensing bottle.
2. Calcium carrier solution, 40 mg Ca mL-1 - dissolve 236 g Ca(NO3)2A4H2O in

2.4M (15%) HNO3 and dilute to 1 L.
3. Iron carrier solution, 10 mg Fe mL-1 - dissolve 143 g Fe(NO3)3 in 0.16M (1%) HNO3
and dilute to 1 L.
4. Oxalic acid wash solution - dissolve 10 g oxalic acid in 1 L of H2O, adjust pH to 3.0.
5. Bio-Rad AG 1-x4 resin (100-200 mesh) - see Specification 7.4, Vol. I.
6. 50% HDEHP (Di(2-ethylhexyl)phosphoric acid) - dissolve 500 mL HDEHP in

500 mL of toluene.
7. 0.1M HCl/0.85M (5%) NaCl solution - dissolve 50 g NaCl in 1 L of H2O containing

8 mL of HCl.
8. 60% ethanol in 2.4M HNO3 solution - mix 600 mL of ethanol with 400 mL of 6M
HNO3 slowly. Store in a cool place.
9. 75% methanol in 1.5M HNO3 solution - slowly mix 750 mL of methanol with
250 mL of 6M HNO3. Store in a cool place.
10. Methyl red indicator solution - dissolve 100 mg of methyl red in 65 mL of ethanol
and dilute to 100 mL with H2O.

SAMPLE PREPARATION
A. Air filters.
1. Place a glass fiber filter in a 100 mL Teflon beaker. Add a known amount (between
0.01 - 0.02 Bq) of 243Am tracer solution, and 1 mL of Fe carrier solution.
2. Add about 30 mL of HNO3 and enough HF to dissolve the glass fiber filter. Wet
ash the sample with HNO3.
3. Evaporate the solution to near dryness on a medium temperature hot plate. Remove
the beaker from the hot plate, cover and cool to room temperature.
4. Dissolve any residue in a minimum of HCl and dilute to about 30 mL with H2O.
5. Transfer the sample solution to a 90 mL centrifuge tube with H2O. Adjust the pH to
8 with NH4OH.
6. Centrifuge the sample at 1500-2000 rpm for 15 min. Decant and discard the
supernate.
7. Dissolve the precipitate in HNO3. Transfer the solution to a 250-mL beaker with
H2O. Proceed to Determination.
B. Water.
1. Transfer 1 L of H2O to a 1500-mL beaker. Add a known amount (between 0.01 -

0.02 Bq) of 243Am tracer solution and 1 mL of iron carrier solution. Evaporate the
sample to near dryness. Wet ash with HNO3.
2. Add 100 mL of HCl and transfer the sample to a 250 mL beaker. Evaporate the
solution to near dryness on a medium hot plate.
3. Dissolve any residue in a minimum of HCl and dilute to about 30 mL with H2O.

4. Transfer the sample solution to a 90 mL centrifuge tube with H2O. Adjust the pH to
8 with NH4OH.
5. Centrifuge the sample at 1500-2000 rpm for 15 minutes. Decant and discard the
supernate.
6. Dissolve the precipitate in HNO3. Transfer the solution to a 250-mL beaker with
H2O. Proceed to Determination.
C. Tissue.
1. Weigh 20 g of freeze-dried tissue into a 1 L beaker. Add a known amount (between

0.01 - 0.02 Bq) of 243Am tracer solution.
2. Add 300 mL of HNO3 and wet ash with HNO3 and H2O2 until all organic matter is
eliminated.
3. Evaporate the solution to near dryness. Remove the beaker from the hot plate, cool
and place in magnetic stirring bar in the beaker.
4. Add 8 mL of calcium carrier solution to the sample solution. Place the beaker on a
magnetic stirrer/hot plate and heat gently with stirring.
5. Dilute the solution to 400 mL. Add 18 g (or 45 g L-1) of granular oxalic acid, and
stir to dissolve the oxalic acid.
6. With stirring, adjust the pH to 3.2 with NH4OH. Stir for an additional 20 min.
7. Remove the beaker from the stirrer/hot plate. Cool the sample for at least 1 h in a
cold water bath.
8. Filter the precipitate by gravity through a 24 cm diameter Whatman No. 42 filter

paper. Wash the precipitate with oxalic acid wash solution. Discard the filtrate and
washings.
9. Return the filter to the 1L beaker and wet ash with HNO3.

10. Repeat the precipitation, filtration and wet ashing, (Steps 6 to 10) until the filtrate is
colorless.
11. Transfer the sample solution to a 250-mL beaker and evaporate to dryness.
12. Dissolve any residue in a minimum of HCl and dilute to about 200 mL. Adjust the
pH to 8 with NH4OH.
13. Warm the beaker and gently filter the precipitate through a 12.5 cm Whatman No.
42 filter paper. Wash the precipitate with H2O and discard the filtrate.
14. Return the filter to the beaker and wet ash with HNO3. Proceed to Determination.
DETERMINATION
1. Prepare a 15 mL resin column by conditioning with 150 mL of 8M HNO3 (see

Note).
2. Dissolve the sample residue in 20 mL of HNO3 and add 20 mL of H2O. Stir and add
200 mg of NaNO2 to the sample. Heat the beaker gently until the evolution of
nitrogen oxides ceases.
3. Cool the beaker to room temperature. Pass the sample solution through an ion
exchange column. Collect the column effluent in a 250-mL beaker.
4. Wash the beaker with a 25-mL portion of 8M HNO3 and pass the wash through the
column. Collect the washings in the 250 mL beaker. Repeat the washings three
more times. Evaporate the combined sample effluent and washings to dryness.
5. Wet ash the residue with 10 mL of HNO3, convert to HCl, and dissolve the residue
in 40 mL of HCl.
6. Prepare a 15 mL resin column by conditioning with 150 mL of HCl.

7. Pass the sample through the column. Collect the effluent in a 250 mL beaker.
Wash the column with 100 mL of HCl. Evaporate sample solution to dryness.
Discard the resin.
8. Wet ash the residue with 10 mL of HNO3.
9. Dissolve the residue in 15 mL of HNO3 with gentle heating. Cool for 1/2 h in a cold
water bath.
10. Adjust the pH of the solution to 3.0 by slowly adding NH4OH (~10 mL) with
stirring.
11. Transfer the sample solution to a 250 mL separatory funnel. Add 100 mL of 50%
HDEHP in toluene to the separatory funnel and shake for 5 min.
12. Allow the phases to separate. Drain the aqueous (lower) phase into a 250 mL
beaker and discard.
13. Wash the organic phase twice with 60 mL of 0.1 M HCl/0.85 M NaCl solution.
Shake for 5 min, allow the phases to separate. Drain and discard the aqueous
(lower) phase.
14. Add 30 mL of HCl to the separatory funnel. Shake the funnel for 5 min, allow the
phases to separate (~1 h). Collect the aqueous (lower) phase in a clean 250-mL
beaker. Discard the organic phase.
15. Evaporate the solution to dryness and wet ash with 10 mL of HNO3.
16. Dissolve the sample residue in 12 mL of 6M HNO3 with heating. Cool the beaker
for 0.5 h in a cold water bath. Add 18 mL of ethanol and stir.
17. Prepare a 15 mL resin column by conditioning with 150 mL of 60% ethanol in 2.4M
HNO3 solution.

18. Pass the sample through the column. Collect the effluent in a 250 mL beaker.
19. Wash the column with 60 mL 75% in 1.5M HNO3 solution. Discard the effluent
and washings.
20. Place a clean 250 mL beaker below the column. Elute the americium with 60 mL of
4M HNO3. Discard the resin.
21. Evaporate the sample solution to dryness and wet ash in HNO3 with H2O2.
22. Evaporate the sample solution to dryness and electroplate according to

Electrodeposition of the Actinides: Mitchell Method, Procedure G-01, Vol. I.
LIMIT OF DETECTION
Yield (%) 60
Blank (cps) -
LLD (400 min) mBq 1.3

LLD (5000 min) mBq 0.15
Note:
Preparation of ion exchange columns. Position a plug of glass wool at the base of
the column. Rinse the column with 130 mL of H2O. Transfer 15 mL of wet, settled Bio-
Rad AG 1-X4 resin (100-200 mesh) to the column, and allow it to settle. Place a second
plug of glass wool on top of the resin and allow the water level to reach the top of the
upper plug. Condition with the appropriate reagents.

Am-05-RC
AMERICIUM IN WATER AND AIR FILTERS
APPLICATION
This procedure is applicable to water and air filters. Americium and plutonium
tracers are added to the sample and a procedure for plutonium, appropriate to the matrix,
is followed. The last step in each procedure will be the ion-exchange technique for the
purification of plutonium (see Procedure Pu-11-RC, Vol. I). The eluate from Step 4 is
combined with the eluate from Step 8. Americium is coprecipitated with calcium
oxalate, followed by coprecipitation with iron hydroxide. The acidified iron hydroxide
solution is loaded onto an ion-exchange column to assure a complete removal of any
traces of plutonium, followed by another ion-exchange column designed to remove iron.
The eluate from the last column is evaporated, converted to HCl and microprecipitated on
NdF3 and the americium isotopes measured by " spectrometry.
SPECIAL APPARATUS
1. Ion-exchange columns - see Specification 7.5, Vol. I.
SPECIAL REAGENTS
243
1. Am tracer solution, about 0.2 Bq g-1, in a dispensing bottle.
2. Bio-Rad AG 1-X4 resin (100-200 mesh) - see Specification 7.4, Vol. I.
3. Bio-Rad AG 1-X8 resin (50-100 mesh) - see Specification 7.4, Vol. I.

4. Calcium carrier solution, 100 mg Ca mL-1 - dissolve 25 g CaCO3 in a minimum of

HNO3 and dilute to 100 mL.
5. Iron carrier solution, 10 mg Fe mL-1 - slowly heat 100 g of iron powder in 50 mL

HCl until reaction ceases. Carefully and slowly add 10 mL HNO3 while stirring.
Cool and dilute to 1 L.
6. Oxalate wash solution, dissolve 10 g of oxalic acid (H2C2O4A2H2O) to make 1 L of

solution 0.06M(1%).
7. Aerosol OT, 0.1% solution.
8. Hydroxylamine hydrochloride, solid (NH2OH@HCl).
SAMPLE PREPARATION
1. Combine eluates from Steps 4 and 8 from Pu-11-RC, Vol. I, in a beaker. Evaporate
to dryness. Place a magnet stirring bar in the beaker. Dissolve the residue in 5 mL
of 8M HNO3, add 45 mL H2O and stir while heating gently.
2. Add 1 mL of Ca carrier solution (100 mg Ca) and 2.5 g (50 g L-1) of granular oxalic
acid to the sample.
3. Adjust the pH of the solution to 2.5-3.5 with NH4OH. Continue to stir the solution
for 30 min. Remove the beaker from the stirrer/hot plate. Remove the magnetic
stirring bar from the beaker.
4. Let the sample stand overnight or for more than 6 h at room temperature. Check for
completeness of precipitation using a drop of saturated oxalic acid solution.
5. Aspirate (or decant) as much liquid as possible without disturbing the precipitate.
Transfer precipitate to a 250 mL centrifuge bottle using oxalate wash solution.
Balance the bottles on a double pan balance and centrifuge for 10 min at 2000 rpm.
Add 1 drop of 0.1% aerosol OT to the centrifuge bottle. Decant and discard the
supernate.

6. Break up the precipitate with a stirring rod and wash the precipitate with 100 mL of
oxalate wash solution. Centrifuge the sample for 10 min at 2000 rpm.. Decant and
discard the wash.
7. Repeat Step 6.
8. Dissolve the precipitate in a minimal amount of HNO3. Transfer the solution with
H2O to a 150 mL beaker. Wet ash the sample with HNO3 to destroy the oxalate ion.
9. Dissolve the sample residue in 5 mL of 8M HNO3 and transfer to a 40-mL

centrifuge tube with H2O. Dilute the solution to 25 mL. Warm the solution in a 90o
hot water bath and add 1 mL iron carrier solution (10 mg Fe).
10. Adjust the pH of the solution to 8-9 with NH4OH while stirring with a glass rod.
Allow solution to digest in the hot water bath for 20 min.
11. Cool the centrifuge table in a cold water bath, rinse and remove the glass rod.
Centrifuge the sample tube for 10 min at 2000 rpm.
12. Add 1 drop of 0.1% aerosol OT to the centrifuge tube. Decant the solution and
discard the supernate. Add 5 drops HCl to dissolve the Fe(OH)3 pellet followed by
25 mL H2O. Stir and heat the solution in a hot water bath.
13. Repeat Steps 10, 11 and 12 three times. Dissolve the final precipitate in 8M HNO3.
14. Transfer the solution to a 250 mL beaker. Rinse the tube with 8M HNO3 and add
the rinse to the beaker. Evaporate the solution to dryness on a hot plate. Add 20
mL 8M HNO3 to the beaker and evaporate to dryness.
15. Dissolve the residue immediately in 40 mL 8M HNO3. Cool the beaker to room
temperature in an ice-water bath. Add 0.6-1.0 g NH2OHAHCl to the sample. Swirl
to dissolve the solid. Allow 15 min reaction time at room temperature. Heat on low
temperature hot plate to decompose the unreacted NH2OHAHCl. Then boil gently
for 1-2 min. Cool the solution.

16. Prepare a 10 mL resin column by conditioning with 100 mL of 8M HNO3 (see Note
1).
17. Adjust the flow rate of the sample through the column to ~0.5 mL min-1. Collect the
effluent in a 400 mL beaker. Wash the column with 150 mL 8M HNO3 and
combine with the sample effluent in the 400 mL beaker. Discard the resin.
18. Evaporate the sample to dryness and convert to the Cl with HCl. Dissolve the final
residue in 30 mL of HCl.
19. Prepare a 10 mL resin column by conditioning with 100 mL of 12 M HCl

(see Note 2).
20. Pass the sample through the chloride column collecting the effluent in a 250 mL
beaker. Wash the column with 100 mL of HCl, and combine with the effluent in the
250 mL beaker. Discard the resin.
21. Evaporate the sample solution to dryness. Dissolve the residue in 1-2 mL 1M HCl.
22. See Procedure G-03, Vol. I, for microprecipitation source preparation for "
spectrometry.
23. Submit the sample for " spectrometry measurement.
Notes:
1. Preparation of 8M HNO3 Column. Position a plug of glass wool at the base of a

small column (i.d. 11 mm). Transfer 10 mL of wet settled Bio-Rad AG-X8 resin
(50-100 mesh) to the column and allow it to settle. Place a second plug of glass
wool on top of the resin, and with the stopcock open allow the H2O to reach the
level of the upper plug. Condition the resin with 100 mL of 8M HNO3, passed
through the resin bed in 50-mL portions. Allow the level of each portion to reach
the top of the upper plug. The conversion of the resin is complete if the effluent
from the column tests negative for Cl- using a dilute silver nitrate solution.

2. Preparation of HCl Column. Position a plug of glass wool at the base of a small
column (i.d. 11 min). Transfer 10 mL of wet settled Bio-Rad AG-X4 resin
(100-200 mesh) to the column and allow it to settle. Place a second plug of glass
wool on top of the resin, and with the stopcock open allow the H2O level to reach
the level of the upper plug. Pass two 50 mL volumes of HCl through the resin bed
and allow each to reach the level of the upper plug.
DATA PROCESSING AND ANALYSIS
For " spectrometry measurements, see A-01-R, Vol. I.
LIMIT OF DETECTION
Yield (%) 60
Blank (cps) -

LLD (5000 min) mBq 0.15

Tritium

3
H-01-RC, Vol. II Rev. 0
3
H-01-RC
TRITIUM IN WATER - ACID ELECTROLYSIS
APPLICATION
This procedure is applicable to liquid water samples obtained by distillation. The

lower limit of detection is 20 3H units (T.U. = 0.12 Bq) or about 2.5 Bq L-1 for a 100 min
count. If the 3H content is lower than 15-20 T.U., Procedure 3H-02 may be used, but acid
electrolysis procedure is much faster for 3H activities >30 T.U.
This is a modification of the procedure developed by Frank Cosalito of New York

University. The sample is completely distilled in the presence of KMnO4 to eliminate
solids and organic matter. The sample is then enriched by electrolysis in an acid medium
(H2SO4) at high current for about 40 h to reduce the initial volume of 50 mL to about
6-8 mL. The final volume is determined on a known aliquot by titration of the H2SO4.
The activity of the sample is determined on an aliquot by liquid scintillation counting.
The degree of 3H enrichment is determined by a calibration of enrichment against volume
reduction.
SPECIAL APPARATUS
1. Electrolysis cells - see Specification 7.20, Vol. I.
2. Vacuum distillation apparatus.
3. Liquid scintillation counter.

3
SPECIAL REAGENTS
1. Scintillation solution - Aqua Fluor (Packard Instrument Co., 2200-T Warrensville

Rd., Downers Grove, IL 60515).
2. Standardized 0.02M NaOH solution - dissolve 0.8g NaOH in 1 L of H2O.
3. Phenolphtalein indicator solution - 0.1%.
SAMPLE PREPARATION
A. Liquid samples.
1. Transfer a measured volume of sample to a 1000 mL distillation flask (not more

than 800 mL at one time) and add about 1 g of KMnO4.
2. Distill to dryness, then bake the distillation flask.
3. Store the distilled sample in an air-tight container until ready for enrichment.
B. Two-phase systems.
Filter the sample, then treat the filtrate as in Liquid Samples, or freeze-dry the
sample and treat the water collected as a liquid sample.
DETERMINATION
A. Enrichment.
1. Pipette 50 mL of sample and 0.7 mL of H2SO4 into an electrolysis cell. Mix well.
Prepare two standard tritiated H2O (HTO) solutions and two blanks (low 3H content
H2O) in the same way for each batch of samples.

3
2. Withdraw a 1 mL aliquot and dilute to 10 mL with water in a volumetric flask.

Reserve for determination of the initial H2SO4 normality as required for measuring
the volume reduction factor.
3. Place the electrolysis cells in a cell holder in a cooling bath maintained between 2
and 3oC.
4. Connect the electrolysis cells to a constant current power supply, observing proper
polarity.
5. Adjust the current to 3 A and electrolyze until the volume is reduced to ~ 6 mL

(electrolysis proceeds at ~ 1 mL h-1).
6. When the electrolysis is completed, place stoppers on the cells and seal the capillary
glass tubes holding the electrodes with putty or similar material to avoid exchange
of the enriched sample with atmospheric moisture.
7. Transfer a 1 mL aliquot of the enriched sample to a 10 mL volumetric flask and

dilute to 10 mL with water. Reserve this solution to determine the final volume.
8. Set up the electrolysis cell for vacuum distillation with a trap to collect the distillate.
9. Cool the trap in liquid N2, connect the vacuum, and completely distill the enriched
sample from the cell.
B. Measurement.
1. Pipette a suitable aliquot (usually 2 mL) of the distillate into a polyethylene liquid
scintillation vial containing 15 mL of scintillator solution.
2. Load the samples into the counter and allow to adapt to dark and cool.
3. Set counter controls for optimum counting conditions.

3
4. With each batch of samples, count two standards prepared from a NIST tritiated
H2O standard. The counting efficiency is determined by the channel ratio and
external standard counting techniques.
5. Count samples, standards, and blanks at least twice each. Subtract the blank count
rate, compute the counter efficiency and calculate the activity for the total sample.
C. Volume determination.
1. Transfer the two volumetric flasks reserved as in the Enrichment Section to

individual 125 mL Erlenmeyer flasks.
2. Dilute with water to about 15-20 mL, washing down the sides of the flask, and add
three or four drops of phenolphthalein indicator solution (0.1%).
3. Titrate with standardized 0.02M NaOH solution to a permanent pink end point.
(Between 15 and 20 mL of NaOH will usually be required.)
4. Calculate the initial and final concentrations of H2SO4.
D. Tritium enrichment factor.
The degree of 3H enrichment is proportional to the volume reduction, but not equal
to it. Thus, the enrichment factor must be determined as a function of the volume
reduction. This is best done with standard samples of moderate activity.
Prepare a series of electrolysis cells with aliquots of a known amount of HTO

standard, and electrolyze to a range of volume reductions covering those expected in
sample analyses. Carry these through the complete analysis described in Determination.
The volume reduction factor is,
Vf
X=
Vi

3
where Vf and Vi are the initial and final H2SO4 normalities.
The enrichment factor is,
Cf
Y=
Ci
where Cf and Ci are the initial and final 3H concentrations. If the values of X and Y
determined from the standards are plotted, a straight line relationship should hold. The
initial 3H concentration can then be calculated from the measured volume reduction
factor and the measured final 3H concentration.


3
3
H-02-RC
TRITIUM IN WATER - ALKALINE ELECTROLYSIS
APPLICATION
This procedure has been applied to liquid samples obtained either by total
distillation or by freeze-drying followed by distillation. The lower limit of detection is
two 3H units (T.U. = 0.12 Bq L-1), about 0.25 Bq L-1 for a 100 min count. If the 3H
content is higher than 15-20 T.U., Procedure 3H-01-RC may be used.
This is a modification of the procedure developed by Ostlund and Werner (1962).

The sample is completely distilled in the presence of KMnO4 to eliminate solids and
organic matter. The sample is then enriched by electrolysis in a basic medium (NaOH) at
high current until the total sample volume (normally 250 mL) has been reduced by a
factor of 10. The current is then decreased and the electrolysis is continued to reduce the
volume by an additional factor of 5 to 10. The final volume is measured by total
distillation directly from the electrolysis cell. The 3H activity is determined on an aliquot
by liquid scintillation counting. The degree of 3H enrichment is determined by a
calibration of enrichment against volume reduction.
SPECIAL APPARATUS
1. Electrolysis cells - see Specification 7.20, Vol. I.
2. Vacuum distillation apparatus.
3. Liquid scintillation counter.

3
SPECIAL REAGENT
Scintillation solution - Aqua Fluor (Packard Instrument Co., 2200-T Warrensville

Rd., Downers Grove, IL 60515).
SAMPLE PREPARATION
A. Liquid samples.
1. Transfer the sample to a 1000 mL distillation flask (not more than 800 mL at one
time) and add about 1 g of KMnO4.
2. Distill to dryness, then bake the distillation flask. (Many samples with appreciable
impurities in the original material will require a second distillation.)
3. Store the distilled sample in an air-tight container until ready for analysis.
B. Two-phase systems.
Filter the sample, then treat the filtrate as in Liquid Sample, or freeze-dry the
sample and treat the H2O collected as a liquid sample.
DETERMINATION
A. Enrichment.
1. Add about 400 mg of NaOH (two average size pellets) and 5-10 mL of the sample
to a clean electrolysis cell. Shake until the pellets are completely dissolved.
2. Add more sample to make the volume ~ 50 mL.
3. Insert the iron and nickel electrode assembly (the tips of the electrodes should
almost touch the bottom of the well in the cell). Stopper the cell and make sure the
leads to the electrodes are outside the closure.

3
4. Place the cell in a cell holder in a cooling bath maintained between 2 and 4oC.
5. Connect the electrolysis cell to a constant current power supply, observing proper
polarity.
6. Adjust the current to 3 A and electrolyze until the volume is reduced to 25 mL.
7. Add another 25 mL of sample and repeat these additions until all of the sample has
been added to the cell (electrolysis proceeds at ~ 1 mL h-1). The volume after the
final addition should be reduced to 25 mL.
8. Reduce the current to 0.3 A and continue the electrolysis until the volume is
2.5-4 mL. (This step typically takes 8-9 days.)
9. Discontinue the electrolysis and keep the cells closed and in the cooling bath until
ready to distill. Immediately prior to distillation, bubble CO2 gas through the
sample for 3-5 min.
10. Set up the electrolysis cell for vacuum distillation with a tared trap to collect the
distillate.
11. Wrap a length of heating tape around the body of the electrolysis cell and connect it
to an autotransformer.
12. Apply the vacuum and distill the bulk of the sample, cooling the trap in liquid N2.
13. Increase the applied voltage so as to heat the body of the cell progressively to
~ 150oC, and continue the distillation.
14. After about 2 h, switch off the heating current, still applying the vacuum and
keeping the trap immersed in liquid N2.
15. Disconnect the vacuum pump, remove the collection trap, thaw, and weigh.
16. Reconnect to the vacuum distillation apparatus and repeat Steps 13-15 until no
further weight increase occurs.

3
B. Measurement.
1. Pipette a suitable aliquot (usually 2 mL) of the distillate into a polyethylene liquid
scintillation vial containing 15 mL of scintillator solution.
2. Load the samples into the counter and allow to adapt to dark and cool.
3. Set counter controls for optimum counting conditions as determined from standards.
4. With each batch of samples, count two standards prepared from a NIST tritiated
H2O standard. Efficiency is also checked with the channel ratio and external
standard counting.
5. With each batch of samples, 10% of the measurements should be performed using
blanks prepared from low HTO H2O.
6. Count samples, standards, and blanks at least twice each. Subtract the blank count
rate, compute the counter efficiency and calculate the activity for the total sample.
C. Tritium enrichment factor.
The degree of 3H enrichment is proportional to the volume reduction, but not equal
to it. Thus, the enrichment factor must be determined as a function of the volume
reduction. This is best done with standard samples of moderate activity.
Prepare a series of electrolysis cells with aliquots of a known standard and

electrolyze to a range of final volumes covering those expected in sample analyses.
Carry these through the complete analysis described above.

3
The volume reduction factor is,
Vf
X=
Vi
where Vi and Vf are the initial and final volumes, the enrichment factor is,
Cf
Y=
Ci
where Cf and Ci are the initial and final 3H concentrations. If the values of X and Y
determined from the standards are plotted, a straight line relationship should hold. The
initial 3H concentration can then be calculated from the measured volume reduction
factor and the measured final 3H concentration.

REFERENCE
Ostlund, H. G. and E. Werner

"The Electrolytic Enrichment of Tritium and Deuterium for Natural Tritium
Measurements"
in: Tritium in Physical and Biological Sciences
International Atomic Energy Agency, Vienna (Ref. No. I-95-104) (1962)

3
3
H-03-RC
ORGANICALLY LABELED TRITIUM - COMBUSTION PROCEDURE
APPLICATION
A combustion procedure is described for the quantitative conversion of organically

labeled 3H to tritiated water. The procedure is applicable to biological samples including
vegetation, foods, and tissues.
The determination of the 3H specific activity of organic materials requires

quantitative combustion to prevent the buildup of pyrolysis products and resulting
isotope effects. The solution to this problem is provided by slow combustion in a
specially designed chamber with a controlled atmosphere. Argon and O2 of ultra-high
purity are used for combustion. The water is collected in a manifold consisting of a
series of traps immersed in a dry ice-alcohol mixture and liquid N2.
SPECIAL APPARATUS
The combustion train consists of: 1) a gas purification system with traps containing
molecular sieve (Figure 1); 2) a gas-heated combustion chamber (Figure 2); and 3) a
collection manifold (Figure 3).
The purification system (Figure 1) consists of separate traps for Ar and O2 which
contain a Linde 4A molecular sieve. This gives a final purification and drying step
before mixing the gases and admission to the combustion tube. In various periods of the
combustion, the gases are used separately and in a 1:1 mixture.

3
The valve system allows for evacuation of the system, introduction of other gases or
transfer to the combustion chamber. A 76 cm -0- 76 cm compound gauge indicates the
pressure in the purification system.
The combustion chamber (Figure 2) consists of an inconel tube 135 cm x 7.6 cm

with O-ring flanges on each end. The O-rings are protected by cooling coils of 1 cm
copper tubing wound around each end as near to the flange as possible. The coils are
connected in series to a cold water tap, and the O-rings are maintained at about room
temperature throughout a combustion. The exit end of the chamber contains 30 cm of
CuO in the form of a large plug prepared from copper wire sandwiched between tightly
wound plugs of rolled heavy copper screen. The screen is rolled so that the plugs require
forced fitting to provide good mechanical support for the finely divided copper wire.
Once in place the wire screen is oxidized to CuO by burning at red heat in air.
Two Meker burners heat the CuO zone and three burners are used under the sample
combustion area. The rest of the inconel tube is covered with Siltemp nonasbestos
thermal barrier.
Throughout any series of combustion runs, it is advisable to maintain the CuO at

700 C. Also, one burner is kept on between runs to maintain the temperature at 450oC.
o
This procedure minimizes shrinkage and settling of the plug, which can lead to
channeling and incomplete combustion. The CuO temperature is monitored by a
thermocouple inserted into the middle of the plug.
The collection manifold (Figure 3) consists of a series of traps for removing H2O.
The three H2O removal traps are immersed in a dry ice-alcohol mixture.
The vacuum pump is capable of evacuating to 0.01 Pa of Hg. A liquid N2 cold trap
is used in the vacuum line to assure that this pressure can be reached.

3
SAMPLE PREPARATION
Freeze-dry a weighed sample and reserve the H2O fraction for 3H analysis.
Compress the residue into pellets weighing up to 60 g in a 2.5 cm diameter pelleting
press. The compression is required to control the combustion process. Store the pellets
in a desiccator. Combustion of about 100 g is required to produce 50 mL of water.
DETERMINATION
A. Combustion procedure.
System preparation.
1. Close valves 1, 3, 4, and 5 (see Figures 1 and 3). Open valve 2 to the vacuum line,
crack valve 3, and pump down the combustion tube. (Too rapid evacuation may
shift the CuO plug.) Open valve 3 all the way and pump for 5-10 min.
2. Close valve 2 and admit the argon slowly to atmospheric pressure, opening valve 1
and the argon tank valve. Close valve 1.
3. Pump down the collection system by opening valve 8, with all other valves closed,
then open valves 7, 9, and 11. Crack valve 6 and complete pumping down the
collection system to full vacuum (about 10-4 0.01 Pa).
4. Close valve 9. Place the dry ice-alcohol mixture around the H2O traps and liquid N2
around the CO2 traps. Continue pumping the system between valves 5 and 9.
5. Bring the CuO section of the combustion tube to 700oC with the two burners.
Combustion.
1. Transfer about 50 g of pelletized sample to a 5 cm x 2 cm x 30 cm combustion boat

lined with 60 mesh alundum.

3
2. Open the flange on the combustion tube and insert the boat as quickly as possible so
that it butts against the CuO plug. Close the combustion tube. The sample is now
in an Ar atmosphere.
3. Crack valve 5 and wait for the pump to start gurgling, using the gauge on the
combustion tube as a guide. Continue pumping throughout the combustion. Wait
5-10 min before proceeding.
4. Open the O2 valve to obtain a 1:1 mixture of O2 and Ar. Slowly crack valve 1 and
allow the gas mixture gauge pressure to drop about 1.25 cm. This is equivalent to a
flow of 0.5 to 1 L min-1.
5. Light the burner nearest the entrance end of the combustion tube. Bring the tube to
red heat in this area and continue heating until the pressure rises. Control pressure
to 56 cm vacuum or more by reducing the gas flow or removing from the burner.
6. When the pressure drops, light the middle burner, and follow the procedure in
Step 5.
7. When the pressure drops, light the third burner, close off the Ar supply and continue
combustion with O2, following the procedure in Step 5.
8. Continue combustion until the pressure attains a minimum and begins to rise. After
15-30 min, the pump should begin to gurgle and the thermocouple in the CuO plug
should rise, indicating reoxidation of the plug. Allow O2 to flow an additional
15-30 min and then close valves 1, 3, 5, 6, and 7. The water should now be retained
in the trap.
B. Tritium collection.
Collect and measure the volume of water in the three water traps. Determine HTO
directly or after enrichment as described in Procedure 3H-01-RC or 3H-02-RC.

3
Figure 1. Gas purification system.

3
Figure 2. Combustion chamber.

3
Figure 3. Collection manifold.

Plutonium

Pu-02-RC
PLUTONIUM IN SOIL SAMPLES
APPLICATION
The plutonium deposited from worldwide fallout and from some nuclear activities
can be completely leached with the treatment described. The total dissolution technique
may be used for any soil sample.
Plutonium isotopes are leached and equilibrated with 236Pu tracer with HNO3 and
HCl from soil samples up to 1 kg in size. An alternate technique for soil samples of 20 g
or less involves total dissolution and equilibration with 236Pu tracer using HNO3, HCl, and
HF. The sample is purified by an ion-exchange method, then electrodeposited on a
platinum disc. The plutonium isotopes are measured by " spectrometry.
SPECIAL APPARATUS
1. Double vented conical gravity funnels - i.e., Fisher Scientific - 10-381.
2. Polyethylene dispensing bottle - see Specification 7.11, Vol. I.
SPECIAL REAGENTS
1. Plutonium-236 tracer - a standard solution containing 0.2 Bq g-1 in a dispensing

bottle. The purity of the tracer is measured by " spectrometry.
2. Standardized 0.1N NaOH.

3. Phenolphthalein indicator - dissolve 500 mg of reagent in 100 mL of 95% ethanol.
DETERMINATION
A. Leach method.
1. Weigh up to 1 kg of prepared soil into an appropriate sized beaker. Add a weighed

amount of 236Pu tracer solution (~ 0.05 Bq) from the dispensing bottle.
2. Place a glass stirring rod in the beaker and cover with a watch glass. Immerse the
beaker in an ice water bath. Cautiously add 900 mL (for a 1 kg sample) or 300 mL
(for a 100 g sample) of concentrated HNO3. Control sample foaming by the
addition of from 1-20 drops, as needed, of n-octyl alcohol. When the reaction
ceases, cautiously add 300 mL (for a 1 kg sample) and 100 mL (for a 100 g sample)
of concentrated HCl. Do Not Stir. Remove the beaker from the ice water bath,
allow the sample to stand at room temperature for 2-4 h, then gradually heat the
sample on a low temperature hot plate overnight. The temperature should be high
enough so that refluxing occurs and HCl will evaporate out.
3. Allow the mixture to cool and settle, add a sufficient amount of deionized water to
provide an 8N HNO3 solution, then filter through an appropriate sized No. 42
Whatman paper on a Büchner funnel. Wash the residue consecutively with 100 mL
of 8N HNO3. Collect the filtrate and transfer to an appropriate sized beaker (3 L for
a 1 kg sample or a 1 L for a 100 g sample).
4. Transfer soil residue and filter back to the original beaker. Add concentrated HNO3
to completely cover the residue. Allow the mixture to react at low heat on a hot
plate for 3-6 h to completely ash the paper and repeat Steps 2 and 3. (If sample is
highly organic, Step 2 may have to be repeated a third time.)
5. Evaporate the filtrate from Step 3 to reduce the sample volume.
6. Repeat Steps 2-5 at least twice. The leaching is complete when the soil appears to
be white to gray in color. Discard the soil residue (save for Total Dissolution
Method).

7. Evaporate the combined leachates to about 300 mL; cover with a watch glass and
boil to oxidize any remaining organic matter under refluxing conditions.
8. Continue to boil and add concentrated HNO3 in 10-20 mL increments as needed to

maintain the volume at ~ 100-300 mL, to avoid salting out, until all organic material
is decomposed. If a precipitate is observed, SiO2 or TiO2 is present in the sample.
A yellow granular precipitate indicates the presence of TiO2 and a F- collection of
plutonium has to be performed. For the F- collection, follow the 12 steps in Note 1.
A white or gray flocculent indicates the presence of SiO2, and in this case treatment
with HF and HNO3 is necessary in the following steps.
9. Add an equal volume of water and filter the SiO2 precipitate through a Whatman
No. 42 filter paper by gravity. Wash the precipitate with 1:1 HNO3, collect the
filtrate in a beaker and reserve.
10. Transfer the filter and precipitate to the original beaker and ash the paper with
concentrated HNO3. Then transfer to a platinum dish with 8N HNO3, add 10 mL of
HF and 5-10 mL of HClO4 and place on a low heat hot plate in a hood and evaporate
to near dryness.
11. Cool, add 5-20 mL of concentrated HNO3 and 5-20 mL of concentrated HF to the
residue in the platinum dish. Evaporate to near dryness and repeat the addition of
acids and evaporations one to three times depending upon the amount of SiO2
present.
12. Evaporate to dryness slowly. Dissolve the residue with 8N and evaporate to dryness
two to four times. Dissolve the SiO2 with 8N HNO3 and filter through Whatman No.
42 paper and combine filtrates with filtrates of Step 9. Discard the precipitate.
13. Evaporate the combined solution very carefully at a low heat to about 50-200 mL.
Cool to room temperature.
14. Dispense two 100-:L aliquots into 150-mL beakers containing 25 mL of water. Add
two to three drops of 0.5% phenolphthalein solution. Titrate the two aliquots with
standardized 0.1N NaOH to the phenolphthalein end point. Calculate the acid

normality of the sample solution; adjust to 8N if necessary. Sample is now ready for
ion-exchange separation.
B. Total dissolution method.
1. Weigh from 1-20 g of prepared soil into an appropriate sized beaker. Add a
weighed amount of 236Pu tracer solution (~ 0.5 Bq) from the dispensing bottle.
2. Place a glass stirring rod in the beaker, cover with a watch glass and immerse the
beaker in an ice bath. Cautiously add 60-150 mL of concentrated HNO3. Control
sampling foaming by the addition of a few drops of n-octyl alcohol. When the
reaction ceases, cautiously add 20-50 mL of concentrated HCl. Do Not Stir.
Remove the beaker from the ice bath, allow the sample to stand at room temperature
for 2-4 h then gradually heat the sample on a low temperature hot plate overnight.
The temperature should be high enough so that refluxing occurs, making sure to boil
off all traces of HCl.
3. Allow the mixture to cool and settle, then dilute to ~ 8N HNO3 with water. Filter the
soil residue onto a Whatman No. 42 filter paper. Wash the precipitate with 8N
HNO3 making sure all traces of Ca are removed. Collect the filtrate in a 400-mL
beaker and reserve.
4. Transfer the filter and soil residue to the original beaker and wet ash with 100-300
mL of concentrated HNO3. Transfer contents to an appropriate sized platinum dish.
5. Add 5-25 mL of concentrated HF to the soil residue in the platinum dish. Evaporate
to dryness at low heat to prevent bumping and repeat the additions of HF and
evaporations at least three more times, making sure the residue is reduced to at least
a tenth of the original amount.
6. Follow Steps 11-14 of Leach Method.
See Plutonium Purification - Ion Exchange Technique, Procedure Pu-11-RC, Vol. I.

ELECTRODEPOSITION
See Electrodeposition of the Actinides: Mitchell Method, Procedure G-01, Vol. I.
Note 1: Fluoride Collection of Plutonium
1. Cool the solution to room temperature and transfer to a 500-mL Teflon beaker with
water.
2. Add 1 g of hydroxylamine hydrochloride and stir until dissolved. Let it stand at

room temperature for ~ 10 min.
3. Add 10-mL portions of HF with stirring until all of the TiO2 precipitate dissolves,
then add 10 mL of HF in excess.
4. Add 100 mg of purified Y carrier solution.
5. Allow the F- precipitate to stand for 1 h.
6. Transfer the precipitate and solution to several 90-mL polyethylene centrifuge tubes
and centrifuge for 5 min. Discard the supernate.
7. Stir the precipitate with a plastic stirring rod in each centrifuge tube thoroughly with
10 mL of 1:1 HNO3 and 10 mL HF, and let stand for about 5 min. Remove the
plastic stirring rod and wash with water.
8. Centrifuge for 5 min and discard the supernate.
9. Add 30 mL of saturated boric acid solution, stir, and add 25 mL of HCl to each
centrifuge tube. Stir with plastic stirring rod to dissolve.
10. Transfer and combine the solutions from the centrifuge tubes in the original Teflon
beaker.

11. Add 1 g of boric acid and evaporate to near dryness. Dissolve with 25 mL of
concentrated HCl and 25 mL of concentrated HNO3. Boil off HCl by two additions
of 25 mL of concentrated HNO3.
12. Evaporate to ~ 25 mL. Cool and dilute with water to 8N HNO3 and proceed to
Plutonium Purification - Ion Exchange Technique, Procedure Pu-11-RC, Vol I.

Yield (%) 75

LLD (1000 min) (mBq) 0.5
LLD (5000 min) (mBq) 0.2

Pu-04-RC
PLUTONIUM IN TISSUE
APPLICATION
This procedure has been applied to the analysis of tissue samples of up to 50 g wet
weight. Larger samples should only require adjustment of reagent quantities in the
sample preparation.
The tissue sample is wet ashed with HNO3 and H2SO4 and plutonium is collected
with Fe(OH)2. Plutonium is then separated by ion exchange and electrodeposited or
microprecipitated for " spectrometry.
SPECIAL REAGENTS
1. Ion exchange columns - see Specification 7.5, Vol. I.
2. Double-vented conical gravity funnels (Fisher No. 10-381).
3. Special apparatus for electrodeposition or microprecipitation for "-spectrometry

measurement are listed under Procedures G-01 and G-03, Vol. I.
SPECIAL REAGENTS
236
1. Pu tracer, ~ 0.2 g-1 - a standard solution is contained in a dispensing bottle. The
purity of the tracer is determined by " spectrometry.

2. Iron carrier, 100 mg Fe mL-1 - slowly heat 100-g of iron wire in 500-mL of HCl
until reaction ceases. Carefully and slowly add 50-mL of HNO3 while stirring.
Cool and dilute to 1 L.
3. Standard 0.1N NaOH.
4. 0.4N HNO3 - 0.01N HF eluting agent.
5. Anion exchange resin, Bio-Rad AG 1-X4 (100-200 mesh).
6. Methyl red indicator solution - dissolve 100 mg of the dye in 65 mL of C2H5OH and
dilute to 1 L with water.
7. Phenolphthalein indicator solution - dissolve 100 mg of the dye in 65-mL of

C2H5OH and dilute to 1 L with water.
SAMPLE PREPARATION
A. Soft tissue.
1. Weigh out the soft tissue samples as received into a 1-L beaker. Add a weighed
amount of 236Pu tracer (0.02-0.04 Bq) to each sample from a dispensing bottle.
2. Place a glass stirring rod in the beaker and cover with a watch glass. Cautiously
add 100 mL of HNO3 and 100-mL of H2SO4. Immediately place the beaker in an
ice water bath to control the reaction, then allow the sample to stand at room
temperature overnight.
3. Place the beaker on a low temperature hot plate. Completely wet ash the tissue by
periodic additions of HNO3 and gradually increase the hot plate temperature to
medium then high until dense SO3 fumes are evolved. Note: This must be done
cautiously to avoid bumping. Cool to room temperature.
4. Wash down the sides of the beaker and the cover glass with the minimum amount of
water, then heat the sample until dense SO3 fumes are evolved again. If organic

removal is incomplete, add HNO3 dropwise at a temperature near the point of SO3
evolution. Cool to room temperature.
5. Add 300 mL of 1:3 HCl, heat the solution to boiling and boil for 10 min. Cool to
room temperature. Add 100 mg of Fe carrier solution.
6. Neutralize the solution with NH4OH and adjust to pH 8. Filter by gravity using
double vented conical funnels through a 24 cm Whatman No. 41 filter paper. Wash
the precipitate with 1:20 NH4OH solution. Discard the filtrate.
7. Transfer the paper and precipitate to the original beaker. Add 100 mL of HNO3,
cover with a watch cover and heat on a medium temperature hot plate until the filter
is decomposed.
8. Add 200 mL of water and repeat Step 6. Transfer the paper and precipitate to the
original beaker. Add 200 mL of HNO3, cover with a watch cover and evaporate to
~ 100 mL. Repeat the addition and evaporation three times.
9. While still hot, immediately add an equivalent volume of water and filter by gravity
through a 15-cm Whatman No. 40 filter paper. Wash the precipitate with 1:1 HNO3
and collect the filtrate in a 1-L beaker and reserve. Transfer the paper to a 100-mL
platinum dish, dry at 110oC and ignite at 600oC.
10. Add 25 mL of HNO3 and 10 mL of HF to the residue in the platinum dish and
evaporate to dryness. Repeat the addition and evaporation.
11. Add 25 mL of HNO3 and 5 mL of HClO4 and evaporate to dryness. Dissolve the
residue with 1:1 HNO3 and combine with the reserved filtrate from Step 9.
12. Evaporate the solution to ~ 100 mL. Cool to room temperature, transfer to a 250-
mL graduated cylinder and record the volume.
13. Dispense a 100-µL aliquot into each of two 150-mL beakers containing 25 mL of
water. Add two to three drops of 0.5% phenolphthalein end point. Calculate the

14. Transfer the sample from the graduated cylinder to the original beaker. Wash the
graduated cylinder with the amount of water necessary to adjust the normality of the
sample solution to 8N HNO3.
B. Bone.
1. Weigh out the bone samples as received into a 1-L beaker. Add a weighed amount
of 236Pu tracer (0.02-0.04 Bq per sample).
2. Place a glass stirring rod in the beaker and cover with a watch glass. Add 100 mL
of HCl and 25 mL of HNO3. Allow the sample to stand overnight at room
temperature.
3. Place the sample on a medium temperature hot plate, bring to a boil and boil for
5 min. Add 100 mL of water and filter the sample by gravity through a 15-cm
Whatman No. 40 filter paper. Wash the filter with ~ 100 mL of water. Collect the
filtrate in a 1-L beaker and reserve.
4. Transfer the filter to a 100-mL platinum dish, dry at 110oC and ignite at 600oC.
Reserve the residue in the platinum dish.
5. Add 100 mg of Fe carrier solution to the reserved filtrate. Dilute the water to
~ 500 mL. Continue the procedure as described in Steps 6-14 of Sample
Preparation.
See Plutonium Purification - Ion Exchange Technique, Procedure Pu-11-RC, Vol. I.


Yield 75
Blank (cps) -
LLD ( 400 min) (Bq) 0.0007

LLD (1000 min) (Bq) 0.0003
LLD (5000 min) (Bq) 0.0002

Pu-05-RC
PLUTONIUM IN TISSUE - SOLVENT EXTRACTION
APPLICATION
This procedure has been applied to tissue samples (Fisenne and Perry, 1978).
Plutonium in tissue is equilibrated with 242Pu tracer during wet ashing with NO3 and
HF. The plutonium is separated by solvent extraction with Aliquat-336 from an HNO3
medium. The plutonium is electrodeposited onto a platinum disc and the plutonium
isotopes are resolved by solid-state " spectrometry. (Note: The isolated plutonium may
be prepared for " spectrometry using the Microprecipitation Procedures, G-03, Vol. I).
SPECIAL APPARATUS
See Eletrodeposition of the Actinides: Talvitie Method, Procedure G-02, Vol. I.
SPECIAL REAGENTS
242
1. Pu tracer solution - about 0.1 Bq g-1 of solution in a dispensing bottle.
2. Aliquat-336 (methyltricapryl-ammonium chloride) - 3:7 toluene (Henkel

Corporation, 2430 N. Huachuca Dr., Tucson, AZ 85745-1273). Wash four times
with an equal volume of 2N HNO3 and once with an equal volume of 1:1 HNO3.
Prepare 100 mL of acid-washed 3:7 Aliquat-336 for each sample.
3. Calcium nitrate solution - dissolve 6 g of Ca(NO3)2 in 100 mL of 1:1 HNO3.

4. Sodium hydroxide, 0.1N - dissolve 4 g of NaOH in H2O and dilute to 1-L.

Standardize the solution against potassium acid phthalate.
5. Phenolphthalein - dissolve 500 mg of reagent in 100 mL of 95% ethanol.
6. 1N HCl - 0.01N HF.
7. Thymol blue indicator - dissolve 400 mg of reagent in 100 mL of water.
SAMPLE PREPARATION
1. Weigh the soft tissue samples as received, place in a Pyrex dish and cut into 2.5 cm
cubes with a surgical knife. Weigh the bone samples and proceed with Step 2.
2. Place 500 mL of HNO3 in a 1500-mL beaker containing a Teflon-coated magnetic

stirring bar. Add a known amount of 242Pu tracer by weight (1.7-3.3 mBq per
sample) from a dispensing bottle.
3. Place the beaker on a low-temperature magnetic stirrer hot plate. Add the cubed
tissue one piece at a time. When the entire sample has been added to the beaker,
gradually increase the temperature of the hot plate. Continue stirring and complete
the wet ashing with small additions of HNO3. (Hydrogen peroxide may be used to
complete the oxidation if necessary).
4. If any insoluble material remains, filter the sample by gravity through Whatman No.
42 filter paper in a conical funnel. Retain the filtrate in a covered 250-mL beaker.
5. Place the filter in a 100-mL platinum dish or Teflon beaker and ash overnight at
500oC.
6. Cool the platinum dish. Add 25 mL of HNO3 and 10 mL of HF to the residue.

Evaporate to dryness on a high temperature hot plate.

7. Add 25 mL of HNO3 and evaporate to dryness. Repeat the evaporation twice.
8. Dissolve any residue in 1:1 HNO3 and combine with the filtrate from Step 4. If
trace element analyses are required, continue with Step 9. Otherwise, proceed to
Step 12.
9. Evaporate the solution to about 50 mL. Cool to room temperature and transfer to a
100-mL volumetric flask. Wash the beaker with water and transfer the washings to
the flask. Repeat the washings to bring the volume to 100-mL.
10. Mix the sample and remove 1-mL for trace elements analyses.
11. Transfer the solution from the volumetric flask to a 400-mL beaker. Rinse the flask
three times with 25-mL portions of concentrated HNO3 and add the washings to the
beaker.
12. Evaporate the solution to about 100-mL. Add 25 mg of solid NaNO2 and heat to
remove excess nitrite. Cool to room temperature in an ice water bath.
13. Transfer a 10-mL aliquot of the sample into a 150-mL beaker containing 25-mL of
water. Add two to three drops of 0.5% phelophtalein. Titrate the aliquot with
0.1 NaOH to the pink phenolphthalein endpoint. Calculate the normality of the
sample solution.
14. If the normality lies between 8 and 8.7N in HNO3, proceed directly to the
extraction. If the normality is > 8.7, transfer the sample to a 150-mL graduated
cylinder and record the volume. Return the sample to the beaker, add an
appropriate volume of water to the cylinder to reduce the acid concentration to
8.5N. Transfer the water from the cylinder to the sample beaker and proceed with
the extraction.
SOLVENT EXTRACTION SEPARATION
1. Transfer 50 mL of acid-washed Aliquat-336 into each of two 250-mL separatory

funnels. Add 5 mL of Ca(NO3)2 solution to the first separatory funnel.

2. Transfer the sample the first separatory funnel. Wash the beaker with 1:1 HNO3 and
add the washing to the funnel.
the aqueous phase into the second separatory funnel. Retain the organic phase in
the first funnel.
the aqueous phase into the second separatory funnel. Retain the organic phase in
the first funnel.
6. Wash the organic phase twice for 3 min with equal volumes of 1:1 HNO3. Discard
the washings.
7. Wash the organic phase twice for 3 min with equal volumes of HCl. Discard the
washings.
8. Strip the plutonium by washing the organic phase twice for 3 min with an equal
volume of 1N HCl-0.1N HF. Combine the strip solutions in a 400-mL beaker.
Discard the organic phase.
9. Evaporate the solution to near dryness.
10. Add 5 mL of HNO3 and 0.5 mL of H2SO4 to the sample.
11. Evaporate to dense fumes of SO3. Remove any organic material with dropwise
additions of HNO3.
12. Electrodeposition the sample according to Procedure G-02, Vol. I, or

microprecipitate the sample according to Procedure G-03, Vol. I.
13. Measure the plutonium isotopes on an " spectrometry system.


Counter Background (cps) 1.7 x 10-5
Yield 75
Blank (cps) -
LLD ( 400 min) (Bq) 0.65

LLD (1000 min) (Bq) 0.50
LLD (5000 min) (Bq) 0.17
*Reagent blanks must be analyzed with the sample.
REFERENCES
Fisenne, I. M. and P. Perry.

"The Determination of Plutonium in Tissue by Aliquat-336 Extraction"
Radiochem. Radioanal. Letters, 33, 259-264 (1978)
Talvitie, N. A.
"Radiochemical Determination of Plutonium in Environmental and Biological Samples
by Ion Exchange"
Anal. Chem., 43, 1827-1830 (1972)

Pu-06-RC
PLUTONIUM IN URINE
APPLICATION
This procedure has been applied to the analysis of 238Pu and 239,240Pu in urine and in
large-area fallout collectors.
The plutonium in urine is equilibrated with a calibrated 236Pu or 242Pu tracer

solution. The tracer serves as an internal standard, as well as an indicator of the chemical
yield of the other plutonium isotopes. The equilibration is accomplished by treatment
with hydrogen peroxide and HNO3, HCl, HF, and H2SO4 during wet ashing. The
plutonium is separated by a double anion-exchange column technique; first from a HCl
medium, and then from a HNO3 medium. Finally, the plutonium is electroplated onto a
platinum disc or microprecipitated and the plutonium isotopes are resolved by a solid-
state " spectrometer.
SPECIAL APPARATUS
See Electrodeposition of the Actinides: Talvitie Method, Procedure G-02, Vol. I.
SPECIAL REAGENTS
1. Standardized 236Pu tracer solution - about 0.17 Bq g-1 in dispensing bottle.
2. 0.4N HCl - 0.01N HF.
3. 0.4N HNO3 - 0.01N HF.

4. Methyl red indicator solution - dissolve 100 mg of dye in 65 mL of ethyl alcohol

and dilute to 100 mL with H2O.
5. Freshly prepared 5% NaNO2 solution.
6. Bio-Rad AG 1-X4 (100-200 mesh, Cl- from) - see Specification 7.4, Vol. I.
7. Bio-Rad AG 1-X4 (100-200 mesh, NO3 form) - see Specification 7.4, Vol. I.
Convert to NO3 form by washing the resin with 1:1 HNO3 until the washings show
no trace of Cl- when tested with AgNO3.
SAMPLE PREPARATION
1. Transfer a measured amount of urine into a 3-L beaker, rinsing the container and
graduate with HNO3 and H2O. Add an exactly weighed amount (10-80 mBq) of
standardized 236Pu or 242Pu tracer solution.
2. Add 500 mL of HNO3, 25 mL of HCl, 10 mL of 1:1 H2SO4, and a few drops of octyl
alcohol and cover. Allow the mixture to react and heat on a magnetic stirrer hot
plate to decompose organic matter.
3. Evaporate to a small volume, adding 30% H2O2 repeatedly to assist oxidation.

Continue to heat until light SO3 fumes appear or the organic matter begins to char,
then cautiously add a few drops of HNO3 at a time until all organic matter is
completely oxidized.
4. Heat to dense SO3 fumes, cool, and transfer to a 250-mL Teflon beaker with
1:1 HNO3.
5. Add 50-mL of HF and heat to SO3 fumes again. Cool and repeat the addition of HF
and HNO3. Heat to SO3 fumes, cool, and transfer to an 800-mL graduated beaker
with 1:1 HNO3.

6. Heat the solution until salts dissolve. Cool. Add about 1 g hydroxylamine
hydrochloride, stir, then add 1:1 NH4OH to precipitate metallic hydroxides and heat
on a hot plate to coagulate the precipitate.
7. Filter by gravity on a Whatman No. 40 filter paper. Wash thoroughly with 1:10
NH4OH. Discard the filtrate and washings.
8. Transfer the paper and precipitate to the original beaker. Add 200 mL of HNO3 and
5 mL of HCl, and heat until the paper completely oxidizes.
9. Gradually add HCl and evaporate repeatedly to convert to a HCl medium.
10. Heat the HCl solution while covered until constant boiling occurs, assume the
constant boiling HCl solution is ~ 6N HCl. Cool and adjust to 8N HCl by adding
half the sample volume of concentrated HCl.
DETERMINATION
1. Cool the 8N HCl solution to room temperature, then add 3 mL of conditioned

Bio-Rad AG 1-X4 (100-200 mesh, Cl- form resin, and then wash with 2:1 HCl until
all the resin settles (at least 125 mL).
2. Prepare a large ion-exchange column (Specification 7.5, Vol. I) with a glass wool
plug, and about 10 mL of the Cl- form resin, and then wash with 2:1 HCl until all
the resin settles (at least 125 mL).
3. Rinse the cover and sides of the beaker with 2:1 HCl. Decant the solution into the
anion exchange column, then wash the resin inthe beaker into the column with 2:1
HCl. Wash the beaker and column with at least 250-mL of 2:1 HCl. Discard the
effluent and washings.
4. Elute the plutonium from the column into the original beaker with 250-mL of 0.4N
HCl - 0.01N HF solution. Discard the resin.
5. Evaporate the eluate to dryness several times with repeated additions of HNO3.

6. Add 25 mL of 1:1 HNO3 and 0.25 mL of freshly prepared 5% NaNO2 solution.

Heat the solution to boiling, then cool in an ice water bath.
7. Add about 1 mL of the conditioned Bio-Rad 1-X4 (100-200 mesh, NO3 form) resin
in 1:1 HNO3 to the solution and stir.
8. Prepare a small ion-exchange column (see Specification 7.6, Vol. I) with a glass-
wool plug and about 3 mL of NO3 form resin and wash with 1:1 HNO3 until the
resin settles.
9. Rinse the cover and sides of the beaker with 1:1 HNO3. Decant the solution into the
anion exchange column, then wash the resin in the beaker into the column with 1:1
HNO3. Wash the beaker and column with at least 50 mL of 1:1 HNO3. Discard the
effluent and washings.
10. Elute the plutonium from the column into a 150-mL beaker with at least 50 mL of
0.4N HNO3 - 0.01N HF. Discard the resin.
11. Evaporate the eluate to dryness several times with repeated additions of HCl.
12. See Procedures G-02 or G-03, Vol. I, for electrodeposition or microprecipitation for
" spectrometry.


Yield (%) 80
Blank (cps) -
LLD ( 400 min) (mBq) 0.60

LLD (1000 min) (mBq) 0.39
LLD (5000 min) (mBq) 0.17
*Reagent blanks must be analyzed with the samples.

Pu-07-RC
PLUTONIUM IN LARGE URINE SAMPLES
APPLICATION
Urine samples up to 20 L have been processed using this procedure. Reagent blanks
must be analyzed along with the samples. This is a modification of the EML procedure
for tissue, Procedure Pu-04-RC.
SPECIAL APPARATUS AND REAGENTS
Apparatus and reagents are the same as for Procedure Pu-04-RC.
SAMPLE PREPARATION
1. Collect large urine samples in 20-L plastic carboys, or other plastic containers.
2. Transfer a known amount of 236Pu or 242Pu tracer by weight (~ 10 mBq for each
sample) to a 3-L beaker containing 20 mL of 1:1 HNO3.
3. Measure out 1 L of urine with a graduated cylinder and transfer to the beaker. Rinse
the cylinder with 300 mL of HNO3. Carefully add the HNO3 to the beaker, rinse the
cylinder with a small amount of H2O, and add to the sample.
4. Place a glass stirring rod in the beaker to prevent bumping and cover.

5. Place the sample on a medium temperature hot plate and wet ash the urine sample.
When the volume in the beaker is low enough to accommodate more sample, add an
additional liter of urine and 300 mL of HNO3. Repeat until the entire sample has
been wet ashed.
6. At the last stage of wet ashing, salting out occurs. Dissolve the salts by adding
30-100 mL of 30% H2O2 and 100-300 mL of HCl and by heating carefully on a low
temperature hot plate.
7. Wash down the sides of the beaker and the cover glass with H2O. Heat the solution
to boiling and boil for 10 min. Cool to room temperature. Add 100 mg of Fe carrier
solution.
8. Neutralize the solution with NH4OH and adjust to pH 8. Filter by gravity using
double vented conical funnels (e.g., Fisher No. 10- 381) onto a 24 cm Whatman No.
541 filter paper. Wash the precipitate with 5:100 NH4OH. Discard the filtrate.
9. Return the paper and precipitate to the original beaker. Add HNO3 to just cover the
paper and precipitate.
10. Cover the beaker with a watch glass and heat on a medium temperature hot plate
until the filter is decomposed. Evaporate to about 100 mL.
11. Immediately add an equivalent volume of H2O and filter by gravity over an 18.5 cm
Whatman No. 42 filter paper. Wash the precipitate with 1:1 HNO3. Collect the
filtrate in a 1-L beaker and reserve for plutonium determination.
12. Transfer the paper to a 100-mL platinum dish. Dry at 110oC and ignite at 600oC to
oxidize all carbonaceous materials.
13. Cool the dish. Add 25 mL of HNO3 and 10 mL of HF to the residue and evaporate
to dryness.
14. Repeat the addition and evaporation.

15. Add 25 mL of HNO3 and 5 mL of HClO4. Evaporate to dryness. Dissolve the

residue in 1:1 HNO3 and combine with the main solution reserved for plutonium de-
termination.
16. Evaporate the solution to about 100 mL. Cool to room temperature, transfer to a
250-mL graduated cylinder, and record the volume. Reserve the beaker.
17. Dispense two 100-:L aliquots to two 150-mL beakers containing 25 mL of

deionized water. Add two to three drops of 0.5% phenolphthalein. Titrate the two
aliquots with standardized 0.1N to a phenolphthalein end point. Calculate the acid
18. Transfer the sample from the graduated cylinder to the original beaker reserved in
Step 16. Wash the graduated cylinder with the amount of H2O necessary to adjust
the normality of the sample solution to 8N HNO3.
19. Proceed to Plutonium Purification - Ion Exchange Technique, Procedure Pu-11-RC,

(see Vol. I).

Pu-08-RC

NITRIC/HYDROCHLORIC ACID METHOD
APPLICATION
This procedure has been applied to the determination of plutonium isotopes in tissue
and vegetation samples.
The sample is slowly ashed in a furnace at 400oC and then dissolved by the addition
of concentrated HNO3 followed by concentrated HCl. After filtration of the sample, any
remaining residue is further decomposed by the addition of HF.
SAMPLE PREPARATION
1. In an appropriate sized Pyrex beaker weigh out 5-50 g of sample.
2. Place the beaker in a muffle furnace at 100oC for 1 h. Increase the temperature
100oC each hour until a final temperature of 400oC is attained. Continue heating the
sample overnight at this temperature.
3. Turn off the muffle furnace and allow the sample to cool to room temperature.
When cool, remove the sample from the furnace and spike with a known amount
(0.04-0.07 Bq) of 236Pu tracer.

4. Add 150 mL of concentrated HNO3 to the sample slowly, making sure there is no
excessive foaming. Have an ice bath prepared to cool the sample in the event of
excessive foaming. After addition of HNO3, allow sample to react at room
temperature for 15 min. Cover with a watch glass. Heat the sample at a low heat on
a hot plate for 30 min. Slowly, add 50 mL of concentrated HCl, allow to react for
15 min. Then heat overnight on a hot plate at a low heat.
5. Remove the sample from the hot plate, add 150-200 mL of H2O. Allow the sample
to cool to room temperature.
6. Using a Büchner funnel with a Whatman No. 42 filter paper, filter the sample under
reduced pressure. Wash the insolubles with 1:1 HNO3 and then with H2O until the
residue becomes colorless.
7. Transfer the filtrate to the beaker, cover with a ribbed watch glass and evaporate the
solution on a hot plate to ~ 100 mL.
8. Transfer the filter paper containing the residue from the HNO3/HCl digestion to a
platinum dish. Place the platinum dish in a muffle furnace and heat at 100oC, raise
the temperature by increments of 100oC every hour until a final temperature of
400oC is reached. Continue heating at this temperature overnight.
9. Turn off the muffle furnace and let the sample cool sufficiently before removing
from the furnace.
10. Add 15 mL of 1:1 HNO3 and 15 mL of concentrated HF. Heat the sample on a hot
12. Add 20 mL of 1:1 HNO3 to the sample and heat on a hot plate at a low setting until
near dryness to remove traces of HF.

14. Add 20 mL of 1:1 HNO3 to the sample.
15. Filter the sample by gravity using a Whatman No. 40 or No. 42 filter paper into a
beaker containing the filtrate fraction. Wash well with 1:1 HNO3 to bring final
volume to ~ 150 mL.

Vol. I.

Pu-09-RC

NITRIC/SULFURIC ACID METHOD
APPLICATION
This procedure may be used as an alternative to the HNO3/HCl digestion procedure

(see Pu-08-RC). The chemical recovery for the preparation of vegetation and tissue
samples by the HNO3/H2SO4 digestion procedure are slightly lower than the recoveries
when samples are digested with HNO3 and HCl.
The sample is digested with HNO3 and H2SO4 until the appearance of SO3 vapors.
Plutonium is coprecipitated with ferric hydroxide by the addition of NH3, which is free of
CO2. The precipitate is dissolved in an HNO3 solution then reprecipitated with the
addition of NH3. The iron hydroxide is then dissolved in HNO3 and the sample is ready
for ion exchange separation (see Procedure Pu-11-RC, Vol. I).
SPECIAL REAGENTS
Iron carrier solution (10 mg of Fe mL-1) 7.2 g of Fe(NO3)3A9 H2O diluted to

100 mL with a dilute solution of HNO3.
SAMPLE PREPARATION
1. In a beaker weigh out 5-50 g of sample.
2. Spike the sample with a known amount (0.04-0.07 Bq) of 236Pu tracer.

3. Slowly add 2 mL of concentrated HNO3 per gram of sample. Have the beaker in an
ice bath to slow the reaction, add n-octyl alcohol if excessive foaming occurs.
4. After addition of HNO3 is complete, slowly add 0.5 mL of concentrated H2SO4 per
gram of sample.
5. Take the beaker out of the ice bath and allow to warm to room temperature. Cover
the beaker with a watch glass and place on a hot plate at medium heating.
6. When the solution turns dark, add 10-20 mL of concentrated HNO3 (Note: It is
necessary to always have an excess of HNO3 to control the rate of the reaction.)
Wash the walls of the beaker with water to remove any remaining residue.
7. Boil solution until there are no HNO3 fumes and the solution remains clear, then
evaporate to vapors of SO3.
8. Dilute the sample with 300-400 mL of water, add Fe carrier solution at an amount
equal to 20 mg of Fe per gram of sample.
9. Cool the sample in an ice bath. At first, slowly add concentrated NH4OH (free of
CO2), continue adding NH3 until a pH of 8 is attained, stirring the solution while
adding the NH3.
10. Filter the precipitated Fe(OH)3 by gravity filtration through Whatman No. 40 filter
paper using a conical funnel. Wash the beaker with a dilute solution of NH3 to
remove any remaining ferric hydroxide and filter the washings.
11. Transfer the filter paper containing the ferric hydroxide to a 400-mL beaker, then
add 100 mL of concentrated HNO3. Cover the beaker with a watch glass and heat
until the filter paper decomposes.
12. Evaporate the sample to a small volume. Cool, carefully add 100 mL of H2O and
add a small amount of concentrated HNO3 to dissolve the Fe. Boil the solution.
13. Repeat Steps 9-11.

14. Add 100 mL of H2O to the solution, allow to cool to room temperature. Filter the
solution by gravity filtration through Whatman No. 40 filter paper into a 400-mL
beaker. Wash with 15-20 mL of 1:1 HNO3 and H2O. Discard the filtered residue.
15. Cover beaker with a ribbed watch glass and reduce volume to ~ 5 mL, dilute to
100 mL with 1:1 HNO3.

Vol. I.

Radium

Ra-05-RC
RADIUM-224 IN URINE
APPLICATION
This procedure has been applied only to urine samples. The 224Ra content of urine is
determined by chemical isolation of 212Pb and radiometric assay of 212Bi and 212Po after
equilibration. Lead-210 and the isotopes of radium, thorium, and actinium are collected
from untreated urine by coprecipitation with calcium phosphate. Thorium, actinium, and
calcium are then removed by coprecipitation of lead with barium nitrate in the presence
of lanthanium hold-back carrier. Radium and added barium are removed by selective
precipitation of barium chromate in the presence of ethylenediaminetetraacetic acid.
Lead in the filtrate is released from the chelate by the addition of nickel and is finally
collected as lead chromate.
The lead precipitate is stored to allow the equilibration of 212Bi and 212Po with 212Pb.
The resulting " activity is then determined by scintillation counting. Instrument response
is converted to the " activity (Bq) by application of corrections for counter efficiency and
background, self-absorption and recovery.
The 224Ra activity (Bq) is calculated from the combined " activity of 212Bi and 212Po
by application of the Bateman function for the decay of the thorium series.
SPECIAL APPARATUS
1. Teflon filter holder - see Specification 7.8, Vol. I, - or filter funnels and sample
mounts - see Specification 7.12, Vol. I.
2. Glass fiber filters - see Specification 7.8, Vol. I.

3. Magnetic stirrers with Teflon - coated magnet bars.
4. Rings and discs.
5. Alpha phosphors - see Specification 7.10, Vol. I.
SPECIAL REAGENTS
1. Lead carrier solution - 7.99 g Pb(NO3)2 L-1 of 1% HCl.
2. Barium carrier solution - 7.58 g BaC12 L-1 of water.
3. Lanthanum carrier solution - 31.2 g La(NO3)3 L-1 of 1% HCl.
4. Sodium chromate solution - 100 g Na2CrO4 L-1 of water.
5. Nickel chloride solution - 110.0 g NiCL2 L-1 of 1% HCl.
6. EDTA solution - 100.0 g (tetrasodium salt) ethylenediaminetetraacetic acid per liter

of water.
SAMPLE PREPARATION
1. Transfer a measured volume of urine to a 250-mL centrifuge bottle.
3. Dissolve the precipitate with 10 mL of HNO3. Dilute to about 100-mL with water.

5. Dissolve the precipitate with 10 mL of HNO3, and transfer to a 100 mL beaker.

Evaporate to near dryness. Repeat the evaporation with 10 mL portions of HNO3
until the solution is clear.
6. Dilute the sample to about 5 mL with water. Add 1 mL each of barium, lead, and
lanthanum carrier solutions.
7. Add 50 mL of 90% (fuming) HNO3. Stir for 20 min, cool, and filter by suction on a
glass fiber filter. Discard the filtrate.
8. Dissolve the precipitate from the filter with water. Collect the solution in a 100-mL
beaker. Evaporate to about 5 mL.
9. Add 50 mL of 90% HNO3. Stir for 20 min, cool, and filter by suction on a glass
fiber filter. Discard the filtrate.
DETERMINATION
1. Dissolve the precipitate from the filter with water. Collect the solution in a 40 mL
centrifuge tube.
2. Add 3 mL of acetic acid. Adjust the pH to 5.5 with NH4OH. Add 1 mL of sodium
chromate solution with stirring. Cool, centrifuge, and discard the supernate.
3. Dissolve the precipitate with 5 mL of 1:11 HC1. Dilute to 20 mL with water. Add
1 mL of EDTA solution and 3 mL of acetic acid.
4. Adjust the pH to 5.5 with 1:1 NH4OH. Heat in a water bath to 95oC. Add 1 mL of
sodium chromate solution with stirring. Cool, centrifuge, and decant the supernate
into a 40-mL centrifuge tube. Discard the precipitate.
5. To the supernate, add 1 mL of nickel chloride solution. Heat to 95oC in a water bath
with stirring. Cool and filter by suction on a weighed glass fiber filter. Wash with
water.

6. Dry the precipitate at 110oC. Weigh and mount with a zinc sulfide phosphor disc.
Store for 10 h and " count in a scintillation counter.
The 212Bi + 212Po disintegration rate is obtained from the net counting rate of the
lead chromate precipitate through the following calculation:
Bq = Rs YTE
where Rs is the net counting rate of the sample, Y is the chemical recovery factor, T is the
precipitate thickness correction, and E is the counter efficiency factor.
The recovery factor, Y, is obtained by weighing the final precipitate and

determining from this measurement the loss incurred through the chemical procedures.
The calculation of the recovery factor is:
where x is the weight of lead added as carrier; w is the total weight of the final precipitate
and filter paper; t is the weight of the filter paper; and f is the gravimetric factor, which
equals 0.641 mg lead per mg of lead chromate.
The precipitate thickness correction, T, is used to normalize self-absorption of the

212
Bi and 212Po " activities in samples and standards to a common thickness. T is
obtained by counting representative " activities within the energy range of 4.8-8.8 MeV
through varying sample thicknesses. The correction is taken as the ratio of counting rates
at the minimum thickness to other thicknesses over the range of probable sample
recoveries. A composite plot of the correction obtained for 230Th, 212Pb, and 226Ra
activities through varying thicknesses of their oxalate, chromate and sulfate derivatives,
respectively, is illustrated in Procedure Ra-07-RC, Vol. I, Figure 1.
The efficiency factor, E, is determined by " counting a standard derived from a

known equilibrated 224Ra activity under sample conditions.

The 224Ra activity (Bq) is obtained from the 212Bi + 212Po activities through the
following calculation:
(Bq 224Ra) = Bq (212Bi + 212Po) C1 x C2/D
where C1 is the theoretical ratio of 224Ra to 212Pb at equilibrium; C2 is the theoretical ratio
of 212Pb and 212Bi to 212Po at equilibrium; and D is the decay factor used to correct for the
decay of 212Pb. The Bateman function for the ratio of 224Ra to 212Pb at equilibrium (C1)
reduces to the following:
where
t1/2, 212Pb = 10.64 h

t1/2, 224
Ra = 87.36 h
Similarly, the ratio of 212Pb to 212Bi, and 212Po (C2) reduces to 0.905. The decay
correction (fraction remaining) is expressed:
Decay Correction = C-8)t
where )t is the interval between the separation of lead from the radium and the final
count. Figure 1 illustrates this correction over a period of 40 h.
The attached computational data sheets show a simplified procedure for the routine
calculation of 224Ra disintegration rates. Experimental data are tabulated as they are
derived and the calculations are performed on a step-by-step basis.


Counter Background (cps) 1.67x10-5
Yield (%) 75
Blank (cps) 1.67x10-3

*
Reagent blanks must be analyzed with each set
of samples.

Figure 1. Decay correction.


Operation
1 Counter number -
STANDARD COUNTING
2 Gross background count -
3 Count time -
4 Background (cps) 2/3
5 Gross standard count -

6 Count time -
7 Standard (cps) 5/6
8 Standard (net cps) 7-4
CORRECTIONS
10 Tare weight -
11 Net weight 9-10
12 Weight of lead 11x0.80
13 Carrier added -
11 Net weight Copy

15 Thickness correction Graph


Operation
16 Counting time (day and h) -
17 Separation time (day and h)
18 Difference (h) 16-17
19 Decay correction Graph
20 Total correction factor 14x15/19

21 Corrected standard (cps) 8x20
22 Added (Bq) -


Operation
1 Counter number -
SAMPLE COUNTING
24 Gross sample counts -
25 Counting interval (s) -
CORRECTIONS
30 Tare weight -
31 Net weight 29-30
32 Weight of lead 31x0.80
33 Carrier added -
31 Net weight Copy

35 Thickness correction Graph


Operation
36 Counting time (day and h) -
37 Separation time (day and h) -
40 Total correction factor 34x35/39

41 Corrected sample (Bq) 28x40


Operation
1 Counter number -
3 Count time Copy
25 Counting interval (s) Copy
26 Sample (cps) Copy
40 Total correction factor Copy
STANDARD
42 Background/count time 4/3
43 Sample/count time (cps) 26/25
44 S2 42+43
45 S for sample (net cps) /44
46 S for sample (Bq) 45x23x40

Strontium

*EPA APPROVED*
Sr-01-RC
STRONTIUM-89
APPLICATION
This procedure may be used for samples other than soils that can be analyzed by the
90
Sr procedure described in Sr-02-RC.
Strontium-89 is ordinarily determined at the same time as 90Sr, thus the

radiochemical procedures are those described in Sr-02-RC. The 89Sr content of the
sample is calculated by correcting the total counting rate of the SrCO3 fraction for the
90
Sr present and for the 90Y, which grows in between separation and counting.
In adapting the 90Sr procedure to include the determination of 89Sr, it is necessary to

make two modifications. First, the yield must be determined gravimetrically since 85Sr
would interfere in the ß counting of total radiostrontium. This may require a correction
for stable Sr which is present in the original sample. Second, the gravimetric procedure
requires complete removal of Ca from the Sr fraction.
SPECIAL APPARATUS
The special apparatus are described in Sr-02-RC.
*

DETERMINATION
1. Transfer the two supernates obtained in Determination, Second Milking, Procedure

Sr-02-RC, to a 150-mL beaker, heat to boiling, and add 5-10 mL of a saturated
sodium carbonate solution slowly with stirring.
2. Cool and filter by suction onto a tared 2.8 cm Whatman No. 42 filter paper. Wash
thoroughly with H2O and alcohol. Record the time of separation of 90Y.
3. Dry, weigh the paper, and precipitate, and then calculate the Sr recovery (Note: A
10 mL aliquot of the original Sr carrier solution (20 mg mL-1) is standardized as the
carbonate by preparing it for weighing in the same way as described here.)
4. Mount the precipitate on a plastic disc, cover with Mylar film, and fasten with a
plastic ring.
5. Beta count the SrCO3 precipitate at 4-day time intervals, recording the measurement
times.
6. Beta count the Y oxalate precipitate obtained for 90Sr determination on the same
counter at as nearly the same time as possible.
STANDARDIZATION
The best standardization is carried out with a 89Sr standard. Because of the
relatively short half-life of this nuclide, however, an indirect standardization may be
used. Since the ß energies of 89Sr and 40K are quite close, K salts may be used as the
working standards.
A 0.02 g quantity of KCl is mounted with a ring and disc. This is counted at the
same time as a precipitated 89Sr standard prepared with 20 mg of Sr carrier as SrCO3. A
factor relating the count rates of the two is then determined, so that an apparent 89Sr Bq
for the KCl standard is obtained.

This correction eliminates the difference in self-absorption in the two standards. The
error is difficult to reduce by counting smaller aliquots of KCl, since its specific activity
is only ~ 15 Bq g-1.
The count rate obtained from the total radiostrontium fraction consists of three
components:
90
1. Y (buildup between separation and counting),
90
2. Sr, and
89
3. Sr.
Each of these components has a different ß energy and to a small extent they are
affected by differences in self-absorption and are counted with slightly different
efficiencies on the same counter. Thus, the correction process for obtaining 89Sr by
difference is quite complicated. In this Laboratory, it is simplified by ignoring the small
corrections for self-absorption.
The 90Y contribution is determined by calculation. Since the 90Sr content of the
sample is known from the original 90Sr determination, the buildup of 90Y between the
time of second milking and counting can be computed or may be read off from the graph
in Figure 1. The 90Y (Bq) obtained is then converted to 90Y (cps) by using the counter
efficiency factor for 90Y.
The 90Sr contribution is determined by counting the corresponding 90Y fraction

(from the determination of 90Sr) on the same counter. The 90Y count rate is then corrected
for decay to the count rate at the time of the second milking. This 90Y count rate must
then be converted to the corresponding count rate for 90Sr. The correction factor is
determined experimentally for the individual counter. Measurements are made by
separating a 90Sr + 90Y standard of relatively high activity and counting the two fractions
as soon as possible. Only slight corrections are then necessary for the buildup and decay
of 90Y.

It should be pointed out that all of these computations must be carried out on the
count rates at the time of counting the total radiostrontium rather than disintegration
rates. The final conversion of the 89Sr (cps) to (Bq) completes the calculation.
The calculation of the standard deviation (SD) due to counting is somewhat more
complex than the calculation of the 89Sr disintegration rate. The computational data
sheets attached have been prepared as aids in calculating and checking the required
values. These sheets cover the gravimetric yield correction applied to the final 89Sr (Bq)
calculation, and are also substituted for the 85Sr yield correction shown in the 90Sr (Bq)
method, the 40K standardization, the determination of the factor for converting the 90Y
count rate to 90Sr count rate, and the final calculation of 89Sr (Bq) (Figure 2).
A B C D
Counter Efficiency (%) 45 45 35 45

Counter Background (cps) 0.005 0.005 0.005 0.005
Yield (%) 80 80 80 100
Blank (cps) - - - -
LLD (400 min) (mBq) 10 20 10 5

LLD (1000 min) (mBq) 5 10 5 3
A = Pure 89Sr
B = 89Sr in a sample containing 1 Bq of 90Sr
C = Pure 90Sr free from 90Y
D = Pure 90Y

Figure 1. Buildup of 90Y

Figure 2. Decay of 89Sr.


Operation
1 Counter number -
90
Sr standard counting*
22 Gross 90Sr count -
23 Count time -
90
24 Sr (cps) 22/23
90
25 Sr (net cps) 24-4
CORRECTIONS
27 Tare weight -
28 Net weight 26-27
29 Weight of Sr 28x0.59
30 Carrier added -
31 Chemical yield factor for Sr 30/29
32 Corrected 90Sr (net cps) 25x31
33 Added (Bq)
*Strontium carbonate counted as soon as possible after 90Y milking.


Operation
50 Efficiency factor (F) 49/48
KCl COUNTING
51 Gross KCl count -
52 Count time -
53 KCl (cps) 51/52
54 KCl (net cps) 53-57
55 KCl (effective Bq) 54x50


Operation
1 Counter number -
SAMPLE COUNTING
56 Gross sample count -
57 Count time -
CORRECTIONS
62 Tare weight -
63 Net weight 61-62
64 Weight of Sr 63x0.59
65 Carrier added -
66 Chemical yield for Sr 65/64
68 Tare weight -
69 Net weight 67-68


Operation
70 Weight of yttrium 69x0.40
71 Carrier added -
72 Chemical yield for Y 71/70
73 Time of counting -
74 Time of second milking -
76 Decay correction Graph*
77 Total correction factor 66x72/740/376
**See Sr-02-RC (Vol. II) for 90Y decay curve.


Operation
1 Counter number -
3 Count time Copy
57 Count time Copy
58 Sample (cps) Copy
77 Total correction factor Copy
60 Sample (Bq) Copy
78 Corrected sample (Bq) Copy
STANDARD DEVIATION
79 Background/count time (cps) 4/3
80 Sample/count time (cps) 58/57
81 S2 79+80
82 S for sample (net cps) /81

83 S for sample (Bq) 82x21x77


Operation
1 Counter number -
55 KCl (effective Bq) Copy
KCl COUNTING
84 Gross KCl count -
85 Count time -
86 KCl (cps) 84/85
87 KCl (net cps) 86-4
TOTAL Sr COUNTING 66x72/740/376
89 Gross total count -
90 Count time -
91 Total (cps) 89/90
92 Total (net cps) 91-4
66 Chemical yield for Sr Copy
93 Corrected total (net cps) 92x66

90
Y SUBTRACTION
94 Time of counting -
74 Time of second milking Copy


Operation
96 Buildup factor for 90Y Graph
78 Corrected sample (Bq) Copy
97 Equilibrium sample (net cps) 78/21

90
98 Y (net cps) 97x96
89
99 Sr + 90Sr (net cps) 93-98
34 Efficiency factor for 90Sr Copy

90
100 Sr (net cps) 78/34
89
101 Sr (net cps) 99-100


Operation
1 Counter number -
89
101 Sr (net cps) Copy
102 89Sr (Bq) 101x88
STANDARD DEVIATION
81 S2 for 90Y (total) Copy
59 Sample (net cps) Copy

90
98 Y (net cps) Copy
103 S2 for 90Y (in Sr fraction) 81x98/59
79 Background/count time (cps) Copy
90 Count time Copy
91 Total (cps) Copy
104 Total/count time (cps) 91/90
105 S2 for total (net cps) 79+104
81 S2 for 90Sr (net cps) Copy
106 S2 for 89Sr (net cps) 81+103+105


Operation
107 S for 89Sr (net cps) /106

108 S for 89Sr (Bq) 107x88
DECAY CORRECTION
109 Counting date -
110 Sampling date -
111 Difference (days) 109-110
113 Corrected 89Sr (Bq) 102/112
114 Corrected S 108/112

*EPA APPROVED*
Sr-02-RC
STRONTIUM-90
APPLICATION
Procedures are described for the preparation, separation, and analysis of fallout
samples, bone, tissue, milk, urine, vegetation, water and soil. Foods and grains are
treated as vegetation.
Strontium is separated from Ca, other fission products and natural radioactive
elements. Fuming HNO3 separations remove the Ca and most of the other interfering
ions. Radium, lead and barium are removed with barium chromate. Traces of other
fission products are scavenged with yttrium hydroxide. After the 90Sr + 90Y equilibrium
has been attained, the 90Y is precipitated as the hydroxide and converted to the oxalate for
counting. Chemical yield is usually determined with 85Sr tracer, but instructions for
gravimetric yield determination are also included.
SPECIAL APPARATUS
1. Teflon filter holder or filter funnel and sample mount - see Specification 7.12,
Vol. I.
2. Rings and discs - see Specification 7.2, Vol. I.
*

3. Magnetic stirrers with Teflon-coated magnet bars.
4. Mylar film - see Specification 7.3, Vol. I.
5. Glass fiber filters - see Specification 7.8, Vol. I.
6. Fisher filtrator, Fisher Chemical Company.
7. Brinkmann dispenser - pipettor or ordinary pipette.
8. Beta phosphor - see Specification 7.9, Vol. I.
SPECIAL REAGENTS
1. Strontium carrier, 20 mg Sr mL-1 - dissolve 48.4 g Sr(NO3)2 in 1 L of 1:99 HNO3.
2. Yttrium carrier, 10 mg Y mL-1 - see the Appendix to this procedure for preparation.
3. Iron carrier, 5 mg Fe mL-1 - dissolve 5 g Fe wire in 1:1 HCl and dilute to 1 L with
1:99 HCl, or dissolve 72 g Fe(NO3)3A9H2O in 1 L of 1:99 HNO3.
4. Barium buffer solution - 500 mL 6M acetic acid (glacial HOAC) plus

1 L 6M NH4OAc plus 0.5 L Ba [Ba(NO3)2) carrier 10 mg mL-1].
5. Calcium carrier, 200 mg Ca mL-1 - dissolve 500 g calcium carbonate (CaCO3) in a

minimum of 1:1 HCl and dilute to 1 L with 1:99 HCl.
85
6. Sr tracer, about 7x104 Bq L-1 - in a well counter, this tracer provides about
50 counts sec-1 mL-1.
7. Sodium carbonate solution, 2M - dissolve 212 g Na2CO3 L-1 of H2O.
8. Sodium chromate solution, 0.3M - dissolve 50 g Na2CrO4 L-1 of H2O.
9. Sodium hydroxide solution, 6M - dissolve 240 g NaOH L-1 of H2O.

SAMPLE PREPARATION
A. Dry ashing.
Since Sr is not volatile, the majority of samples are prepared by dry ashing. These
procedures are described here. Where wet ashing is desirable or preferable, the
procedure is given under the analysis of the particular sample type. Freeze-drying is a
useful preliminary to many wet-ashing procedures, particularly if it is necessary to take a
subsample of the material for the analysis of a volatile element.
Obtaining the required precision and accuracy in radiochemical analyses for natural
or fallout radionuclides in materials such as food, vegetation, soils, and water usually
requires large samples. Therefore, the ordinary problems of obtaining a suitable ash are
magnified. Sample identification, original weight, and ash weight determinations are the
same operations as those performed for standard chemical analysis. However, ash
weights as taken at EML are not considered as basic data, but are used as an intermediate
step in calculating the activity in the original sample. Thus, a completely carbon-free ash
is not a necessity.
Dry ashing at EML is conducted as a two-stage process. The first stage is done at
about 125oC to completely dry the sample. Subsequently, the temperature is raised at
intervals over an 8-h period to 500oC to produce an ash with a small amount of carbon.
The length of time required for drying large samples is 16-24 h. Table 1 lists
critical temperatures where ignition will occur. The temperature of the furnace should be
raised slowly over a period of 8 h (or more, if necessary) in this critical temperature
range. When the upper limit has been reached without sample ignition, the furnace
temperature can be raised more rapidly to 500oC and the samples ashed for 16 h.
With the proper adjustment of temperature over the 8-h period, ignition can be
avoided on all materials except those containing large amounts of fats such as meat and
fish. Although ignition of the sample can be prevented, it is almost impossible to prevent
the carbonaceous material from glowing due to oxidation of carbon. The glowing does
not interfere with subsequent chemical analyses, except that volatile elements, for
example, may be lost since the temperature of the glowing material is considerably

higher than the maximum ashing temperature. Therefore, if cesium is to be included in

the chemical analysis, smaller samples ashed at relatively low temperatures should be
used in order to minimize the loss of this element. The alternative is to use a wet ashing
method.
Different classes of samples require slightly different preparation, however, similar

materials may be discussed as a group. In general, food products are prepared as for
home use, while other materials are ashed as received. The minimum amounts of raw
materials (as determined by this Laboratory) required for a single analytical aliquot are
shown in Table 2. Table 3, prepared by the U.S. Federal Food and Drug Administration,
gives a more generalized picture of ash percentages and quantities required for specified
amounts of Ca.
Edible weights are determined by difference since loss of moisture from the edible
portion during the time required for preparation may amount to a sizeable fraction of the
mass. Therefore, it is important that the weight of inedible material be determined.
There is, of course, some loss of water from the inedible fraction, but this is minimized
due to the considerable smaller amount of material involved.
Canned goods are weighed as received and the contents removed. The cans are not
washed but are weighed as emptied (including lids), since only the contents removed are
the sample. Small amounts of syrup, juices, and solid material sticking to the container
are not transferred.
Grains, powdered milk, and macaroni require no preliminary treatment. The sample
is placed in stainless steel trays and dried overnight before ashing.
Liquid milk and fruit juices are weighed into deep stainless trays and evaporated at
o
125 C. The dry material is broken up with a spatula before ashing.
Hay and grass are oven dried below 100oC ground and transferred to stainless trays.
The drying is completed at 125oC and the ashing then follows the conditions shown in
Table 1.
Fresh vegetables and fruits are prepared as for eating. Thus, green beans are
stringed, rinds are removed from oranges and bananas, seeds and rinds are removed from

melons, and cores are removed from apples. The outer leaves and central core are
removed from the leafy vegetables such as lettuce and cabbage and the heads cut into
small pieces before placing in trays. The refuse is weighed; this weight is deducted from
the original weight in order to determine the true sample weight (edible portion).
Root vegetables and potatoes are washed before cutting up into ~ 2.5-cm cubes.
Tops are removed and any waste is weighed in order to obtain the edible portion.
Inedible portions of eggs and shellfish are removed and discarded. Thus, eggshells
and the shells of the shrimp or clams are removed. The weight of the waste is deducted
from the weight of the purchased material to obtain the edible weight.
Three hundred grams of center slices of bread are removed from each loaf, placed in
large stainless trays, and dried at 125oC before ashing.
Flour samples are placed in large trays, saturated with distilled water, and kneaded
into dough. The samples are then dried in the muffle furnace at 125oC, prior to ashing.
Poultry, meat, fish and similar oily samples are heated in a muffle furnace at 150oC
for 1 h. The bones are then easily separated from the soft tissue. The sample is returned
to the muffle furnace for drying at 125oC, prior to ashing.
If considerable amounts of carbon remain after 16 h at 500oC, the sample should be

crushed, transferred to a smaller metal tray and placed in a muffle furnace regulated at
550oC for 24 h or until ashing is complete. There is always a danger that samples will
fuse at this temperature and, therefore, some balance between this problem and the
excessive carbon must be reached.
After thorough ashing, the material usually may be removed readily from the tray
with a spatula, followed by brushing. A small paint brush is adequate. Except for very
small original samples, the weight loss of residual ash in the trays is negligible. Before
reuse, the trays are thoroughly scrubbed with detergent and water.
After ashing, all samples should be weighed before further processing. This gives
weight of ash per unit weight of original material. The sample must then be ground to
pass a 40 mesh screen. Experiments at EML have shown that ash of a coarser size,

though blended, may give anomalous analytical results. Since sieving will produce an
inhomogenous sample, the ash should be blended thoroughly before analysis. If the
entire ash sample is to be consumed in a single analysis, the grinding and sieving is not
necessary.
B. Equipment.
Muffle furnaces in several sizes are used in this Laboratory primarily because of the
large variety of samples prepared. A large capacity (1 m3) muffle furnace which may be
operated at 500oC (900oF) continuously is ideal since many different samples or very
large samples may be accommodated.
Silica, porcelain, enameled steel, monel metal, stainless steel, and pyrosuran trays
have been used. Each type presents its own problems when ashing large samples at
500oC. In all cases, there is deterioration of the tray due to effects of high temperature
and of chemical action on the surfaces.
Fused silica trays are useful, but fragile and expensive. After ashing several
samples, they tend to become rough from loss of silica by fusion with materials with high
alkali salt content such as milk or potatoes. Once these trays are etched, it becomes
difficult to completely clean them. Therefore, some ash is lost and a possible source of
contamination of future samples is produced. The loss of ash may be unimportant, but
the chance of cross-contamination cannot be passed off lightly. Also, the addition of
silica to the sample poses a problem in the chemical analysis. Silica trays are of most
value when ashing bone, where there is minimal attack on the vessel.
Porcelain trays are similar in behavior to silica. However, they will retain their
smooth surface longer than silica trays even though traces of metals fuse into the glaze.
Enameled steel is only satisfactory for sample drying, but is easy to clean.
Stainless steel and monel metal trays have proven satisfactory for all ashing
operations. They are relatively inexpensive and sturdy. However, if the addition of
traces of iron, nickel or chromium to the sample is detrimental to the chemical analyses,
these trays should not be used. Cleaning can be accomplished readily with detergents or
with dilute mineral acids (usually HCl).

Miscellaneous items that are needed or are useful in the ashing of large samples are
several sizes of spatulas, knives, food blenders, food processors, mortars and pestles, ash
blenders (preferably of the Patterson-Kelly V type), and sieves.
All large capacity furnaces used in ashing operations should be fitted with fire
retardant screens and should exhaust to the laboratory vent system since, during the early
part of the ashing, considerable quantities of volatile compounds with low flash points
are evolved. These compounds tend to condense in the stack close to the furnace and
present a serious fire hazard. The large capacity furnaces should not have forced draft
attachments. The forced draft will tend to disturb the ash with a consequent loss of
material and possible cross-contamination from one sample to another.

TABLE 1
PRELIMINARY ASHING TEMPERATURES
Material Temperature (oC)
Eggs 150 - 250o

Meat Burning
Fish Burning
Fruit (fresh) 175 - 325o
Fruit (canned) 175 - 325o
Milk (dry) -
Milk (wet) 175 - 325o
Buttermilk (dry) -
Vegetables (fresh) 175 - 225o
Vegetables (canned) 175 - 250o
Root vegetables 200 - 325o
Grass 225 - 250o
Flour Burning
Dry beans 175 - 250o
Fruit juices 175 - 225o
Grains 225 - 325o
Macaroni 225 - 325o
Bread 225 - 325o

TABLE 2
KILOGRAM OF MATERIAL REQUIRED FOR 10 g OF ASH
Item % Ash* kg Original Material
Beans (dry) 3.8 0.3

Bread (white) 2.0 0.5
Bread (whole wheat) 2.4 0.4
Eggs (shelled) 0.94 1.1
Fish 1.2 0.8
Flour 0.52 1.9
Fruit (canned) 0.30 3.3
Fruit (fresh) 0.68 1.5
Juices (fruit) 0.59 1.7
Macaroni 0.67 1.5
Meat 0.94 1.1
Milk (buttermilk powder) 11 0.1
Milk (liquid) 0.7 1.4
Milk (powder) 6 0.2
Potatoes 1.1 0.9
Poultry 0.75 1.3
Rice 0.62 1.6
Shellfish 1.8 0.6
Vegetables (canned) 1.1 0.9
Vegetables (fresh) 0.77 1.3
Vegetables (root) 0.72 1.4
Vegetation (hay) 2.3 0.4
Wheat 1.7 0.6
*
Mean for 1963-1982
Note: Percent ash is an average value found in routine work. Variations have been
found as large as 25% depending upon particular sample composition and
ashing conditions.

TABLE 3
SAMPLE SIZE AND ASH WEIGHT FOR 90Sr ANALYSES
Average Composition Amount to yield 1 g Ca

Total wt.
Water Ash Calcium of product Ash wt.
Product (%) (%) (mg 100 g-1) (g) (g)
Apples, raw 84.1 0.3 6 16700 50

Applesauce,
sweetened 79.8 0.2 4 25000 50
Apricots, dried 24. 3.5 86 1160 40.6
Asparagus,
frozen and fresh 93.0 0.7 21 4760 33.4
Beans, snap
frozen and fresh 88.9 0.8 65 1540 12.3
Beets, raw peeled 87.6 1.1 27 3700 41.0
Broccoli,
raw 89.9 1.1 130 770 8.5
frozen 92.2 0.8 100 1000 8.0
Cabbage, raw 92.4 0.8 46 2170 17.4
Carrots, raw 88.2 1.0 39 2560 25.6
Cauliflower,
frozen and fresh 91.7 0.8 22 4550 36.4
Celery, raw 93.7 1.1 50 2000 22.0
Cheese, cheddar 37 3.7 725 138 5.1
Cherries, red,
canned, filled 86.6 0.4 11 9100 36.4
Clams, canned 86.7 2.3 87 1150 26.4
Cod, raw 82.6 1.2 10 10000 120
Collards, raw 86.6 1.7 249 400 6.8
Corn,
raw 73.9 0.7 9 11100 78
canned 80.5 0.9 4 25000 225
frozen 78.0 0.6 8 12500 75
Crabs,
raw 80.0 1.7 (39) 2560 43.5
canned 77.2 1.7 45 2220 37.8
Dates,
fresh and dried 20 1.8 72 1390 25.0

TABLE 3 (Cont'd)
Total wt.
Product (%) (%) (mg 100 g-1) (g) (g)
Eggs, dried, whole 5.0 3.6 190 526 18.9

Figs, dried 24 2.4 186 538 12.9
Grapes, raw 81.9 0.4 17 5900 23.5
Halibut, raw 75.4 1.0 13 7700 77.0
Kale, raw 86.6 1.7 225 445 7.5
Lettuce, head 94.8 0.9 22 4550 41.0
Lobster, canned 77 2.7 65 1540 41.5
Mackerel, canned,
Pacific 66.0 2.5 260 38 59.6
Atlantic 66.4 3.2 185 540 17.3
Milk,
whole 87.0 0.7 118 850 5.9
evaporated 73.7 1.5 243 411 6.2
dried (non-fat) 3.5 7.9 1300 77 6.1
Oysters, raw 80.5 2.0 94 1065 21.3
Peaches,
raw 86.9 0.5 8 12500 62.4
syrup, canned 80.9 0.3 5 20000 60.0
Peanuts,
roasted, shelled 2.6 2.7 74 1350 36.5
Pears,
raw 82.7 0.4 13 7700 30.8
syrup, canned 81.1 0.2 8 12500 25.0
Peas,
raw 74.3 0.9 22 4550 41.0
canned 82.3 1.0 25 4000 40.0
frozen 80.3 0.8 17 5880 47.0
Pineapple, canned 78.0 0.4 29 3450 13.7
Plums, canned 78.6 0.5 8 12500 62.4
Potatoes, raw 77.8 1.0 11 9100 91.0
Prunes, dried 24.0 2.1 54 1850 38.8
Raisins, dried 24.0 2.0 78 1280 25.6
Rice, milled, raw 12.3 0.4 24 4160 16.6
Salmon, raw,
TABLE 3 (Cont'd)

Total wt.
Product (%) (%) (mg 100 g-1) (g) (g)
Pacific 63.4 1.0 - - -

canned, King (bones) 64.7 2.4 154 650 15.5
canned, Red (bones) 67.2 3.0 259 385 11.6
Sardines, in oil,
Atlantic 47.1 3.9 354 282 10.9
Pilchards, Pacific 65.2 2.9 (381) 262 7.6
Shrimp, canned
drained 66.2 5.8 115 870 50.4
Soybeans,
dried, whole 7.5 4.7 227 440 20.6
Spinach,
fresh and frozen 92.7 1.5 81 1240 18.5
Squash,
fresh and frozen 95 0.4 15 6700 26.7
Strawberries, fresh 89.9 0.5 28 3600 18.0
Sweet Potatoes, raw 68.5 1.1 30 3330 36.7
Swordfish, raw 75.8 1.3 19 5260 68.4
Tomatoes, canned 94.2 0.7 (11) 9100 63.6
Tuna fish, canned 52.5 2.3 7 14300 330
Walnuts 3.3 1.7 83 1200 20.5
Wheat, whole grain 13.0 1.7 36 2780 47.3
Flour,
80% extract 12 0.65 24 4170 27.1
all purpose 12 0.43 16 6250 26.8

SEPARATIONS
A. General.
After ashing, grinding and blending, a suitable aliquot of the ash is taken for
analysis. Different sample types are subjected to preliminary separations to bring them to
a common point for determination.
B. Bone.
1. Weigh 10 g of bone ash and transfer to an 800-mL beaker. Add 1 mL of Sr carrier

solution, 1 mL of 85Sr tracer solution, and 75-100 mL of 1:1 HNO3 to the sample.
2. Digest the sample on a hot plate for 30 min with occasional stirring. Complete
solubilization should be obtained except for traces of carbon and silica.
3. Suction filter the sample into a 250-mL filter flask using a Büchner funnel with a
double 7-cm diameter glass fiber filter. Police and wash the beaker with 1:1 HNO3.
Pour the washings through the filters. Wash the residual traces of carbon and silica
on the filters with 1:1 HNO3, followed by a H2O wash. Discard the filters and
residue.
4. Place a magnetic stirrer bar in the original 800-mL beaker. Transfer the filtered
sample solution to the beaker. Rinse the filter flask with H2O and add the rinsings
to the beaker.
5. Dilute the sample solution to 500 mL with H2O. Place the beaker on stirrer/hot
plate. Stir and heat the solution to just below boiling.
6. Add 2-3 mL of H3PO4 to the heated sample solution while continuing to stir.
7. Adjust the pH of the solution to 4-5 by slowly adding NaOH pellets while stirring.
Adjust the pH to 10 by adding NaOH solution (240 g NaOH L-1) to precipitate
phosphates. Stir for 30 min.

8. Remove the beaker from the stirrer/hot plate. Allow the phosphate precipitate to
cool and settle overnight.
9. Suction filter the sample into a 1-L filter flask through a Büchner funnel with a15-
cm diameter glass fiber filter backed with a Whatman No. 42 filter paper.
10. Remove the funnel from the flask and set aside. Test the filtrate for excess
phosphate by adding a few drops of BaCl2 solution (15.2 g BaCl2 L-1 of H2O). If no
precipitate is observed, insufficient phosphate is present for complete precipitation.
In that case, transfer the filtrate to the original 800-mL beaker, add 2 mL of H3PO4
to the solution and repeat Steps 7-9, filtering through the filters reserved in Step 9.
11. Discard the filtrate. Rinse the filter flask with H2O and discard the rinsings.
12. Replace the Büchner funnel containing the phosphate precipitate on the filter flask.
Without suction, slowly add 150 mL of hot 1:1 HNO3 to the Büchner funnel to
dissolve the phosphate precipitate.
13. Apply suction and wash the filters with 1:1 HNO3. Discard the filters.
14. Transfer the solution to the original 800-mL beaker containing the magnetic stirrer
bar. Rinse the filter flask with 1:1 HNO3 and add the rinsings to the beaker. Place
the beaker on a hot plate and evaporate the solution to dryness.
15. Cool the beaker and add 60 mL of H2O. Place the beaker on the stirrer/hot plate.
Add 25 mL of 90% fuming HNO3 to dissolve any solid material. Stir and warm the
solution. While continuing to stir, slowly add an additional 195 mL of 90% fuming
HNO3 to the sample. [Note: Do this in a well-ventilated hood.] Continue to heat
and stir for 30 min.
16. Complete the analysis as described under Determination.

C. Ion exchange resin (monthly collection).
1. Transfer the resin and paper pulp to a 150-mL platinum crucible. Dry the contents
of the crucible under a heat lamp. Place the crucible in a 500-550oC muffle furnace
and ash overnight. Analyze a blank from the same batch of ion exchange resin with
each group of samples.
2. Remove the crucible from the furnace and cool to room temperature.
3. Add four times the ash volume (visually determined) of Na2CO3 to the crucible and
mix thoroughly with the ash.
4. Fuse the sample to a clear melt in a 900oC muffle furnace. Remove the crucible
from the furnace and cool to room temperature.
5. Place a Teflon coated magnetic stirrer bar in a 400-mL beaker. Transfer the fused
sample to the beaker with 300 mL of H2O. Place the beaker on a magnetic
stirrer/hot plate and stir.
6. Add 1 mL of Sr carrier, 1 mL of Ca carrier, and 1 mL of 85Sr tracer solution to

sample. Heat the sample to just below boiling and stir for 1 h.
7. Place a 7-cm glass fiber filter backed with a Whatman No. 42 filter paper into a
Büchner funnel. Mount the funnel on a 1-L filter flask.
8. Filter the sample with suction through the funnel. Wash the carbonates retained on
the filter with H2O. Discard the filtrate.
9. Replace the funnel on the filter flask. Dissolve the carbonates on the filter with hot
1:1 HNO3. Turn on the vacuum and wash the filter with hot 1:1 HNO3, followed by
H2O. Discard the filters and any residual material.
10. Transfer the solution with 1:1 HNO3 washings to the original 400-mL beaker
containing a magnetic stirrer bar. Stir and evaporate the solution to dryness.

11. Add 40 mL of H2O and 25 mL of 90% fuming HNO3 to the beaker to dissolve solid
matter. (Note: Do this in a well-ventilated hood.) Stir and slowly add an
additional 115 mL of 90% fuming HNO3 stirring continuously for 30 min.
D. Milk.
1. Weigh 10 g of milk ash and transfer to an 800-mL beaker. Add 1 mL of Sr carrier

solution, 1 mL of 85Sr tracer solution and 100 mL of 1:1 HNO3 to the sample.
2. Digest the sample on a hot plate for 15-30 min with occasional stirring. Complete
solubilization should be obtained except for traces of carbon and silica.
3. Suction filter the sample into a 250-mL filter flask using a Büchner funnel with a
double 5.5-cm diameter glass fiber filter. Police and wash the beaker with 1:1
HNO3. Pour the washings through the filters. Wash the residual traces of carbon
and silica on the filters with 1:1 HNO3. Discard the filters and residue.
4. Place a magnetic stirrer bar in the original 800-mL beaker. Transfer the filtered
sample solution to the beaker. Rinse the filter flask with H2O and add the rinsings
to the beaker.
5. Dilute the sample solution to 500 mL with H2O. Place the beaker on stirrer/hot
plate. Stir and heat the solution to just below boiling.
6. Add 2-3 mL of H3PO4 to the heated sample solution while continuing to stir.
7. Adjust the pH of the solution to 4-5 by slowly adding NaOH pellets while stirring.
Adjust the pH to 10 by adding NaOH solution (240 g NaOH L-1) to precipitate
phosphates.
8. Remove the beaker from the stirrer/hot plate. Allow the phosphate precipitate to
cool and settle overnight.

9. Suction filter the sample into a 2-L filter flask through a Büchner funnel with a15-
cm diameter glass fiber filter backed with a Whatman No. 42 filter paper.
10. Remove the funnel from the flask and set aside. Test the filtrate for excess
phosphate by adding a few drops of BaCl2 solution (15.2 g BaCl2 L-1). If no
precipitate is observed, insufficient phosphate is present for complete precipitation.
In that case, transfer the filtrate to the original 800-mL beaker, add 2 mL of H3PO4
to the solution and repeat Steps 7-9, filtering through the filters reserved above.
11. Discard the filtrate. Rinse the filter flask with H2O and discard the rinsings.
12. Replace the Büchner funnel containing the phosphate precipitate on the filter flask.
Without suction, slowly add 150 mL of hot 1:1 HNO3 to the Büchner funnel to
dissolve the phosphate precipitate.
13. Apply suction and wash the filters with 1:1 HNO3. Discard the filters.
14. Transfer the solution to the original 800-mL beaker containing the magnetic stirrer
bar. Rinse the filter flask with 1:1 HNO3 and add the rinsings to the beaker. Place
the beaker on a hot plate and evaporate the solution to dryness.
15. Cool the beaker and add 60 mL of H2O. Place the beaker on the stirrer/hot plate.
Add 25 mL of 90% fuming HNO3 to dissolve any solid material. Stir and warm the
solution. While continuing to stir, slowly add an additional 195 mL of 90% fuming
HNO3 to the sample. (Note: Do this in a well-ventilated hood.) Continue to heat
and stir for 30 min.
E. Rainwater (pot collection).
1. Add 1 mL of HNO3 L-1 of rainwater collected in the stainless steel pot during the
sampling period. Add 1 mL of Sr carrier and 1 mL of 85Sr tracer solution to the pot.
Evaporate the sample to 100 mL.

2. Transfer the solution to an 800-mL beaker with H2O. Police the inside of the pot
thoroughly with 1:1 HNO3 and add the washings to the beaker.
3. Evaporate the solution gently to near dryness and transfer the residue to a 150-mL
platinum crucible with a minimum of H2O and 1:1 HNO3 washes.
4. Evaporate the solution gently to dryness and ash in a 450-500oC muffle furnace to
destroy organic material.
5. Add four times the ash volume (visually determined) of solid Na2CO3 to the crucible
and mix thoroughly with the ash.
7. Place a Teflon coated magnetic stirrer bar in the original 800-mL beaker. Transfer
the fused sample to the beaker with 400 mL of H2O. Place the beaker on a magnetic
stirrer/hot plate. Heat the sample to just below boiling and stir for 1 h.
8. Remove the beaker from the hot plate and cool. Place a 7-cm glass fiber filter
backed with a Whatman No. 42 filter paper into a Büchner funnel. Mount the
funnel on a 1-L filter flask.
1:1 HNO3. Turn on the vacuum and wash the filter with hot 1:1 HNO3. Discard the
filters and any residual material.
containing a magnetic stirrer bar. Evaporate the solution to dryness.
12. In a well-ventilated hood, add 60 mL of H2O and 25 mL of 90% fuming HNO3 to

the beaker to dissolve solid matter. Stir and slowly add an additional 195 mL of
90% fuming HNO3 stirring continuously for 30 min.

F. Soil (complete solution method).
1. Air dry the entire soil sample and record the weight. Break up the lumps with a
wooden roller, sieve through a No. 10 mesh screen. Record the weights of both the
fines (soil passing through the sieve) and unsieved soil.
2. Weigh a 100-g representative sample of fines and transfer to a 500-mL platinum

crucible. Place the crucible in a 450-500oC muffle furnace overnight to destroy
organic matter. Remove the crucible from the furnace and cool to room
temperature.
3. Add 400 g of Na2CO3 to the crucible and mix thoroughly with the soil. Fuse the
sample at 900oC in a muffle furnace until a clear melt is obtained. Remove the
crucible from the furnace and cool to room temperature.
4. Tap the bottom of the crucible with a mallet and allow the fused mass to fall into a
large mortar. Break up the fused mass with a pestle and grind it to a fine powder.
5. Place a Teflon coated magnetic stirrer bar in a 3-L beaker. Transfer the ground,
fused soil sample to the beaker. Wash the mortar and pestle with 200 mL of hot
water and transfer the washes to the beaker.
6. Add 10 mL of Sr carrier solution and 1 mL of 85Sr tracer solution to the beaker.

Place the beaker on a stirrer/hot plate.
7. Slowly, with continuous stirring, add 1 L of HCl. Heat and evaporate with stirring
to a paste.
8. Add 2.5 L of H2O to the beaker and stir. Remove the beaker from the hot plate and
allow the silica to settle.
9. Place a double 24-cm glass fiber filter backed with a Whatman No. 42 filter into a
Büchner funnel. Mount the funnel in a 4-L filter flask.

10. Filter the sample with suction through the funnel. Wash the filters with 200-300 mL
of hot 1:1 HNO3, followed by 250 mL of H2O. Turn off the vacuum, remove the
filters from the funnel, and discard.
11. Transfer the filtrate to a 4-L beaker containing a magnetic stirrer bar. Wash the
filter flask with H2O and transfer the washings to the beaker.
12. Place the beaker on the stirrer/hot plate. Stir and warm the solution.
13. Add 50 g of H2C2O4 (oxalic acid) to the sample and continue to stir until the salt
14. While stirring adjust the pH to 5.5-6.0 with NH4OH. If the brown color of
FeO(OH) persists, add additional H2C2O4 and readjust the pH. (The optimum
condition for the precipitation is an excess of H2C2O4 in solution insufficient to
cause crystallization of (NH4)2C2O4 upon cooling.)
15. Remove the beaker from the hot plate and allow to stand at room temperature for
several hours or overnight.
16. Place a 15-cm Whatman No. 42 filter paper in a Büchner funnel. Mount the funnel
in a 3-L filter flask.
17. Stir the sample manually and filter with suction into the flask. Wash and police the
beaker with a 10% H2C2O4 solution and pour through the filter.
18. Turn off the vacuum and transfer the filter paper and precipitate to a 150-mL
platinum dish. Place the dish in a 110oC oven to dry the filter and precipitate.
Discard the filtrate.
19. Place the platinum dish in a 450-500oC muffle furnace for 2 h. Raise the
temperature slowly to 700oC and continue the ashing for 2 h.
20. Remove the platinum dish from the furnace and cool to room temperature. Transfer
the residue to a 250-mL beaker. Rinse the dish with 1:1 HNO3 and add the rinsings
to the beaker.

21. Dissolve the residue in a minimum of 1:1 HNO3. Add six drops of H2O2 to the
beaker to facilitate the dissolution. Place the beaker on a hot plate and gently boil.
22. Remove the beaker from the hot plate and cool to room temperature. If insoluble
material is present, suction filter the sample through a double 7-cm glass fiber filter
into a 250-mL filter flask.
23. Wash the beaker and filters with a minimum of hot 1:1 HNO3, followed by H2O.
Turn off the vacuum and discard the filters.
24. Return the filtrate to the 250-mL beaker. Rinse the filter flask with H2O and add the
rinsings to the beaker. Gently evaporate the sample to dryness.
25. Dissolve the residual salt in H2O and perform successive fuming HNO3 separations,
the first two separations at concentrations of slightly > 75%, until the Sr is separated
from the bulk of the Ca. Soils with a high Ca content will require five or six
additional fuming HNO3 separations. (The volumes of the 75% HNO3 solutions
may be changed as required by the mass of Ca present, bearing in mind that
minimum volumes are desirable.)
G. Soil (HCl leach method).
wooden roller and sieve through a No. 10 mesh screen. Record the weights of both
the fines (soil passing through the sieve) and the unsieved soil.
2. Weigh a 500-g representative sample of fines and transfer to a 3-L beaker

containing a Teflon coated magnetic stirrer bar (see Note). Add 10 mL of Sr carrier
solution and 1 mL of 85Sr tracer solution to the beaker. Place the beaker on a
stirrer/hot plate.
3. Slowly, with continuous stirring, add 1 L of 1:1 HCl. (It may be necessary to add a
few drops of CH3(CH2)6CH2OH [octyl alcohol] to control excessive frothing.)

Continue stirring for 30 min. Remove the beaker from the stirrer/hot plate and
allow the insoluble material to settle for at least 2 h.
4. Add 2.5 L of H2O to the beaker and stir. Remove the beaker from the hot plate and
allow the silica to settle.
5. Place a double 24-cm glass fiber filter backed with a Whatman No. 42 filter into a
Büchner funnel. Mount the funnel in a 4-L filter flask.
6. Filter the sample with suction through the funnel. Wash the filters with 200-300 mL
of hot 1:1 HNO3, followed by 250 mL of H2O. Turn off the vacuum, remove the
filters from the funnel, and discard.
7. Transfer the filtrate to the original beaker containing the magnetic stirrer bar. Wash
the filter flask with H2O and transfer the washings to the beaker.
8. Place the beaker on the stirrer/hot plate. Stir and warm the solution.
10. While stirring, adjust the pH to 5.5-6.0 with NH4OH. If the brown color of
FeO(OH) persists, add additional H2C2O4 and readjust the pH. (The optimum
condition for the precipitation is an excess of H2C2O4 in solution insufficient to
cause crystallization of (NH4)2C2O4 upon cooling.)
11. Remove the beaker from the hot plate and allow to stand at room temperature for
several hours or overnight.
13. Stir the sample manually and filter with suction into the flask. Wash and police the
beaker with a 10% H2C2O4 solution and pour through the filter.

15. Place the platinum dish in a 450-500oC muffle furance for 2 h. Raise the
to the beaker.
material is present, suction filter the sample through a double 7-cm glass fiber filter
into a 250-mL filter flask.
19. Wash the beaker and filters with a minimum of 1:1 HNO3, followed by H2O. Turn
off the vacuum and discard the filters.
20. Return the filtrate to the 250-mL beaker. Rinse the filter with H2O and add the
the first two separations at concentrations of slightly >75%, until the Sr is separated
Note:

Comparative analyses of soils at EML showed that the HCl leach method yielded
90
Sr values which averaged 91% of those obtained by the complete solution method.

H. Soil (NaOH-HCl method).
wooden roller, sieve through a No. 10 mesh screen. Record the weights of both the
fines (soil passing through the sieve) and unsieved soil.
2. Weigh a 250-g representative sample of fines and transfer to a 3-L beaker

containing a Teflon coated magnetic stirrer bar (see Note). Add 700 mL of H2O, 10
mL of Sr carrier solution, and 1 mL of 85Sr tracer solution to the beaker. Place the
beaker on a mechanical stirrer.
3. Stir the sample for 10 min. While continuing to stir, add 40 mL of 50% NaOH.
(The solution should be 1N with respect to NaOH.)
4. Remove the beaker from the mechanical stirrer and cover with a watch glass.
Digest the sample overnight on a 70-80oC hot plate.
5. Remove the beaker from the hot plate and allow to cool. While stirring
mechanically, cautiously add 900 mL of HCl to neutralize the NaOH and increase
the H+ concentra-tion to 6N. [An additional 500 mL of HCl should be added when
analyzing highly calcareous soils to replace the acid required to decompose the
carbonates.] A few drops of CH3(CH2)6CH2OH (n-octyl alcohol) may be added to
the sample to prevent excessive frothing.
6. Digest the sample overnight on a 70-80oC hot plate. Remove the beaker from the
hot plate and cool to 40-50oC.
8. Stir the sample. Suction filter the sample into the flask. Police and wash the beaker
with three 300-mL portions of hot 1:1 HCl, followed by two 300-mL portions of hot
H2O. Pour the washes through the funnel.

9. Turn off the vacuum. Remove the filter paper and residue from the funnel and place
in a 250-mL platinum crucible. Proceed with Soil Residue (HF-HNO3 - Complete
Solution).
10. Transfer the filtrate to a 3-L beaker containing a Teflon coated magnetic stirrer bar.
Wash the filter flask with H2O and transfer the washings to the beaker.
11. Place the beaker on a stirrer/hot plate. Stir and warm the solution. Add HNO3 very
cautiously until the vigorous reaction subsides. A few drops of CH3(CH2)6CH2OH
(n-octyl alcohol) may be added to the sample to prevent excessive frothing.
Continue adding HNO3 to a total of volume of 500 mL.
12. Continue to stir while evaporating the sample to 300 mL. Add 500 mL of H2O to
the sample and stir. Remove the beaker from the stirrer/hot plate and cool to room
temperature.
13. Place a double 15-cm glass fiber filter in a Büchner funnel. Mount the funnel on a
1-L filter flask.
14. Suction filter the sample through the Büchner funnel. Wash and police the beaker
with 50 mL of hot 1:9 HNO3. Pour the acid through the funnel. Wash the beaker
and filter with H2O several times.
15. Turn off the suction, remove the funnel from the flask and discard the filters.
16. Transfer the filtrate to a 3-L beaker containing a magnetic stirrer bar. Rinse the
filter flask with H2O and add the rinse to the beaker. Place the beaker on a magnetic
stirrer/hot plate and stir while warming the solution.
18. While stirring adjust the pH to 5.5 with NH4OH. If the brown color of FeO(OH)
persists, add additional H2C2O4 and readjust the pH. (The optimum condition for
the precipitation is an excess of H2C2O4 in solution insufficient to cause

crystallization of (NH4)2C2O4 upon cooling. In most cases, the sample solutions are
bright green with white precipitates visible at pH 5.5.)
19. Add a moderate excess of H2C2O4 (50-70 g) and readjust the pH to 5.5 with NH4OH.
Continue to heat and stir the solution for 30 min. Check the pH and adjust to 5.5
with NH4OH if necessary.
20. Turn off the stirrer, remove the beaker from the hot plate, and allow the precipitate
to settle overnight.
21. Slowly agitate the supernatant solution with a stirring rod without disturbing the
precipitate at the bottom of the beaker. Add 5 mL of Ca carrier solution
(200 mg Ca mL-1) and mix into the supernatant solution without disturbing the
precipitate. (The additional Ca gives more complete precipitation of SrC2O4,
especially in the presence of large amounts of Fe.)
22. Allow the new C2O4 precipitate to settle for 10-15 min. Place a 25-cm Whatman
No. 42 filter paper in a Büchner and mount the funnel in a 3-L filter flask.
23. Suction filter the sample through the funnel. Wash and police the beaker with H2O
adding the washes to the funnel. Wash the precipitate with H2O until the filtrate is
clear. If excess (NH4)2C2O4 is present, rewash the precipitate with hot water.
25. Place the platinum dish in a 450-500oC muffle furnace for 2 h. Raise the
to the beaker.

material is present, suction filter the sample through a double 11-cm glass fiber
filter into a 250-mL filter flask.
29. Wash the beaker and filters with 50 mL of 1:1 HNO3, followed by 50 mL of H2O.
Turn off the vacuum and discard the filters.
30. Return the filtrate to the 250-mL beaker. Rinse the filter flask with H2O and add the
the first two separations at concentrations of slightly > 75%, until the Sr is separated
Note:
This method was developed at the U.S. Department of Agriculture Soil Survey
Laboratory, Soil Conservation Service, Beltsville, MD. Comparative soil analyses at
EML showed that the 85Sr tracer could be completely equilibrated with 90Sr present in the
soils when treated consecutively with NaOH and HCl. The NaOH-HCl method yielded
results equal to those obtained with the complete solution method.

I. Soil residue (HF-HNO3 - complete solution).
1. To the residue in a 250-mL crucible reserved in Step 9 of the Soil (NaOH-HCl)

Method, add 10 mL of Sr carrier and 5-10 mL of Ca.
2. Dry the contents of the crucible in a 100oC oven. Place the crucible in a 500oC
muffle furnace and ash overnight.
3. Remove the crucible from the furnace and cool. Place the crucible on a low
temperature hot plate and cautiously add 20-30 mL each of HNO3 and HF.
Evaporate the sample to dryness. Repeat the acid additions several times (see Note
1).
4. Transfer the dry residue to a mortar and pestle and grind to a fine powder. Return
the residue to the platinum crucible.
5. Add 1 mL of 85Sr tracer solution to the crucible. Dry the contents of the crucible in
a 100oC oven.
6. Add Na2CO3 equivalent to four times the weight of the residue and mix thoroughly.
Place the crucible in a 900oC muffle furnace and fuse to a clear melt.
7. Remove the crucible from the oven and cool. Proceed with Step 4 in the Soil -
Complete Solution Method, but eliminate further addition of Sr carrier and 85Sr
tracer solutions (see Note 2).
Notes:
1. Upon initial addition of HNO3 and HF, strong effervescence will occur. After three
or four acid additions, the reaction subsides. Final acid additions may be performed
with increased heat (medium hot plate setting). When all reaction has ceased, add
only HNO3 and allow the sample to evaporate to dryness. Repeat the HNO3
addition twice to remove all traces of HF.
2. Adjust the reagent volumes in Step 5 in Soil (Complete Solution Method) to the
smaller mass of the fused residue (usually 50-100 g).

J. Tap water (monthly composite).
1. Measure 5 L of tap water and pour into a 20-L stainless steel pot. Add 20 mL of
HNO3 and evaporate slowly. Record all tap water and HNO3 additions.
2. Add 5-L aliquots of tap water daily and 20 mL of HNO3 weekly to the pot. After
the second week, add 1 mL of Sr carrier and 1 mL of 85Sr tracer solution to the pot.
Evaporate successively until a 1-month collection has been obtained (100 L).
3. After the final tap water aliquot has been added, evaporate the solution to 100 mL.
Transfer the solution to an 800-mL beaker with H2O. Police the inside of the pot
thoroughly with 1:1 HNO3 and add the washings to the beaker.
4. Evaporate the solution gently to near dryness and transfer the residue to a 15-mL
platinum crucible with a minimum of H2O and 1:1 HNO3 washes.
5. Evaporate gently to dryness and ash in a 450-500oC muffle furnace to destroy

organic material.
6. Add four times the ash volume (visually determined) of solid Na2CO3 to the crucible
and mix thoroughly with the ash.
8. Place a Teflon coated magnetic stirrer bar in an 800-mL beaker. Transfer the fused
9. Remove the beaker from the hot plate and cool. Place a 9-cm glass fiber filter
backed with a Whatman No. 42 filter paper into a Büchner funnel. Mount the
funnel on a 1-L filter flask.


K. Tissue and vegetation (wet ashing).
1. Cut the tissue or vegetation into small pieces (see Note).
2. Heat 500 mL of HNO3 in a 1-L beaker. Add the sample in small portions to the hot
acid.
3. When all the sample has been added to the beaker and the reaction has subsided,
add 1 mL of Sr carrier and 1 mL of 85Sr tracer solution to the beaker.
4. Evaporate the solution to 50 mL. If the solution is turbid and NO2 fumes are
evolving, repeat the evaporation with additional HNO3.
5. Complete the wet ashing with dropwise additions of HNO3 and H2O2. Gently
evaporate the solution to near dryness on a sand bath.
6. Dissolve any solid material in a minimum of 1:1 HNO3. Transfer the solution to a
400-mL beaker containing a Teflon coated magnetic stirrer bar. Wash and police
the 1-L beaker with H2O, transfering the washings to the sample beaker. Dilute the
sample to 200 mL with additional H2O.

7. Place the beaker on the magnetic stirrer/hot plate and stir. Adjust the pH to 5-6 with
solid NaOH pellets. While continuing to stir, add 2-3 g of solid Na2CO3. Heat the
sample to just below boiling and stir for 30 min.
the filter with Na2CO3 solution (100 g Na2CO3 L-1). Discard the filtrate.
1:1 HNO3. Turn on the vacuum and wash the filter with H2O. Discard the filters
and any residual material.
12. Transfer the solution with 1:1 HNO3 washings to the original 1-L beaker containing
a magnetic stirrer bar. Stir and evaporate the solution to dryness.

Note:
Most food samples may be simply leached with 1:1 HNO3, the leachate filtered and
diluted to 500 mL with H2O. After a carbonate collection, the procedure may be
continued with Step 6 above.
L. Tissue and vegetation ash (fusion).
1. Weigh 10 g of ash (see Note) and transfer to a 150-mL platinum crucible.
2. Add ~ 40 g of solid Na2CO3 to the crucible and mix thoroughly with the ash.

4. Place a Teflon coated magnetic stirrer bar in an 800-mL beaker. Transfer the fused
stirrer/hot plate and stir.
5. Add 1 mL of Sr carrier and 1 mL of 85Sr tracer solution to the sample. Heat the
sample to just below boiling and stir for 1 h.
containing a magnetic stirrer bar. Stir and evaporate the solution to dryness.

Note:
Most food samples may simply be leached with 1:1 HNO3, the leachate filtered and
diluted to 500 mL with H2O. After a carbonate collection, the procedure may be
continued with Step 6 above.

M. Urine.
1. Collect a measured 5-L volume of urine (smaller samples are adequate for suspected
occupational exposure) in a flask or bottle containing 50 mL of HNO3 and 1 mL of
Sr carrier. After the collection is completed, add 1 mL of 85Sr tracer to the sample.
2. Shake or stir the urine in the collection container to mix. Transfer a 1500-mL
aliquot of urine to a 3-L beaker. Add 750 mL of HNO3 to the beaker and stir the
sample.
3. Heat the sample and evaporate to 100 mL. Continue the addition of urine and
HNO3 in a 2:1 ratio until all the sample has been added to the beaker. Rinse the
sample container with HNO3 and add the rinse to the beaker.
4. Evaporate the sample to a small volume (< 100 mL) and complete the wet ashing of
the urine with dropwise additions of H2O2.
5. Place a Teflon coated magnetic stirrer bar in a 2-L beaker. Transfer the urine
sample from the 3-L beaker to the 2-L beaker. Wash and police the 3-L beaker with
H2O, adding the washes to the sample.
6. Dilute the sample to 1 L with H2O. Place the sample beaker on a magnetic
stirrer/hot plate. Heat gently and stir for 15 min.
7. Remove the beaker from the hot plate and cool. Place a 7-cm Whatman No. 42
filter paper into a Büchner funnel. Mount the funnel on a 2-L filter flask.
8. Filter the sample with suction. Wash and police the beaker with 1:1 HNO3 and add
the washings to the funnel. Wash the filter with H2O.
9. Turn off the vacuum and transfer the filter paper to a 150-mL platinum crucible.
Reserve for Step 13.
10. Transfer the filtrate back to the 2-L beaker containing the magnetic stirrer bar.
Rinse the filter flask with H2O and add the rinsings to the beaker.

11. Place the beaker on a magnetic stirrer/hot plate. While stirring, add 203 mL of
H3PO4 to the sample. Adjust the pH to 5-6 with the addition of solid NaOH pellets.
Raise the pH to 10 with the addition of NaOH solution (240 g NaOH L-1).
12. Continue stirring the sample for 30 min. Remove the beaker from the stirrer/hot
plate and allow the phosphate precipitate to settle overnight.
13. Dry the reserved filter paper (from Step 9) in a 110oC oven. Place the crucible in a
450-500oC muffle furnace and ash to destroy organic material.
14. Add approximately four times the ash volume (visually determined) of solid
Na2CO3 to the crucible and mix thoroughly with the ash.
16. Place a Teflon coated magnetic stirrer bar in a 400-mL beaker. Transfer the fused
17. Filter the two precipitates from Steps 12 and 16 with suction into a 2-L filter flask
through the same 15-cm glass fiber filter backed with a Whatman No. 42 filter
paper. Remove the funnel from the filter flask and discard the filtrate.
18. Replace the funnel on the filter flask. Dissolve the mixed phosphate-carbonate
precipitates on the filter with hot 1:1 HNO3. Turn on the vacuum and wash the filter
with hot 1:1 HNO3. Discard the filters and any residual material.


DETERMINATION
A. Final HNO3 separation.
1. Remove the beaker from the stirrer/hot plate. Cool the beaker and allow the nitrates
to settle (see Note).
2. Place a 5.5-cm glass fiber filter in a Büchner funnel and mount the funnel in a 1-L
filter flask.
3. Suction filter the sample into the flask. Turn off the vacuum, remove the funnel
from the flask and set aside.
4. Discard the filtrate and rinse the filter flask with H2O. Discard the wash.
5. Replace the funnel in the flask. Apply a vacuum while washing the beaker and
filter with H2O to dissolve the precipitate.
6. Turn off the vacuum, remove the funnel and discard the filter.
7. Transfer the solution from the filter flask to a 150-mL beaker with H2O rinsings.
Evaporate the solution slowly to dryness.
8. Place a magnetic stirrer bar in the beaker. Add 23 mL of H2O to the beaker, stir,
and warm to dissolve the residue. Add 77 mL of 90% fuming HNO3 to the beaker
and continue heating and stirring for 30 min.
9. Turn off the stirrer and remove the beaker from the hot plate. Cool the sample,
allowing the Sr(NO3)2 to settle.
10. Suction filter the precipitate through a double 2.8-cm glass fiber filter with a Fisher
filtrator and Teflon filter assembly into a 250-mL beaker.
11. Turn off the vacuum and remove the beaker from the filtrator. Discard the filtrate.

12. Place a 40-mL heavy wall conical centrifuge tube in a 250-mL beaker and set inside
the filtrator under the filter assembly.
13. Dissolve any remaining precipitate in the sample beaker with a minimum of H2O.
Pour through the funnel, collecting the solution in the centrifuge tube. Wash the
filter with H2O, keeping the volume < 20 mL.
Note:
If the yield is to be determined by the gravimetric method all the Ca must be

separated from the Sr. A sufficient number of fuming HNO3 separations, usually four to
five, must be performed to ensure complete Ca separation. Under these conditions Ba
and Pb also precipitate but are removed in subsequent OH-1 and CrO4-2 scavenging steps.
If the yield is to be determined by measurement of the 85Sr tracer, a few mg of Ca may
remain with the Sr.
B. First milking.
1. Add 1 mL of Fe carrier solution to the separated Sr fraction in the centrifuge tube.

Stir the solution and place the tube in a 90oC water bath to warm.
2. While stirring, adjust the pH of the sample to 8 with NH4OH. Remove the
centrifuge tube from the water bath and cool to room temperature in a cold water
bath. Remove and rinse the stirring rod.
3. Centrifuge the sample for 5 min. Decant the supernate into a second 40-mL
centrifuge tube. Reserve the supernate for Step 6 and note the hour and date of this
initial OH-1 precipitation as "First Milk Separation Time."
4. Dissolve the precipitate in the first centrifuge tube in a few drops of HCl and dilute
to 5-10 mL with H2O. Stir the solution and warm the tube in the hot water bath.
bath. Remove and rinse the stirring rod with H2O.

supernate reserved from Step 3. Discard the residue in the first centrifuge tube.
Adjust the volume of the combined supernates to 20 mL with H2O.
7. While stirring, add 4 mL of Ba buffer solution to the sample. Adjust the pH of the
sample to 5.5 with either 1:1 HCl or NH4OH (see Note 1).
8. Return the centrifuge tube to the hot water bath. While stirring, add 1 mL of 0.3M
Na2CrO4 dropwise to the sample. If necessary, while stirring add additional
Na2CrO4 solution dropwise to give a strong yellow CrO4-2 color to the solution (see
Note 2). Allow the sample to digest in the water bath for 10 min.
9. Remove and rinse the stirring rod with H2O. Remove the sample tube from the hot
10. Centrifuge the tube for 5 min. Decant the supernate into a 30-mL polyethylene
bottle. Discard the residue in the centrifuge tube.
11. Add 10-15 drops of HCl and exactly 1 mL of Y carrier solution to the sample in the
polyethylene bottle.
12. Store the sample for 2 weeks to allow equilibration of 90Y (see Note 3).
Notes:
1. The pH of the solution is critical at this point. Complete precipitation of BaCrO4

will not occur in a more acid solution and Sr will partially precipitate in more basic
solutions.
2. If large quantities of Ba are present in the sample; i.e., soils, a partial precipitation
as the BaCrO4 may occur. The sample is centrifuged and the supernate decanted
into another 40-mL centrifuge tube. The precipitation is completed by the dropwise
addition of 0.3M Na2CrO4 and the analysis is continued with Step 10.

3. If less than complete buildup of 90Y is acceptable, the "First Milk Separation Time"
noted in Step 3 is the start of the build-up period. A correction for 90Y buildup
between the first and second milking must be included in the calculation.
C. Strontium-85 yield measurement.
1. Dilute the sample solution from Step 12 of First Milking to the bottom of the neck
of the polyethylene bottle with H2O.
2. Measure the activity of the sample with a NaI(Tl) crystal, collecting at least 104
counts. Transfer a 1-mL aliquot of the original tracer solution in a 30-mL poly-
ethylene bottle and dilute to the bottom of the bottle neck with 1N HCl. Measure
the activity of the tracer solution.
3. Calculate the 85Sr yield of the sample compared with the unprocessed tracer
solution.
D. Second milking.
1. Transfer the sample from the polyethylene bottle to a 40-mL, heavy-walled, conical
centrifuge tube. Rinse the bottle with a minimum of H2O and add the rinse to the
centrifuge tube. Stir the solution and place the tube in a 90oC water bath to warm.
2. While stirring, adjust the pH of the sample to 8 with NH4OH. Add six drops of
H2O2 to the sample and heat for 1 h to remove excess H2O2. Remove the centrifuge
tube from the water bath and cool to room temperature in a cold water bath.
Remove and rinse the stirring rod.
3. Centrifuge the sample for 5 min. Decant the supernate into a 60-mL polyethylene
bottle. Record the hour and date of the precipitation as "Second Milk Separation
Time."
4. Dissolve the precipitate in the centrifuge tube with four drops of HCl and stir.
Dilute the sample to 15-20 mL with H2O. Stir the solution and warm the tube in the
hot water bath.

bath. Remove and rinse the stirring rod with H2O.
supernate reserved from Step 3. Reserve the supernates for possible additional
milking. (Note: Steps 7-10, below, are designed to remove traces of 85Sr from the
90
Y fraction. If a gravimetric yield determination is to be made, these steps may be
omitted.)
7. Add 25-30 mL of H2O to the precipitate. Add four drops of HCl to the tube and stir
until the precipitate dissolves.
8. Add 20 mg of Sr holdback carrier to the tube and stir. Place the centrifuge tube in
the hot water bath. While stirring, adjust the pH to 8 with NH4OH.
9. Remove and rinse the stirring rod with H2O. Remove the sample tube from the hot
10. Centrifuge the tube for 5 min. Decant and discard the supernate.
11. Add three drops of HCl to dissolve the precipitate (from Step 6 or Step 10), stir to
dissolve, and add 25-30 mL of H2O.
12. Stir the sample and place the tube in a hot water bath. Add 1 mL of saturated
H2C2O4 (oxalic acid) dropwise with vigorous stirring.
13. Add two to three drops of NH4OH with stirring. Continue the dropwise addition of
NH4OH to adjust the pH to 2-3. Digest the sample in the hot water bath for 1 h.
14. Remove the tube from the hot water bath. Rinse and remove the stirring rod from
the tube. Cool the tube to room temperature in a cold water bath.
15. Centrifuge the tube for 10 min. Decant and discard most of the supernate.

16. Using a Teflon filter funnel assembly, filter the precipitate by suction through a
weighed 2.8-cm Whatman No. 42 filter paper, backed with a 2.8-cm glass fiber
filter.
17. With the suction on, remove the filter funnel. Turn off the vacuum and remove the
filtered precipitate. Discard the filtrate.
18. Dry the filtered precipitate in a 110oC oven. Weigh the filtered precipitate to
determine the gravimetric yield.
19. Mount the filtered precipitate on a nylon disc, place a plastic ß scintillation
phosphor directly on the precipitate, cover the phosphor with Mylar, and fasten the
assembly with a nylon ring.
20. Store the mounted sample for 3 h prior to measurement to allow the decay of short-
lived 222Rn progeny present due to the filtration operation.
21. Measure the sample in a low-level ß scintillation counter, recording the hour and
date of the beginning of the measurement period.
22. Calibrate the beta counter with a 90Y standard which has been precipitated and
mounted in the identical manner as the sample.
E. Gravimetric Sr yield determination.
1. Transfer the solution from the polyethylene bottle, Step 6 under Second Milking, to
a 150-mL beaker and gently heat to a boil on a hot plate.
2. With continuous stirring, cautiously add 5-10 mL of saturated Na2CO3 solution to

the sample. Continue to heat gently for 10 min.
3. Remove the beaker from the hot plate and cool to room temperature. Place a
preweighed 5.5-cm glass fiber filter in a Büchner funnel mounted in a 250-mL filter
flask.

4. Suction filter the precipitate using care to prevent the precipitate from creeping
under the filter. This can be accomplished by filtering only through the center area
of the filter.
5. Wash the beaker, precipitate, and filter thoroughly with H2O, followed by C2H5OH.
Turn off the vacuum and remove the filtered precipitate from the funnel.
6. Dry the filter in a 110oC oven. Weigh the filter.
7. Determine the Sr concentration of the original Sr carrier solution by precipitating

SrCO3 from a 10-mL aliquot of the solution as described above.
8. Determine the gravimetric Sr yield of the sample.
F. Gravimetric Y yield measurement.
1. Determine the weight of yttrium oxalate as described in Steps 15-18 of Second

Milking.
2. Standardize triplicate 10-mL aliquots of the original Y carrier solution each time a
fresh batch is made by precipitating the oxalate as described and filtering on a
weighed 5.5-cm glass fiber filter.
CALCULATIONS
The ß counting data obtained from the 90Y precipitate must be corrected to give the
proper radioactivity rate representing the 90Sr in the sample. The corrections include
those for buildup of 90Y, counter background, 90Y efficiency, Sr yield, Y yield, and 90Y
decay. As the 90Y beta is very energetic and is always counted with the same weight of
precipitate, no correction for self-absorption is necessary.
Ordinarily no correction is made for the degree of buildup of 90Y during the
equilibration since a 2-week build-up period gives over 97% of the expected equilibrium
value. When shorter build-up periods are used to hasten analysis, however, appropriate
correction must be made.

The counter background is determined weekly, but the value used is a running mean
for 8 weeks. The efficiency is determined twice a month by counting the 90Y derived
from a 90Sr standard of known activity rate. The procedure at EML is to weight 20 mg of
SrCO3 prepared with a known specific activity (~ 0.1 Bq mg-1). The 90SrCO3 is dissolved
in H2O and HCl and the second milking procedure is carried out. The running mean for 8
weeks is used for the efficiency.
The Sr yield is ordinarily determined by measuring the recovery of 85Sr tracer added
to the sample. Since an aliquot of the original 85Sr tracer solution is counted at the same
time as the samples, there is no need to know the radioactivity rate of the tracer nor to
apply decay corrections.
A correction must be made for the decay of 90Y from the time of the second milking
to the time of measurement. This may be done graphically by reading the decay factor
from the graph shown in Figure 1.
A sample computational data sheet, which is used for recording and checking
calculations, is reproduced on the following pages. The present calculations are handled
entirely by computer.

Yield (Sr) (%) 80
Yield (Y) (%) 100
Blank (cps)
LLD (400 min) (Bq) 0.007

LLD (1000 min) (Bq) 0.003

APPENDIX
A. Purification of yttrium carrier.
1. Dissolve 100 g of Y nitrate, Y(NO3)3 6H2O, in 80 mL of water. Add a few drops of

HNO3. Transfer to a 1-L separatory funnel using two 20-mL portions of H2O.
2. Add 120 mL of saturated NH4NO3 to the separatory funnel. Add 240 mL of tributyl
phosphate (TBP) to the separatory funnel and shake for 5 min. Allow the phases to
separate for 10 min.
3. Draw off the aqueous (lower layer) into a second separatory funnel. Add 240 mL of
fresh TBP and shake for 5 min. Allow the phases to separate and discard the
aqueous (lower layer).
4. Combine both TBP phases in one separatory funnel, add 20 mL of H2O and shake
for 5 min. Allow the phases to separate and transfer the aqueous (lower layer) to a
clean separatory funnel.
5. Repeat the H2O wash and combine the aqueous fractions. Discard the TBP.
6. Add 50 mL of CCl4 to the H2O solution, shake for 1 min, and allow to separate.
Discard the CCl4.
7. Dilute to 2 L with H2O and store in polyethylene.
B. Yttrium carrier counting check.
1. Pipette 1 mL of Y carrier into each of three 40-mL centrifuge tubes. Dilute to 20

mL with H2O.
2. Heat in a water bath to about 90oC. With stirring, adjust the pH to 8 with NH4OH.
Digest for 10 min and cool in a cold water bath.
3. Centrifuge for 5 min. Decant and discard the supernate.

4. Break up the precipitate with a few mL of H2O. Dilute to 20 mL with H2O. Add a
few drops of concentrated HCl to just dissolve the precipitate. Heat the solution in a
water bath to about 90oC and add 1 mL of saturated H2C2O4 (oxalic acid) dropwise
while stirring.
5. Allow the precipitate to digest for about 1 h. Cool to room temperature and filter on
a 2.8-cm Whatman No. 42 filter paper. Discard the filtrate.
6. Dry in a 110oC oven. Mount with a nylon ring and disc with a ß scintillation
phosphor and count.

Figure 1. Decay of 90Y (T1/2 = 64.6 h).

Technetium

HASL-300, 28th Edition November 1999
Tc-01-RC
TECHNETIUM-99 IN WATER AND VEGETATION
APPLICATION
This procedure has been applied to the analysis of water and vegetation.
Technetium-99 is equilibrated with 95mTc tracer. The technetium is separated from

other elements by anion exchange and electrodeposition. The 99Tc is $ counted. Gamma
spectrometry measurement of 95mTc provides the chemical yield.
SPECIAL APPARATUS
1. Virgin platinum discs - 17.6 mm diameter x 0.127 mm mirror finish on one side.
2. Plating cells - see Specifications 7.15 and 7.16, Vol. I.
3. Electrodeposition power supply - constant, capacity 0-1.5 A, 0-20 V; transistorized

variable speed stirring motor.
5. Mylar film - see Specification 7.3, Vol. I.
6. Beta phosphor - see Specification 7.9, Vol. I.
7. Rings and discs - see Specification 7.2, Vol. I.
8. Germanium lithium, Ge(Li), (-ray spectrometer.

SPECIAL REAGENTS
99
1. Tc standard solution - available from NIST.
2. Technetium-95m tracer solution (free from 97mTc) - prepared by helium nuclei

bombardment of pure 93Nb foil in a cyclotron. (Special production on request at
Brookhaven National Laboratory, Upton, NY).
3. Methyl red indicator solution - dissolve 100 mg of the dye in 65 mL of ethyl alcohol
and dilute to 100 mL with water.
4. Bio-Rad AG 1-X4 (100-200 mesh, Cl- form) anion exchange resin or equivalent -
see Specification 7.4, Vol. I.
5. 6M sodium hydroxide solution - 240 g NaOH L-1 of water.
6. 2M sodium carbonate solution - 212 g Na2CO3 L-1 of water.
7. Calcium solution - 200 mg Ca mL-1 - dissolve 500 g CaCO3 in a minimum of 6M

HCl and dilute to 1 L with 0.1M HCl.
8. Barium solution - 20 mg Ba mL-1 - 30.4 BaCl2 L-1 of 0.1M HCl.
9. Iron solution - 5 mg Fe mL-1 - dissolve 36 g Fe(NO3)3•9 H2O in 1 L of 0.2M HNO3.
10. 5M HNO3 eluting solution - dilute 310 mL of HNO3 to 1 L.
11. 0.1M HNO3 wash solution - dilute 6.5 mL of HNO3 to 1 L.
SAMPLE PREPARATION
A. General.
Technetium is volatile at elevated temperatures. The samples are prepared by wet

ashing with nitric acid.

To a measured quantity of sample in a glass beaker, add a known amount of 95mTc

tracer which gives 60 counts sec-1 at 204 keV as of count date on a Ge(Li) (-ray
spectrometer.
B. Water.
Evaporate the sample to a small volume. Cool and transfer the sample solution to a
1 L beaker. Dilute the sample solution to 800 mL with H2O. Stir the sample solution and
filter with suction through a 15 cm glass fiber filter. Wash the filter with H2O. Discard
the filter which contains the silica and insoluble material.
C. Vegetation.
Wet ash the sample with HNO3. After wet ashing is completed, evaporate the to the
smallest volume possible with no salting out. Cool and transfer the sample solution to a
1 L beaker. Dilute the sample solution to 800 mL with H2O. Stir the sample solution and
filter with suction through a 15 cm glass fiber filter. Wash the filter with H2O. Discard
the filter which contains the silica and insoluble material.
SEPARATION
1. Transfer the filtrate into the original 1 L beaker and evaporate to about 200 mL.
2. Add 1 mL of 200 mg Ca mL-1, 5 mL of 20 mg Ba mL-1, and 10 mL of 5 mg Fe mL-1

to the sample solution. Place a magnetic stirring bar in the beaker and stir to mix.
3. With continuous mechanical stirring, add 6M NaOH until the solution is alkaline to
pH paper. Then add about 60 mL of 2M Na2CO3.
4. Filter the sample with suction through a double 15-cm glass fiber filter. Discard the
precipitate, which should contain any alkaline earth metals, transition metals, rare
earths, Sr, actinides, Ra, Pb, CrO4-2, PO4-3, and SO4-2.
5. Transfer the filtrate with water back into the 1 L beaker.
6. Add five drops of methyl red indictor to the filtrate.

7. Adjust the pH to the red end point of the indicator (pH 4.2) with 8M HNO3.
8. Prepare an ion exchange column containing 10 mL of settled Bio-Rad AG 1-X4

(100-200 mesh, Cl- form). Place a 1 L beaker under the column and condition the
resin with 100 mL of 0.1M HNO3.
9. Pass the sample solution from Step 5 through the resin bed at a full flow.
10. Wash the column with 500 mL of 0.1M HNO3. Discard the column effluent and
washes.
11. Place a 250 mL beaker under the column. Elute the technetium with 100 mL of 5M
HNO3. (Note: This anion exchange procedure separates the technetium from most
other elements, but not from chromate. However, the chromate should have
precipitated as a barium chromate during the earlier alkaline precipitation.)
12. Evaporate the eluate to dryness or near dryness, avoiding excessive heat.
ELECTRODEPOSITION
1. Add 1 mL of HCl to dissolve the sample residue in the beaker. Transfer the sample
solution to an electroplating cell which contains a platinum disc, using three
successive 1 mL water washes to complete the transfer.
2. Add one drop of 0.1% methyl red indicator. Add NH4OH dropwise until the
solution is yellow. Add the minimum amount of 2.5M dropwise until the solution is
red, then add two drops of 2.5M in excess.
3. Dilute the sample solution in the electrodeposition cell to 5 mL with water and
connect to the electrodeposition apparatus. Electroplate onto the platinum disc
cathode while stirring at a current of 1.2 A. The plating cell is supported on a lucite
pedestal which is immersed in an ice water bath throughout the electrodeposition.
4. Observe the voltage versus time. (A strip chart recorder recorder may be used.).
When the curve breaks (after about 1 h), quench the electrolyte with 1 mL of

NH4OH. Immediately turn off the current, dismantle the cell, and rinse the
electroplated disc with water and ethanol. Dry the disc on a hot plate with gentle
heat.
5. Mount the plated platinum disc on a nylon disc. Centering is facilitated if the
plastic discs are machined with an appropriate sized, shallow depression. Place a $
scintillation phosphor directly over the platinum disc, cover with Mylar, and fasten
with a nylon ring.
MEASUREMENTS
Measure the platinum sample disc with a Ge(Li) (-ray spectrometer, integrate the
204 keV line and record the date and time. Determine the spectrometer response at this
energy for a 100% chemical yield with platinum discs onto which known quantities of
95m
Tc from the stock tracer solution have been electroplated. The ratio of these two
activities, corrected to the same date, provides the chemical yield of the sample.
Measure the platinum sample disc in a low-level $ scintillation counter and record
the date and time. Determine the counting efficiency of this system for 99Tc with
platinum discs containing known quantities of 99Tc. Also measure the platinum discs
electroplated with known quantities of 95mTc and record the date and time. The 99Tc
activity in the sample is determined by correcting for counter background and for the $
contribution from the 95mTc tracer, and by adjusting for chemical yield and counting
efficiency:
99
Tc (Bq sample-1) =
where
A = net $ cps of sample
C = $ cps from 95mTc tracer
Y = chemical yield
E = counting efficiency

and
C=(•R
where
( = net ( cps of sample from the Ge(Li) (-ray spectrometer at 204 keV, decay
corrected to the time of the sample $ count.
R = mean ratio of the net $ cps of the 95mTc standard discs to the net ( cps of these
same discs from the Ge(Li) (-ray spectrometer at 204 keV; both activities are
decay corrected to the same time. For the EML systems, this ratio (R) is
about 0.5.

Yield (%) 80
95m
Tc Interference* (cps) 0.007
LLD (1000 sec) (mBq) 6.7

LLD (3000 sec) (mBq) 3.3
LLD (10,000 sec) (mBq) 1.7
*
The 95mTc tracer interacts with the phosphor in the EML
low-level $ scintillation counters producing about 0.5
counts sec-1 for each counts sec-1 registered in the 204 keV
photopeak of our Ge counts (Li) (-ray spectrometer. The
95m
Tc interference can be reduced by a factor of two if the
sample is held 61 days, one half-life of 95mTc, before $
counting.

Thorium

Th-01-RC
THORIUM IN URINE
APPLICATION
This procedure was developed primarily for the estimation of Th in urine from
medically and occupationally exposed persons (Fisenne et al., 1986).
Thorium is equilibrated with 234Th tracer and collected from wet-ashed urine by
coprecipitation with Ca as the acidic oxalate. The Th is then separated from Ca by
coprecipitation with Fe hydroxide and purified from Ra and most other " emitters by
anion exchange in an 8N HNO3 medium. Finally, Th is electrodeposited on a platinum
disc from a dilute HCl solution. (Note: The Th may be prepared for " spectrometry by
the microprecipitation method, Procedure G-03, Vol. I). The 228Th, 230Th, and 232Th
contents are determined by " spectrometry after measuring the total Th recovery by ß
counting the 234Th tracer. Radium can be determined in the same sample.
SPECIAL APPARATUS
2. Plating cells - see Specification 7.16, Vol. I.
SPECIAL REAGENTS
1. Thorium-234 tracer solution (see Appendix).
2. Bio-Rad AG 1-X4 (100-200 mesh) anion exchange resin - see Specification 7.6,
Vol. I.
3. Oxalic wash solution - prepare a dilute oxalic solution so that the pH is 3.5.

SAMPLE PREPARATION
1. Add a weighed amount of 234Th tracer (about 2000 ß cps) to the urine sample and
reagent blanks.
2. Wet ash the urine with HNO3 and evaporate to a small volume.
3. Add 500 mL of H2O, 100 mg of additional Ca, and 1 g of oxalic acid. Stir with a
magnetic stirrer.
4. Adjust the pH to about 3.5 with NH4OH.
5. Cool and filter by gravity on a Whatman No. 42 filter paper. Wash the precipitate
with oxalic acid wash solution. (Note: Save the filtrate and washings for Ra
determination.)
6. Place the precipitate and filter paper in a 400 mL beaker and wet ash with HNO3.
Evaporate just to dryness.
7. Dissolve the residue with HNO3, add 200 mL H2O, and 10 mg of Fe carrier. Adjust
the pH to 8 with NH4OH.
8. Cool and filter by gravity on a Whatman No. 42 filter paper. Wash the precipitate
with H2O. (Note: Save the filtrate and washings for Ra determination. Combine
with the filtrate from Step 5.)
9. Place the precipitate and filter paper in a 250-mL beaker and wet ash with HNO3.
Evaporate just to dryness.
10. Dissolve the residue with HNO3 and transfer to a 90-mL centrifuge tube with H2O.
Adjust the pH to 8 with NH4OH.
11. Centrifuge and add the supernate to the solutions reserved for Ra determination.
12. Dissolve the precipitate in the centrifuge tube with 40 mL of 8N HNO3.
DETERMINATION

1. Prepare an ion exchange column (see Specification 7.5, Vol. I) with 15 mL of

purified Bio-Rad AG 1-X4 (100-200 mesh) resin (see Specification 7.5, Vol. I).
Condition with 200 mL of 8N HNO3. Check the column effluent with AgNO3 to
insure that the column is Cl- free.
2. Pass the sample from Sample Preparation, Step 12, through the column at a flow
rate of 1 mL min-1.
3. Wash the column with 200 mL of 8N HNO3. (Note: Combine the effluent and
wash solutions with the solutions reserved for Ra determination. This combined
solution may be used for the determination of Ra by coprecipitation with Ba as the
SO4-2 and measurement by Rn emanation.)
4. Elute the Th into a 250 mL beaker with 200 mL of 1N HNO3. Discard the resin.
5. Evaporate the solution to dryness, wet ash the residue with HNO3 and evaporate to
dryness again.
6. See Electrodeposition of the Actinides: Talvite Method, G-02, Vol. I.
7. Measure the 234Th activity by ß counting to determine the Th recovery.
8. Measure the 232Th, 230Th, and 228Th by " spectrometry and correct for 234Th recovery.

230
Th, 232Th 228
Th
Counter Efficiency (%) 40 40

Counter Background (cps) 1.7x10-5 8.3x10-5
Yield (%) 70 70
Blank (cps) - -
LLD (400 min) (mBq) 0.44 1.0
LLD (1000 min) (mBq) 0.28 0.62
* Reagent blanks must be analyzed with the samples.

APPENDIX
PREPARATION OF 234Th TRACER SOLUTION
A. Column preparation.
Prepare three anion exchange columns (see Specification 7.5, Vol. I) with 25 mL of
Bio-Rad AG 1-X4 (100-200 mesh, Cl- form) resin (see Specification 7.4, Vol. I).
Convert the resin to the proper form by washing with 10 column volumes (250 mL) of
7N HCl.
B. Initial separation.
1. Weigh 5 g of U3O8 into a 250-mL beaker and dissolve in HCl.
2. Dilute the solution with 100 mL of 7N HCl.
3. Transfer the solution to the ion exchange column, police, and wash the beaker with
7N HCl. Transfer the washings to the column.
4. Wash the column with 250 mL of 7N HCl.
5. Discard the effluent and washings containing 234Th and 230Th.
6. Strip the U from the column with 250 mL of 1N HCl into a 400-mL beaker.
Evaporate the solution to dryness.
7. Allow the 234Th (24.1 day) to build up for 24 h. (Note: Allowing a 24 h build-up
period produces about 1500 Bq of 234Th and only 0.17 Bq of 230Th.)
C. Final tracer preparation.
1. Dissolve the previously separated U salt in 100 mL of 7N HCl.
2. Transfer the solution to a 7N HCl anion exchange column, police, and wash the
beaker with 7N HCl. Transfer the washings to the column.
3. Allow the solution to drain into a 250-mL beaker.

4. Transfer the effluent to a second ion exchange column. Collect the effluent
containing the 234Th in a 400-mL beaker.
5. Wash the second column with 50 mL of 7N HCl. Combine with the effluent in the
400-mL beaker.
6. Strip the U from the two columns with 250 mL of 1N HCl. Combine the solutions,
evaporate to dryness, and retain the salt for future additional tracer production.
Discard the resin.
7. Evaporate the 234Th solution to near dryness, wet ash with HNO3, and make up to
50 mL of 1N HNO3. Store the 234Th tracer solution in a polyethylene bottle.
8. Weigh an aliquot of 234Th tracer solution onto a platinum disc, dry, flame, and beta
count.
Note:
For sequential U-Th analyses, the 234Th tracer solution must be checked either by
fluorimetry or " spectrometry for possible U contamination.

Uranium

U-01-RC
ENRICHED URANIUM IN URINE
APPLICATION
The procedure described is capable of handling up to 1 L of urine or water

(Hindman, 1983; Sill and Williams, 1981; Welford et al., 1960).
Uranium is collected by alkaline phosphate precipitation and is isolated from urine

constituents by ion exchange. The uranium is microprecipitated for "-spectrometry
measurement. Uranium-232 tracer is used to determine the chemical recovery.
SPECIAL APPARATUS
2. Mercury cathode apparatus, Eberbach Dyna-Cath or similar.
3. Polyethylene dispensing bottles - see Specification 7.11, Vol. I.
procedure, G-03, Vol. I.
SPECIAL REAGENTS
1. Bio-Rad AG 1-X4 (100-200 mesh), anion exchange resin - see Specification 7.4,
Vol. I.

3. Mercury - triply distilled.
SAMPLE PREPARATION
1. Add 20 mL of 1:9 phosphoric acid and 150 mL of HNO3 to 1 L of a 24 h urine

specimen in a 1500-mL beaker. Add a known aliquot, about 0.1 g of 232U tracer
solution (see Note 1).
2. Cover and boil gently for 1 h. Allow to cool slightly and add NH4OH to precipitate
the alkaline earth phosphates (~ pH of 9). Add 10 mL of NH4OH in excess.
3. Digest on a steam bath with occasional stirring for 1 h.
4. Filter by gravity on a 15 cm Whatman No. 41 filter paper and discard the filtrate.
5. Wash the original beaker with four 25-mL portions of 1:1 HNO3, pouring the acid
through the paper each time to dissolve the precipitate. Collect the solution in a
250 mL beaker. Discard the filter paper.
6. Wet ash the residue to a white salt by the addition of small amounts of HNO3 and
evaporate to near dryness on a medium hotplate.
7. Convert the solution to the Cl- form with two successive 5-mL portions of HCl.
Evaporate the solution to dryness on a medium hotplate.
8. Dissolve the residue in a minimum of 7N HCl (#50 mL), with heating and stirring.
Cool the solution to room temperature.
DETERMINATION
1. Pass the solution through a prepared resin column (see Note 2) at a flow rate of
<2 mL min-1. Discard the effluent.
2. Wash the column with 400 mL of 7N HCl at a flow rate of 2 mL min-1.

3. Elute the U from the resin with 200 mL of 1N HCl, collecting the eluate in a 250-
mL beaker. Discard the resin.
4. Evaporate the eluate to near dryness.
Notes:
results.
2. Transfer 10 mL of the wet resin to the ion exchange column, pass 7N HCl through
the column until the effluent is 7N. About 200 mL of 7N HCl is necessary. Use
fresh resin for each sample.
GENERIC MERCURY CATHODE ELECTROLYSIS SEPARATION
Note:
Removal of iron is not required when the microprecipitation source preparation is

performed, see Procedure G-03, Vol. I.
2. Evaporate the solution to dryness. Dissolve the residue in a few drops of HCl. Cool
the beaker and add 75 mL of 2:98 H2SO4. Warm the beaker gently to dissolve any
residue and cool to room temperature.
3. Add 20 mL of Hg to the beaker. Electrolyze the solution with the Hg cathode unit
for 1 h at 5 A. Remove the electrodes and rinse with H2O.
4. Gravity filter the sample through a 15 cm Whatman No. 41 paper into a 250-mL
beaker. Wash the filter and Hg with hot water. Reserve the Hg for cleaning and
reuse. Discard the filter.
5. Evaporate the filtrate to SO3 fumes. Destroy any organic matter with dropwise
additions of HNO3.

6. Convert the sample to the Cl- form with three successive additions of 5 mL of HCl.
Evaporate the solution to dryness.
7. Follow Microprecipitation of the Actinides, Procedure G-01. Note:The sample may

be prepared for " spectrometry using Electrodeposition of the Actinides, Talvitie
Method, Procedure G-02, Vol. I.

3.33x10-6 for 235U
6.67x10-6 for 234U
Yield (%) 75

5.00x10-5 for 235U
1.00x10-3 for 234U
LLD (400 min) (Bq) 6.7x10-4 for 238U

6.7x10-4 for 235U
3.2x10-3 for 234U
LLD (1000 min) (Bq) 4.7x10-4 for 238U

4.7x10-4 for 235U
2.0x10-3 for 234U
LLD (5000 min) (Bq) 2.0x10-4 for 238U

2.0x10-4 for 235U
8.3x10-4 for 234U

REFERENCES
Hindman, F. D.
"Neodymium Flouride Mounting for Alpha Spectrometric Determination of Uranium,
Anal. Chem, 55, 2460-2461 (1983)

Anal Chem, 53, 412-415 (1981)
Welford, G. A., R. S. Morse and J. S. Alercio

Am. Ind. Hyg. Asso. J., 21 (1960)

*EPA APPROVED*
U-04-RC
URANIUM IN BIOLOGICAL AND ENVIRONMENTAL MATERIALS
APPLICATION
This procedure has been used to analyze bone, soil, food, tissue, air filters, and
water samples (Welford et al., 1960).
Uranium is leached from the dry-ashed residue, isolated by anion exchange

chromatography plus Hg cathode electrolysis and is determined by its fluorescence when
fused with NaF and exposed to ultraviolet light.
SPECIAL APPARATUS
See Uranium in Urine - Fluorimetry (Procedure U-01-E).
In addition:
2. Mercury cathode electrolysis unit (Eberbach Dyna-Cath or similar).
3. Polyethylene dispensing bottle - see Specification 7.11, Vol. I.
*

SPECIAL REAGENTS
In addition:
1. Bio-Rad AG 1-X4 (100-200 mesh) anion exchange resin - see Specification 7.4,
Vol. I.
232
2. U tracer solution ~ 40 Bq g-1 of solution in a dispensing bottle.
3. Mercury - triply distilled.
SAMPLE PREPARATION
A. Bone and tissue.
1. Dry ash the sample according to the procedure used for 90Sr (see Sr-02-RC).
2. Weigh out 10 g of ash into a 400-mL beaker. Add a weighed aliquot (~ 0.1 g) of
232
U tracer solution (see Note 1).
3. Add 200 mL of HNO3 to the beaker and evaporate slowly to dryness.
4. Repeat acid addition and evaporation with 25-mL portions of HNO3 until a white
residue is obtained (see Note 2).
5. Add 25 mL of HCl. Evaporate to dryness and repeat the HCl addition and
6. Dissolve the residue in a minimum (# 50 mL) of 7N HCl.
7. Continue with Separation.

B. Food and soil.
1. Weigh 10 g of food ash or soil into a 100-mL platinum dish and add a weighed
amount (~ 0.1 g) of 232U tracer solution (see Note 1).
2. Dry on a hot plate and fuse with four times the sample weight of Na2CO3 in an
electric muffle furnace at 900oC.
3. Cool and transfer the melt to a 400-mL beaker. Place a magnetic stirring bar in the
beaker.
4. Wash the platinum dish with 25 mL of HNO3. Add the washings slowly to the
beaker. Add an additional 75 mL of HNO3 to the beaker. Cover the beaker and
place on a pyromagnetic stirrer unit.
5. Add 100 mL of HClO4 to the beaker and heat while stirring until perchloric acid
fumes are evolved.
6. Remove the beaker from the stirrer unit. Cool, add 100 mL of HNO3 and heat with
stirring until the total volume is reduced to ~ 75 mL.
7. Cool the beaker and add 150 mL of H2O. Filter by gravity through a Whatman
No. 42 filter paper.
8. Wash the precipitate with 100 mL of hot 1:10 HNO3 followed by an equal volume
of hot water. Discard the residue.
9. Evaporate the filtrate slowly to dryness. Repeat the acid treatment and evaporation
if necessary to obtain a white residue.
10. Add 25 mL of HCl. Evaporate to dryness and repeat the HCl addition and the

C. Water.
1. Evaporate the total H2O sample to a small volume.
2. Add a weighted quantity of 232U tracer solution (~ 0.1 g) and evaporate to dryness.
Dissolve the residue in 100 mL of HNO3 (see Note 1).
3. Evaporate several times with additions of 25-mL portions of HNO3 (see Note 2).
addition and evaporation twice more.
5. Dissolve the residue in a minimum (# 50 mL) of 7N HCl and continue with

Separation.
D. Air filters.
1. Add a weighted aliquot (~ 0.1 g) of 232U tracer directly to the filter in a platinum
dish and dry ash in an electric muffle at 550oC overnight (see Note 1).
2. Dissolve the residue in HNO3 and transfer the solution to a 250-mL beaker.
3. Evaporate to dryness several times with 25-mL additions of HNO3 (see Note 2).
4. Add 25 mL of HCl and evaporate to dryness. Repeat the HCl addition and
SEPARATION
1. Pass the 7N HCl sample solution obtained during sample preparation through a
prepared anion exchange column (see Note 3).
2. Wash the column with 400 mL of 7N HCl.

3. Elute with 200 mL of 1N HCl and collect the eluate in a 250-mL beaker. Evaporate
the solution to dryness.
4. Perform Generic Mercury Cathode Electrolysis Separation (see Procedure

U-01-E).
5. Evaporate the filtrate to dryness. Add 5 mL HNO3 and evaporate to dryness.
6. Dissolve the residue in 2-3 mL of HNO3. Cool, transfer to a 10 mL volumetric

flask, and dilute to the mark with H2O.
7. Deposit 0.1 mL on a stainless steel disk, dry, and " count for recovery of 232U.
Correct the fluorimetric readings by this recovery factor.
8. Measure the U fluorimetrically as described in Procedure U-01-E.
Notes:
results.
2. If silicious material is present, transfer the sample to a 100-mL platinum dish or a

100-mL Teflon beaker with HNO3. Add 10 mL of HF to the vessel and evaporate to
dryness. Repeat additions of 25 mL HNO3 and 10 mL of HF as necessary to
volatilize the silica. Remove the HF by adding three successive 10-mL volumes of
HNO3 to the vessel and evaporating to dryness.
3. 10 mL of Bio-Rad AG 1-X4 is used, prepared according to Specification 7.4, Vol. I,

and conditioned with 200 mL of 7N HCl.
DETERMINATION

REFERENCE
Welford, G. A., R. S. Morse and J. S. Alercio

Am. Ind. Hyg. Asso. J., 21 (1960)


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PManCvr.gif (GIF Image, 488 × 498 pixels) http://www.nbl.doe.gov/htm/EML_Legacy_Website/ProcMan/support/P...

Volume I Introduction and Preface

Volume II (procedures not currently performed at EML)

* Contains EPA Approved Procedures

The Procedures Manual is no longer being updated.

Please note that the special facilities in Section 6 no longer exist.

Please send questions regarding the Procedures Manual to: NUSTL.webmaster@hq.dhs.gov

Links to sections and subsections inside the chapters:

http://www.nbl.doe.gov/htm/EML_Legacy_Website/ProcMan/support/Info.htm[4/12/2012 3:43:30 PM]

EML Procedures Manual

THE PROCEDURES MANUAL OF THE ENVIRONMENTAL

Mitchell D. Erickson, Director

Nancy A. Chieco, Editor

U.S. Department of Homeland Security

http://www.nbl.doe.gov/htm/EML_Legacy_Website/ProcMan/support/Intro.htm[4/12/2012 3:43:39 PM]

U.S. Department of Energy

Environmental Measurements Laboratory

Units and Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-2

The Chemical Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-7

Greek Alphabet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-8

Chemical Conventions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-9

Concentration of Common Acids and Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . G-10

Julian Date Calendar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-12

Environmental Measurements Laboratory

Environmental Measurements Laboratory

UNITS AND ABBREVIATIONS

PREFIXES FOR UNITS IN THE INTERNATIONAL SYSTEM

exa E 1018 deci d 10-1

BASE UNITS OF THE INTERNATIONAL SYSTEM

Quantity Name of unit Symbol

Environmental Measurements Laboratory

Units cm m km inch foot mile

1 cm = 1. 0.01 1x10-5 0.39370 0.032808 6.2137x10-6

Units cm2 m2 ha km2 foot2 mile2

1 cm2 = 1. 1x10-4 1x10-8 1x10-10 1.08x10-3 3.861x10-11

1 cm3 = 1. 1x10-3 1x10-6 0.0610237 3.53x10-5 1.0567x10-3

Environmental Measurements Laboratory

1g = 1. 1x10-3 1x10-6 0.0352740 2.20x10-3 1.1023x10-6

Units g cm-3 g L-1 kg m-3 oz in-3 lb ft-3 lb gal-1

1 g cm-3 = 1. 1000 1000 0.5780365 62.42795 8.345403

1 Pascal = 1. 10 1x10-5 9.869x10-6 7.501x10-3 2.953x10-4

Environmental Measurements Laboratory

1 int J = 1. 0.2388853 9.48x10-4 2.78x10-7 3.73x10-7 9.871x10-3

becquerel disint./minute Curie picoCurie

1 Bq = 1. 60. 2.70x10-11 27.

UNITS OF RADIATION EXPOSURE

UNITS OF ABSORBED DOSE

Environmental Measurements Laboratory

UNITS OF RADIATION DOSE EQUIVALENT

joule/kilogram roentgen equivalent

1 Sievert = 1. 1.0 100.

Environmental Measurements Laboratory

THE CHEMICAL ELEMENTS

Environmental Measurements Laboratory

!," Alpha H,0 Eta N,< Nu T,J Tau

Environmental Measurements Laboratory

Environmental Measurements Laboratory

CONCENTRATIONS OF COMMON ACIDS AND BASES

Hydrofluoric acid, HF 1.17 48 28 28

Hydrochloric acid, HCl 1.18 37 12 12

86 'HSDUWPHQW RI (QHUJ\