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Standardization of Sample Preparation

for Trace Element Determination Through
Microwave-Enhanced Chemistry
H.M. Skip Kingston
Duquesne University, Department of Chemistry and the
Environmental Science and Management Program
Pittsburgh, PA 15282 USA

INTRODUCTION This standardization is exempli- have been validated in Method

fied by the first total decomposition 3052 (5). The method is adaptive
The development of standard method for trace element determi- and provides optimization proce-
sample preparation protocols by nation for U.S. Environmental Pro- dures for specific matrix types
microwave have simplified and tection Agency (EPA) Resource and elemental chemistries (Table
unified trace element determina- Conservation and Recovery Act III). The original closed-vessel
tions in thousands of analytical lab- (RCRA) Method 3052 (4,5). It is microwave protocol that became
oratories. The rational is one that the inherent robustness of the EPA Method 3052 was based on
was articulated by Berzelius over method that permits it to handle all earlier work at the National Insti-
170 years ago when he instructed, 26 RCRA elements simultaneously tute of Standard and Technology
“seek to find the method of analysis in one sample preparation. Before (NIST) for elemental certification
that depends least on the skill of Method 3052 was developed, sev- of Standard Reference Materials
the operating chemist...” (1). eral analytical procedures were (SRMs) (5).
Berzelius was seeking a method required to thoroughly evaluate
that is robust, dependable, and a sample for its elemental compo- Procedure
reproducible from one laboratory nents. These procedures, some
and instrument to another. Control, A summary of the steps and
taking many hours, have been a brief overview provide some of
transferability, reproducibility, replaced by a single microwave
and robustness are the traits that the key aspects of Method 3052.
procedure producing equivalent A 0.2-g to 2.0-g sample, depending
permit a method to become a stan- results for all 26 elements simulta-
dard instrumental procedure and on the reactivity and the potential
neously. Many more elements for the production of gaseous by-
protocol. Once the sample prepara- than the validated 26 EPA elements
tion method is instrumented, the products during digestion, is trans-
are possible from a single sample ferred into a microwave digestion
apparatus takes part in the control preparation using Method 3052
and transfer of the procedure and vessel (5). Subsequently, 9 mL of
for general applications. sub-boiled distilled concentrated
enables instrumental assistance
with many steps in the process. nitric acid and various quantities
Generic Digestion Protocol of sub-boiled distilled concentrated
After a decade of development Method 3052
and evaluation, microwave sample hydrofluoric and hydrochloric acid
preparation has emerged as the In the United States, perhaps are added to each vessel. The
method of choice for spectroscopic the most useful standard method choice of digestion reagents is
trace element determination. is also the most flexible. Method dependent on many factors includ-
3052 was developed to handle ing the matrix, analytes of interest,
Standard Microwave Trace such a diversity of matrix types and the detection technique. The
Element Methods and elements that it provides an vessels are capped, sealed, and
excellent starting point for indus- heated simultaneously for a total
The efficiency and robustness trial development of process con- of 15 minutes. The first stage
of microwave sample preparation trol and quality assurance elemental involves heating of the samples
for trace element determination is analysis produres. This method is to at least 180±5°C in 5.5 minutes.
exemplified by the number of also being adopted and applied The temperature is then maintained
international and multiple standard internationally. at 180±5°C for 9.5 minutes. The
agencies that now depend on heating profile may be altered for
microwave procedures. Table I Method 3052 is applicable for reactive matrices or excessively
lists over a dozen examples of the general analysis of at least slow decomposing components.
microwave trace element standards 80–90% of industrial and common Figure 1 shows a typical digestion
from a variety of standards agencies samples. Table II lists some of the temperature and pressure profile
and countries (2,3). matrix types and elements that of a soil.

AS Atomic Spectroscopy
Vol. 19(2), March/April 1998
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 TABLE I After heating, the sample is
Standard Microwave Sample Preparation Methods (2,3) filtered and diluted for analysis.
Dissolution
The chemistry can be adjusted to
Organization Method Type Matrix Analytes optimize the sample matrix com-
ASTM D4309-91 Leach Water Al, Cd, Cr, Cu, Fe, patibility with the instrument.
Mn, Ni, Pb, Zn To maintain clean chemistry con-
ASTM D5258-92 Leach Sediment, Soil As, Cd, Cu, Mg, Mn, ditions of low and controlled analyt-
Ni, Pb, Zn ical blank conditions, the operating
ASTM D5513-94 Total Industrial Furnace Ag, As, Ba, Be, Cd, steps involving reagent addition,
Feedstreams, Coal, Cr, Hg, Pb, Sb, Tl capping microwave vessel, and
Coke, Cement, Raw post-digestion procedures should
Feed Materials, Waste
be performed in clean environ-
Derived Fuels
ments. The use of microwave
ASTM E1645-94 Leach Paint Pb
sample preparation for ultratrace
U.S. EPA 3015 Leach Water, Wastewater Al, Ag, As, Ba, Be,
Ca, Cd, Co, Cu, Cr, elemental analysis is discussed
Fe, K, Mg, Mn, Mo, extensively in the new microwave
Na, Ni, Pb, Sb, Se, reference text from the American
Tl, V, Zn Chemical Society and includes
U.S. EPA 3031 Total Oil Ag, As, Ba, Be, Cd, protocols and procedures to
Co, Cr, Cu, Mo, Ni, enhance the reduction of the
Pb, Sb, Se, Tl, V, Zn analytical blank (5).
U.S. EPA 3050B Leach Sediment, Al, As, Ba, Be, Ca, Cd,
Sludge, Soil Co, Cr, Cu, Fe, K, Mg, Synergy of Clean Chemistry
Mn, Mo, Na, Ni, Pb,
Se, Tl, V, Zn
and Microwave Dissolution
U.S. EPA 3051 Leach Oil Al, Ag, As, B, Ba, Be,
Improve Quality Control in
Sediment Ca, Cd, Co, Cu, Cr, Trace Element Determination
Sludge Fe, Hg, K, Mg, Mn, The improvements in efficiency
Soil Mo, Na, Ni, Pb, Sb, and reproducibility due to micro-
Se, Sr, Tl, V, Zn
wave-based sample preparation also
U.S. EPA 3052 Total Fly Ash , Al, Ag, As, B, Ba,
can be Oil, Be, Ca, Cd, Co, reduces significant sources of error
used as a Sediment, Cu, Cr, Fe, Hg, K, that were previously obscured by
screen for Sludge, Mg, Mn, Mo, Na, lengthy sample preparation proce-
TCLP Soil Ni, Pb, Sb, Se, Sr, dures. The analytical blank plays
1311 Tl, V, Zn an important role in the chemical
(sec 1.2) determination of trace metals and
U.S. EPA EMMC Leach Oil, Al, Ag, As, B, Ba, Be, are a primary source of error in
Sediment, Ca, Cd, Co, Cu, Cr,
Sludge, Fe, Hg, K, Mg, Mn,
many instances. Trace element
Soil Mo, Na, Ni, Pb, Sb, determination depends as much
Se, Sr, Tl, V, Zn on the control of the analytical
U.S. EPA NPDES Leach Domestic and Al, As, Ba, Cd, Cr, Cu, blank as it is does on the accuracy
Industrial Fe, Mn, Ni, Pb, Sb, and precision of the instrument
Wastewater Se, Zn used. The inability to control sam-
Standard 3030K Leach Water Ag, Al, As, Au, Ba, Be, ple contamination that is external
Methods for the Bi, Ca, Cd, Ce, Co, to the sample, or those contribu-
Examination of Cr, Cu, Hg, Ir, K, Li,
tions of the analyte coming from
Water and Mg, Mn, Mo, Na, Ni,
Wastewater Os, Pb, Pd, Pt, Rh, Sb, sources other than the sample,
Se, Si, Sn, Sr, Th, Ti, are frequently the limiting factor
Tl, V, Zn in trace (ppm/ppb) and ultratrace
Republic of NIEA Total Fish, Shellfish Al, As, Ba, Be, Ca, Cd, (ppb/ppt) determinations. The
China C303.01T Co, Cr, Cu, Fe, K, Mg, major sources of analytical blank
Mn, Mo, Na, Ni, Os, contributions are:
Pb, Se, Th, V, Zn
France Kjeldahl Total Milk, Meat Products, N • atmosphere in which the
N V 03-100 Animal Food, Starch sample preparation and analysis
and Starchy Foods are conducted,

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 AStomic
pectroscopy
Vol. 19(2), Mar./Apr. 1998

TABLE II
Overview of EPA Method 3052: Microwave-Assisted
Acid Digestion of Siliceous and Organically-Based Matrices
Type Matrices Analytes Detection Control

Temperature (°C)

Pressure (atm)
Microwave Soil Al, Ag, As, B, Ba, FAAS Temperature
Total Digestion Oil Be, Ca, Cd, Co, ET-AAS Feedback
Sludge Cu, Cr, Fe, Hg, K, ICP-AES Control and
Biological Mg, Mn, Mo, Na, ICP-MS provisions
Foods Ni, Pb, Sb, Se, Sr, other analytical for calibration
Glass Tl, V, Zn, techniques control
Metals other elements provided
Fly Ash provided validation
Sediment validation achieved
other matrices achieved

Fig. 1. A typical microwave digestion profile

for temperature and pressure with a soil (sili-
cate-based material) in a high-pressure vessel.

TABLE III • purity of the reagents used in sample

Digestion Parameters Used in the Analysis of preparation,
Several Matrices by EPA Method 3052
• materials used in the digestion or
Matrix HNO3 HF HCl extraction vessels that come in contact
Soil with the sample,
NIST SRM 2710 9 3 0 –2a • analyst’s technique and skill in prepar-
Highly Contaminated Montana Soil ing the samples and in performing the
NIST SRM 2711 9 3 0 – 2a analysis.
Moderately Contaminated Montana Soil
Sediment The sources of each of these potential
contaminants and the solutions to control
NIST SRM 2704 9 3 0 – 2a them are presented elsewhere along with
Buffalo River Sediment
an extensive discussion of the synergy
Biological
between clean chemistry and microwave
NIST SRM 1566a 9 0 0 – 1a sample preparation for trace element
Oyster Tissue determination (5). The development of
NIST SRM 1577a 9 0 0 – 1a microwave sample preparation, coupled
Bovine Liver with clean chemistry techniques, has
Botanical broken some of the traditional barriers to
NIST SRM 1515 9 0 0 – 1a blank limitations, and permits measure-
Apple Leaves ments at lower concentration levels.
NIST SRM 1547 9 0 0 – 1a Microwave sample preparation has
Peach Leaves improved analytical blank control in syn-
NIST SRM 1567a 9 0 0 – 1a ergistic ways by lowering the blank level,
Wheat Flour increasing blank precision, and improving
NIST SRM 1572 9 0.5 0 – 1a quality control.
Citrus Leaves
Microwave sample preparation reduces
Waste Oil blank contribution from environmental
NIST SRM 1084a 9 0.5 0 – 2a exposure, reagent use, and losses from
Wear-Metals in Lubricating Oil evaporation, and in addition reduces sam-
a ple preparation times. It also offers a
HCl is added to stabilize elements such as Ag and Sb.
If elements that need to be stabilized with HCl are not being analyzed, then HCl was more reproducible method for duplicat-
not used. ing ultratrace determination, both within
a laboratory or between laboratories. The
required overall skill level of the analyst

29
is less critical in deciding the fate issue, because inefficiencies exist in REFERENCES
of an analysis. This certainly shows an analytical scheme where one
1. J.J. Berzelius, “Lehrbuch der
that we have reached the point of portion is usually waiting for prod- Chemie,” F. Wöhler, Arnoldsche
providing a method of analysis, as uct from another. Plasma-based Buchhandlung: Dresden, Vol. 4,
suggested by Berzelius in 1814, instruments require rapid, efficient, 2nd part, p. 74 (1831).
that “depends least on the skill of and reliable sample preparation
2. P.J. Walter, S.J. Chalk, and H.M.
the operating chemist....” Because technology to complement their Kingston, Chapter 2: Overview of
of its efficiency, capability, and efficiency and capability. Increas- Microwave Assisted Sample Prepa-
reproducible contribution to the ingly, microwave sample prepara- ration In Microwave Enhanced
overall sample preparation and tion is becoming the standard Chemistry; H. M. Kingston, S.
analysis process, microwave technique for sample preparation Haswell, Eds.; American Chemical
sample preparation is emerging in trace and ultratrace determina- Society: Washington, D.C. (1997).
as the appropriate tool of choice tions. Used in conjunction with 3. H.M. Kingston, and Peter J. Walter,
in controlling the quality of sample clean chemistry techniques, “The Art and Science of Microwave
preparation in elemental analysis microwave sample preparation is Sample Preparation for Trace and
as well as being one of the most a natural complement that Ultra-trace Elemental Analysis” , in
efficient methods. improves the overall analytical Inductively Coupled Plasma Mass
process. Below the nanogram per Spectrometry: From A to Z, Akbar
CONCLUSION gram range, other traditional sam- Montaser (Ed.), VCH-Wiley, 1998.
ple preparation techniques offer 4. SW-846 EPA Method 3052:
Until the last decade, chemists Microwave assisted acid digestion
few advantages. In contrast,
accepted the mismatch in technol- of siliceous and organically based
microwave closed-vessel and con-
ogy levels between analysis and matrices, In Test Methods for Eval-
trolled-atmosphere open-vessel
detection instrumentation. In real- uating Solid Waste, 3rd edition,
are being effectively used at lower
ity, sample preparation should be 3rd update; U.S. EPA: Washington,
concentration ranges for trace and DC (1995).
done at the same level of instrumental
ultratrace analysis. As trace analysis
sophistication as the analysis. 5. H.M. Kingston, P.J. Walter,
is more frequently extended to the
Microwave sample preparation S.J. Chalk, E. Lorentzen, and
ultratrace region by more sensitive
provides practical and efficient D. Link, Chapter 3: Environmental
and efficient instrumentation, sam- Microwave Sample Preparation
approaches for multielement deter-
ple preparation is keeping pace Fundamentals, Methods, and Appli-
minations by using the advanced
with appropriate technological cations In Microwave Enhanced
technologies in ICP-MS, ICP-AES,
advances that complement and Chemistry: Fundamentals, Sample
ET-AAS, and AA instrumentation.
enhance detection capabilities. Preparation, and Applications;
Time compatibility is an important H.M. Kingston and S. Haswell, Eds.;
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