Quality Assurance and Quality Control Requirements For For The Massachusetts Contingency Plan (MCP)

WSC-CAM Section: VI B
Massachusetts Department of Environmental

Protection Bureau of Waste Site Cleanup 20 August 2004 Revision No. 3
Final Page 1 of 20
Quality Assurance and Quality Control Requirements and Performance Standards

Title:
for SW-846 Method 7196A, Hexavalent Chromium by UV-Visible Spectrophotometry
WSC – CAM – VI B
Quality Assurance and Quality Control Requirements for

SW-846 Method 7196A, Hexavalent Chromium by UV-
Visible Spectrophotometry for the Massachusetts
Contingency Plan (MCP)
Document Status: Final
Donald Muldoon
Department of Environmental Protection
One Winter Street
Boston, MA 02108
[email protected]
Document Chronology
Revision Status Date
0 Public Comment Draft 20 December 2002

1 Final 30 May 2003
2 Final 30 July 2003
3 Final 20 August 2004
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Title:
VI. Miscellaneous Wet Chemical Methods

B. Quality Assurance and Quality Control Requirements and Performance
Standards for SW-846 Method 7196A, Hexavalent Chromium [Cr (VI)]
by UV-Visible Spectrophotometry
B.1 TABLE OF CONTENTS
1.0 QA/QC Requirements for SW-846 Method 7196A 3
1.1 Overview of Method 3
1.2 Summary of Methods 4
1.3 Method Interferences 6
1.4 Specific QA/QC Requirements and Performance Standards for SW-846
8
Methods 7196A and 3060A
2.0 Analytical Data Usability Assessment for SW-846 Method 7196A 14
3.0 Analytical Reporting Requirements for SW-846 Method 7196A 14
3.1 General Analytical Reporting Requirements for SW-846 Method 7196A 14
3.2 Specific Analytical Reporting Requirements for SW-846 Method 7196A 14
Regulatory Limits for Total Chromium, Chromium (VI) and Chromium (III) under
4.0 16
310 CMR 40.0000
List of Tables, Exhibits and Appendices
Number Title Page

Quality Assurance and Quality Control Requirements and Performance
Table VI B-1 10-13
Standards for SW-846 Method 7196A
Table VI B-2 Routine Analytical Reporting Requirements for SW-846 Method 7196A 15
Regulatory Limits for Total Chromium, Chromium (VI) and Chromium (III)
Table VI B-3 16
under 310 CMR 40.0000
Sample Preservation, Container and Analytical Holding Time
Specifications for Surface Water, Groundwater, Soil and Sediment
Appendix VI B-1 17
Samples Analyzed for Chromium (VI) in Support of MCP Decision
Making
Appendix VI B-2 Eh/pH Phase Diagram 18
Quality Control Flow Diagram SW-846 Method 3060A Alkaline
Appendix VI B-3 19-20
Digestion for Hexavalent Chromium, Including Figure 1 and 2
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Title:
1.0 QA/QC Requirements for SW-846 Method 7196A
1.1 Overview of Methods
SW-846 Method 7196A, Determination of Hexavalent Chromium by UV-Visible

Spectrophotometry, may be used directly for the determination of dissolved hexavalent
chromium (Cr (VI)) in aqueous environmental samples. This analytical method may also be
used as the determinative step in the analysis of Cr (VI) in soils, sludges, sediments and
similar waste materials that have been pre-digested using SW-846 Method 3060A, Alkaline
Digestion for Hexavalent Chromium. All references to SW-846 methods in this document refer
to the United States Environmental Protection Agency‘s most recently published version.
1.1.1 Reporting Limits for SW-846 Method 7196A
Reporting Limits (RL), sensitivity, and/or the optimum linear concentration range can vary with
sample matrix and laboratory operating conditions.
SW-846 Method 7196A may be used directly to determine dissolved hexavalent chromium
(VI) in aqueous samples containing concentrations from 0.005 œ 50 mg/L. This method may
also be used in combination with the SW-846 Method 3060A alkaline digestion procedure for
the analysis of hexavalent chromium in soils, sludges, sediments and similar waste materials
containing concentrations from 1.0 œ 2000 mg/kg on a dry weight basis.
Sample preservation, container and analytical holding time specifications for surface water,
groundwater, soil, and sediment matrices for hexavalent chromium analyzed in support of
MCP decision-making are presented in Appendix VI Bœ1 of this document and Appendix VII-A,
WSC-CAM-VII A, —Quality Assurance and Quality Control Guidelines for the Acquisition and
Reporting of Analytical Data in Support of Response Actions Conducted Under the
Massachusetts Contingency Plan (MCP)".
1.1.2 General Quality Control Requirements for SW-846 Method 7196A
Each laboratory that uses SW-846 Method 7196A are required to operate a formal quality
assurance program to demonstrate the precision and bias of the method as performed by the
laboratory and procedures for determining the method reporting limit (RL). The minimum
requirements of this program consist of an initial demonstration of laboratory capability, ongoing
analysis of standards and blanks as a test of continued performance, and the analysis of
laboratory control samples (LCSs), and LCS duplicates to assess accuracy and/or precision.
Project-specific matrix duplicates or matrix spike duplicates (MSDs) may be used in lieu of LCS
duplicates to evaluate precision when such samples are analyzed either at discretion of
laboratory or at request of data-user. Refer to SW-846 Methods 7196A, and 3060A Sections
8.0 and 9.0 for general quality control guidelines for these chromium determinative methods.
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Laboratories must document and have on file an Initial Demonstration of Capability for each
combination of sample preparation and determinative chromium methods being used. These
data must meet or exceed the performance standards as presented in Section 1.4 and Table VI
B-1 of this method. Procedural requirements for performing the Initial Demonstration of
Laboratory Capability can be found in SW-846, Chapter One, Section 4.4.1. The data
associated with the Initial Demonstration of Laboratory Capability for hexavalent chromium
analyses must be kept on file at the laboratory and made available to potential data-users on
request and must include the following:
QC Element Performance Criteria

Initial Calibration WSC-CAMœVI B, Table VI B-1
Continuing Calibration WSC-CAMœVI B, Table VI B-1
Method Blanks WSC-CAMœVI B, Table VI B-1
% Percent Recovery for MS/LCS WSC-CAMœVI B, Table VI B-1
Relative Percent Difference (RPD)
WSC-CAMœVI B, Table VI B-1
for MSD/LCS Duplicate
Soluble Cr (VI)/ Insoluble Cr (VI)
WSC-CAMœVI B, Table VI B-1
Matrix Spike (solid samples only)
Laboratories are encouraged to continually strive to minimize variability and improve the
accuracy and precision of their analytical results. . In some cases, the standard laboratory
acceptance criteria for the various QC elements may have to be modified to accommodate
more rigorous project-specific data quality objectives prescribed by the data user. The
laboratory may be required to modify routine sample introduction and/or analytical conditions to
accommodate project-specific data quality objectives.
Use of this method is restricted to use by, or under the supervision of, analysts who are knowledgeable of
UV-Visible spectrophotometry as a quantitative tool, and the correction of the chemical, and physical
interferences described in this method.
1.2 Summary of Methods
1.2.1 SW-846 Method 7196A, Determination of Hexavalent Chromium by UV-Visible

Spectrophotometry
SW-846 Method 7196A may be used to determine the concentration of dissolved hexavalent
chromium (Cr (VI)) from 0.5 to 50 mg per liter (PPM) in EP/TCLP characteristic extracts,
surface water and groundwater. Dissolved Hexavalent Chromium, in the absence of
interfering amounts of substances such as molybdenum, vanadium, and mercury, may be
determined spectrophotometrically. Cr (VI) is determined by the addition of an excess of
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diphenylcarbazide in acid solution yielding a red-violet product of unknown composition. The

reaction is very sensitive, with an absorbency index (absorptivity) of 40,000 per gram atom of
chromium at 540 ηm. Absent interfering substances, this method may also be applicable to
the analysis of hexavalent chromium (Cr (VI)) in certain domestic and industrial wastes.
Determinative methods that utilize automated flow injection analysis

(FIA) systems manufactured by Lachat, Technicon and OI
Corporation, etc. that use diphenylcarbazide as the color
development reagent and maintain the ratio of reagent and sample
volumes specified by SW-846 Method 7196A, to accommodate
automation, are considered equivalent for the analysis of dissolved
Analytical Note:
hexavalent chromium both in aqueous environmental samples and
the alkaline digestate produced by SW-846 Method 3060A.
Manufacturer‘s instructions should be consulted for a more detailed
discussion of potential method-specific interferences and operational
issues. The quality control requirements and performance standards
described in Table VI Bœ1 may be applied directly to these methods.
1.2.2 SW-846 Method 3060A, Alkaline Digestion for Hexavalent Chromium
SW-846 Method 3060 is an alkaline digestion procedure for extracting hexavalent chromium
(Cr (VI) from soluble, adsorbed, and precipitated forms of chromium compounds in soils,
sludges, sediments, and similar waste materials. The pH of the digestate must be carefully
adjusted and monitored during the digestion procedure. Failure to meet the pH
specifications of the method will necessitate re-digestion of the samples.
To quantify all Cr (VI) species contained in a solid matrix, three criteria must be satisfied:
(1) The extracting solution must solubilize all forms of Cr (VI),

(2) The conditions of the extraction must not induce reduction of native Cr (VI) to Cr (III), and
(3) The method must not cause oxidation of native Cr (III) contained in the sample to Cr (VI).
SW-846 Method 3060A meets these criteria for most solid matrices. Under the alkaline
conditions of the extraction, minimal reduction of Cr (VI) or oxidation of native Cr (III) occurs.
The addition of Mg+2 in a phosphate buffer to the alkaline solution has been shown to suppress
oxidation. The efficiency (as % Recovery) of the extraction procedure is assessed using spike
recovery data for soluble and insoluble forms of Cr (VI) (e.g., K2Cr2O7 and PbCrO4), coupled
with the measurement of other soil properties, such as oxidation reduction potential (ORP),
pH, organic matter content, ferrous iron, and sulfides as indicators that oxidative conditions will
be maintained during digestion of the Cr (VI) spike.
Recovery of an insoluble Cr (VI) spike is used to assess efficiency and maintenance of non-
reductive conditions during the solubilization process. Method-induced oxidation (Cr (III)
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converted to Cr (VI)) is usually not observed except in soils high in manganese and amended
with soluble Cr (III) salts or freshly precipitated Cr (OH) 3.
Alkaline digestion is the required preparative step for the analysis soils, sludges, sediments
and similar waste materials under the MCP.
The quantification of Cr (VI) in Method 3060A digestates may be performed using any
analytical technique with suitable accuracy and precision. The following summary table
presents the recommended alternative SW-846 methods that may be used in conjunction with
the alkaline digestion procedure for the analysis of Hexavalent Chromium in soils, sludges,
sediments, and similar waste materials. Other less commercially-available analytical
techniques such as ion chromatography (IC) coupled with inductively coupled plasma œ mass
spectrometric (ICP-MS) detection, high performance liquid chromatography (HPLC) with ICP-
MS detection, capillary electrophoresis (CE) with ICP-MS detection, etc. may be considered
once their performance effectiveness has been validated.
1.2.3 Determination of Total Chromium and Chromium (III)
Total Chromium may be determined by flame or flameless atomic absorption methods, ICP-
AES or by ICP-MS. Refer to the appropriate MADEP Analytical Method (WSC-CAM III A, III C
or III D) for specific analytical and reporting details. Chromium (III) is defined as the difference
between the Total Chromium concentration and the Chromium (VI) concentration.
Chromium (III) = Total Chromium œ Chromium (VI)
1.3 Method Interferences
1.3.1 General Interferences Associated with Trace Metal Analyses
Samples submitted to a laboratory for trace metal analysis may be subject to contamination
during both sampling and analysis. Potential sources of contamination may include:
‹ Metallic or metal-containing containers and sampling equipment,

‹ Laboratory acids or reagents,
‹ Improperly cleaned or stored equipment, and
‹ Atmospheric inputs such as dirt and dust.
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1.3.2 Specific SW-846 Method 7196A Interferences
The chromium reaction with diphenylcarbazide is usually free from interferences. However,
certain substances may interfere if the chromium concentration is relatively low. Hexavalent
molybdenum and mercury salts also react to form color with the reagent; however, the red-
violet intensities produced are much lower than those for chromium at the specified pH.
‹ Concentrations of up to 200 mg/L of molybdenum and mercury can be tolerated.

‹ Vanadium interferes strongly, but concentrations up to 10 times that of chromium can
be tolerated.
‹ Iron
in concentrations greater than 1 mg/L may produce a yellow color, but the ferric
iron color is not strong and difficulty is not normally encountered if the absorbance is
measured spectrophotometrically at the appropriate wavelength.
1.3.3 Specific SW-846 Method 3060A Interferences
1.3.3.1 Oxidizing/Reducing Conditions in Sample Matrix
Under the MCP, determination of the reducing/oxidizing tendency of each soil type and/or
sediment matrix for each analytical batch is required when measuring hexavalent chromium.
This is accomplished by characterization of each sample for two (2) additional analytical
parameters:
‹ pH (SW-846 Method 9045C), and
‹ Oxidation Reduction Potential (ORP) (ASTM Method D 1498-93).
Section 7.2 of SW-846 Method 9045C should be referenced as the preparatory method for
solid samples for ORP. The ORP and pH probes are inserted directly into the soil slurry. The
displayed ORP and pH values are allowed to equilibrate and the resulting measurements are
recorded. Additional optional parameters include:
‹ Ferrous iron (ASTM Method D3872-86), and
‹ Sulfides (SW-846 Method 9030B).
Other indirect indicators of reducing/oxidizing tendency include:
‹ Total Organic Carbon (TOC),
‹ Chemical Oxygen Demand (COD), and
‹ Biological Oxygen Demand (BOD).
Analysis of these parameters establishes the tendency of Cr (VI) to exist or not exist in the
unspiked sample(s) and assists in the interpretation of QC data for matrix spike recoveries
outside of the acceptance criteria.
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1.3.3.2 Interfering Substances Present in Digestate

Certain substances, not typically found in the alkaline digestates of soils, may interfere in the
analytical methods for Cr (VI) following alkaline extraction if the concentrations of these
interfering substances are high and the Cr (VI) concentration is low. Refer to Section 2.2 for
a discussion of the specific metals that may interfere with Cr (VI) quantification. Reducing
agents such as soluble fulvic acids, which are sometimes present in alkaline digestates, may
also be potential interferents for this method. Analytical techniques that reduce bias caused
by co-extracted matrix components may be effective to minimize these biases after validation
of their performance.
1.3.3.3 Elevated Chromium (III) Native Concentrations in Sample
Cr (VI) results obtained using this method may be biased high due to method-induced
oxidation for waste materials or solid samples containing soluble Cr (III) concentrations
greater than four times the laboratory Cr (VI) reporting limit. The addition of Mg2+ in a
phosphate buffer to the alkaline extraction solution has been shown to suppress this
oxidation. The presence of soluble Cr (III) can be approximated by extracting the solid
sample with deionized water (ASTM methods D4646-87, D5233-92, or D3987-85) and
analyzing the resultant leachate for both Cr (VI) and total chromium. The difference between
these two values approximates the concentration of soluble Cr (III).
1.4 Specific QA/QC Requirements and Performance Standards for SW-846 Methods 7196A
and 3060A
Specific QA/QC requirements and performance standards for SW-846 Methods 7196A are
presented below in Tables VI B-1. Strict compliance with the QA/QC requirements and
performance standards for this method, as well as satisfying other analytical and reporting
requirements will provide a data user with —Presumptive Certainty“ regarding the usability of
analytical data to support MCP decisions. The concept of —Presumptive Certainty“ is explained
in detail in Section 2.0 of WSC-CAM-VII A.
While optional, parties electing to utilize these protocols will be assured of —Presumptive
Certainty“ of data acceptance by agency reviewers. In order to achieve —Presumptive
Certainty“, parties must:
(a) Comply with the procedures described and referenced in WSC-CAMœVI B;
(b) Comply with the applicable QC analytical requirements prescribed in Table VI B-1 for this
test procedure;
(c) Evaluate, and narrate, as necessary, compliance with performance standards prescribed
in Table VI B-1 for this test method; and
(d) Adopt the reporting formats and elements specified in the CAM.
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In achieving the status of —Presumptive Certainty“, parties will be assured that analytical data
sets:
V Will satisfy the broad QA/QC requirements of 310 CMR 40.0017 and 40.0191
regarding the scientific defensibility, precision and accuracy, and reporting of
analytical data;
V May be used in a data usability assessment, and if in compliance with all MCP
Analytical Method standards, laboratory QC requirements, and field QC
recommended limits and action levels, the data set will be considered useable
data to support site characterization decisions made pursuant to the MCP; and
V May be used to help support a data representativeness assessment.
Widespread adherence to the —Presumptive Certainty“ approach will promote inter-laboratory

consistency and provide the regulated community with a greater degree of certainty regarding
the quality of data used for MCP decision-making. The issuance of these requirements and
standards is in no way intended to preempt the exercise of professional judgement by the LSP
in the selection of alternative analytical methods. However, parties who elect not to utilize the
—Presumptive Certainty“ option have an obligation, pursuant to 310 CMR 40.0017 and
40.0191(2)(c), to demonstrate and document an overall level of (laboratory and field) QA/QC,
data usability, and data representativeness that is adequate for and consistent with the
intended use of the data.
WSC-CAM Table: VI B-1
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Quality Assurance and Quality Control Requirements and Performance Standards for SW-846 Method 7196A
Hexavalent Chromium by UV-Visible Spectrophotometry
Required Data Quality Required Recommended Analytical

Performance Standard
QA/QC Objective Deliverable Corrective Action Response Action
Suspend all analyses until
(1) Frequency œ Daily or each time instrument initial calibration
is set up, prior to sample analysis nonconformance is
(2) Minimum of a calibration blank plus five rectified.
Laboratory calibration standards Recalibrate as required
Initial Calibration Analytical (3) Low-level standard in calibration must be No If linear regression is not
by method.
Accuracy at the laboratory reporting limit (RL) used for analyte
(4) Linear curve fit with correlation coefficient r quantitation (e.g., a
> 0.995. Second order curve fit may be quadratic equation is used),
used if r > 0.995. this must be noted in the
case narrative.
(1) Frequency œ Immediately after each initial

calibration Suspend all
Laboratory (2) Separate-source from calibration Recalibrate/
Initial Calibration analyses until ICV
Analytical standards No Re-analyze ICV as
Verification (ICV) non-conformance
Accuracy (3) ICV percent recovery must be 80-120% required by method.
is rectified.
(4) Concentration of ICV must be within the
calibration range.
(1) Frequency - Every 10 samples and at end

Continuing of run
Laboratory Re-analyze CCV; if still outside
Calibration (2) Same-source as calibration standards; Narrate non-
Analytical No limits, recalibrate and reanalyze all
Verification concentration near mid-point of calibration compliance.
Accuracy samples since last compliant CCV.
(CCV) range
(3) CCV percent recovery must be 80-120%
Laboratory Analytical
Continuing Sensitivity (1) Frequency - Every 10 samples and at end Re-calibrate/re-analyze all
Narrate non-
Calibration (instrument drift and of run immediately after CCV No samples since last compliant
compliance.
Blank (CCB) contamination (2) Cr (VI) must be < RL CCB.
evaluation)
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(1) Frequency - One per digestion batch

Determine source of
Laboratory of < 20 field samples.
contamination. Re-digest/
Method Method (2) Must be matrix-matched (the same
Re-analyze all associated Narrate non-
(Preparation) Sensitivity reagent concentration as calibration Yes
samples unless all detected compliance.
Blank (contamination and QC standards) and digested with
results are > 10x method blank
evaluation) the samples
level.
(3) Cr (VI) must be < RL
Narrate non-
(1) Frequency - One per digestion batch of < compliance.
20 field samples.
Laboratory (2) LCS must be media-matched (aqueous or Note: MADEP
Laboratory solid) to field samples and digested with Re-digest/reanalyze all
Control Sample Yes modification to
Method Accuracy the samples. associated samples.
(LCS) frequency of
(3) LCS percent recovery for Cr (VI) must be LCS for
within 80-120% or certified acceptance consistency with
limits, whichever is applicable. other methods.
(1) Locate and
rectify source of
(1) Frequency - One per digestion batch of < non-
20 field samples. conformance
(2) LCS Duplicate must be media-matched before
(aqueous or solid) to field samples; proceeding with
prepared using the standard source and the analyses of
concentration as the LCS, and digested subsequent
with the samples. sample batches.
Laboratory (3) Recommended to be run immediately after Re-digest/reanalyze all
LCS Duplicate Yes (2) Narrate non-
Method Precision LCS in analytical sequence. associated samples.
compliance.
(4) Laboratoryœdetermined Relative
Percent Difference (RPD) must be ≤ 20 Note: MADEP
(aqueous) and ≤ 35 (soils/sediments), modification
and to frequency
(5) A project-specific MD or MSD may be of LCS for
substituted to evaluate precision in lieu of consistency
an LCS duplicate. with other
methods.
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(1) Frequency - One per digestion batch of < Yes, if MS
Project Evaluate LCS. If LCS
20 field samples per matrix at the requested by
Specific Matrix within acceptance
Method discretion of the laboratory or at the data user or
Spike (MS) limits, no further action Narrate non-
Accuracy in request of data user. run by
needed. If LCS is compliance
Sample Matrix laboratory as
Aqueous outside acceptance
Percent recoveries of Cr(VI) must be routine
Samples Only limits, reanalyze MS.
between 75 œ125%. QA/QC
(1) Optional (may be done in lieu of MD);
Frequency - One per digestion batch of Yes, if MSD
Refer to corrective
Project < 20 field samples per matrix at the requested by
action for the
Specific Matrix discretion of the laboratory or at the data user or
Method Precision associated MS Narrate non-
Spike request of data user. run by
in Sample Matrix (Aqueous MS, Soluble compliance
Duplicate (2) Percent recoveries must be between 75 œ laboratory as
Cr[VI] MS, or Insoluble
Sample*(MSD) 125%. routine
Cr[VI] MS)
(3) MSD RPD criteria: aqueous samples: < 20; QA/QC
soil and sediment samples: < 35.
Narrate non-
(1) Optional (may be done in lieu of MSD)-
compliance.
Frequency: One per digestion batch of <
Project Specific Method 20 field samples at the discretion of the
Note:
Matrix Precisio laboratory or at the request of data user. Yes, if MD
No corrective action acceptance
n in (2) MD RPD criteria: aqueous results > 5x RL: requested by
Duplicate* required, criteria
Sample + 20%; aqueous results < 5x RL: data user
(MD) consistent with
Matrix difference < RL; soil and sediment results
USEPA Region I
> 5x RL: + 35%; soil and sediment results
data validation
< 5x RL: difference < 2x RL.
guidance
* It is recommended that a matrix spike duplicate analysis be performed if analytes are not suspected to be detected. A matrix duplicate
analysis should be performed if analytes are suspected to be detected.
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Evaluate LCS. If LCS within
acceptance limits, evaluate
(1) Frequency - One per digestion batch of < oxidation/reduction Narrate non-
Project Specific Yes, if MS
Method 20 field samples per matrix at the characteristics of sample, as compliance and
Soluble Cr (VI) requested by
Accurac discretion of the laboratory or at the specified on Figures 1 and 2 in note
Matrix Spike data user or
y in request of data user. Appendix VI B-4. Alternatively, oxidation/reducti
run by
Sample (2) Percent recoveries of Cr (VI) must be perform mass balance as per on
Solid Samples laboratory as
Matrix between 75 œ125%. Section 8.5.2 of SW-846 characteristics
Only routine QA/QC
method 3060A. If reducing of sample.
conditions exist, no further
action required.
Evaluate LCS. If LCS within
acceptance limits, evaluate
Project Specific (1) Frequency - One per digestion batch oxidation/reduction Narrate non-
Yes, if MS
Insoluble of < 20 field samples per matrix at the characteristics of sample, as compliance and
requested by
Cr (VI) Method discretion of the laboratory or at the specified on Figures 1 and 2 in note
data user or
Matrix Spike Accuracy in request of data user. Appendix VI B-4. Alternatively, oxidation/reducti
run by
Sample Matrix (2) Percent recoveries of Cr (VI) must be perform mass balance as per on
laboratory as
Solid Samples between 75 œ125%. Section 8.5.2 of SW-846 characteristics
routine QA/QC
Only method 3060A. If reducing of sample.
conditions exist, no further
action required.
(1) Non-detected values must be reported with
the sample-specific reporting limit for each
analyte.
(2) The RL must be supported by the low-level
standard in the calibration curve.
Sample (3) Results for solid matrices must be reported
Quantitation on a dry- weight basis to compare to MCP
and NA standards. Yes Not applicable.
General (4) Sample concentrations that exceed the
Reporting calibration range must be diluted (in the
same acid matrix) to fall within the
calibration range when re-analyzed.
pH and ORP must be performed and
reported for each soil type and/or
sediment matrix for each analytical batch.
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2.0 Analytical Data Usability Assessment for SW-846 Method 7196A
Overall data usability is influenced by uncertainties associated with both sampling and
analytical activities. This document provides detailed quality control requirements and
performance standards for SW-846 Methods 7196A and 3060A which may be used to assess
the analytical component of data usability. The sampling component of data usability, an
independent assessment of the effectiveness of sampling activities to meet data quality
objectives, is not substantively addressed in this document.
3.0 Analytical Reporting Requirements for SW-846 Method 7196A

3.1 General Reporting Requirements for SW-846 Method 7196A
General environmental laboratory reporting requirements for analytical data used in

support of assessment and evaluation decisions at MCP disposal sites are presented in
CAM VII A, Section 2.4. This guidance document provides recommendations for field QC,
as well as the required content of the Environmental Laboratory Report, including
‹ Laboratory identification information presented in WSC-CAM-VII A, Section 2.4.1,
‹ Analytical results and supporting information in WSC CAM-VII A, Section 2.4.2,
‹ Sample- and batch-specific QC information in WSC CAM-VII A, Section 2.4.3,
‹ Laboratory Report Certification Statement in WSC CAM-VII A, Section 2.4.4,
‹ Copy of the Analytical Report Certification Form in WSC CAM-VII A, Exhibit VII A-1,
‹ Environmental Laboratory Case Narrative contents in WSC CAM-VII A, Section 2.4.5,
‹ Chain of Custody Form requirements in WSC CAM-VII A, Section 2.4.6
3.2 Specific Reporting Requirements for SW-846 Method 7196A
Specific Quality Control Requirements and Performance Standards for SW-846 Method
7196A are presented in Table VI B-1. Specific QA/QC Requirements and Performance
Standards for SW-846 Method 7196A are summarized below in Table VI B-2 as —Required
Analytical Deliverables (YES)“. These routine reporting requirements should always be
included as part of the laboratory deliverable for this method. It should be noted that
although certain items are not specified as —Required Analytical Deliverables (NO)“, these
data are to be available for review during an audit and may also be requested on a client-
specific basis.
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Table VI B-2 Routine Analytical Reporting Requirements for SW-846 Method 7196A
Parameter Required Analytical Deliverable

Initial Calibration NO
Initial Calibration Verification (ICV) NO
Continuing Calibration Verification (CCV) NO
Continuing Calibration Blank (CCB) NO
Method (Preparation) Blank YES
Laboratory Control Standard (LCS) YES
LCS Duplicate YES
Project-Specific Aqueous Matrix Spike (MS) YES, if requested by data user
Project-Specific Matrix Spike Duplicate (MSD)
YES, if requested by data user
(Aqueous or solid)
Project-Specific Matrix Duplicate (MD) (Aqueous or
solid)
Project-Specific Solid Soluble Cr (VI) Matrix Spike
(MS)
Project-Specific Solid Insoluble Cr (VI) Matrix Spike
(MS)
pH and ORP (for each soil type and/or sediment
YES
matrix for each analytical batch)
General Reporting YES 1
1. Non-detected values must be reported with the sample-specific reporting limit.
Protection Bureau of Waste Site Cleanup

20 August 2004 Revision No. 3
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4.0 Regulatory Limits for Total Chromium, Chromium (VI) and Chromium (III) under
310 CMR 40.0000
The Reportable Quantity (RQ) together with the most stringent (lowest) MCP Reportable
Concentrations (RCs) and Method 1 Standards for Chromium (VI), Chromium (III) and Total
(or undifferentiated) Chromium are listed below in Table VI B-3:
Table VI B-3 Regulatory Limits for Total Chromium, Chromium (VI) and Chromium
(III) under 310 CMR 40.0000
Total Chromium
MCP Regulatory Criteria Regulatory Limit

RQ
100 Pounds
RC GW-1
100 µg/L (ppb)
RC S-1
1000 mg/kg (ppm)
Groundwater Method 1 GW-1 Standard
100 µg/L (ppb)
Method 1 Soil Category S-1 & GW-1 Standard

1000 µg/g (ppm)
Chromium (VI)

RQ 10 Pounds
RC GW-1 50 µg/L (ppb)
RC GW-2 100 µg/L (ppb)
RC S-1 200 mg/kg (ppm)
Groundwater Method 1 GW-1 Standard 50 µg/L (ppb)
Groundwater Method 1 GW-3 Standard 100 µg/L (ppb)
200 µg/g (ppm)
Chromium (III)

RQ 100

pounds
RC GW-1
1000 µg/L (ppb)
RC S-1
1000 mg/kg (ppm)
Groundwater Method 1 GW-1 Standard
100 µg/L (ppb)
1000 µg/g (ppm)
WSC-CAM Appendix: VI B-1
Final Page 17 of 20
Sample Preservation, Container and Analytical Holding Time Specifications
Title: for Surface Water, Groundwater, Soil and Sediment Samples Analyzed for
Chromium (VI) in Support of MCP Decision Making
Sample preservation, container and analytical holding time specifications for surface
water, groundwater, soil, and sediment matrices for Chromium (VI) conducted in
support of MCP decision-making are summarized below and presented in Appendix VII-
A of WSC-CAM-VII A, —Quality Assurance and Quality Control Guidelines for Sampling,
Data Evaluation, and Reporting Activities for the Massachusetts Contingency Plan
(MCP)“. Additional guidance may be found in SW-846, Chapter Three.
Sample Container Preservation Holding Time 1

Matrix
Extract within 30 days

125 mL wide-mouth of collection. Analyze
Concentrated Waste within 7 days after
glass or polyethylene Cool, 4 ± 2o °C
Samples All Species
bottle extraction. Store at 4°C
until analyzed.
Aqueous 500 mL glass or

Cool, 4 ± 2o °C 24 Hours
Chromium (VI) polyethylene bottle
Filter (0.45 µm) on site; or at
Dissolved 500 mL glass or the laboratory (prior to
24 Hours
Chromium (VI) polyethylene bottle extraction)
Cool, 4 ± 2o °C
Extract within 30 days
Samples should be collected of collection. Analyze
Soil/Sediment (1) 4-ounce glass jar with non-metallic devices and within 7 days after
Chromium (VI) with teflon-lined cap
stored field-moist at 4 ± 2o°C extraction. Store at 4°C
until analyzed.
Soil/Sediment (1) 4-ounce glass jar

Cool, 4 ± 2o °C 24 hours
pH and ORP with teflon-lined cap
Soil/Sediment
Ferrous iron and (1) 4-ounce glass jar
Cool, 4 ± 2o °C 7 days
Sulfide with teflon-lined cap
(optional analyses)
1. Holding time begins from time of sample collection.
WSC-CAM Appendix: VI B-2

Final Page 18 of 20
Title: Eh/pH Phase Diagram
* Figure from SW-846 method 3060A

WSC-CAM
Appendix: VI B-3

Final
Page 19 of 20
Quality Control Flow Diagram for SW-846 Method 3060A
Title: Alkaline Digestion for Hexavalent Chromium (Figure 1 of 2)
* Figure from SW-846 method 3060A

WSC-CAM
Appendix: VI B-3

Final
Page 20 of 20
Quality Control Diagram for SW-846 Method 3060A
Title: Alkaline Digestion for Hexavalent Chromium (Figure 2 of 2)
* Figure from SW-846 Method 3060A

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WSC-CAM Section: VI B

Massachusetts Department of Environmental

Quality Assurance and Quality Control Requirements and Performance Standards