Standard Operating Procedure

3051a Microwave Assisted Acid Digestion of Soil

Soil Environmental Chemistry Program, The Ohio State University
Version 12

1.0 SCOPE

1.1 This method is a microwave-assisted extraction using aqua regia and HNO3.
This method is more aggressive in dissolving the sample matrix than methods
using conventional heating with nitric acid (HNO3), or alternatively, nitric acid and
hydrochloric acid (HCl), according to EPA Methods 200.2 and 3050. However,
because Method 3051a does not accomplish total decomposition of the sample,
the extracted analyte concentrations may not reflect the total content in samples
where the analytes are occluded in recalcitrant mineral phases. This method is
applicable to the microwave-assisted acid extraction/dissolution‡ of sediments,
sludges, and soils, for the following elements: Aluminum (Al)*, Antimony (Sb)*,
Arsenic (As), Barium (Ba)*, Beryllium (Be)*, Boron (B), Cadmium (Cd), Calcium
(Ca), Chromium (Cr)*, Cobalt (Co), Copper (Cu), Iron (Fe)*, Lead (Pb),
Magnesium (Mg)*, Manganese (Mn), Molybdenum (Mo), Nickel (Ni), Potassium
(K), Selenium (Se), Silver (Ag)*, Sodium (Na), Strontium (Sr), Thallium (Tl),
Vanadium (V)*, Zinc (Zn). *Indicates elements which typically require the addition
of HCl to achieve equivalent results with EPA Method 3050, as noted in
reference 3. This method is intended to provide a rapid multi-element acid
extraction or dissolution prior to analysis. Many types of samples will be
dissolved by this method. A few refractory sample matrix compounds, such as
quartz, silicates, titanium dioxide, alumina, and other oxides may not be
dissolved and in some cases may sequester target analyte elements. These
bound elements are considered non-mobile in the environment and are excluded
from most aqueous transport mechanisms of pollution.

2.0 DEFINITIONS

2.1 Laboratory Control Sample: The laboratory control used for the microwave
digestion is a standard reference material (SRM) or certified reference material
(CRM) that goes through the same extraction/preparation procedure as the
samples. The analyte composition of the laboratory control sample is certified by
acid dissolution method 3051a, 3050, or equivalent.

2.2 Preparation Blank: The Preparation Blank is a sample that contains only the
reagents used in the extraction procedure. The preparation blanks is processed
through the same preparation procedures as the samples and therefore gives an
indication of any contamination picked up during the sample preparation process.

2.3 Interference Check Standards: To verify interelement and background correction

factors for the ICP, an Interference Check Samples (ICS) shall be analyzed with
each microwave batch. The Interference Check Samples consist of two solutions:
Solution A and Solution AB. Solution A consists of the interferents, and Solution
AB consists of the analytes mixed with the interferents. An ICS analysis consists
 Standard Operating Procedure
3051a Microwave Assisted Acid Digestion of Soil
Soil Environmental Chemistry Program, The Ohio State University
Version 12

of analyzing both solutions consecutively (starting with Solution A) for all

wavelengths used for each analyte reported by ICP

2.4 Duplicate Samples: A duplicate test involves splitting a sample two sub-samples
and processing each through the same sample preparation procedure in order to
determine the precision of the method.

2.5 Pre-digestion Spike: A duplicate sample is spiked prior to digestion in order to

provide information about the effect of the sample matrix on the digestion and/or
measurement methodology.

2.6 ICP-AES: Inductively Coupled Plasma-Atomic Emission Spectrometry.

2.7 ICP-HG-AES: ICP-AES with sample introduction using automated hydride

generation

2.8 ICP-MS: Inductively Coupled Plasma-Mass Spectrometry.

3.0 EQUIPMENT AND SUPPLIES

3.1 MARS 1600 watt microwave (CEM corporation, Mathews, NC).

Note: The microwave power output test, power calibration, and temperature
probe calibration should be performed according to manufactures specifications
every six months.

3.2 Trace metal grade nitric acid.

3.3 Trace metal grade hydrochloric acid.

3.4 ≥18 MΩ deionized water (DI).

3.5 15ml Falcon tubes

3.6 Spex CeriPrep Spike Sample Standard 1 (Cat# SPIKE-1-500)

4.0 PROCEDURE

4.1 Weigh 0.5g of well-mixed samples in duplicate to the nearest 0.01 g into an acid
washed Teflon vessel (4.1a) equipped with a controlled pressure relief
mechanism.

4.2 Vessels should go through acid bath and DI rinse followed by 3x rinse with 3%
acid from squirt bottle, then 3x rinse with reagent DI from squirt bottle.
Note: Store washed vessels inverted in plastic racks.
 Standard Operating Procedure
3051a Microwave Assisted Acid Digestion of Soil
Soil Environmental Chemistry Program, The Ohio State University
Version 12

4.3 Record mass of sample on analysis sheet.

4.4 Add 1.0 mL of spiking solutions to the spike sample. Check pipette accuracy and
record results in Appendix prior to spiking the sample.

4.5 Add 3.0 ± 0.1 mL concentrated trace metal grade hydrochloric acid and 9.0 ± 0.1
mL concentrated trace metal grade nitric acid with pipettes checked for accuracy
(Section 9.0, Appendix) to each vessel in a fume hood.
4.5.1 Pipette acids from disposable plastic dixie/solo cups.
4.5.2 Any remaining acid should be collected into glass bottle for ICP
torch cleaning.
4.5.3 Seal the vessel according to manufacturer’s specifications.
4.5.4 Record the mass of each sample+vessel+acids.

4.6 Properly place the vessel in the microwave system according to the
manufacturer’s recommended specifications.

4.7 Enable appropriate 3051a method in the MARS unit software according to
number of samples.

4.8 Once the digests have cooled to less than 75°C, remove from the microwave,
remove one vessel at a time and:
4.8.1 Record the mass on sample worksheet.
4.8.2 The mass must be within 1.0 g of the pre-digest mass.
4.9 Remove cap, tare on vessel and add 38 g ≥18 MΩ DI water.
4.10 Return cap and invert several times.
4.11 Allow sediment to settle and pour off approximately 12 ml into labeled falcon
tubes.

4.12 Pour off approximately 10ml of ICSA and 10ml of ICSB into labeled falcon tubes.
4.12.1 Make sure ICSA and ICSB are on the analysis sheet (one
set/analysis sheet).

5.0 QUALITY CONTROL

5.1 Laboratory Control Sample (LCS): The laboratory control sample must fall within
± 20% of the known value or within the 95% prediction interval of the certified
value. The laboratory control sample must be run with each batch of microwave
digestions.

5.2 Sample Duplicates: The relative percent difference (RPD) must be no more than
±20%. One sample duplicate must be run with every microwave batch.

RPD = 100 x (S – D)
 Standard Operating Procedure
3051a Microwave Assisted Acid Digestion of Soil
Soil Environmental Chemistry Program, The Ohio State University
Version 12

Avg. (S,D)

5.3 Preparation Blank: If any analyte concentration is above the detection limit in the
preparation blank, the lowest concentration of the analyte reported in associated
samples must be ≥ 10 times the preparation blank concentration. A preparation
blank must be performed with each batch of microwave digests.

5.4 Pre-digestion Spike: Spike recoveries must fall within the limits of 75-125%. At
least one spike analyses (matrix spikes) shall be performed on each batch of
digests.

5.5 Interference Check Standard: The analytical results for those target analytes
with MDLs < 10 ug/L shall fall within + 2x MDL of the analyte's true value (the
true value shall be zero unless otherwise stated) in the ICS Solution A (ICSA).
For example, if the analysis result(s) for Arsenic (MDL = 10 ug/L, ICSA true value
= 0 ug/L) in the ICSA analysis during the run is + 19 ug/L, then the analytical
result for Arsenic falls within the + 2x MDL window for Arsenic in the ICSA.
Results for the ICP analyses of Solution AB during the analytical runs shall fall
within the control limit of +20% of the true value for the analytes included in the
Interference Check Samples.

5.6 INTERFERENT AND ANALYTE ELEMENTAL CONCENTRATIONS USED FOR

ICP INTERFERENCE CHECK SAMPLE
Analytes (mg/L) Interferents (mg/L)
ICS B ICS A & ICS B
Se 0.05 Tl 0.1 Al 500
As 0.1 Zn 1.0 Ca 500
Ba 0.5 Fe 200
Be 0.5 Mg 500
Cd 1.0
Co 0.5
Cr 0.5
Cu 0.5
Mn 0.5
Ni 1.0
Pb 0.05

6.0 REPORTING

6.1 Worksheets: Fill in appendix for pipettes used during the course of this SOP.
 Standard Operating Procedure
3051a Microwave Assisted Acid Digestion of Soil
Soil Environmental Chemistry Program, The Ohio State University
Version 12

7.0 CORRECTIVE ACTION

Pass/ Flag Measurement QA/QC Frequency Acceptance Corrective Action

Fail Check1 Criteria
i 3051a Method LCS 1/batch ±20% or Check microwave
w/in 95% PI function and re-digest
batch.
ii Sample prep Blank 1/batch Below MDL Check ICP for
or samples carryover and dish
>10x washing procedures
re-digest batch.
iii Reproducibility Duplic 1/batch RPD ±20% Check microwave
ate function and re-digest
batch.
Iv 3051a Method/ Pre- 1/batch ±25% Check microwave
Matrix affects Digest function and ICP for
Spike signs of matrix affects.
Re-digest batch if ICP
is acceptable.
v Interferences ICS 1/batch See 5.5 Determine how to
correct the problem
with the ICP and re-
analyze samples by
ICP.

8.0 REFERENCES

8.1 Brobst, R. 1995. Biosolids management handbook. U.S. Environmental

Protection Agency, Denver, CO.
https://www.epa.gov/sites/production/files/documents/handbook1.pdf.

8.2 USEPA. 2007. Method 3051a. Microwave assisted acid digestion of sediments,
sludges, soils, and oils. In SW-846. U.S. Environmental Protection Agency,
Washington, DC.

8.3 USEPA. 2007. Method 6010C. Inductively coupled plasma-atomic emission

spectrometry. In SW-846. U.S. Environmental Protection Agency, Washington,
DC.

8.4 US Geological Survey. National Geochemical Survey database. US Department

of Interior, http://mrdata.usgs.gov/geochemistry/ngs.html.
 Standard Operating Procedure
3051a Microwave Assisted Acid Digestion of Soil
Soil Environmental Chemistry Program, The Ohio State University
Version 12

9.0 APPENDIX

Pipette Calibration Verification

Volume g DI g DI g DI g DI g DI date initials

Volume g DI g DI g DI g DI g DI date initials

Volume g DI g DI g DI g DI g DI date initials

Volume g DI g DI g DI g DI g DI date initials

Volume g DI g DI g DI g DI g DI date initials

Volume g DI g DI g DI g DI g DI date initials

Volume g DI g DI g DI g DI g DI date initials

 Standard Operating Procedure
3051a Microwave Assisted Acid Digestion of Soil
Soil Environmental Chemistry Program, The Ohio State University
Version 12

10.0 INTERPRETATION

10.1 Soil blends and soil blend components should be screened for elemental toxicity
according to the USEPA part 503 table 3 limits (Table 1). US Geological Survey
background soil data from Ohio (Table 1) should also be used to assess whether
soil blend elemental content falls within typical soil ranges.

Table 1. Background soil ranges for the state of Ohio from the US Geological Survey
database (USGS), and USEPA Part 503 limits (Brobst, 1995).
Part 503
Element Min Max Mean Median 95th
Table 3
----------------------------------------------------- mg kg -----------------------------------------------------
-1

Ag <1 <1 . . .
Al 2.87 7.75 5.05 5.00 7.23
As 4.30 26.6 9.97 9.70 16.9 41
Ba 242 565 438 450 529.5
Be 0.800 2.80 1.54 1.50 2.45
Bi 0.110 0.410 0.215 0.210 0.345
Ca 0.0800 4.29 0.582 0.440 1.625
Cd <0.1 0.900 . 0.300 0.8 39
Ce 30.4 101 62.3 60.1 83.85
Co 3.30 32.4 11.6 10.7 20.55
Cr 16.0 66.0 38.4 37.0 58
Cs <5 10.0 . 5.00 8
Cu 7.50 55.1 20.4 19.1 37.15 1500
Fe 1.17 4.29 2.48 2.46 3.55
Ga 5.89 16.8 10.0 9.61 15.15
Hg 0.0200 0.190 0.0561 0.0500 0.13 17
In 0.0300 0.0800 0.0462 0.0400 0.07
K 1.03 2.59 1.67 1.68 2.36
La 14.4 51.4 31.2 30.1 43.4
Li 14.0 66.0 30.2 28.0 51.5
Mg 0.160 1.94 0.482 0.420 0.97
Mn 155 2710 822 684 2200
Mo 0.690 12.7 2.94 2.25 7.115
Na 0.210 1.06 0.556 0.530 0.9
Nb 6.30 14.0 10.7 10.8 13.75
Ni 7.80 39.3 21.2 20.2 37.1 420
P 310 3840 873 770 1545
Pb 16.6 148 33.8 29.8 50.75 300
Rb 40.3 126 76.9 76.5 107
 Standard Operating Procedure
3051a Microwave Assisted Acid Digestion of Soil
Soil Environmental Chemistry Program, The Ohio State University
Version 12

S 0.0200 0.0900 0.0458 0.0500 0.075

Sb 0.400 1.74 0.781 0.720 1.255
Sc 3.90 14.0 7.61 7.30 11.9
Se 0.300 0.900 0.578 0.600 0.85 100
Sn 1.10 11.0 2.27 1.90 5
Sr 42.0 193 97.3 89.7 167.5
Te <0.1 0.300 . 0.100 .
Th 4.60 16.6 10.6 10.3 14.2
Ti 0.210 0.420 0.327 0.330 0.41
Tl 0.300 1.50 0.743 0.700 1.05
U 1.70 9.00 4.14 3.90 6.2
V 31.0 120 65.6 66.0 96.5
W 0.600 2.40 1.24 1.20 1.8
Y 10.3 30.9 16.9 15.8 26.8
Zn 33.0 423 91.9 85.0 158 2800