Environ. Sci. Technol.

1998, 32, 3628-3632

Development and Validation of the municipal sewage processing, and dumping of metal-
containing wastes. Many of these metals are potentially toxic
New EPA Microwave-Assisted Leach to both humans and ecosystems, and the mobility and
bioavailability of these metals must be determined. Acid
Method 3051A leaching of solid samples is the most common method for
estimating the mobility or bioavailability of toxic heavy metals
in an environmental sample (2, 3). Leach methods for solid
DIRK D. LINK, PETER J. WALTER, AND
samples currently listed in the EPA’s SW-846 manual of
H. M. KINGSTON*
methods include Methods 3050B and 3051. These methods,
Department of Chemistry and Biochemistry, 308 Mellon Hall, outlined in Table 1, are used when it is more appropriate to
Duquesne University, Pittsburgh, Pennsylvania 15282-1503 determine the amount of analyte that may become available
under worst case environmental conditions rather than either
the total amount of analyte present or a TCLP evaluation
(EPA Method 1311 (4)). EPA Method 3051, originally
An updated, optimized method has been developed to developed in 1988, was restricted to the exclusive use of HNO3
minimize the chemical biases and inefficiencies between to minimize potential instrumental interferences from HCl
two EPA SW-846 alternative leach methods, microwave- and its resulting species on some analytical detection
assisted Method 3051 and open vessel Method 3050B, for methods, such as graphite furnace atomic absorption
the determination of metals in solid samples. The spectroscopy (GFAAS) and inductively coupled plasma mass
microwave method is more easily transferred and provides spectrometry (ICP-MS).
more reproducible leach results, mainly from more EPA Method 3051 was developed as a microwave-
precise control of the temperature during the extraction enhanced alternative to leach Method 3050B and has been
process. Previously, reagent limitations originally placed on a promulgated SW-846 method for several years (4, 5). Closed
Method 3051 did not allow these alternative methods to vessel microwave heating offers several advantages over hot
plate heating for acid leaching of environmental samples.
yield similar results for some analytes. This work describes
Higher pressures attainable in closed vessels allow elevated
the development and validation of EPA Method 3051A, temperatures to be reached, thus reducing reaction times
which includes an option to add HCl to improve the chemistry from several hours to minutes. Closed fluoropolymer vessels
of the microwave method, making it comparable to open also minimize potential losses of analytes due to volatilization
vessel Method 3050B. Including HCl provides complexation (1, 6). In addition, use of temperature feedback control in
and stabilization of some analytes by Cl- species, leading microwave leaches typically provides much better control of
to improved recoveries. Optimizing the acid combination the temperature than is possible on a hot plate, typically
involved adding either 1, 3, or 5 mL of HCl to 9 mL of HNO3 (2.5 °C or less. This is an important advantage because
and performing a series of leaches on standard reference leach levels are highly dependent on the reaction conditions
materials (SRMs). Optimum recoveries are achieved achieved, and temperature has been proven to be one of the
most important parameters in determining leach precision
for “problem” analytes, such as Ag and Sb, by adding 3
(1). Because precision is used as accuracy when comparing
mL of HCl. Recovery of other metals, such as Cu and Ni, leach results, this precise temperature control becomes even
are unaffected. Method validation was provided by more significant. Leachable amounts are not absolute
leaching and analysis of SRMs. quantities, which forces the precision of the measurement
to be used as an indicator of the accuracy of the measurement.
Also, using microwave energy and temperature feedback
Introduction control allows for better transfer of standard methods
between analysts, laboratories, and even foreign countries
The method of expressing analyte concentrations when
as compared to the wide variability and subjectivity associated
environmental leach methods are used poses unique quan-
with hot plate methods. Despite these advantages, Method
tification problems. When analyte concentrations from leach
3051 shows a negative bias for certain analytes as compared
methods are compared, the precision of the measurement
to Method 3050B leaches (6-9). Biases on recoveries of
is used as a defacto expression of accuracy. In contrast to
certain RCRA-regulated metals have been demonstrated.
total decomposition methods, such as EPA SW-846 Method
Recently, an updated version of the microwave leach method
3052, that provide absolute analyte concentrations, leach
was accepted by the EPA and is included in Update IVA of
methods provide only relative concentrations based on the
the SW-846 manual. As shown in Table 1, the new EPA
sample preparation procedure and reaction conditions
Method 3051A provides the analyst with options to perform
achieved. Standard methods are used by a large number of
either a HNO3-only or a HNO3-HCl mixed-acid leach when
different laboratories. Achieving comparable results among
appropriate for the recovery of the target analyte(s). This
these laboratories depends on achieving comparable oper-
paper describes the control and transfer of elemental leach
ating conditions. Control and transfer of leach methods is
methods, presents the development and validation of EPA
more difficult than for total decomposition methods. The
Method 3051A, and extends the fundamental understanding
reproducibility of the results depends on the conditions
of key parameters and acid chemistry to achieve optimum
achieved during the leach process. Microwave heating with
leach recoveries.
temperature feedback control has demonstrated more precise
temperature control than is possible using a hot plate (1).
Heavy metals enter the environment as a result of
Experimental Section
industrial processes, incineration, fossil fuel production, Sample Preparation and Analysis. Microwave leaches were
performed using the MLS 1200-Mega with the microwave
* Corresponding author phone: (412)396-5564; fax: (412)396-5359; digestion rotor MDR-300/10 from Milestone USA (Monroe,
e-mail: kingston@duq.edu. CT) and the MDS-2100 using HDV (heavy duty vessels) from
3628 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 32, NO. 22, 1998 10.1021/es980559n CCC: $15.00  1998 American Chemical Society
Published on Web 09/19/1998
TABLE 1. Comparison of Three EPA SW-846 Leach Methods (4)
EPA Method 3050B EPA Method 3051 EPA Method 3051A
vessels open vessel closed vessel closed vessel
heating method hot plate microwave microwave
heating block
open vessel microwave
reagents HNO3 HNO3 HNO3 or HNO3 and HCl
HCl
H2O2
heating program series of 95 °C 175 °C in 5.5 min 175 °C in 5.5 min
refluxes 2-8 h or more hold at 175 °C for 4.5 min hold at 175 °C for 4.5 min

TABLE 2. Recoveries of Selected RCRA-Regulated Elements

from SRM 2704 (Buffalo River Sediment) Using Alternative
EPA SW-846 Leach Methods 3050B and 3051 (6-8)a
Method 3050B Method 3051 bias at
element leach leach 95% CIb
Co 11.1 ( 1.0 10.7 ( 0.5 no
Cr 83.3 ( 5.3 81.7 ( 1.9 no
Ni 37.7 ( 2.0 36.4 ( 1.0 no
Pb 147 ( 6 143 ( 3 no
B 55.4 ( 9.7 34.6 ( 3.3 yes
Be 1.05 ( 0.10 0.69 ( 0.22 yes
Fe 3.29 ( 0.14% 2.91 ( 0.22% yes
V 49.4 ( 5.6 25.1 ( 3.0 yes
a Results reported in mean µg/g analyte (or %) (95% confidence

FIGURE 1. Typical temperature and pressure profiles for the heating interval. b Bias signifies no overlap at 95% confidence interval.
of leaching acids using EPA Method 3051A.
sample is present) increases as the volume of HCl is increased
CEM (Matthews, NC). Concentrated HNO3 and HCl were (9). Heating 10 mL of HNO3, labeled 10:0, results in a pressure
obtained (ACS reagent grade, Fisher Scientific, Pittsburgh, of approximately 5 atm. As HCl is added, the pressures inside
PA) and purified by subboiling distillation using a DuoPUR the vessel increase dramatically, with the 9 mL of HNO3: 3
quartz still (Milestone USA, Monroe, CT) prior to use. The mL of HCl mixture reaching approximately 12 atm. The
standard reference materials (SRMs) used in this study, SRM increased pressures result from the formation of several
2704 (Buffalo River sediment), SRM 4355 (Peruvian soil), SRM additional species, including chlorine gas and nitrosyl
1084a (wear-metals in lubricating oil), and SRM 1634c (trace chloride (NOCl), which further decomposes into Cl2 and NO
metals in fuel oil), were obtained from the National Institute (10). These gaseous products increase both the pressure
of Standards and Technology (NIST) in Gaithersburg, MD. and the reactivity of the reagent mixture. Pressures of nearly
These SRMs were also used in the original NIST round-robin 30 atm have been reached during the heating of 250-mg
validation study evaluating Method 3051 versus Method samples of oil-type matrices, which produce greater amounts
3050B (7, 8), allowing for appropriate extension of these of CO2 and NOx gas upon decomposition of the matrix (1).
studies for comparison and validation of the mixed-acid This is possible only when the reagents have sufficient
option of Method 3051A. For validation of Method 3051A, oxidizing strength to provide total decomposition of the
appropriate masses of the solid samples were leached matrix, as in an HNO3-only digestion. Typically, mixed-acid
according to method specifications (see Table 1). After leaches of soils and sediments generate higher pressures due
filtration and dilution, elemental analysis was performed to heating of the acids themselves (Figure 1), while leaches
using either flame atomic absorption spectroscopy (FAAS) of oils generate less pressure due to incomplete decomposi-
(AAS 1100, Perkin-Elmer) or ICP-MS (PlasmaQuad II, VG tion of the matrix. It is also important to note that internal
Elemental). To minimize the potential for cross-contamina- pressures will vary somewhat depending on the vessel
tion, all microwave vessels and materials coming in contact manufacturer due to the various heat loss characteristics of
with samples were cleaned using either hot or room- different vessel materials and designs. A more detailed
temperature acid cleaning procedures prior to use and evaluation and discussion of this concept is given elsewhere
between each set of leaches. All procedures prior to and (1).
following microwave leaching were performed in a class 100
As another safeguard, when using the mixed-acid option
clean laboratory (1).
of Method 3051A, the order of adding the acids is also
specified. The analyst is cautioned that “The addition of
Results and Discussion hydrochloric acid must be in the form of concentrated
Safety. Because Method 3051A involves heating reagents in hydrochloric acid and not from a premixed combination of
closed vessels, pressure must be considered from a safety acids as a buildup of chlorine gas, as well as other gases, will
standpoint. The reagent change causes the pressure during result from a premixed acid solution. These gases may be
a typical leach to nearly triple, making certain vessels specified violently released upon heating” (4).
for use in the original EPA Method 3051 inappropriate for Reagent Chemistry. Several studies have determined that
use in the updated Method 3051A. Prior pressure specifica- alternative leach methods do not yield comparable results
tion in Method 3051 was 10 atm (110 psi), but vessels for use for some RCRA-regulated elements (6-8). As Table 2
in Method 3051A must be capable of withstanding pressures demonstrates, the results using the microwave method in
of at least 30 atm (435 psi). Figure 1 shows that the pressure general show better precision due to more precise control
resulting from heating the leaching acid(s) (i.e., no solid of temperature. However, Method 3051 demonstrates a bias

VOL. 32, NO. 22, 1998 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3629
 Increasing the temperature of HNO3 to 175 °C provides
TABLE 3. Some Possible Species Produced during Acid similar oxidizing strength as compared to the open vessel
Leaches with Methods 3050B and 3051 (1, 6) leach using both HNO3 and H2O2. The key difference between
EPA EPA Methods 3050B and 3051 and the new Method 3051A is the
Method 3051 Method 3050B complexation and stabilization properties gained by adding
HCl. The following equations describe specific reactions of
reagents HNO3 HNO3
certain metals that form stabilized chloro complexes. Ad-
HCl
H2O2 ditional information on the chemistry of typical mineral acid
reactive species H2O H2O decomposition reagents with most elements is provided on
H3O+ H3O+ the worldwide web at Duquesne University’s SamplePrep
NO3- NO3- website, which is coordinated with references (14). A recent
NO2+ NO2+ review of acid chemistry is also available (1).
NO2 NO2 Antimony. Sb has been documented to be unstable and
O2 O2 insoluble in the oxidizing environment encountered with
digest productsa Cl- HNO3 leaches (15). This environment typically oxidizes Sb
NOCl
to the 5+ oxidation state. Losses of Sb in the 5+ state have
Cl2
HO2- been reported due to an oxidation/sorption process (16-
O22- 19). Various mechanisms, shown in eqs 3 and 4, have been
O2 b proposed for this process whereby Sb is oxidized in strongly
digest productsa oxidizing environments and subsequently adsorbs either onto
a Digest products may include such species as aqueous metal nitrates, undigested reactive silicate particles in the solid matrix or
carbon dioxide, water, etc. b Free radical oxygen species. onto glass surfaces such as vessel walls (20):

Sb(III) + HNO3 + HClO4 f Sb2O5‚nH2O f Sb2O5 (18)

for some analytes as compared to Method 3050B results. (3)
This bias can be attributed to the reagents used in each
method. Excluding the complexation and stabilization Sb + HNO3 f Sb2O3 and/or Sb4O4(OH)2(NO3)2 f
properties of HCl from the microwave method reduces its Sb2O3 + O2, ∆ f Sb2O5 (10, 19) (4)
effectiveness for recovering certain analytes. The inclusion
of HCl and H2O2 in Method 3050B results in the formation Sb species in the 3+ state can also be lost in the presence
of several reactive species that are not found in the Method of HCl by complexing with chloride ions to form a volatile
3051 leach mixture (Table 3). The inherent drawback of the species that can be readily lost from solution, especially when
HNO3-only microwave leach is that it does not reproduce heated (11, 12). More complete recovery of Sb requires initial
the chemistry of the open vessel leach, which uses HNO3, oxidation to the 5+ state, followed by complexation with
HCl, and H2O2. The difference between the chemistries of HCl to form SbCl6- (eq 5). This stable, aqueous anion remains
the leach methods is attributed to the absence of HCl in the soluble in solution and does not adsorb onto undigested
microwave method. siliceous materials (16, 17):
H2O2 is included in Method 3050B as an oxidizer because
of the lower temperature limitation (95 °C) of these methods. Sb + HNO3 f Sb5+ + HCl f SbCl6-(aq) (5)
The oxidizing power of H2O2 increases as the acidity of the
solution increases (1, 11, 12). H2O2 is added to the HNO3 Iron. High concentrations of Fe are frequently found in
multiple times to increase the overall oxidizing strength of contaminated soils and sludges and can be stabilized in
the solution. The combination of repeated additions of H2O2, solution. In the presence of a complexing anion such as Cl-,
modestly elevated temperatures, and lengthy reaction times the Fe(II) species can form the aqueous anion FeCl42-, while
(up to 8 h or more) provide the oxidizing ability of the open the Fe(III) species can form FeCl4- (10). Both of these species
vessel leach methods. The closed vessel microwave method are stable in solution:
heats the leaching mixture to 175 °C. Because the oxidizing
strength of a solution increases as the temperature increases Fe2+ or 3+ + HCl f FeCl42- or -(aq) (6)
(13), HNO3 at 175 °C is a stronger oxidizer than HNO3 at 95
°C. At these higher temperatures, the need for increasing Silver. Most environmental samples contain trace quan-
the oxidizing strength by the addition of H2O2 is eliminated. tities of Cl- as a matrix component. In the presence of these
Two common reactions occurring in the leaching of solid trace quantities of Cl-, Ag precipitates out of solution as solid
matrices are oxidation reactions, as illustrated below (1). AgCl. The solubility of AgCl increases with increasing Cl-
Oxidation of Most Metals into Nitrates: concentration due to the formation of complex anions of the
formula AgCln1-n (11). By adding HCl in Method 3051A, the
M0 + HNO3 f M(NO3)x(aq) + NO(g) + H2O (1) Cl- concentration is increased, and the AgCln1-n complex
anions that are formed are stabilized in solution (eq 7):
It should be noted that certain metals (high-purity iron, for
example) passivate in the presence of concentrated HNO3, Ag+ + Cl- f AgCl(s) + Cl- f AgCl2-(aq) (7)
and stainless steel and other alloys are resistant to decom-
position in pure HNO3 (11, 12). The three elements discussed above are examples of those
Oxidation of Most Organic Material: reported to suffer recovery problems with HNO3-only leaches.
The presence of Cl- species acts to complex and stabilize
other metals as well. However, these examples give specific
(CH2O)x + HNO3 f CO2(g) + NOx(g) + H2O (2) rationale for including HCl in the microwave method to match
the chemistry of open vessel Method 3050B. These reactions
The oxidation of organic material (represented by (CH2O)) are also important for achieving better recoveries using total
produces the gases CO2 and NOx as final products, which decomposition methods. HCl should also be employed in
result in the increased pressures inside closed vessels when these methods when losses or incomplete recoveries of
organically based matrices are digested. certain analytes have been noted.

3630 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 32, NO. 22, 1998
TABLE 4. Comparison of Recoveries of Analytes from SRM 2704 (Buffalo River Sediment) Using both Digest Options of EPA
Method 3051A (7-9)a
element 10:0 leachb 9:1 leachb 9:3 leachb 9:5 leachb 3050Bc 3051c total
Co 12.2 ( 1.84 11.7 ( 2.66 11.8 ( 1.15 12.3 ( 3.78 11.1 ( 2.75 10.7 ( 1.46 14.0 ( 0.22
Cd 3.40 ( 0.34 3.60 ( 0.36 3.62 ( 0.17 3.35 ( 0.50 3.32 ( 0.43 3.19 ( 0.61 3.45 ( 0.22
Cr 84.7 ( 5.6 79.0 ( 10.1 77.7 ( 12.6 82.2 ( 12.2 83.3 ( 14.0 81.7 ( 5.33 135 ( 5
Ni 45.5 ( 5.94 36.5 ( 1.26 42.2 ( 3.17 38.9 ( 6.11 37.7 ( 5.15 36.4 ( 2.52 44.1 ( 3.0
Pb 163 ( 8.6 148 ( 6.9 161 ( 17 151 ( 8.4 147 ( 16.6 143 ( 9.46 161 ( 17
V 16.5 ( 3.00 19.5 ( 2.69 21.9 ( 3.68 22.3 ( 2.57 24.2 ( 7.21 21.0 ( 2.46 ncd
a Results reported in mean µg/g analyte ( 95% confidence interval. Total analyte concentration taken from NIST SRM certificate of analysis.
b Results of analysis for current validation study. c Results of analysis from validation study of Method 3051 vs Method 3050B. d nc, not certified.

TABLE 5. Comparison of Recoveries of Analytes from SRM 4355 (Peruvian Soil) Using both Digest Options of EPA Method 3051A
vs Validation Data for EPA Methods 3050B and 3051 (8, 9)a
element 10:0b 9:3b 3050Bc 3051c total
Ag 1.28 ( 0.11 1.61 ( 0.16 <4 <4 (1.90)
Cd 0.86 ( 0.16 0.85 ( 0.17 1.03 ( 0.08 0.90 ( 0.09 (1.50)
Cr 14.6 ( 0.47 19.0 ( 0.69 17.1 ( 2.37 13.8 ( 1.18 28.9 ( 2.8
Ni 9.9 ( 0.33 11.2 ( 0.44 9.93 ( 1.45 9.59 ( 1.10 (13)
Pb 124 ( 5.3 130 ( 3.6 131 ( 5.4 121 ( 3.0 129 ( 26
V 64.5 ( 1.6 86.1 ( 2.0 81.4 ( 6.5 61.2 ( 2.1 (151)
a Results reported in mean µg/g analyte ( 95% confidence interval. Total analyte concentration taken from NIST SRM certificate of analysis.

Values in parentheses indicate reference concentrations. b Results of analysis for current validation study. c Results of analysis from validation
study of Method 3051 vs Method 3050B.

FIGURE 3. Percent recovery of antimony and iron from SRM 4355

using both digest options of EPA Method 3051A.

no further enhancement in recovery for either analyte, and

a slight decrease was observed for Fe for the 9:5 acid ratio.
It was also important to demonstrate that the mixed-acid
Method 3051A leach preserves the recoveries of those analytes
that did not demonstrate any previous recovery bias between
Method 3050B and Method 3051. Recoveries for additional
analytes from SRM 2704, along with the results from the
original validation study for Method 3051 versus Method
3050B, are shown in Table 4. Analyte recoveries are either
enhanced or preserved by the mixed-acid leaches. However,
FIGURE 2. Percent recovery of antimony and iron from SRM 2704
the results of analysis for some of the 9:5 mixed-acid leaches
using various mixed-acid combinations according to EPA Method
3051A. demonstrate increased variability. This variability may be
due in part to preparing all analytical standards and spike
solutions in dilute HNO3 (∼1%) instead of matrix matching
Reagent Optimization. The reagent combination of the
by adding HCl (21). Because the 9:5 mixed-acid leach either
method was optimized so that the oxidizing power of HNO3
does not provide enhancement in recoveries or shows lower
was not reduced by adding excessive amounts of HCl. Initial
recoveries than the 9:3 mixed-acid leach, the 9:3 ratio is most
studies to refine the acid ratio in terms of oxidizing strength
appropriate and is specified in Method 3051A.
and complexation were performed using samples of SRM
2704. The ratios of HNO3 to HCl that were tested (in mL) Method Performance. The performance of Method
were 10:0, 9:1, 9:3, and 9:5. Recoveries for several of the 26 3051A was evaluated on three other matrix types. Figure 3
RCRA-regulated elements were determined. As shown in compares the recovery of Sb and Fe from SRM 4355 for the
Figure 2, adding HCl leads to enhanced recoveries of Sb and HNO3-only and mixed-acid leaches. Recovery of Sb increased
Fe (9). Recoveries for Sb increase from 0% in the HNO3-only from almost 0% in the HNO3-only (10:0) leach to ap-
leach to 80% in the 9 mL of HNO3: 3 mL of HCl leach, while proximately 75% in the mixed-acid (9:3) leach, while the
recoveries for Fe increase from approximately 73% to over recovery of Fe increased from approximately 60% to over
78%. Additional quantities of HCl (the 9:5 ratio) provided 75%.

VOL. 32, NO. 22, 1998 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3631
 has both national and worldwide importance. This requires
TABLE 6. Comparison of Recoveries of Analytes from SRM methods that provide reproducible control and accurate
1084a (Wear-Metals in Lubricating Oil) Using both Digest transfer. As demonstrated, use of microwave energy and
Options of EPA Method 3051A (9)a temperature feedback control exceeds other methods in
element 10:0 leach 9:3 leach total terms of the reproducibility of conditions and ease of method
transfer from one user to another. Temperature, the
Ag 93.3 ( 2.9 98.2 ( 6.2 101.4 ( 1.5
parameter that controls reactions, can be maintained more
Al 96.7 ( 4.2 99.0 ( 5.2 (104)
Cr 91.2 ( 3.3 94.3 ( 3.1 98.3 ( 0.8 accurately, resulting in more precise results.
Cu 91.6 ( 4.0 93.0 ( 2.6 100.0 ( 1.9 Summary. The data presented here provide additional
Mg 93.2 ( 3.6 93.5 ( 2.8 99.5 ( 1.7 validation for the updated EPA Method 3051A. The ef-
Ni 91.6 ( 3.9 92.9 ( 3.4 99.7 ( 1.6 fectiveness of including HCl in the leaching acid mixture for
Pb 104 ( 4.1 99.5 ( 5.1 101.1 ( 1.3 enhancing the recoveries of problem RCRA-regulated metals,
a Results reported in mean µg/g analyte ( 95% confidence interval. such as antimony and iron, has been shown. The mixed-
Total analyte concentration taken from NIST SRM certificate of analysis. acid leach option also shows comparable recoveries for other
Values in parentheses indicate reference concentrations. nonbiased analytes. The chemistry of the open vessel
methods, which include HCl and H2O2, is more closely
reproduced by the mixed-acid option of microwave Method
TABLE 7. Comparison of Recoveries of Analytes from 3051A. The mixed-acid microwave Method 3051A provides
Simulated Sludge (∼0.25 g of SRM 2704 (Buffalo River an efficient, unified leaching chemistry for all 26 RCRA-
Sediment) and ∼0.25 g of SRM 1634c (Trace Metals in Fuel regulated elements in a single microwave leach method.
Oil)) Using both Digest Options of EPA Method 3051A vs
Validation Data for EPA Methods 3050B and 3051 (8, 9)a
element 10:0 leachb 9:3 leachb 3050B leachc 3051 leachc
Literature Cited
(1) Kingston, H. M.; Walter, P. J.; Chalk, S. J.; Lorentzen, E. M.; Link,
Ag 0.23 ( 0.04 0.25 ( 0.07 <4.0 <4.0 D. D. Environmental Microwave Sample Preparation: Funda-
Cd 1.74 ( 0.13 1.78 ( 0.33 1.67 ( 0.09 1.50 ( 0.09 mentals, Methods, and Applications. In Microwave Enhanced
Co 6.99 ( 0.71 6.08 ( 0.95 5.89 ( 0.63 5.89 ( 0.52 Chemistry: Fundamentals, Sample Preparation, and Applica-
Cr 49.4 ( 2.9 44.7 ( 2.4 42.3 ( 2.8 43.1 ( 2.1 tions; Kingston, H. M., Haswell, S., Eds.; American Chemical
Mo 1.61 ( 0.16 2.00 ( 0.51 <2.5 <2.5 Society: Washington, DC, 1997; Chapter 3.
Ni 29.8 ( 2.0 25.5 ( 3.6 31.4 ( 2.5 30.5 ( 2.1 (2) Kane, J. S. Fresenius J. Anal. Chem. 1995, 352, 209-213.
Pb 84.6 ( 5.5 77.1 ( 6.9 76.4 ( 3.8 74.5 ( 3.9 (3) Lorentzen, E. M. L.; Kingston, H. M. Anal. Chem. 1996, 68, 4316-
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(4) U.S. EPA. Test Methods for Evaluating Solid Waste, Physical/
b Results of analysis for current validation study. c Results of analysis Chemical Methods, SW-846, 3rd ed.; U.S. Government Printing
from validation study of Method 3051 vs Method 3050B. Office: Washington, DC, 1995.
(5) U.S. EPA. Fed. Regist. 1995, 60, 37974-37980.
(6) Kingston, H. M.; Walter, P. J. Spectroscopy 1992, 7, 22-27.
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Table 5. These data demonstrate that for other “problem” of a Method for Determining Elements in Solid Waste by
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which signifies that the reagent-induced bias has been ed.; John Wiley & Sons: New York, 1988.
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flexibility over the original Method 3051 protocol. (20) Gallorini, M.; Greenberg, R. R.; Gillis, T. E. Anal. Chem. 1978,
50, 1479-1481.
Method Control and Transfer. Because of the special (21) Skelley-Frame, E. Personal communication, 1997.
conditions under which leach results are compared, the
reproducibility of the reaction conditions is critical. Also, it
Received for review June 2, 1998. Revised manuscript re-
is the practice of some testing labs and agencies in foreign
ceived August 5, 1998. Accepted August 13, 1998.
countries to adopt EPA methods as their standard methods.
Thus, the development of reproducible standard methods ES980559N

3632 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 32, NO. 22, 1998