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M ARIA CSUROS
Environmental
Sampling and
Analysis
Lab Manual
Boca Raton N ew York

Published in 1997 by
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 1997 by Taylor & Francis Group, LLC

CRC Press is an imprint o f Taylor & Francis Group
No claim to original U.S. Government works

Printed in the United States o f America on acid-free paper
15 14 13 12 11 10 9 8
International Standard Book Number-10: 1-56670-178-3 (Softcover)

International Standard Book Number-13: 978-1-56670-178-5 (Softcover)
Library o f Congress catalog number: 96-37154
This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with
permission, and sources are indicated. A wide variety o f references are listed. Reasonable efforts have been made to publish
reliable data and information, but the author and the publisher cannot assume responsibility for the validity o f all materials
or for the consequences o f their use.
No part o f this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or
other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information
storage or retrieval system, without written permission from the publishers.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for
identification and explanation without intent to infringe.
Library of Congress Cataloging-in-Publication Data
Catalog record is available from the Library o f Congress
informa Taylor & Francis Group

is the Academic Division o f Infomia pic.
Visit thè Taylor & Francis Web site at
http://www.taylorandfrancis.com
and thè CRC Press Web site at
http://www.crcpress.com
D edication
To My Father
B iography
Maria Csuros is an environmental chemist with many years of varied experience. She
received her Ph.D. in Environmental Chemistry from Janus Pannonius University in Pecs,
Hungary, and her Master of Science Degree in Chemistry from Jozsef Attila University in
Szeged, Hungary. Her postgraduate work involved research in environmental chemistry
under a grant from the Environmental and Public Health Insitution, Budapest, Hungary.
Most of her professional life has revolved around environmental testing laboratories
and teaching.
Her first encounter with environmental science occurred at the Environmental and
Public Health Laboratory, Pecs, Hungary, where she worked as a supervisor of the Water
Department. Her main area of interest at that time was the prevention and elimination of
methemoglobinemia caused by high nitrate content of private well waters. She spent six
years in Benghasi, Lybia, as part of an international team, studying the health effects of
brackish drinking water.
After moving to the United States, she continued to dedicate her knowledge and time
to environmental analytical work and education. She has designed and developed an
Environmental Science program for Pensacola Junior College focused on environmental
sampling and analysis. She presently is the coordinator of the this program and teaches
chemistry and environmental science courses.
She also conducts various continuing education programs for local, state, and federal
agencies as well as regional companies.
Her first book, "Environmental Sampling and Analysis," published by CRC/Lewis
Publishers in 1994, and has been on the "Best Sellers" list since.
She lives in Pensacola, Florida, with her husband, who is professor of Microbiology
and Anatomy and Physiology. She has two sons, and five grandchildren.
Preface
Satisfying the requirements of the environmental laws and regulations is possible only
with défendable and accurate laboratory results, based on approved methodologies, up
dated instrumentation and technologies, well-trained and qualified laboratory personnel,
and sufficient QC data.
Environmental analytical laboratories must offer a wide-scale analytical repertoire,
from the simple determination of physical properties to the most modern analytical per
formances of trace organic pollutants. The concern of the microbiological quality of the
environment is also increasing and demands extended testing.
Chemists working in the environmental analytical field should be familiar not only
with the general laboratory techniques, and with the chemical background of different
analytical procedures and instrumentation, but they must also be knowledgeable about
approved methodologies, QC requirements, calculations, evaluations of analytical data,
and generation of correct, défendable analytical results, along with their regulatory levels.
The large diversity of the literature in this field and the diffuse sources of the necessary
information make this wide-scale training difficult. The goal of this text is to give com
prehensive and easy-to-read information for any individual who is working in the envi
ronmental analytical chemistry arena, and to provide essential information to consultants
and regulators about analytical and quality control procedures helpful in their evaluation
and decision-making procedures. The text also gives useful information for college and
university students taking chemistry and environmental courses, for graduate students,
and for chemists who need a ready source of information that meaningfully relates to
actual laboratory practice.
The book is designed as the first part of a comprehensive laboratory manual specially
designed for environmental professionals. It contains general laboratory considerations,
laboratory safety procedures, and laboratory techniques emphasized on the determination
of inorganic nonmetallic constituents in environmental samples along with their chemistry,
occurrence, source, fate, and their control by regulations and standards. Sample collection,
preparation for analysis, step-by-step easy to follow methodology with detailed quality
control procedures, as well as calculations for correct reporting units concerning different
matrices are discussed for each parameter.
All in all, this book will provide a valuable advantage to environmental education
and special training programs; as a practical handbook it will also assist environmental
chemists in their everyday chores; and it will give a helping hand to the reader to under
stand analytical reports.
A cknowledgments
I owe a great debt of gratitude to all the people who participated in making this book
possible.
My most sincere appreciation goes to James Tucci, manager of Law Engineering and
Environmental Services, Inc., for his valuable suggestions, comments, and technical infor
mation. His professional input and respected expertise considerably contributed to the
correctness of the information contained in this publication. I can't imagine completing
this task without his help and support.
My very special thanks go to Bernie Fuson, project manager at Law Engineering and
Environmental Services, for his support, patience, and accuracy in proofreading and
correction of the text.
I also am pleased to express my thanks to my student and friend, Ken Connor, for
the preparation of the figures and tables.
I gratefully acknowledge the support of the outstanding editorial and production staff
of CRC/Lewis Publishers. My personal thanks to Ken McCombs, Acquiring Editor, and
Susan Alfieri, for their friendship, understanding and encouragement. I am grateful to the
project editor, Albert Starkweather, who guided the project with his careful work and
patience through the complexities of production. Thank you also for the superb design
work.
It is with particular pleasure that I thank my husband for his patience, support,
excellent ideas, and his cheerful spirit. Warm words of thanks also to my sons, Geza and
Zoltán, for their love, encouragement and technical assistance.
T able of C ontents
Chapter 1 INTRODUCTION TO CHEMICAL ANALYSIS............................................ 1

1.1 The Nature of Analytical Chem istry........................................................................... 1
1.2 General Direction of Chemical A nalysis..................................................................... 1
1.2.1 The Responsibility and Psychology ofthe Analyst.................................... 2
1.2.2 Cleanliness in the Laboratory..........................................................................3
1.2.3 Recording Analytical Data................................................................................3
1.2.4 Planning Laboratory W ork.............................................................................. 4
1.2.5 Documents to be Saved..................................................................................... 7
Chapter 2 SAFETY AND LABORATORY W ORK............................................................ 9

2.1 Laboratory Hazards..........................................................................................................9
2.1.1 Chemical H azards.............................................................................................. 9
2.1.2 Fire Hazards..................................................................................................... .13
2.1.3 Careless H abits..................................................................................................14
2.2 Safe Handling of Compressed Gases......................................................................... 14
2.2.1 General Precautions When Workingwith Compressed G ases..............15
2.2.2 Hazardous Properties of Compressed Gases.............................................15
2.3 Stockroom Safety Rules................................................................................................. 15
2.3.1 Checklist for Safety Storage Room ...............................................................15
2.3.2. Storage of Chemicals.........................................................................................17
2.4 Laboratory Safety R ules................................................................................................18
Chapter 3 QUALITY ASSURANCE OF CHEMICAL MEASUREMENTS................ 21

3.1 Introduction..................................................................................................................... 21
3.1.1 Quality Assurance (QA)....................................... 21
3.1.2 Quality Control (Q C )........ ..............................................................................21
3.1.3 Quality Assessment.......................................................................................... 22
3.2 Laboratory Quality Assurance Program .................................................................. 23
3.2.1 Sampling............................................................................................................. 23
3.2.2 Sample C ustody............................................................. 27
3.2.3 Sample Preparation for Analysis..................................................................28
3.2.4 Analytical M ethodology.................................................................................28
3.2.5 Analytical System Calibration...................................................................... 30
3.2.6 Detection Lim its........................... 31
3.2.7 Statistics in Chemical Analysis..................................................................... 33
3.2.8 Quality Control C h arts...................................................................... ...........35
3.2.9 Items for the Essential Control of Chemical Measurements.................36
Chapter 4 LABORATORY APPARATUS AND GLASSWARE..................................... 39

4.1 Labware M aterials........................................................................................................... 39
4.1.1 Soft Laboratory Glassware vs. Heat-Resistant Glassware..................... 39
4.1.2 Plastic Labware ..................................................................................... 39
4.1.3 Porcelain Labware ................................................................................. 40
4.1.4 Platinum Crucible ................................................................................. 40
4.1.5 Nickel Crucible ...................................................................................... 40
4.2 Volumetric Glassware ........................................................................................ 40
4.2.1 Volumetric Flask .................................................................................... 41
4.2.2 Pipets and Their Use ............................................................................. 44
4.2.3 Burets and Their Use ............................................................................. 46
4.2.4 Cleaning of Volumetric Glassware ...................................................... .48
4.3 The Analytical Balance ...................................................................................... 48
4.4 Desiccator ........................................................................................................... 50
Chapter 5 CHEMICALS, REAGENTS, AND STANDARDS ........................................ .51

5.1 Chemicals ........·................................................................................................... 51
5.1.1 Grades and Purity of Chemicals ........................................................... 51
5.1.2 Proper Storage of Chemicals and Standards ....................................... 52
5.2 Laboratory Pure Water ............................................................................... ,...... 52
5.2.1 Methods for Preparation of Laboratory Pure Water ........................... 53
5.3 Reagents and Solutions ............................................................... ,..................... 54
5.3.1 Expressing Concentration of a Solution ............................................... 56
5.3.2 Diluting Solutions ................................................................................. 60
5.3.3 Handling Reagents and Solutions ........................................................ 60
Chapter 6 STANDARD SOLUTIONS ................................................................................ 67

6.1 Stock Standard Solutions .................................................................................. 67
6.2 Standardization of Solutions ............................................................................ 67
6.3 Preparation and Standardization of Common Standard Solutions ................ 68
6.3.1 Sulfuric Acid (H 2S04 ) Solution 0.1 N ................................................... 68
6.3.2 Hydrochloric Acid (HCI) Solution 0.1 N .............................................. 69
6.3.3 Sodium Hydroxide (NaOH) Solution 0.1 N ......................................... 70
6.3.4 Iodine (1 2 ) Solution 0.1 N ...................................................................... 71
6.3.5 Sodium Thiosulfate (Na 2S20 3 ) Solution 0.1 N ...................................... 72
6.3.6 Potassium Permanganate (KMn04 ) Solution 0.1 N ............................. 73
Chapter 7 COMMON LABORATORY TECHNIQUES ................................................... 75

7.1 Filtration ............................................................................................................ 75
7.1.1 Filtration Methods ................................................................................. 75
7.1.2 Filter Media ........................................................................................... 75
7.1.3 Gravity Filtration .................................................................................. 79
7.1.4 Vacuum Filtration .................................................................................. 80
7.2 Centrifugation ................................................................................................... 81
7.2.1 Using a Common Laboratory Centrifuge ............................................ 83
7.2.2 Centrifuge Safety Rules ........................................................................ 84
7.3 Distillation ......................................................................................................... 84
7.3.1 Simple Distillation ................................................................................ 84
7.3.2 Fractional Distillation ........................................................................... 86
7.3.3 Vacuum Distillation .............................................................................. 87
7.4 Refluxing ............................................................................................................ 88
7.5 Ion Exchange ...................................................................................................... 89
7.6 Drying and Ashing Samples ............................................................................. 90
7.6.1 Drying Samples ..................................................................................... 90
7.6.2 Ashing .................................................................................................... 90
7.7 Dissolving the Sample ....................................................................................... 91
7.7.1 Decomposition under Pressure in a Closed System ............................ 91
7.7.2 Decomposition in an Open System ...................................................... 91
7.7.3 Digestion ................................................................................................ 91
7.7.4 Fusion .................................................................................................... 92
7.8 Extraction ........................................................................................................... 92
7.8.1 Liquid-Liquid Extraction by Separatory Funnel.. ............................... 92
7.8.2 Continuous Liquid-Liquid Extraction ................................................. 94
7.8.3 Sohxlet Extraction ................................................................................. 95
Chapter 8 GRAVIMETRIC METHODS OF ANALYSIS ................................................. 97

8.1 General Principles ............................................................................................. 97
8.1.1 Types of Precipitate ............................................................................... 97
8.1.2 Aging and Digestion of the Precipitate ................................................ 98
8.1.3 Manipulations Associated with the Filtration Process ....................... 98
8.2 Gravimetric Calculation .................................................................................. 100
8.2.1 Utilization of the Gravimetric Factor ................................................. 101
8.3 Gravimetric Analysis and Modern Analytical Chemistry ............................. 102
Chapter 9 TITRIMETRIC ANALYSIS .............................................................................. 105

9.1 General Principles ........................................................................................... 105
9.1.1 Chief Requirements for a Titration .................................................... 105
9.1.2 Indicators ............................................................................................. 106
9.1.3 Volumetric Glassware ......................................................................... 106
9.1.4 Reactions Used for Titration ............................................................... 106
9.1.5 Performing a Titration ........................................................................ 107
9.2 Calculating the Result of a Titration .............................................................. 107
9.2.1 Results Given in the Same Concentration as the Titrant .................. 107
9.2.2 Results Given in Concentrations, Using Normality .......................... 108
9.3 Back-Titration .................................................................................................. 108
Chapter 10 ACID-BASE TITRATION ................................................................................ 111

10.1 Acids and Bases ............................................................................................... 111
10.1.1 Arrhenius Theory of Acids and Bases ................................................ 111
10.1.2 Bronsted-Lowry Concept of Acids and Bases ................................... 112
10.2 Basic Concept of Chemical Equilibrium ........................................................ 112
10.2.1 Acid-Base Equilibrium ....................................................................... 112
10.2.2 Self-Ionization of Water ...................................................................... 113
10.2.3 pH Calculations ................................................................................... 114
10.2.4 Measurement of pH ............................................................................ 117
10.2.5 Buffers .................................................................................................. 117
10.3 Acid-Base Titration ......................................................................................... 117
10.3.1 Acid-Base Titration Curves ................................................................ 117
10.3.2 Acid-Base Indicators ........................................................................... 120
Chapter 11 COMPLEXOMETRIC, OXIDATION-REDUCTION,

AND OTHER TITRATIONS ........................................................................... 123
11.1 Complexometric Titration ............................................................................... 123
11.1.1 Complex Formation ............................................................................ 123
11.1.2 Complexometric Titration ................................................................... 126
11.2 Oxidation-Reduction Titration ....................................................................... 127
11.2.1 Theory of Oxidation-Reduction ......................................................... 127
11.2.2 Redox Titrations .................................................................................. 129
11.3 Precipitation Formation Titration ................................................................... 131
11.3.1 Mohr Method for Halides ................................................................... 131
11.3.2 Volhard Method ................................................................................... 131
11.3.3 The Use of Adsorption Indicators: The Fajans Method .................... 132
Chapter 12 SPECTROPHOTOMETRY ............................................................................... 133

12.1 Fundamentals of Spectroscopy ....................................................................... 133
12.1.1 Early History of the Nature of Light .................................................. 133
12.1.2 Electromagnetic Radiation .................................................................. 134
12.1.3 Continuous and Line Spectra ............................................................. 136
12.1.4 Beer's Law ........................................................................................... 138
12.2 Molecular Spectrophotometry ........................................................................ 139
12.2.1 Molecular Absorption and Color ....................................................... 139
12.2.2 Molecular Absorption Spectrophotometry ........................................ 139
12.2.3 Basic Components of Spectrophotometers ........................................ 140
12.2.4 Single-Beam and Double-Beam Spectrophotometer ......................... 142
12.2.5 UV, Visible, and Infrared Spectrophotometers .................................. 144
12.3 Calibration of Spectrophotometers ................................................................ 147
12.3.1 General Rules in Preparation of Calibration Curves ........................ 148
12.3.2 Linear Regression Calculation ............................................................ 148
12.3.3 Performance Check of UV /VIS and IR Spectrophotometers ............ 149
12.3.4 Maintenance of UV /VIS and IR Spectrophotometers ....................... 150
Chapter 13 POTENTIOMETRY AND ION-SELECTIVE ELECTRODES ................... 153

13.1 Principles of Electrochemistry ........................................................................ 153
13.1.1 Galvanic Cell ....................................................................................... 153
13.1.2 Dependence of EMF on Concentration .............................................. 155
13.1.3 The Nernst Equation .................•......................................................... 155
13.2 Determining Concentrations from Cell Potential.. ........................................ 156
13.2.1 The Saturated Calomel Reference Electrode ...................................... 156
13.2.2 Potentiometer and Electronic Voltmeter ............................................ 157
13.2.3 Ion-Selective Electrodes (ISEs) ........................................................... 158
Chapter 14 ENVIRONMENTAL TESTING LABORATORIES .....................................165

14.1 Environmental Regulations ............................................................................ 165
14.1.1 Overview of Federal Regulations ....................................................... 165
14.1.2 Overview of State Programs ............................................................... 168
14.2 Laboratory Operations for the Analysis of Regulated Substances ............... 168
14.2.1 Methodology ....................................................................................... 169
14.2.2 EPA-Approved Methods and References for Analyzing Water
Samples ........................................................................... .-.................... 169
14.2.3 EPA-Approved Methods and References for Analyzing Soils,
Sediments, and Residuals ................................................................... 170
14.2.4 Approved Modifications of EPA Methods ......................................... 171
14.2.5 EPA Contract Laboratory Protocol ..................................................... 171
14.3 Laboratory QA/QC ......................................................................................... 171
14.4 Standards ......................................................................................................... 172
14.4.1 Drinking Water Standards .................................................................. 172
14.4.2 Waste Characterization ....................................................................... 172
14.4.3 Irrigation Water Quality ..................................................................... 176
14.5 Analytical Departments in Environmental Testing Laboratories ................. 178
Chapter 15 RAW DATA CONVERSION INTO REPORTABLE RESULTS ................ 181

15.1 Raw Data and Reportable Data ...................................................................... 181
15.2 Calculations for Final Values .......................................................................... 181
15.2.1 Temperature Correction for pH Values .............................................. 181
15.2.2 Temperature Compensation for Conductivity ................................... 182
15.2.3 Solids, Moisture, and Ash Calculation ............................................... 182
15.2.4 Calculations Related to Titrimetric Analysis ..................................... 183
15.2.5 Calculations Related to Spectrophotometric and Potentiometric
Analytical Performances ..................................................................... 183
15.2.6 Calculating the Results for Solid Matrixes ........................................ 183
15.2.7 Calculation of Total Hardness from Calcium and Magnesium
Values ................................................................................................... 184
15.2.8 Calculation of Magnesium Values from Total Hardness as CaC03
and Calcium as CaC03 •••••••••••••••••••••••.••••••••••• _. ••••••••••••••••••.•••••••••••••••.• 185
15.2.9 Calculation of Carbonate, Bicarbonate, and Hydroxide from
Alkalinity ............................................................................................. 185
15.3 Calculation of Calcium Carbonate Saturation, Corrosivity .......................... 187
15.4 Dilutions and Concentrations ......................................................................... 188
15.5 Significant Figures ........................................................................................... 189
15.5.1 Exponential Notation .......................................................................... 189
Chapter 16 EVALUATION AND APPROVAL OF ANALYTICAL DATA................... 191

16.1 Validation of Analytical QC Checks ............................................................... 191
16.1.1 Documentation of the Out-of-Control Condition .............................. 194
16.2 Checking the Correctness of the Analysis ...................................................... 194
16.2.1 Calculation of TDS .............................................................................. 195
16.2.2 TDS and Electrical Conductance Ratio .............................................. 195
16.2.3 Anion-Cation Balance ......................................................................... 195
16.2.4 Relation between Conductivity and Total Cations and Anions ....... 196
16.2.5 Relation between Total Hardness and Calcium and Magnesium
Values ................................................................................................... 196
16.2.6 Relation of the Different Forms of Nitrogens .................................... 197
16.2.7 Relation of the Different Forms of Phosphorus ................................. 197
Chapter 17 REPORTING ANALYTICAL DATA ............................................................... 199

17.1 Required Documentation ................................................................................ 199
17.1.1 Documentation Required to Approve and Defend Reported Data .. 199
17.2 Significant Figures in Analytical Reports ....................................................... 200
17.3 Units used to Express Analytical Results ....................................................... 200
17.4 Report with Confidence Interval .................................................................... 201
17.5 Report Format .......................................................................................... .- ....... 201
Chapter 18 DETERMINATION OF COLOR, ODOR, AND CONDUCTIVITY .......203

18.1 Introduction to the Physical Properties ......................................................... 203
18.2 Color ................................................................................................................. 203
18.2.1 General Discussion .............................................................................. 203
18.2.2 Sample Collection and Storage ........................................................... 203
18.2.3 Sample Pretreatment ........................................................................... 204
18.2.4 Color Determination by Platinum-Cobalt Method ........................... 204
18.3 Odor ................................................................................................................. 205
18.3.2 Sample Collection and Handling ....................................................... 205
18.3.4 Measurement of Odor with Threshold Odor Test ............................. 206
18.4 Conductivity .................................................................................................... 206
18.4.3 Measurement ....................................................................................... 208
Chapter 19 ANALYSIS OF SOLIDS AND TURBIDITY ................................................ 211

19.1 Solids ................................................................................................................ 211
19.1.4 Determination of Total Solids (TS) Dried at 103-105°C .................... 211
19.1.5 Determination of Total Dissolved Solids (TDS) Dried at 180°C ....... 212
19.1.6 Determination of Total Suspended Solids (TSS) Dried at
103-105°C ............................................................................................ 215
19.1.7 Fixed and Volatile Solids Ignited at 500°C ....................................... :216
19.1.8 Total, Fixed, and Volatile Solids in Solid and Semisolid
Samples ................................................................................................ 217
19.1.9 Settleable Fluids .................................................................................. 218
19.2 Turbidity .......................................................................................................... 218
· 19.2.1 General Discussion .............................................................................. 218
19.2.3 Measurement of Turbidity by Nephelometric Method ..................... 219
Chapter 20 ALKALINITY AND pH CALCIUM CARBONATE

SATURATION .....................................................................................................221
20.1 Alkalinity ......................................................................................................... 221
20.1.3 Potentiometric Titration Method ........................................................ 222
20.1.4 Titrimetric Method by Color Change ................................................. 224
20.1.5 Calculation of Alkalinity Relationships ............................................. 225
20.1.6 Conversion of the Three Forms of Alkalinity Expressed as CaC03 to
Their Ionic Forms ................................................................................ 226
20.2 Determination of pH ...................................................... :................................ 226
20.2.2 Sample Collection and Holding Time ................................................ 226
20.2.3 Potentiometric Determination of pH ................................................. 226
20.3 Calcium Carbonate Saturation ........................................................................ 229
20.3.1 General Discusson ............................................................................... 229
20.3.2 Calculation of the Saturation Index ................................................... 230
Chapter 21 ANALYSIS OF FLUORIDE AND TOTAL HARDNESS ........................... 231

21.1 Fluoride ............................................................................................................ 231
21.1.2 Sampling and Storage ......................................................................... 231
21.1.3 Determination of Fluoride by Ion-Selective Electrode ...................... 231
21.2 Total Hardness as CaC03 ................................................................................ 238
21.2.3 Determination of Hardness by EDTA Titrimetric Method ................ 239
21.2.4 Total Hardness by Calculation ........................................................... 242
21.2.5 Calculation of Carbonate and Noncarbonate Hardness ................... 242
21.3 Calcium Determination by EDTA Titrimetric Method .................................. 243
21.4 Determination of Magnesium by Calculation ................................................ 244
Chapter 22 DETERMINATION OF RESIDUAL CHLORINE, CHLORIDE,

AND CYANIDE ..................................................................................................245
22.1 Chlorine Residual ............................................................................................ 245
22.1.3 Measurement ....................................................................................... 246
22.1.4 Chlorine Determination by Iodometric Titration Method ................ 246
22.2 Chloride ........................................................................................................... 248
22.2.3 Analysis by Mercuric Nitrate Titrimetric Method ............................. 249
22.3 Total Cyanide ................................................................................................... 251
22.3.3 Determination of Cyanide by Colorimetric Method After
Distillation ........................................................................................... 251
22.4 Cyanides Amenable To Chlorination After Distillation ................................ 257
22.4.2 Analysis ............................................................................................... 257
Chapter 23 NITROGEN COMPOUNDS AND ANALYSIS OF AMMONIA

NITROGEN ......................................................................................................... 259
23.1 Nitrogen Compounds and Nitrogen Cycle .................................................... 259
23.2 Ammonia-Nitrogen ......................................................................................... 260
23.2.3 Ammonia-Nitrogen Determination by Nesslerization ...................... 260
23.2.4 Ammonia Determination by Ion-Selective Electrode ........................ 264
23.2.5 Ammonia Determination by Titrimetric Method .............................. 268
23.2.6 Automated Phenate Method ............................................................... 269
23.2.7 Ammonia Determination in Soil, Sludge, or Sediment
Samples ................................................................................................ 270
Chapter 24 ANALYSIS OF NITRITE AND NITRATE, AND TOTAL KJELDAHL

NITROGEN ......................................................................................................... 273
24.1 Nitrite-Nitrogen, N02 -N ................................................................................. 273
24.1.1 General Discusssion ............................................................................ 273
24.1.3 Determination of N02-N by Colorimetric Method ............................ 273
24.2 Nitrate-Nitrogen, N03-N ................................................................................ 275
24.2.3 Nitrate Analysis by Ion-Selective Electrode Method ........................ 276
24.2.4 Nitrite + Nitrate Nitrogen Determination by Cadmium
Reduction Method ............................................................................... 279
24.2.5 Automated Cadmium Reduction Method ......................................... 282
24.2.6 Determination of Nitrite-Nitrogen in Soils and Sediments .............. 282
24.3 Total Kjeldahl Nitrogen (TKN) and OrganiC Nitrogen .................................. 283
24.3.3 Analysis of Total Kjeldahl Nitrogen (TKN) ....................................... 283
Chapter 25 DETERMINATION OF PHOSPHORUS .......................................................287

25.1 Phosphate-Phosphorus as P04-P .................................................................... 287
25.2 Determination of Phosphate, P0 4-P ............................................................... 288
25.2.1 Acid Hydrolysis for Condensed Phosphate ...................................... 288
25.2.2 Persulfate Digestion Method for Total Phosphates ........................... 289
25.2.3 Determination of Phosphorus by Ascorbic Acid Method ................. 290
25.2.4 Automated Ascorbic Acid Reduction Method .................................... 293
Chapter 26 DETERMINATION OF SULFIDE ..................................................................295

26.1 Analysis of Hydrogen Sulfide .................................................................. ,...... 295
26.1.3 Sulfide Determination by Iodometric Method .................................. 295
26.1.4 Calculation of Uni-lonized Hydrogen Sulfide ................................... 298
26.2 Determination of Total Sulfide in Liquid and Solid Wastes .......................... 299
26.2.3 Distillation Followed by Iodometric Method .................................... 300
Chapter 27 DETERMINATION OF SULFITE AND SULFATE ..................................... 305

27.1 Analysis of Sulfite, SOj- .................................................................................. 305
27.1.3 lodometric Titration Method .............................................................. 305
27.2 Determination of Sulfate, SOi-........................................................................ 307
27.2.3 Sulfate Determination with Turbidimetric Method .......................... 308
27.2.4 Automated Methylthymol Blue (MTB) Method ................................ 310
Chapter 28 CATION EXCHANGE CAPACITY................................................................. 313

28.1 General Discussion .......................................................................................... 313
28.2 Cation Exchange Capacity by Ammonium Acetate Method ......................... 313
Appendix A LABORATORY FIRST AID .......................................................................... .317

General Rules .......................................................................................................... 317
Important Steps ...................................................................................................... 317
First Aid for Thermal Burns ................................................................................... 318
First Aid for Chemical Burns ................................................................................. 318
First Aid for Wounds and Fractures ...................................................................... 318
First Aid for Shock ................................................................................................. 319
First Aid for Electric Shocks .................................................................................. 319
First Aid for Ingested Poisons ............................................................................... 320
First Aid for Inhaled Poisons ................................................................................. 320
Artificial Respiration .............................................................................................. 320
First Aid for Foreign Object in the Eye ................................................................. 321
Appendix B SALINITY DETERMINATION BY HYDROMETRIC

METHOD ...........................................................................................................323
Appendix C LOGBOOK FORMS AND USEFUL TABLES APPLICABLE

IN ANALYTICAL WORK ..............................................................................331
Appendix D DOCUMENTATION FORMS FOR QUALITY CONTROL

DATA ...................................................................................................................351
References .................................................................................................................................... 359
Index .............................................................................................................................................361
L ist of T ables and F igures
TABLES
2.1 Hazardous properties of compressed gases............................................................ 16
2.2 LabGuard safety label system..................................................................................... 18
2.3 LabGuard safety label system: acids and bases..................................................... 18
3.1 Recommended volumes, containers, preservatives, and holding tim es........24
3.2 Storage and preparation frequency of selected stock and standard
solutions........................................................................................................................... 31
3.3 Student's t variate ta b le ............................................................................................... 33
5.1 Storage of chemicals, reagents, and standards...................................................... 52
5.2 Reagent-grade water specification ................................................ 54
5.3 Quality check of laboratory pure w ater...................................................................54
5.4 Concentration units of solutions............................................................................... 61
5.5 Preparation of common acid solutions..................................................................... 61
5.6 Preparation of standard alkaline solutions: sodium hydroxide (NaOH).......61
5.7 Preparation of standard alkaline solution: ammonium hydroxide
(NH4O H )................................................................................................................. ........ 61
7.1 Commonly used filter pap ers..................................................................................... 77
7.2 Properties of Whatman filter papers.........................................................................77
10.1 Acid ionization constants at 25°C............................ 116
10.2 Base ionization constant at 25°C...............................................................................116
10.3 Some acid-base indicators.........................................................................................120
11.1 Some typical com plexes............................................................................................. 124
12.1 Wavelength region for each color............................................................................ 136
12.2 Visible spectrum and complementary colors........................................................139
12.3 Ultraviolet and visible radiation sources...............................................................140
12.4 Ultraviolet and visible radiation detectors........................................................... 144
12.5 Summary of spectrophotometry techniques.........................................................145
13.1 Proper storage of ion-selective electrodes............................................................ 163
14.1 Drinking water standards established by the 1986 amendments to the Safe
Drinking Water A c t........................ 173
14.2 Recent requirements for drinking water standards............................................ 174
14.3 Maximum concentration of contaminants in characterization of EP
toxicity............................................................................................................................ 176
14.4 Toxicity characteristic leachate contaminants and regulatory levels............ 177
14.5 Recommended maximum concentrations of trace elements in irrigation
water........................................................................................ 178
14.6 Analytical values needed to evaluate irrigation waters.................................... 179
14.7 Ambient air quality standard................................................................................... 179
15.1 Constant A as a function of water temperature................................................... 187
15.2 Constant B as a function of Total Dissolved Solids............................................ 187
15.3 Logarithms of calcium and alkalinity concentrations........................................188
16.1 Conversion factors milligrams per liter to milliequivalent per liter............. 196
18.1 Conductivity of potassium chloride solutions at 2 5 °C ..................................... 207
18.2 Threshold odor numbers corresponding to various dilutions.........................207
26.1 Values for pK', logarithm of practical ionization constant for hydrogen
sulfide.................................................................... 299
B-1 Values for converting hydrometer readings at certain temperatures to density
at 1 5 X ............................................................................................................................. 324
B-2 Corresponding densities and salinities.................................................................. 328
C-1 SI units and conversion factors................................................................................. 345
C“2 Molecular and equivalent w eights.......................................................................... 346
C-3 Gravimetric factors................................................................ 348
FIGURES
1.1 Analytical chemistry can be classified as either qualitative
or quantitative................................................................................................................... 2
1.2 Working paper for pH measurement...........................................................................4
1.3 Working paper for titrimetric analysis....................................................................... 5
1.4 Working paper for spectrophotometric analysis..................................................... 6
2.1 Safety sign s.......................................................................................................................10
2.2 Eye protection device................................................... 10
2.3 Eye wash fountain.......................................................................................................... 11
2.4 Protective respiratory device........................................... 12
2.5 Safety stepladder............................. 14
2.6 Material safety data sheet............................................................................................ 19
3.1 Chain of custody............................................................................................................. 26
3.2 Sample label..................................................................................................................... 27
3.3 Sample holding time lo g .............................................................................................. 29
3.4 Sample preparation lo g .................................................................................................29
3.5 Interpretation of QC charts..........................................................................................36
4.1 Useful technique for reading a meniscus.................................................................41
4.2 Avoiding parallax error in reading the m eniscus..................................................42
4.3 Volumetric flask................................................................................................... 43
4.4 Correct use of volumetric flask...................................................................................44
4.5 Technique for using a volumetric p ip et...................................................................45
4.6 Different types of p ip ets.............................................................................................. 47
4.7 Buret and method of grasping stopcock..................................................................48
4.8 Different types of burets.............................................................................................. 49
4.9 Desiccator..........................................................................................................................50
5.1 Ionic substances are soluble in w ater........................ 55
5.2 Temperature influences solubility............................................................................. 57
5.3 Temperature versus solubility of selected solutes in w ater............................... 57
5.4 Steps involved in the preparation of standard solutions.................................... 62
5.5 Pouring liquids from beakers and other containers............................................. 63
5.6 Transferring solutions into containers from pipets.............................................. 64
5.7 Label formats for reagents and solutions.................................................................64
7.1 Gravity filtration setu p .................................................................................................76
7.2 Vacuum filtration............................................................................................................76
7.3 Grades of fritted glassware.......................................................................................... 78
7.4 Gooch crucible with perforated bottom ................................................................... 78
7.5 Rubber adapter for suction filtration....................................................................... 79
7.6 Buchner funnels.............................................................................................................. 79
7.7 A funnel with a fritted-glass disk.............................................................................. 80
7.8 The Hirsch and other funnels.............. 80
7.9 Folding filter paper.........................................................................................................81
7.10 Varied shapes of glass funnels.................................................................................... 81
7.11 Technique of filtration with filter paper...................................................................82
7.12 Funnel with a wire gauze cone................................................................................... 82
7.13 Common laboratory centrifuge..................................................................................83
7.14 Decanting off supernatant liq u id .............................................................................. 84
7.15 Withdrawing liquid after centrifugation................................................................. 85
7.16 Centrifuge tu bes............................................................................................................. 85
7.17 Apparatus for simple distillation.............................................................................. 85
7.18 Fractional distillation apparatus............................................................................... 87
7.19 Vacuum distillation with gas-capillary bubbler......... .......................................... 88
7.20 The two most common reflux condensers............................................................... 89
7.21 Separating immiscible liquids by means ofa separatory funnel........................94
7.22 How to use a separatory fu n n el.................................................................................95
7.23 Sohxlet extraction...................................................... ................................................... 96
8.1 Decanting and transferring precipitate to filter paper.........................................98
8.2 Ignition of a precipitate...............................................................................................100
10.1 Curve for the titration of a strong acid by a strong b a se .................................. 118
10.2 Curve for the titration of a weak acid by a strong b ase.....................................119
10.3 Curve for the titration of a weak base with a strong acid................................. 119
11.1 The structure of the chelate formed when the anion of EDTA envelopes a
lead(II) io n ..................................................................................................................... 124
11.2 Glutathione reaction with a m etal........................................................................... 125
11.3 British anti-lewisite (BAL) chelation of a heavy metal io n ...............................126
11.4 The structure of hemoglobin......................................................................................126
11.5 The structure of chlorophyll......................................................................................127
12.1 The nature of w aves.................................................................................................... 134
12.2 The electromagnetic spectrum.................................................................................. 134
12.3 Continuous and line spectrum .................. 137
12.4 Electronic energy transition.......................................................................................137
12.5 Basic construction of a simple single-beam spectrophotometer.......................140
12.6 Schematic diagram of a phototube.......................................................................... 142
12.7 Block diagram showing components of a single-beam
spectrophotometer........................................................................................................143
12.8 Schematic diagram of a double-beam spectrophotometer................................143
12.9 A demountable cell.......................................................................................................145
12.10 Interconversion of wavelength and wavenumber...............................................146
12.11 Infrared spectrum of acetonitrile............................................................................. 146
12.12 Documentation of spectrophotometer wavelength calibration check........... 150
12.13 Documentation of spectrophotometer linearity check.......................................150
13.1 A galvanic cell................................................................................................................154
13.2 A saturated calomel reference electrode................................................................157
13.3 A glass electrode........................................................................................................... 159
13.4 Liquid membrane ion-selective electrode............................................................. 160
13.5 Solid-state ion-selective electrode........................................................................... 160
13.6 Gas-sensing electrode.................................................................................................. 161
16.1 Deficient incident report............................................................................................ 194
21.1 Direct distillation apparatus for fluoride.............................................................. 234
22.1 Cyanide distillation apparatus.................................................................................252
23.1 The nitrogen cy cle .................... 260
24.1 Reduction colum n........................................................................................................280
26.1 Proportions of H2S and HS" in dissolved sulfide.................................................300
26.2 Gas evolution apparatus to determine reactive sulfide released
from wastes.................. .................................................................................................302
A-1 Pressure points on arm and le g .................................................................................318
A-2 Mouth-to-mouth method of artificial respiration................................................ 320
C-1 Aqueous titrimetric determination of alkalinity................................................. 332
C-2 Potentiometrie determination of p H ....................................................................... 333
C-3 Titrimetric determination of hardness as CaC03................................................. 334
C-4 Colorimetric determination of total and amenable cyanide in waters......... 335
C-5 Potentiometrie determination of fluoride.............................................................. 336
C-6 Titrimetric determination of total sulfides in w aters......................................... 337
C-7 Turbidimetric determination of sulfate in solids................................................. 338
C-8 Titrimetric determination of sulfite in waters.......................................................339
C"9 Titrimetric determination of reactive sulfide........................................................ 340
C-10 Phosphate preparation log..........................................................................................341
C-11 Total Kjeldahl nitrogen (TKN) preparation lo g ....................................................342
C-12 Total sulfide and total cyanide preparation log......................... ...343
C-13 Periodic table of the elements....................................................................................344
D-1 Method blank summary.................... 352
D-2 Duplicate analyses record...........................................................................................353
D-3 Water matrix spike/matrix spike duplicate (MS/MSD) recovery.................. 354
D-4 Soil matrix spike/matrix spike duplicate (MS/MSD) recovery...................... 355
D-5 Initial calibration verification standard (IC V )............................. 356
D-6 Sample limits table for nitrate-nitrite........... ...........................................................357
chapter 1
Introduction
TO C hemical A nalysis
1.1 THE NATURE OF ANALYTICAL CHEMISTRY

Chemical analysis of a sample of matter is the determination of the chemical compo
sition of that sample. Chemical analysis consists of a set of chemistry laboratory operations
designed to reveal the chemical makeup of a material. Analytical chemistry is a branch
of chemistry dealing with the separation and analysis of chemical substances.
Analytical chemistry can be divided into two major categories: qualitative and quanti
tative analytical chemistry. Qualitative analysis is concerned with what is present, quanti
tative analysis with how much. Analysis procedures can be additionally classified into wet
chemistry procedures and instrumentation procedures (see Figure 1.1). Wet techniques are those
that employ chemical reactions and classical reaction stoichiometry for results.
Wet chemistry procedures give excellent accuracy, but their major disadvantages are
the time requirement and subsequent tedium. Instrumental or "modern" techniques give
speed and offer a much greater scope and practicality to the analysis. In addition, the
much lower detection limits of the instrumentation analytical methods make possible the
quantitation of the minor constituents in a substance. Although a number of purely
instrumental methods of analysis have been developed, chemical methods are still vital
and widely used, for several reasons. Many instruments require extensive calibration for
each type of sample to be analyzed, whereas chemical methods can be quickly adapted
to analyzing new types of samples. Few instrumental methods can match the accuracy
and precision of chemical methods. For example, instrumental methods are excellent for
the analysis of trace constituents, but their accuracy with respect to major constituents is
greatly deficient to that achieved by wet chemistry methods. By proper selection, both
instrumentation and wet chemistry methods are used equally in laboratories, and they
supplement each other. On the other hand, knowledge of chemical methods provides the
background to understanding instrumental analysis and analytical problems.
1.2 GENERAL DIRECTION OF CHEMICAL ANALYSIS

The results of a chemical analysis could affect important decisions, such as suitability
of a material for an intended purpose, the quality of the environment, the health of
ENVIRONMENTAL SAMPLING AND ANALYSIS LAB MANUAL
ANALYTICAL CHEMISTRY
QUALITATIVE QUANTITATIVE
WET CHEMISTRY INSTRUMENTAL

METHODS METHODS
Gravimetric Titrimetric
technique technique
Figure 1.1
Analytical chemistry can be classified as either qualitative or quantitative. All analytical procedures can be
additionally classfied into those that are wet procedures and those that are instrumental procedures. Wet chemical
methods are divided into gravimetric technique (based on weight) and titrimetric technique (based on volume).
individuals, the freedom of a prisoner on trial, etc. Stringent requirements in a chemical

laboratory are the basis of reliable and comparable data from a chemical analysis.
1.2.1 The Responsibility and Psychology of the Analyst

"Chemical analysts and chemical technicians are professionals in every sense of the
word. They should look, think, and act as professionals are expected to do. They are
entitled to all the privileges of professionals and at the same time are expected to shoulder
the responsibilities of professionals." A true analyst, or analytical chemist, has several
characteristics. He or she has a knowledge of the methods and instruments used for
analysis, and understands the principles of the analysis. Laboratory analysts should have
a chemistry background adequate to understand and correctly apply all of the laboratory
rules and to evaluate and interpret the results of their analysis. They have to know how*
to plan and organize laboratory work so the time is used efficiently. Thus, a laboratory
technician should be a skilled, well-trained chemist — in sharp contrast with the so-called
"determinators" who simply twist the dials of an instrument or follow "cookbook" ana
lytical procedures.
The analyst should be familiar with the test methods described in the laboratory
standard operation procedures (SOP) as well as the required quality assurance-quality
control (QA/QC) applications as stated in the laboratory comprehensive QA/QC manual.
The analyst should run the test by following the approved method and incorporate all
QC checks according to the laboratory comprehensive QA/QC program. He or she should
be able to recognize problems, initiate and conduct corrective actions, and keep all doc
INTRODUCTION TO CHEMICAL ANALYSIS
umentation related to the analysis clean and in order to be ready for inspection at any
time. The analyst should be able to protect and defend all of the raw data as well as the
reported results.
Laboratory personnel must understand the potential hazards in the laboratory and
then become familiar with the precautions and safety rules to be followed in laboratory
work. Accidents can be minimized by recognizing their causes and by being alert. They
should know basic emergency first-aid treatment for minor injuries and also the location
and use of emergency equipment. Laboratory safety procedures are discussed in Chapter 2.
1.2.2 Cleanliness in the Laboratory

Good analysts should be scrupulously clean and neat. An orderly laboratory bench
is not prone to mix up samples, use wrong reagents, spill solutions, and break glassware.
Much time can be wasted in searching for a small item in a jumble of glassware or in
finding a certain reagent bottle that has been misplaced on the shelf. Cleanliness also
includes laboratory equipment, ovens, hot plates, hoods, balances, sinks, floors, shelves,
cabinets and laboratory clothes.
The result of a chemical analysis depends on clean glassware. Glassware that looks
clean may or may not be clean for chemical analysis. Surfaces on which no visible dirt
appears are often contaminated by minute quantities of a substance that interfere with
the analysis and give false results. The analyst must carefully read the method and consider
any special recommendation for glassware washing procedures.
1.2.3 Recording Analytical Data

Data obtained in the analytical laboratory should be recorded. The record should be
complete, understandable, and easy to find.
Laboratory notebook — The key to successful work in the analytical laboratory is an

orderly notebook with well-organized data. All documentation related to the raw data
and the reported results should be in a bound form, easy to identify, and ready for
inspection at any time. A bound notebook is preferred to a loose-leaf one. The size of the
notebook should be adequate and comfortable to use. Preferably, it should fit easily around
the balance and working table, leaving space for glassware, reagents, etc. necessary for
the analysis. Larger notebooks, especially when opened, tend to get in the way and can
cause spills and other problems. The first two pages should be reserved for an index,
which can list the page numbers and the subject. If the pages of the notebook are not
numbered, the analyst must number each page in the upper corner.
The title heading should be used to identify and date data on each page. All raw data
and any observations should be recorded directly in the notebook at the time the work is
performed. Especially forbidden is the recording of data on loose paper with the idea of
copying it into the notebook later. All data should be written in ink to avoid smearing
and erasures. Nothing should be erased; anything not needed should be crossed out with
a single line, followed by an explanatory note, initialed, and dated.
Working sheets — Analytical raw data with related QC work and calculated final results
may be documented in specified worksheets. The worksheets are designed for each type
of analytical performance, and contain the information relating the sample, such as ID
number (identification number), sample type, source, analytical method or method num
ber with reference, method detection limit (MDL), specification of instrument used, ana-
Method No.; 150.1. Date

Reference : EPA 600/4-79-020 Analyst:
Model of pH meter : _______
Sample Sample Sample

I.D. description Measured temperature Remarks
No. pH °C
Buffer pH 7.00
Buffer pH 4.00
Buffer pH 10.00
Q.C. sample
Duplicate
QC sample true value

Precision (RPD) Accepted limit
Accuracy {% R) Accepted limit
RPD (Relative Percent Deviation) = (A-B)/ (A+B) 200

A and B = duplicates
% R Recovery) = (Measured value x 100) / True value
Figure 1.2
Working paper for pH measurement.
lytical and QC data, calculated values and proper units. Shortly, the worksheet contains
all information necessary for validation of the analytical process, and the reported values.
Figures 1.2, 1.3, and 1.4 are examples of laboratory worksheets. The designs of these
documentation forms are just examples; each laboratory has its own patterns as approved
in its QA/QC programs. As with all documentation, these sheets should be stored in
bound form per analytical groups and parameters with document title, date start and end,
identification number start and end. Strip charts, documented AA calibration curves, and
raw data should be stored in file boxes and identified as mentioned above. Additional
examples for working paper formats can be found in Appendix C.
1.2.4 Planning Laboratory Work

It is essential to plan laboratory work ahead of time, so as to use the laboratory time
efficiently and to avoid delays in using equipment that must be shared with other analysts.
The following questions should be asked before the actual preparation for analysis: which
kind of samples will be analyzed, how many samples analyzed, what is the source of the
Parameter : Method N o. Reference

Method Detection Limit (MDL) : _ _ _ _ _ _ _ _ _ _
Titrant and Normality (standardized) _____
Analyzed by __________________________ Date
ID Sample Sample Sajople Titrant Result Remark

No, Identification type ml ml mg/l
Blank
Q.C. sample
Duplicate
Spiked sample
INFORMATIONS RELATED TO QC CEECKS
True value of QC sample ___ ID of duplicate samples

ID NO. of spiked sample ____ _ Sample ml spiked ______
Concentration of spike stock solution
ml or ul spike stock added _______ _ Added spike value
Precision as Relative Percent Deviation (RPD) _______

Accuracy as % Recovery (% R) _________________________
% Recovery of Spike (% Rspike)
Approval, of Supervisor Date
Figure 1.3
Working paper for titrimetric analysis.
samples, which tests should be performed, which method should be used, which preser
vative was used, which pretreatment is necessary, etc.
The following list contains the duties of the analyst from the choosing of proper
samples for the particular analysis through the actual analytical performance, QC checks,
documentation, calculations, recognition and correction of problems, and giving accurate,
défendable results.
The analyst should be familiar with the method and the method should be followed as
described in the laboratory standard operation procedure (SOP).
If the sample needs pretreatment prior the actual analysis, such as drying, filtration,
distillation, digestion, extraction, etc., start as soon as possible, because these are time-
consuming procedures. If sample preparation is the duty of another laboratory depart-
Parameter _________ Method No-_ Reference

Method Detection Limit (MDL) __
Model of spectrophotometer Wavelength
Correlation Coefficient of the calibration curve
Analyzed by ____________ _______ Date
ID Sample
No Identifica Sample Sample Ahsor Dilut Result Remarks
tion type ml banca ion mg/L
Blank
Standard 1
2
3
4
CCS
CVS
Duplicate
Spiked s.
Blank
INFOBmTIONS BELATED TO QC CHECKS
% Recovery of Continuing Calibration Standard (CCS) _

True Value of Calibration Verification Standard (CVS)
% Recovery of CVS ____________ ID of Duplicate Sample”
ID No. of Spilced Sample Sample ml spiked
Cone, of Spike Stock solution _ _ _ _ Added spike value
Precision as Relative Percent Deviation (RPD) __________
Accuracy as % Recovery (%R) _____________________ _
% Recovery of spike (%Rspike) ____________ _______________
Approval of supervisor Date
Figure 1.4
Working paper for spectrophotometric analysis.
ment, collect all of the information needed for calculation of the final result (original
volume, weight, final volume after treatment, etc.).
• When samples are stored in a refrigerator, remove them in time to allow the samples to
warm up to room temperature prior to starting the analysis.
• Carefully check sample label for identification and select samples according to the ap
propriate bottle type and preservation for the analysis.
• Collect all standards and reagents needed and check their preparation date. When the
expiration date arrives, discard the solution and prepare a fresh one. When reagents are
stored in the refrigerator, leave time for warming up to room temperature before using
them. If necessary, standardize solutions and document on designated log form.
• Select the worksheet according to the analytical procedure and sample type, and fill out
initial information.
Collect the necessary glassware, check its cleanliness, use special treatment (for example
1+1 HNO3 rinse for metal analysis) if applicable. Number the glassware with sample ID
number.
Switch instrument to "'on" position (if instrumental analysis) to give time to "'warm up.''
Start the analytical procedure according to the approved method and incorporate all QC
checks required by the laboratory QA/QC program. (Detailed QA/QC requirements and
documentation during analytical work are discussed in Chapter 3.) All raw data and
information should be documented in the laboratory notebook or worksheet.
At the end of the analysis, switch off instrument, collect analytical wastes in designated
containers, collect dirty glassware and transfer to the washing area, and transfer stan
dards, reagents and samples to their storage area or into the proper refrigerator if needed.
Clean the work area.
Calculate the results and collect all documentation to be ready for further questions or
checking. If all the QC data agree with the analytical values, transfer all of the calculated
results to the analytical report sheet or computer as specified by the laboratory rules.
1.2.5 Documents to be Saved

The numerous documentation used during analytical work should be saved and
stored in the same way as the above-mentioned worksheets, in bound forms or file boxes
as described previously in Section 1.2.3.
A list of the stored documentation follows.
All notebooks, data forms, and log forms that belong to laboratory operation. All calcu
lation related to the sample result.
Chromatograms, charts, and other instrument response readouts.
Calibration curves, preparation of calibration standards.
Target limits for each analytical group and parameters.
Method detection limits (MDLs).
Summary log form for accuracy and precision data per parameters.
QC charts.
Records concerning receipt of solutions from commercial sources.
Laboratory custody reports (holding times, sample transmittal forms, sample storage logs,
sample disposal log).
Sample preparation logs.
Instrument maintenance and instrument performance check logs.
Copies of final reports.
Field records (field notebooks, field tests, field custody reports).
Records must be retained for a period of a least 3 years. Drinking water reports require
a retention time of up to 10 years.
Chapter 2
Safety and Laboratory W ork
Before entering into laboratory work, it is important to understand the potential

hazards in the laboratory, to be familiar with the precautions and rules, and to recognize
and avoid the causes of those hazards. According to the Occupational Safety and Health
Act (OSHA)," ... each employer has the general duty to furnish each of the employees a
workplace free from recognized hazards causing or likely to cause death or serious harm."
No one can start to work in any laboratory without comprehensive safety training!
Laboratory supervisors and managers, and laboratory instructors in schools are
responsible for ensuring adherence to the rules. Safety is the number one concern for
everybody working in the laboratory. Accidents can be minimized by recognizing their
causes and by being alert at all times. Everybody working in the laboratory should know
basic emergency first aid treatment for minor injuries (see Appendix A) and also the
location and use of emergency equipment such as safety showers, fire extinguisher, and
spill kits. All hazards should be identified whether they are visible or hidden, and appro
priate safety signs should be posted wherever applicable in conspicuous locations. Selected
safety signs are shown in Figure 2.1.
2.1 LABORATORY HAZARDS

Laboratory hazards can be divided into three groups: (1) chemical hazards, (2) fire
hazards, and (3) careless habits.
2.1.1 Chemical Hazards

Virtually all chemicals are toxic to some extent, and care should be taken in handling
them. Chemical hazards may be minimized by taking the following precautions.
Cleanliness
• Wash hands periodically and immediately after contact with chemicals and just before
leaving the laboratory.
• Never drink from laboratory glassware.
• Clean the working area before and after work.
10 ENVIRONMENTAL SAMPLING AND ANALYSIS LAB MANUAL
CAUTION
CAUTION CHEiyBCM
HESFIRATO»
R&OUIRCD SIDRAGi
IN THIS AREA
Figure 2.1
Safety signs can inform of possible risks and needed precautions within a facility.
• Laboratory coats and aprons are designed to protect the body from chemical spills. Dirty
clothes can be a health hazard and a source of contamination.
Protection of the eyes — The eyes are specially susceptible to injury from chemicals. The
most common types of accidents that threaten the eyes are breaking of glass containers
of acid, bases, etc. and reactions that go out of control. Both accidents can cause chemicals
to be sprayed into the eyes. For this reason, safety glasses, goggles, or face shields should
be worn during laboratory work. Eye hazards are constant in a chemical laboratory;
therefore eye protective devices should be worn at all times except when perfect vision
is required for measurements. Never wear cracked, pitted, or damaged eye protective
devices! (An eye protective device is shown in Figure 2.2.)
If any chemical is sprayed into the eyes, immediately flood the eyes with water; use
the specially designed eye wash fountain (Figure 2.3). Quick flushing with water from the
nearest tap also will minimize the damage. See a physician as soon as possible.
Injuries from contact of certain chemicals with the skin
• Skin contact with certain chemicals, such as those from strong acids or bases, can cause
chemical burns.
• Certain chemicals can absorb through the skin. Because many chemicals absorb rapidly
through the skin, prompt cleanup is important. Remove contaminated clothing immedi
ately (forget modesty, if necessary!) and flush affected areas with large volumes of water.
If more than a minor amount of chemical is involved, medical attention is necessary.
Figure 2.2
Eye protection device.
SAFETY AND LABORATORY WORK 11
Figure 2.3
Eye wash fountain.
Protection for the body
® Laboratory workers should wear appropriate safety clothing, such as laboratory coats or
aprons. The material of the laboratory coats gives protection against acids and bases. A
laboratory apron is not affected by ordinary corrosive fluids or other chemicals.
® Never wear open-toed shoes and sandals, because they offer little or no protection against
chemical spills or broken glass.
• Keep ties or scarves secured with fasteners.
• Tie long hair up and out of the way.
• When handling corrosive chemicals, use protective gloves. Gloves are selected according
to the need; asbestos gloves protect against heat, but they are not advisable for handling
corrosive chemicals (acids or bases), because asbestos absorbs the substance and increases
the contact time and area. When working with hot objects or organic solvents, rubber or
plastic gloves should not be used, as they may soften and dissolve.
Hazards from swallowing toxic chemicals — There should be no food or drinks in the
laboratory. It is too easy to contaminate food, especially with traces of chemicals on the
hand. To avoid any possibility of swallowing chemical solutions while using a pipet, all
pipeting should be done using a pipeting bulb and not the mouth.
Inhalation of volatile liquids and gases — The presence of these substances in the air
(even in low concentration) is hazardous. Acute exposure to extremely high concentration
of vapors (above the maximum allowable concentration) can cause unconsciousness and
even death, if the person is not removed from the area and is not given medical attention.
Exposure to solvent and chemical vapors may be avoided by working with such chemicals
under chemical hoods, and wearing protective respiratory device (Figure 2.4). Also, good
ventilation is essential to a safe laboratory
Toxicity of metallic elements — Metals with a specific gravity of greater than 5 are called
heavy metals. In the metallic state they are harmless, but in vapor state are toxic, and so
are their soluble compounds. The most common heavy metals are antimony (Sb), arsenic
(As), cadmium (Cd), chromium (Cr), lead (Pb), mercury (Hg), nickel (Ni), silver (Ag), and
thallium (Tl).
Figure 2.4
Protective respiratory device.
Chemical dust — Finely powdered chemicals can be inhaled as dust; therefore, such
chemicals should also be handled under a laboratory hood.
Chemical spills — Solid, dry substances — These can be swept together, brushed into a
dustpan or cardboard, and then deposited in the proper waste container.
Acid spills — These should be cleaned by using the proper spill kit and following the
enclosed instructions. The materials neutralize and absorb the acid for easy cleanup.
Afterwards, the area should be washed with water. Alternatively, soda ash (Na2C03) or
sodium bicarbonate (NaHC03) solution can be used for neutralization, followed by water
flushing of the area. CAUTION: When water is poured on spills of concentrated sulfuric
acid (H2SO4), tremendous heat is formed (exothermic reaction) and the acid spatters.
Deluge with water to dilute the acid to minimize heat generation and splattering.
Alkaline spills — Alkaline spills are treated similarly to acid spills, using an alkaline spill
kit and following the instructions. Alternatively, a weak acid solution, such as diluted
acetic acid, can be used for neutralization. The floor should be flushed with water to a
floor drain; a mop and bucket also can be used. Flush mop and bucket, replacing water
frequently. CAUTION: Alkali solutions make the floor slippery! Clean sand can also be
used; throw sand over the spill and sweep up. The wet sand is then discarded.
Volatile solvents spills — These evaporate very rapidly because of the extremely large sur
face area. This kind of spill can create a fire hazard if the solvent is flammable, and it will
invariably cause high, dangerous concentrations of fumes in the laboratory. These fumes
can have serious physiological effects when inhaled. They can also form explosive mixtures
with air. Cleanup procedures are as follows: if minor quantities of solvents are spilled,
wipe up the liquid with rags or towels and discard them in the proper waste receptacle.
If a large amount of solvent is involved in the spill, use a mop and pail. Squeeze out the
mop in the pail and continue as needed.
Spill of oily substances — Oily substances should be cleaned up with a selected nonflam
mable volatile solvent. Pour some on an absorbent rag, and wipe up the spilled substance.
The rag will need to be rinsed in a pail of the solvent to remove all the spilled material,
because oily floors are slippery and dangerous. Finally, a thorough detergent-water scrub
will clean up oily remains.
Mercury spills — These are one of the most common sources of mercury vapor in the
laboratory air. As a result of the spill, mercury may be distributed over a wide area,
exposing a large surface area of the metal. In any mercury spill, unseen droplets are
trapped in crevices. Unless the laboratory has adequate and reasonable ventilation, the
combined mercury vapor concentration may exceed the recommended limit.
CAUTION: Surfaces which are apparently free of mercury will harbor microscopic
droplets. Vibrations increase vaporization.
Clean up mercury spills as follows: (1) push droplets together to form pools. To pick
up the mercury, use a suction device. (2) If there are many crevices or cracks in the floor
which trap small droplets of mercury that cannot be picked up, seal over the cracks with
a thick covering of floor wax or an aerosol hair spray. The covering will dramatically
reduce vaporization. (3) Sulfur powder can also be used to fix mercury. (4) Mercury spill
kits are also available for proper mercury cleanup.
2.1.2 Fire Hazard

A fire in a chemical laboratory can be dangerous and devastating. In case of fire, keep
calm and think! Sources of fires can be electrical equipment, friction, mechanical sparks,
flames, hot surfaces, and flammable organic compounds. Accidental ignition of volatile
organic solvents is perhaps the most common source of laboratory fires. To avoid acci
dental spills and reduce fire hazards, keep volatile solvents in small containers and never work
with a volatile solvent around an open flame. The sooner you attack the fire, the easier it is to
control. All fires are different. The use of the wrong type of firefighting equipment may
increase the intensity of the fire.
Fires are classified according to the type of material being consumed. Class "A" fires
are caused by burning of paper, wood, textiles, etc. Almost any type of extinguisher is
satisfactory. Class "B" fires are caused by burning of oil, grease, organic solvents, paint,
etc. Use dry-chemical, liquid, CO2, or foam extinguisher. Class "C" fires are electrical fires
in equipment. Do not use a water or foam extinguisher! You may become a part of the
electrical circuit and be electrocuted! Use CO2 or dry chemical fire extinguisher only! Class
fires are caused by sodium, potassium, magnesium, lithium, and all metal hydrides.
Use dry soda ash fire extinguisher, sodium chloride, or dry sand.
Fire in clothing — Smother in fire blanket or heavy toweling. Use an emergency shower.
General fires — Select the proper fire extinguisher according to the type of fire. First cool
the area around the fire with extinguisher to prevent the fire from spreading. Then use
extinguisher at base of the fire, and finally extinguish any scattered remnants of the fire.
Electrical fires — First disconnect the apparatus by pulling the safety switch to avoid the
possibility of being electrocuted. Then use Class C (CO2 or dry chemical) extinguisher.
Poisonous gas fires — Use proper respirator. Select the proper fire extinguisher. If the fire
gets beyond the control of the available fire extinguisher, get out of the room immediately.
Figure 2.5
Safety stepladder.
Close the door to prevent drafts and gas spread. Always be certain that no one is left
behind.
As always, in case of fire be certain that the local fire department is immediately
notified!
2.1.3 Careless Habits

Most accidents in the laboratory are caused by doing something impulsive that later
seems thoughtless. As a general rule, think about what you are doing before doing it!
Hazards from falling objects — Falling objects can cause serious injuries. Do not place
heavy objects on high shelves! If a heavy object must be put on a shelf, secure it with a
belt or chain. Be careful in moving heavy instruments or heavy objects; use a laboratory
cart where possible.
Hazards from falling — Never climb on drums, cartons, or boxes to reach objects located
on high shelves. You may be severely injured, and the injury can be compounded by
breakage of glassware or chemical splash. Always use a safety stepladder (Figure 2.5),
which provides high stability due to its design and does not slip or move because special
locking devices ensure that its rubber-tipped legs engage the floor firmly.
Transporting large bottles — Moving large bottles and carboys is a dangerous operation
because of bottle breakage and liquid spillage. Always use safety carts and safety bottle
carriers when transporting large bottles of chemicals. The safety bottle carriers secure the
bottle from shock and breakage.
2 .2 SA FE H A N D L IN G O F C O M P R E S S E D G A S E S
Compressed gas cylinders can be dangerous because gases are contained under very
high pressures. Always handle cylinders of compressed gas with safety precautions.
2.2.1 General Precautions When Working with Compressed Gases

General precautions
• Close off main cylinder valve when not in use.

• Close needle valve or auxiliary cut-off valve in the line as well as that located at the
cylinder. Do not rely solely on the cylinder valve.
• Replace cylinders in reasonable time. Replacement for corrosive gases should be 3 months
or less.
• Always use gases in areas where adequate ventilation is provided.
• Keep cylinders in outside storage, or have manifolds piping low-pressure gas into build-
ings.
• Use the smallest cylinder practical for the purpose.
Safety Rules of Using Compressed Gases
• Cylinder contents must be properly identified. Do not accept cylinders that do not identify
contents by name. Do not rely on color codes for identification. Do not destroy identifi
cation tags or labels.
• Cylinder valves must be protected. Accept only cylinders provided with cylinder valve
protective caps. Leave caps in place until ready to use the gas.
• Store properly. Provide specifically assigned location, preferably in a fire-resistant, dry,
and well-ventilated area, away from sources of ignition or heat. Outdoor storage area
should have proper drainage, and should be protected from direct sunlight. Secure cyl
inders by chaining or other means to keep them from falling accidentally.
• Transport cylinders by means of a suitable hand truck. Do not roll!
• Never drop cylinders or permit them to strike each other.
• Return in condition received. Close valve, replace cylinder valve protective cap, and dust
cap. Mark or label cylinder ''EMPTY'' or "MT."
• Prevent confusing empties with full cylinders. Store empty cylinders apart from full
cylinders. Connecting empty cylinder by mistake to pressurized system could cause
contamination or violent reaction in cylinder.
2.2.2 Hazardous Properties of Compressed Gases

It is very important that the properties of a compressed gas be well known before the
gas is put to use. Hazards presented by compressed gases are flammability, toxicity, and
corrosivity. Hazardous properties of compressed gases are listed in Table 2.1.
2 .3 S T O C K R O O M SA FETY RULES
The laboratory stockroom should be adequate and efficiently planned for safe oper
ation.
2.3.1 Checklist for Safety Storage Room
• The safety storage room should be well planned with wide aisles and adequate lighting,
and no blind alleys. It should be orderly and clean.
TABLE 2 J
Hazardous Properties of Compressed Gases
Gas Toxic Flammable Corrosive
Acetylene X
Air
Ammonia X X X
Argon
Arsine X X
Boron trichloride X X
Boron trifluoride X X
Butane X
Butenes X
Carbon dioxide
Carbon monoxide X X
Carbonyl sulfide X X
Chlorine X X
Cyanogen X X
Cyclopropane X X
Deuterium X
Diborane X X
Dimethylamine X X X
Dimethylether X
Ethane X
Ethyl acetylene X X
Ethyl chloride X X
Ethylene X
Ethylene oxide X X
Fluorine X
Helium X
Hexafluoropropane X
Hydrogen X
Hydrogen bromide X X
Hydrogen chloride X X
Hydrogen fluoride X X
Hydrogen sulfide X X
Isobutane X
Isobutylene X
Krypton
Methane X X
Methylacetylene X
Methyl bromide X X
Methyl chloride X X
Methylmercaptan X X
Neon
Nitric oxide X X
Nitrogen
Nitrous oxide
Oxygen
Ozone X
Phosgene X X
Phosphine X X
Propane X
Propylene X
Silane X X
Sulfur dioxide X X
Sulfur hexafluoride
Sulfur tetrafluoride X X
Trimethylamine X X
Xenon
• It should be well ventilated, with an emergency exhaust system.

• Exits should be well marked.
• Emergency exits should be available.
• It should be equipped with adequate fire-protection and firefighting equipment.
Storage area
• Heavy items should be stored near the floor.

• Proper storage should be available for glass apparatus and tubing (never projecting
beyond shelf limits).
• Eragile and bulky equipment should be secured to shelving.
• Shelving should be fitted with ledges to prevent items from falling off.
• Liquids and hazardous chemicals should be grouped and separated.
• No waste accumulation of any kind should be permitted.
Other safety precautions in the storage room
• Safety ladders should be used. Safety ladders prevent accidents and save time and effort.
• No excessive heat should be permitted, because of fire hazard.
• Good housekeeping should be maintained, with vigilant and constant maintenance for
safe storage.
• Commonsense behavior is necessary of all personnel using storage facilities.
2.3.2 Storage of Chemicals

Chemicals are manufactured in varying degrees of purity. Carefully select the grade of
the chemical that meets the need of the work to be done. Always recheck the label of the
chemical that you are using! The use of a wrong chemical can cause an explosion, or ruin the
analytical work. Check the information carefully on the chemical container: name, formula,
formula weight, percentage of impurities, analytical grade, health hazards, and safety codes.
Storage of acids — Acids should be stored in original containers in an ''ACIDS"-labeled

cabinet, grouped by safety color codes. Bottles having impact-resistant plastic coating are
preferred.
Storage of flammable solvents — Store in original containers that are specially designed
and put in a "FLAMMABLE"-labeled cabinet. Large quantities should be stored in metal
safety cans and outside of the laboratory in marked "FLAMMABLE STORAGE AREA."
Storage of solvents — Store solvents in separate solvent cabinet, in the original container,
and in a well-ventilated area.
Storage of chemicals used for volatile organic (VOC) analysis — Store in a separate
solvent cabinet, in original containers, and in a well-ventilated area. No other chemicals
should be stored in this area.
Storage of chemicals — Chemicals should be stored in alphabetical order in the storage

room, with record of "date of arrival" and "date of opening" on each container. Phenol
TABLE 2.2
LabGuard Safety Label System
Color
Code Hazard Storage
White Contact hazard Corrosion-proof area
Yellow Reactivity hazard Store separately from flammables and combustibles
Blue Health hazard Store in a secure "poison"-marked area
Red Flammable hazard Store in an area segregated for flammables
Gray Minimum or no hazard Store in a general storage area
N ote: The storage code color band runs the entire width of the label of the chemical
container, so it is perfectly visible regardless of the container's orientation on the
shelf. Store chemicals with like colors together according to recommendation. In
compatible substances that should not be stored alongside chemicals with the same
color labels should carry a blue color band at the bottom of the label. Recommended
protective equipment, warning statements, and first aid instructions are carried
within the lablel's safety information portion.
and hydrogen peroxide should be stored in "chemical storage"-marked refrigerator. The

LabGuard Safety Label System (see Tables 2.2 and 2.3) on chemical bottles assists the
proper storage of chemicals. Each chemical used in the laboratory should be accompanied
with the material safety data sheet (MSDS). The MSDSs for every substance give the identity
of ingredients, the physical and chemical characteristics of the substance, the physical
hazards, the reactivity and health hazards involved, and safe handling and safety precau
tions. In addition, the control measures to reduce harmful exposures are also listed in
every MSDS. An example of an MSDS is shown in Figure 2.6.
2 .4 LA B O R A T O R Y SA FETY RULES
1. Safety glasses/corrective glasses shall be worn at all times in the laboratory Visitors to
the laboratory must be appropriately warned and safety glasses made available to them.
2. Participation in practical jokes or "horseplay" in the laboratory is not permitted.
3. Each laboratory worker is expected to cooperate in keeping his/her working area in a
neat and orderly condition and to cooperate with others in making this possible through
out the laboratory. A CLEAN LABORATORY IS A SAFE LABORATORY.
TABLE 2 .3
LabGuard Safety Label System: Acids and Bases
Color Code Chemical
Yellow Sulfuric acid
Red Nitric acid
Blue Hydrochloric acid
Brown Acetic acid
Black Phosphoric acid
Green Ammonium hydroxide
N ote: Besides the colored lable, the containers also
have color-coded polystyrene screw caps that
simplify identification and prevent contamina
tion. Acid bottles have dripless pouring rings
and finger grips for easy handling, as well as
impact-resistant plastic coating. Although the
bottle can break, the coating keeps glass frag
ments and the reagent trapped within.
VII « Heaiilt Hazard Data

Material Safety Data Sheet
LaMotte Ciicmksl Products Compatiy Toxicity: Unknown
PO Box 329 • ClitsttrtowB« MarySaud • 2UW Primasj Rome of Entry: inhalmioni ]SkìnÌ X j ingestion I /
# for liiformailofi 39I*778-3I0@
In an emtfgeacj: Local Poison Cwitroi Center T arget O rgan: N/A
Signs & Symptoms o f Exposure: Irritating to eyes, nose and skin.
! * Product Identiflcatioa
M edical Cont&Uon A ggram ed by Exposure: N/A
N am e: N itric Acid C ode If: 3933
C ard m g en kity : ( X JN !A / } N IT j / lARC
VIP * Emergeiicy First Aid Procedures
II » Hazardous Ingredients
Eye C ontact: Flush thoroughly with water for 15 minutes. Consult a
N am e CAS# PEL IIV
physician.
N itric A cid 7697-37-2 0.6 1 mg/m^ 1 mg/m^
m » Noa-Haaafdoua lagrcdieats except water (7732-1IL5)
Skin C ontact: Flush with water, remove affected clothing and wash
Name CAS»
skin with soap and water.
in gestion : Rinse mouth, drink g lass of water and consult

IV •Physical Data
physician.
A ppearance: Cfoar, colorless Hquid O dor: None
in h d ation : N/A
SohUfility in w ater: ^hjble p fí: 1
B oiling p oin t: unkîiown M elting poin t: N/A
IX " Spili à Disposal Procedures
V apor pressu re {m m //g):U nknow n V apor D ensity (A ir^ J): Unknown
Spin & L eak: Cover spül with sodium bicarbonate. Scoop up skirry
and wash down drain with excess water.
V » Fire & Exploskm Data
D isposai: Add slowty to a solution of soda ash and slaked im e.
F lash point {m ethod u sed):
Pour tWs neulraSzed solution down drain wHh excess water.
Flam m able lim it: LE L : U EL:
X « Precautionary Measurts
Extinguishing M edia: Not a fire hazard
In H andling: G loves ( X ) Eye P rotection ( X JO ther: Lab Coat
S pecial F ire Fighting P rocedu res:
V entilation: N orm al (X } M echanical { } Respiratory Protection ( }
Unusual F ire à E xplosion H asard:
W ork/Hygienic P ractices: Avoid contact with skin and dothing
VI » Reactivity Data
XI •Speciai PrecmitioiijR N/A
S tability: S table / X J U nstable / /
Date; 8/^0
C onditions to A void: N/A
The abo^ infoosatrân i$ believed to be comet, but doei oot claim to be eli mchuive and
Incom pataM ity (M aterials to A void): N/A shoidd seed as 8 pide.
H azardous D ecom position P roducts: N/A a
M(|40CFK 372«diemteal sidiiect to ie|R»tin| requiranaxs ci setíkso 313of BPCRA
Figure 2.6
Material safety data sheet.
4. The proper techniques shall be utilized when lifting, pushing, pulling or carrying mate
rials to prevent injuries.
5. The location of fire extinguishers, safety showers, eye wash stations, and spill kits must
be known to all workers.
6. All laboratory workers must know how and when to use the items listed in #5 above.
7. Eating, drinking, and smoking in the laboratory are never allowed. Never use laboratory
containers (beakers or flasks) for drinking.
8. No food or edible substance for human consumption is to be stored in refrigerators in
the laboratory.
9. All chemicals used in the laboratory must have a material safety data sheet (MSDS).
10. All chemicals should be clearly labeled. Do not use material from unlabeled containers.
Clearly identify chemicals before using them.
11. In the case of chemicals splashed in the eyes, use the eye wash station and report the
incident to the laboratory supervisor.
12. Respirators must be used when working with hot acids or solvents not under a hood.
13. Pouring of volatile liquids should be done only in a well-ventilated hood remote from
sources of ignition.
14. Only the minimum amount of flammable liquids necessary for making the test shall be
kept on work benches.
15. Heavy reagent containers, such as 5 gallon containers, must not be carried or placed on
a shelf by one person alone.
16. Face shields, rubber gloves, and protective rubber aprons should be used when preparing,
transporting, or pouring corrosive chemicals such as concentrated acids and bases.
17. If it is necessary to dilute acid with water, always add the acid to the water, stirring
constantly. Never add water to the acid, as this produces a violent reaction.
18. When drawing liquid into a pipette, always use a suction bulb. Mouth-pipetting is never
allowed.
19. Pouring mercury into a sink or drain is strictly prohibited. Mercury will remain in the
trap and continue to vaporize and contaminate the air.
20. In the event of acid spills on a person, flush thoroughly with water immediately. Be aware
that acid-water mixtures will produce heat. Removing clothes from the affected area
while flushing may be important so as not to trap hot acid-water mixtures against the
skin. Acids or acid-water mixtures can cause very serious burns if left in contact with
skin only for a very short period of time.
21. Weak acids should be used to neutralize base spills, and weak bases should be used to
neutralize acid spills. Such solutions should be available in the laboratory in case of
emergency. Acid and base spill kits are also available.
22. There must be no unsupervised or unauthorized work going on in the laboratory.
23. Never wear open-toed shoes or sandals, because they offer little or no protection against
chemical spills and broken glassware.
24. Keep ties and scarfs secured with fasteners. Do not wear medallions or other hanging
objects.
25. Tie long hair up and out of the way.
26. Asbestos gloves should be worn when handling or working with hot materials.
27. Gloves will be worn when opening jars, bottles, or other containers when necessary to
exert pressure.
28. A face shield will be worn whenever handling a container with more than 1 L of acid,
alkali, or corrosive liquid.
29. Chemicals should never be transported, transferred, poured, or otherwise handled at the
height above one's head.
30. Any injury sustained, regardless of how superficial, should be reported to the laboratory
supervisor or instructor in schools, and appropriate first aid action should be taken.
31. A leak check shall be made on all gas lines and connections whenever a line is broken
and reconnected.
32. Report immediately to the laboratory supervisor any failure of exhaust fans to evacuate
vapors completely, defective electrical equipments, faulty or empty fire extinguisher, worn
or defective rubber gas burner hose, or other gas hazards.
33. If it is necessary to reach a high shelf, use a step ladder provided for this purpose.
34. Operations involving explosives or flammable mixtures shall not be left unattended.
35. When transporting a large quantity of bottles, do so with a basket or receptacle designed
for this purpose.
36. Damaged glassware shall not be used.
37. Glassware shall not be placed close to the edge of the laboratory bench; a passerby may
knock it off.
38. Goggles or face shields shall be worn when working with glass apparatus which is under
pressure or vacuum.
39. When making a vacuum distillation, use a shield to guard against explosion and fire
hazard.
40. All broken glass shall be cleaned up immediately and placed in a container provided for
broken glass. Never dispose of broken glassware in a regular garbage container!
Chapter 3
Q uality A ssurance
OF C hemical M easurements
3 J IN T R O D U C T IO N
A laboratory is expected to be able to specify the quality of its data in quantitative

terms. This requires the existence of some degree of quality assurance.
3.1.1 Quality Assurance (QA)

Quality assurance is a definite plan for laboratory operation that specifies standard
procedures that help to produce data with defensible quality and reported results with a
high level of confidence. It is a necessary part of data production, and it serves as a guide
for the operation of the laboratory for production data quality. The basic requirements of
a quality assurance program is to recognize possible errors, understand the measurement
system used, and develop techniques and plans to minimize errors. It also includes
evaluating what was done, and reporting evaluated data which are technically sound and
legally defensible. Quality assurance is the statistical control of quality.
The elements of the quality assurance are quality control and quality assessment. The
activities related to each are summarized below.
Quality Assurance
Quality Assessment Quality Control
Reference material CLP, GMP, SOP
Replicates Calibration
Splits Standardization
Spikes Instrument maintenance
Surrogates Facilities maintenance
Collaborative tests Education and training
Statistical analysis Inspection and validation
3.1.2 Quality Control (QC)

Quality control is a mechanism established to control errors. It is a set of measures
within a sample analysis methodology to assure that the process is in control. It helps to
21
provide quality that is satisfactory, adequate, dependable, and economical. It consists of

the use of a series of procedures that must be rigorously followed. Good quality control
systems should include provisions for inspection, both periodical and unannounced, to
ascertain how well the procedures are functioning. Large laboratories have a quality
control officer or group, independent of the laboratory management, that oversees the
operation of the system.
The elements of quality control are
• Competent personnel with adequate educational background with specific training and
experience.
• Suitable and properly maintained laboratory equipment and facilities. Modern equipment
increases the need for QA/QC.
• Properly selected methodology.
• Good laboratory practices (GLP) — see below.
• Good measurement practices (GMP) — see below.
• Standard operation procedures (SOP) — see below.
• Documentation.
• Inspection and validation.
Good laboratory practices (GLP)
• Laboratory safety
• Cleaning, housekeeping, temperature, humidity control, glassware cleaning
• Storage, handling, labeling, shelf-life, and disposal of chemicals
• Sample custody (documentation, routing, storage, preparation, retention)
• General laboratory operations
• Use, maintenance, and calibration of equipment
• Statistical procedures
• Data reporting, format, documentation
Good measurement practices (GMP) — Guidelines should be written for each measure
ment technique, addressing subjects such as maintenance and records for equipment, and
specified calibration procedures. General instruction manuals should be available with
the requirements and precautions for each technique.
Standard operation procedures (SOP) — SOPs are written for basic operations to be
done in the laboratory. SOPs should include sampling, measurement, calibration, and data
processing in a standard format.
The difference between GLPs, GMPs^ and SOPs — GLPs and GMPs (practice) provide
guidance, allowing some judgment of the user. They are written in indicative mode. SOPs
(procedure) provide direction. Every departure from the laboratory SOP must be justified.
They are written in imperative mode.
3.1.3 Quality Assessment

Quality assessment is the mechanism to verify that the system is operating within acceptable
limits. It is the overall system of activities whose purpose is to provide assurance that the
QUALITY ASSURANCE OF CHEMICAL MEASUREMENTS 23
overall quality control job is being done effectively. Quality assessment is a process to
determine the quality of the laboratory measurements through internal and external
quality control evaluations, and includes performance evaluation samples, laboratory
comparison samples, and performance audits.
3.2 L A B O R A T O R Y Q U A L IT Y A S S U R A N C E P R O G R A M
In Quality Assurance in Chemical Measurements, John K. Taylor states that "the objective
of quality assurance programs for analytical measurements is to reduce errors to tolerable
limits and provide a means of ensuring that the measurements generated have a high
probability of being of acceptable quality" (Taylor, J.K., 1988). Acceptable quality is variable
and depends on the analytical parameter and measurement process. Each laboratory
involved in environmental analytical processes has to develop its own quality assurance
program, which should be delineated in a QA/ QC manual, and should be comprehensive
enough to apply to most of the operation. This program should be continually reviewed
and updated as needed. The laboratory should also have a separate quality assurance
"project plan" for each of the projects. Understanding the quality assurance program helps
the analysts to be responsible participants in the laboratory system, who produce défend
able, precise, and accurate analytical data.
3.2.1 Sampling
The sample is one of the critical elements of the analytical process. The quality of any
data produced by any analytical system primarily depends on the sample analyzed. A
sample must be representative of the whole so that the final result of the chemical analysis
represents the entire system that it is intended to represent. Samples collected at a particular
time and place are called grab or individual samples. This type of sample represents condi
tions at the time it was collected. Therefore, a grab sample should not be used as a basis
for a decision about pollution abatement. However, some sources are quite stable in
composition, and may be represented well by single grab samples. If results for an entire
system are to be reported, a series of smaller samples are collected in a single container
and blended for analysis. The mixing process averages the variations in sample composi
tion and minimizes analytical effort and expense. These types of samples are called com
posite samples. When a time factor is being taken into consideration, grab samples are
collected in suitable intervals, chosen according to the expected changes. Composite sam
ples reflect the average characteristics during the sampling period, and in most cases a 24-
hour period is standard. The volume of the subsamples should be constant, at least 200 mL.
Depending on the analytical parameter or parameter group, the required material and
type of sample bottles used and the preservation of the samples are different. Recom
mended containers, preservatives, and holding times for environmental analytical param
eters are shown in Table 3.1. Sample preservation may be accomplished by ready, com
mercially available prepreserved bottles or by addition of preservative to the sample in
the field after sample collection. The pH of the preserved sample should be checked by
narrow-range pH paper on an aliquot of preserved sample poured into a small disposable
container. More preservative should be added as needed until the pH of the sample is
satisfactory. In this case, a corresponding blank sample should be taken with the same
amount of preservative. The pH result and the additional quantity of the preservative
should be documented.
Documentation during sample collection and transportation includes the chain of
custody form (Figure 3.1) and field notebook containing all information about field activities.
TABLE 3,1
Recommended Volumes, Containers, Preservatives, and Holding Times for Collecting Samples
Parameters Volume (mL) Container Preservative Holding Time
P h y s ic a l p ro p er tie s
Color 50 P, G Cool, 4°C 48 hours

Conductance 1 0 0 P,G Cool, 4°C 28 days
Hardness 1 0 0 P,G HNO3 to pH <2 6 months
Odor 2 0 0 G only Cool, 4°C 24 hours

pH 25 P,G None required Analyze immediately
Residue filtrable 1 0 0 P,G Cool, 4°C 48 hours
Residue nonfiltrable 1 0 0 P,G Cool, 4°C 7 days
Residue total 1 0 0 P,G Cool, 4°C 7 days
Residue volatile 1 0 0 P,G Cool, 4°C 7 days
Settleable matter 1 0 0 0 P,G Cool, 4°C 48 hours
Temperature 1 0 0 0 P,G None required Analyze immediately
Turbidity 1 0 0 P,G Cool, 4°C 48 hours
M e ta ls
Dissolved 2 0 0 P,G Filter on site 6 months

HNO3 to pH <2
Suspended 2 0 0 P,G Filter on site 6 months
HNO3 to pH <2
Total 1 0 0 P,G HNO3 to pH <2 6 months
Chromium + 6 2 0 0 P, G Cool, 4°C 24 hours
Mercury dissolved HN0 3 to p H < 2 28 days
Total 1 0 0 P,G HNO3 to pH < 2 28 days
In o r g a n ic n o n m eta llic
Acidity 1 0 0 P,G Cool, 4°C 14 days

Alkalinity 1 0 0 P,G Cool, 4°C 14 days
Bromide 1 0 0 P,G None required 28 days
Chloride 1 0 0 P,G None required 28 days
Chlorine 1 0 0 0 P, G None required Analyze immediately
Cyanides 500 P,G Cool, 4°C 14 days
NaOH to pH >12
Fluoride 300 P,G None required 28 days
Iodide 1 0 0 P,G Cool, 4°C 24 hours
Nitrogen ammonia 400 P,G Cool, 4°C 28 days
H2 SO4 to pH <2
Kjeldahl 500 P,G Cool, 4°C 28 days
H2 SO4 to pH <2
Nitrate plus nitrite 1 0 0 P,G Cool, 4°C 28 days
H2 SO4 to pH <2
Nitrate 1 0 0 P,G Cool, 4°C 48 hours
Nitrite 50 P,G Cool, 4°C 48 hours
Dissolved oxygen 300 G bottle and top None required Analyze immediately
probe
Winkler 300 G bottle and top Fix on site, store in 8 hours
dark
Phosphorus ortho-P 50 P,G Filter on site 48 hours
dissolved Cool, 4°C
Hydrolyzable 50 P,G Cool, 4°C 28 days
HSSO4 to pH <2
Total 50 P,G Cool, 4°C 28 days
H2 SO4 to pH <2
Total dissolved 50 P,G Filter on site 24 hours
Cool, 4°C
H2 SO4 to pH <2
TABLE 3.1 (continued)

Silica 50 P only Cool, 4°C 28 days
Sulfide 500 P,G Cool, 4°C 7 days
2 mL zinc acetate +
2NNaOH to pH >9
Sulfite 1 0 0 pc None required Analyze immediately
Sulfate 1 0 0 P,G Cool, 4°C 28 days
O rg a n ic s
BOD 1 0 0 0 P, G Cool, 4°C 48 hours

COD 50 P, G Cool, 4°C 28 days
Oil and grease 1 0 0 0 G only Cool, 4°C 28 days
H2 SO4 to pH < 2
Organic carbon 50 P, G, G brown Cool, 4°C 28 days
H2 SO4 to pH <2
Phenolics 500 G only Cool, 4°C 28 days
H2 SO4 to pH <2
Surfactants 500 P,G Cool, 4°C 48 hours
Purgeable 40 G, teflon-lined Cool, 4°C 14 days
halocarbons septum 0.008% Na2 S2 0 3 ’^
Purgeable aromatics 40 G, teflon-lined Cool, 4°C 14 days
septum 0.008% Na2 S2 0 3 *
HCl to pH <2
Acrolein and 40 G, teflon-lined Cool, 4°C 14 days
acrylonitrile septum 0.008% Na2 S2 0 3 ^
pH 4 to 5
Phenols 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
cups 0.008% Na2 S2 0 3 ^ 40 days after extraction
Phthalate esters 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
cups 0.008% Na2 S2 0 3 * 40 days after extraction
Nitrosamines 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
cups 0.008% Na2 S2 0 3 =^ 40 days after extraction
store in dark
PCBs 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
cups 40 days after extraction
Nitroaromatics and 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
isophorone cups store in dark 40 days after extraction
Polynuclear aromatic 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
hydrocarbons cups store in dark 40 days after extraction
TCDD (Dioxin) 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
cups 0.008% Na2 S2 0 3 =^ 40 days after extraction
Chorinated 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
hydrocarbons cups 40 days after extraction
Pesticides 1 0 0 0 G, teflon-lined Cool, 4°C 7 days until extraction.
cups pH 5 to 9 40 days after extraction
S o il, s e d im e n t, s lu d g e
Organic extractable 8 oz. Widemouth G Cool, 4°C ASAP

teflon-lined cup
Organic volatile 8 oz. Widemouth G Cool, 4°C ASAP
teflon-lined cup
Metal 1 pint P Cool, 4°C 6 months
F ish S a m p les
Wrap in A1 foiP"^ Freeze ASAP

TABLE 3.1 (continued)

C h e m ic a l w a s te s
8 oz. Widemouth None ASAP

teflon-lined cap
B a c te r io lo g y
100 P, G sterile Cool, 4°C 6 hours

Total and fecal coli 0.008% Na2 S2 0 3
Fecal streptococcus
R a d io lo g ic a l
1000 P,G HNO, 6 months

Alpha, Beta, Radium pH <2
N o te:ASAP = as soon as possible; P = polyethylene container; G = glass container. Sample preservation should
be performed immediately upon sample collection. For composite samples, each aliquot should be pre
served at the time of collection. When use of an automated sampler makes it impossible to preserve each
aliquot, then chemical samples may be preserved by maintaining 4°C until compositing and sample
splitting is completed. Samples should be analyzed as soon as possible after collection. The holding times
listed should be the maximum time that samples may be held before analysis and still be considered valid.
For dissolved parameters, samples should be filtered immediately on site before preservation. Reference
40 CFR Part 136.
* Required if residual chlorine is present.
Plastic containers may be used if only metals are required.
¥m\v> S^Ntme .
Sumfik Rfiwaved _ Aé$m$ .
Saropkits) _____
Mi
taM fii
Toni Ntaabor ofConlMnas
Rdmouiib8áB> R tx m éB r. OmMmtém:
Time: Dm: Tkm:
Düe; Dm TIm :
Ml,^w)
Figure 3.1
Chain of custody form.
Field Sequence No.

Field Sample No. ___ Date Time
Sample Location__
Sample Source___
Preservative used_
Analyses required ___
Collected by
Remarks
Final pH checked_____________________________________________________________
Additional preservative used (if applicable)_______________________________________
Figure 3.2
A sample label should be affixed to all sample containers. This is an important part of sample identification. It
should be waterproof, and all of the information should be written in waterproof ink.
Each sample should be labeled with the exact sample identification (including preservation
and preservation checks). A typical sample label form is shown in Figure 3.2.
It should be noted that the effectiveness of sample collection and related field activities
is supported by field quality control checks.
Equipment blanks — Equipment blanks are used to detect any contamination from sam
pling equipment. They are prepared in the field before sampling begins, by rinsing the
equipment with analyte-free water, filling the appropriate sample bottle with analyte-free
water, and preserving with appropriate preservative.
Field blanks — Field blanks are collected at the end of the sampling event by filling the
appropriate sample bottle with analyte-free water and preserving the same manner as the
samples.
Trip blanks — These are used to verify contaminations that may occur during sample
collection and transportation. Trip blanks are blanks of analyte-free water that are prepared
by the laboratory; the blank is transported to the field and remains unopened during the
sampling event and is transported back to the laboratory with the samples.
Duplicate samples — These samples are collected for checking the preciseness of the
sampling process. Duplicate samples are collected at the same time and from the same
source as the study samples.
Split samples — These samples are taken to check analytical performance. The sample is
taken in one container, mixed thoroughly, and split into another container. Both halves
are now samples that represent the same sampling point.
3.2.2 Sample Custody

Sample custody is the process of protecting the samples collected and analyzed. If a
sample decomposes or is contaminated prior to the actual analysis, the results are unre
liable. Proper sample handling is essential. All the paperwork involved in the sample
custody process defends and secures the quality of the reported data. It shows how
samples are collected, preserved, stored, transported to the laboratory, treated, numbered,
and tracked during the analytical process. All records have to be maintained so that they
are easy to find and ready at all times for immediate inspection. All documentation must
be signed or initialed by the responsible person and recorded with waterproof ink, without
any erasures or marking. All corrections must be made with one line marked through the
error, accompanied with a signature or initial, date, and the corrected form.
An important rule to remember is that "it did not happen if it is not documented."
Since a large number of the work done in today's laboratories potentially could go to
litigation, all aspects of the sample must be documented. This starts with the purchase of
the bottles used to collect the samples and ends in the laboratory with the record of the
individual who mailed the data package.
Documentation must be related to
• Sample collection, field activities

• Sample receipt, sample distribution, and holding time
• Sample preparation prior analysis
• Analytical methods
• Reagents and standards preparation
• Calibration procedures and frequency
• Analytical data and calculations
• Detection limits
• Quality control requirements and quality control routine checks related to the analysis
• Data validation and reduction
• Data reporting
3.2.3 Sample Preparation for Analysis

Once sampling and sample preservation schemes have been properly executed, the
sample is ready for analysis. Most of the time, however, it is still not in a state in which
the chosen analytical technique can be properly applied. Sample preparation techniques,
such as distillation, digestion, extraction, etc. will be discussed in Chapter 5 and in specific
analytical methodologies. A sample holding time log form is shown in Figure 3.3, and a
sample preparation log form is shown in Figure 3.4.
3.2.4 Analytical Methodology

The above requirements are closely related to the measurement methodology to be
used. The method used should be adequate for the intended purpose and it must be
properly utilized. The necessary characteristics of a suitable method include adequate
sensitivity, selectivity, accuracy, and precision. The method selection should also entail a
large dynamic measurement range, easy operation, required operational skill, low cost,
detection limit, biases, interferences, and calibration requirements. A method, once
adopted, must be used in a reliable and consistent manner in order to provide reproducible
data. This is best accomplished by following detailed, written standard operation proce
dures (SOPs). In environmental testing, all analyses must be performed using methods
approved by the U.S. Environmental Protection Agency (EPA) or state Department of
Environmental Protection (DEP), specified according to the sample matrices. Before apply-
SâtnpÎD “ Samf!^ Identifioatkm Number rec. = R<Hi$eived

Anaiym Required =Aml>'sis leqiÉred S^. ^ Signature o f Logger
-Pre|»rcd
ami. * Analysis
éspo -CHiqx)sdl
KU^hMi Tiae EinlMirtioii:

jnêp. =»nuisbôfday$bê<m die date sMtple received and date s a m |^ l» e ^ e d
anal = number of days between tlw date ssanpte prq>aied and fee date o f aebud analysk
diapo. »mimberofdays between the date saempk recaved m d fes date sample disposed
R.T, ~ Room Tempmtufe m desi^gnated area

Ref O. Re&^getîdm', de^gnated for o^^snk samples
Ref i « Re&êrator^ desagnafod for meugame s « n | ^
Fr = Freezer, designated tot samples
Figure 3.3
Sample holding time log.
SasnÎe Method Mdhod Daté Fimi

ID. No. Mstrix Tesifw No. No Sanale Sanqsle Sample Size Volimae Sipaliife
Analysis . Pf«p Rec-d Prep. ml. .....A — mi.
Figure 3.4
Sample preparation log (per analyte group).
Exploring the Variety of Random
Documents with Different Content
Then he added:
"And Sam Butler, Democrat, is elected to the House of Delegates,

chiefly by the mountain vote, which seems to have been pretty nearly solid
for him."
Judy Peters beamed upon Colonel Conway, and ventured the remark:
"'Tain't no use a-votin', Colonel, ef you don't stick together an' vote to
'lect. That's our way up in the mountings."
"Ah, Judy," the Colonel replied, "I'm afraid you're a sad sinner. I'm afraid
you manipulated that vote."
"I ain't close acquainted with that big word o' your'n, Bob, but I was
purty nigh right in my jedgment as to how this here 'lection was a goin' to
come out. Say, Bob, what d'you think that there comb-cut rooster William
Wilberforce Webb thinks of hisself by now? I wonder ef he'll unload some
o' that name?"
Westover and his bride left as soon as the ceremony was over, but
Colonel Conway kept the festivities going all day, and there was a dance at
night.
The occasion was rich in opportunities for Jack Towns, and, with the
alert energy which was characteristic of him, he made the most of them.
When, two days later, he left for Boston as Millicent's escort, there was no
room for doubt in anybody's mind as to the outcome of his visit to the blue
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It was a month later, and winter had begun, when Westover and Margaret
—just entering the house—went to the clock and set it going. She said
something—no matter what. He said nothing, but gathering her head to his
breast, he caressed her. Words seemed superfluous.
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Environmental Sampling and Analysis Lab Manual

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Lab Manual to Accompany Geography 1011 Environmental

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International Standard Book Number-10: 1-56670-178-3 (Softcover)

Library of Congress Cataloging-in-Publication Data

Catalog record is available from the Library o f Congress

informa Taylor & Francis Group

Chapter 1 INTRODUCTION TO CHEMICAL ANALYSIS............................................ 1

Chapter 2 SAFETY AND LABORATORY W ORK............................................................ 9

Chapter 3 QUALITY ASSURANCE OF CHEMICAL MEASUREMENTS................ 21

Chapter 4 LABORATORY APPARATUS AND GLASSWARE..................................... 39

Chapter 5 CHEMICALS, REAGENTS, AND STANDARDS ........................................ .51

Chapter 6 STANDARD SOLUTIONS ................................................................................ 67

Chapter 7 COMMON LABORATORY TECHNIQUES ................................................... 75

Chapter 8 GRAVIMETRIC METHODS OF ANALYSIS ................................................. 97

Chapter 9 TITRIMETRIC ANALYSIS .............................................................................. 105

Chapter 10 ACID-BASE TITRATION ................................................................................ 111

Chapter 11 COMPLEXOMETRIC, OXIDATION-REDUCTION,

Chapter 12 SPECTROPHOTOMETRY ............................................................................... 133

Chapter 13 POTENTIOMETRY AND ION-SELECTIVE ELECTRODES ................... 153

Chapter 14 ENVIRONMENTAL TESTING LABORATORIES .....................................165

Chapter 15 RAW DATA CONVERSION INTO REPORTABLE RESULTS ................ 181

Chapter 16 EVALUATION AND APPROVAL OF ANALYTICAL DATA................... 191

Chapter 17 REPORTING ANALYTICAL DATA ............................................................... 199

Chapter 18 DETERMINATION OF COLOR, ODOR, AND CONDUCTIVITY .......203

Chapter 19 ANALYSIS OF SOLIDS AND TURBIDITY ................................................ 211

Chapter 20 ALKALINITY AND pH CALCIUM CARBONATE

Chapter 21 ANALYSIS OF FLUORIDE AND TOTAL HARDNESS ........................... 231

Chapter 22 DETERMINATION OF RESIDUAL CHLORINE, CHLORIDE,

Chapter 23 NITROGEN COMPOUNDS AND ANALYSIS OF AMMONIA

Chapter 24 ANALYSIS OF NITRITE AND NITRATE, AND TOTAL KJELDAHL

Chapter 25 DETERMINATION OF PHOSPHORUS .......................................................287

Chapter 26 DETERMINATION OF SULFIDE ..................................................................295

Chapter 27 DETERMINATION OF SULFITE AND SULFATE ..................................... 305

Chapter 28 CATION EXCHANGE CAPACITY................................................................. 313

Appendix A LABORATORY FIRST AID .......................................................................... .317

Appendix B SALINITY DETERMINATION BY HYDROMETRIC

Appendix C LOGBOOK FORMS AND USEFUL TABLES APPLICABLE

Appendix D DOCUMENTATION FORMS FOR QUALITY CONTROL

References .................................................................................................................................... 359

1.1 THE NATURE OF ANALYTICAL CHEMISTRY

1.2 GENERAL DIRECTION OF CHEMICAL ANALYSIS

WET CHEMISTRY INSTRUMENTAL

individuals, the freedom of a prisoner on trial, etc. Stringent requirements in a chemical

1.2.1 The Responsibility and Psychology of the Analyst

1.2.2 Cleanliness in the Laboratory

1.2.3 Recording Analytical Data