NATIONALFUNCTIONALGUIDELINES
for Inorganic Superfund Data Review
&EPA
Office of Superfund Remediation and Technology Innovation (OSRTI)
United States Environmental Protection Agency (EPA)
Washington, DC 20460
OSWER 9355.0-131
EPA-540-R-013-001
AUGUST 2014
-------
This page is intentionally left blank.
August 2014
-------
NOTICE
The policies and procedures set forth here are intended as guidance to the United States Environmental
Protection Agency (EPA) and other governmental employees. They do not constitute rule making by the
EPA, and may not be relied upon to create a substantive or procedural right enforceable by any other
person. The Government may take action that is at variance with the policies and procedures in this
manual.
This document can be obtained from the EPA's Contract Laboratory Program (CLP) website at:
http://www.epa.gov/superfund/programs/clp/guidance.htm
August 2014 iii
-------
This page is intentionally left blank.
August 2014 iv
-------
TABLE OF CONTENTS
LIST OF TABLES vii
ACRONYMS AND ABBREVIATIONS ix
I. Terminology ix
II. Target Analyte List xi
INTRODUCTION 1
I. Purpose of Document 1
II. Limitations of Use 1
III. Document Organization 1
IV. For Additional Information 1
PART A: GENERAL DATA REVIEW 3
I. Preliminary Review 5
II. Data Qualifier Definitions 6
III. Data Review Narrative 7
PART B: METHOD-SPECIFIC DATA REVIEW 9
ICP-AES DATA REVIEW 11
Example Analytical Sequence 13
I. Preservation and Holding Times 15
II. Calibration 17
III. Blanks 20
IV. Interference Check Sample 24
V. Laboratory Control Sample 27
VI. Duplicate Sample Analysis 30
VII. Spike Sample Analysis 33
VIII. Serial Dilution 36
IX. Regional Quality Assurance and Quality Control 38
X. Overall Assessment of Data 39
XI. Calculations 41
ICP-MS DATA REVIEW 43
Example Analytical Sequence 45
I. Preservation and Holding Times 47
II. Tune Analysis 49
III. Calibration 51
IV. Blanks 54
V. Interference Check Sample 58
VI. Laboratory Control Sample 61
VII. Duplicate Sample Analysis 63
VIII. Spike Sample Analysis 66
IX. Serial Dilution 69
X. Internal Standards 71
XI. Regional Quality Assurance and Quality Control 73
XII. Overall Assessment of Data 74
XIII. Calculations 76
August 2014
-------
MERCURY DATA REVIEW 77
Example Analytical Sequence 79
I. Preservation and Holding Times 81
II. Calibration 83
III. Blanks 86
IV. Duplicate Sample Analysis 90
V. Spike Sample Analysis 93
VI. Regional Quality Assurance and Quality Control 95
VII. Overall Assessment of Data 96
VIII. Calculations 98
CYANIDE DATA REVIEW 99
Example Analytical Sequence 101
I. Preservation and Holding Times 103
II. Calibration 105
III. Blanks 109
IV. Duplicate Sample Analysis 113
V. Spike Sample Analysis 116
VI. Regional Quality Assurance and Quality Control 119
VII. Overall Assessment of Data 120
VIII. Calculations 122
APPENDIX A: GLOSSARY A-l
APPENDIX B: INORGANIC DATA REVIEW SUMMARY B-l
August 2014 vi
-------
Inorganic Data Review
LIST OF TABLES
Table 1. Data Qualifiers and Definitions 6
Table 2. Preservation and Holding Time Actions for ICP-AES Analysis 16
Table 3. Acceptance Criteria for ICV and CCV Standards for ICP-AES Analysis 17
Table 4. Calibration Actions for ICP-AES Analysis 19
Table 5. Blank Actions for ICP-AES Analysis 22
Table 6. Interference Check Actions for ICP-AES Analysis 26
Table 7. LCS Actions for ICP-AES Analysis 29
Table 8. Duplicate Sample Actions for ICP-AES Analysis 32
Table 9. Spike Sample Actions for ICP-AES Analysis 35
Table 10. Serial Dilution Actions for ICP-AES Analysis 37
Table 11. Preservation and Holding Time Actions for ICP-MS Analysis 48
Table 12. ICP-MS Tune Actions for ICP-MS Analysis 50
Table 13. Acceptance Criteria for ICV and CCV Standards for ICP-MS Analysis 51
Table 14. Calibration Actions for ICP-MS Analysis 53
Table 15. Blank Actions for ICP-MS Analysis 56
Table 16. Interference Check Actions for ICP-MS Analysis 60
Table 17. LCS Actions for ICP-MS Analysis 62
Table 18. Duplicate Sample Actions for ICP-MS Analysis 65
Table 19. Spike Sample Actions for ICP-MS Analysis 68
Table 20. Serial Dilution Actions for ICP-MS Analysis 70
Table 21. Internal Standard Actions for ICP-MS Analysis 72
Table 22. Preservation and Holding Time Actions for Mercury Analysis 82
Table 23. Acceptance Criteria for ICV and CCV Standards for Mercury Analysis 83
Table 24. Calibration Actions for Mercury Analysis 85
Table 25. Blank Actions for Mercury Analysis 89
Table 26. Duplicate Sample Actions for Mercury Analysis 92
Table 27. Spike Sample Actions for Mercury Analysis 94
Table 28. Preservation and Holding Time Actions for Cyanide Analysis 104
Table 29. Acceptance Criteria for ICV and CCV Standards for Cyanide Analysis 105
Table 30. Calibration Actions for Cyanide Analysis 108
Table 31. Blank Actions for Cyanide Analysis Ill
Table 32. Duplicate Sample Actions for Cyanide Analysis 115
Table 33. Spike Sample Actions for Cyanide Analysis 118
August 2014
VII
-------
Inorganic Data Review
This page is intentionally left blank.
August 2014 viii
-------
Inorganic Data Review
I. Terminology
The following
definition, see
CCB
CCS
CCV
CLP
COR
CRQL
CSF
DF
DQO
EDM
EPA
EXES
ICB
ICP
ICP-AES
ICP-MS
ICS
ICV
LCS
LEB
MDL
NFG
%D
%R
%RSD
%Solids
PE
QA
QAPP
QC
RPD
ACRONYMS AND ABBREVIATIONS
acronyms and abbreviations may be found throughout this document. For further
Appendix A: Glossary at the end of the document.
Continuing Calibration Blank
Contract Compliance Screening
Continuing Calibration Verification
Contract Laboratory Program
Contracting Officer Representative
Contract Required Quantitation Limit
Complete SDG File
Dilution Factor
Data Quality Objective
EXES Data Manager
United States Environmental Protection Agency
Electronic Data Exchange and Evaluation System
Initial Calibration Blank
Inductively Coupled Plasma
Inductively Coupled Plasma - Atomic Emission Spectroscopy
Inductively Coupled Plasma - Mass Spectrometry
Interference Check Sample
Initial Calibration Verification
Laboratory Control Sample
Leachate Extraction Blank
Method Detection Limit
National Functional Guidelines
Percent Difference
Percent Recovery
Percent Relative Intensity
Percent Relative Standard Deviation
Percent Solids
Performance Evaluation
Quality Assurance
Quality Assurance Project Plan
Quality Control
Relative Percent Difference
August 2014
IX
-------
Inorganic Data Review
SDG Sample Delivery Group
SEDD Staged Electronic Data Deliverable
SMO Sample Management Office
SOP Standard Operating Procedure
SOW Statement of Work
SPLP Synthetic Precipitation Leaching Procedure
TAL Target Analyte List
TCLP Toxicity Characteristic Leaching Procedure
TDS Total Dissolved Solids
TOC Total Organic Carbon
TR/COC Traffic Report/Chain of Custody
TSS Total Suspended Solids
August 2014
-------
Inorganic Data Review
II. Target Analyte List
The EPA Contract Laboratory Program (CLP) Statement of Work (SOW) for Inorganic Superfund
Methods (Multi-Media, Multi-Concentration) ISM02.2 applies CLP analytical methods for the
isolation, detection, and quantitation of the following target analytes and parameter:
Al
Sb
As
Ba
Be
Cd
Ca
Cr
Co
Cu
CN
Fe
Pb
Mg
Mn
Hg
Ni
K
Se
Ag
Na
Tl
V
Zn
Hardness
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Cyanide
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
August 2014
XI
-------
Inorganic Data Review
This page is intentionally left blank.
August 2014 xii
-------
Inorganic Data Review Introduction
INTRODUCTION
I. Purpose of Document
This document contains guidance to aid the data reviewer in determining the usability of analytical
data generated using the United States Environmental Protection Agency (EPA) Contract Laboratory
Program (CLP) Statement of Work (SOW) for Inorganic Superfund Methods (Multi-Media, Multi-
Concentration) ISM02.2. The SOW includes metals by Inductively Coupled Plasma-Atomic
Emission Spectroscopy (ICP-AES), metals by Inductively Coupled Plasma-Mass Spectrometry (ICP-
MS), mercury, and cyanide analytical methods.
The guidelines presented in this document are designed to assist the reviewer in evaluating (a)
whether the analytical data meet the technical and Quality Control (QC) criteria specified in the
SOW, and (b) the usability and extent of bias of any data that do not meet these criteria. This
document contains definitive guidance in areas, such as blanks, calibration verification standards,
Interference Check Samples (ICSs), QC audit samples, and instrument performance checks (e.g.,
tuning), in which performance is fully under a laboratory's control. General guidance is provided to
aid the reviewer in making subjective judgments regarding the use of data that are affected by site
conditions (e.g., sample matrix effects) and do not meet SOW-specified requirements.
II. Limitations of Use
This guidance is specific to the review of analytical data generated using CLP SOW ISM02.2. It
applies to the current version of the SOW, as well as future versions that contain editorial changes.
To use this document effectively, the reviewer should have an understanding of the analytical
methods and a general overview of the Sample Delivery Group (SDG) or Case at hand. This
guidance is not appropriate for use in conducting contract compliance reviews and should be used
with caution in reviewing data generated using methods other than CLP SOW ISM02.2, although the
general types of QC checks, the evaluation procedures, and the decisions made after consideration of
the evaluation criteria may be applicable to data from any similar method.
While this document is a valuable aid in the data review process, other sources of guidance and
information, along with professional judgment, are useful in determining the ultimate usability of the
data. This is particularly critical in those cases where data do not meet SOW-specified technical and
QC criteria. To make the appropriate judgments, the reviewer needs to gain a complete
understanding of the intended use of the data and is strongly encouraged to establish a dialogue with
the data user prior to and following data review, to discuss usability issues and resolve questions
regarding the review.
III. Document Organization
Following this introduction, the document is presented in two major parts: Part A - General Data
Review, which applies to all methods; and Part B - Method-Specific Data Review. In Part B, each
method is addressed individually in a stand-alone format. A complete list of acronyms used in this
document appears preceding this introduction, and a Glossary is appended as Appendix A.
IV. For Additional Information
For additional information regarding the CLP and the services it provides, refer to the CLP website at
http://www.epa.gov/superfund/programs/clp/index.htm
August 2014
-------
Inorganic Data Review
This page is intentionally left blank.
August 2014
-------
Inorganic Data Review General
PART A: GENERAL DATA REVIEW
August 2014
-------
Inorganic Data Review General
This page is intentionally left blank.
August 2014
-------
Inorganic Data Review General
I. Preliminary Review
A preliminary review should be performed on the data, prior to embarking on the method-specific
review (see Part B). During this process, the reviewer should compile the necessary data package
elements to ensure that all of the information needed to determine data usability is available. The
preliminary review also allows the reviewer to obtain an overview of the Case or Sample Delivery
Group (SDG) under review.
The initial review should include, but is not limited to, verification of the exact number of samples,
their assigned number and matrices, and the Contractor laboratory name. It should take into
consideration all the documentation specific to the sample data package, which may include Modified
Analysis requests, Traffic Report/Chain of Custody (TR/COC) Record, SDG Narrative, and other
applicable documents.
The reviewer should be aware that minor modifications to the Statement of Work (SOW) that have
been made through a Modified Analysis request, to meet site-specific requirements, could affect
certain validation criteria such as Contract Required Quantitation Limits (CRQLs) and Target Analyte
Lists (TALs). Therefore, these modifications should be applied during the method-specific review
(Part B) process.
The Cases or SDGs routinely have unique field quality control (QC) samples that may affect the
outcome of the review. These include field blanks, field duplicates, and Performance Evaluation (PE)
samples which must be identified in the sampling records. The reviewer should verify that the
following items are identified in the sampling records (e.g., TR/COC Records, field logs, and/or
contractor tables):
1. The United States Environmental Protection Agency (EPA) Region where the samples were
collected; and
2. The complete list of samples with information on:
a. Sample matrix
b. Field blanks (if applicable)
c. Field duplicates (if applicable)
d. Field spikes (if applicable)
e. PE samples (if applicable)
f Sampling dates
g. Sampling times
h. Shipping dates
i. Preservatives
j. Types of analysis
k. Contractor laboratory
The laboratory's SDG Narrative is another source of general information which includes notable
problems with matrices; insufficient sample volume for analysis or reanalysis; samples received in
broken containers; preservation information; and unusual events. The reviewer should also inspect
any email or telephone/communication logs in the data package detailing any discussion of sample
and/or analysis issues between the laboratory, the Contract Laboratory Program (CLP) Sample
Management Office (SMO), and the EPA Region.
The reviewer should also have a copy of the Quality Assurance Project Plan (QAPP), or similar
document, for the project for which the samples were analyzed, to assist in the determination of final
usability of the analytical data. The reviewer should contact the appropriate Regional Laboratory
August 2014 5
-------
Inorganic Data Review
General
Contracting Officer Representative (COR) to obtain copies of the QAPP and relevant site
information.
For data obtained through the CLP, the Staged Electronic Data Deliverable (SEDD) generated by the
CLP laboratories is subjected to the following reviews via the Electronic Data Exchange and
Evaluation System (EXES): 1) automated data assessment for Contract Compliance Screening (CCS)
based on the technical and QC criteria in CLP SOW ISM02.2, and 2) automated data validation based
on the criteria in the EPA CLP National Functional Guidelines (NFG) for Inorganic Superfund Data
Review. In addition, completeness checks are manually performed on the hardcopy data. The
automated CCS results and hardcopy data issues are subsequently included in a CCS defect report
that is provided to the laboratory. The laboratory may then submit a reconciliation package for any
missing items or to correct non-compliant data identified in the report. The automated data validation
results are summarized in criteria-based NFG reports that are provided to the EPA Regions. The data
reviewer can access the CCS and NFG reports through the EXES Data Manager (EDM) via the SMO
Portal and may use them in determining data usability.
For more information about EXES and EDM, refer to the following CLP website:
http://www.epa.gov/superfund/programs/clp/data assessment.htm
For access to the SMO Portal, refer to the following CLP website to contact the Regional Laboratory
COR from the Region where the data review is being performed and to obtain the necessary username
and password information:
http: //www. epa.gov/superfund/programs/clp/contacts .htm
For concerns or questions regarding the data package, contact the Regional Laboratory COR from the
Region where the samples were collected.
II. Data Qualifier Definitions
The following definitions provide brief explanations of the national qualifiers assigned to results
during the data review process. The reviewer should use these qualifiers as applicable. If the
reviewer chooses to use additional qualifiers, a complete explanation of those qualifiers shall
accompany the data review.
Table 1. Data Qualifiers and Definitions
Data
Qualifier
U
J
J+
J-
UJ
R
Definition
The analyte was analyzed for, but was not detected above the level of the reported sample
quantitation limit.
The result is an estimated quantity. The associated numerical value is the approximate
concentration of the analyte in the sample.
The result is an estimated quantity, but the result may be biased high.
The result is an estimated quantity, but the result may be biased low.
The analyte was analyzed for, but was not detected. The reported quantitation limit is
approximate and may be inaccurate or imprecise.
The data are unusable. The sample results are rejected due to serious deficiencies in
meeting QC criteria. The analyte may or may not be present in the sample.
August 2014
-------
Inorganic Data Review General
III. Data Review Narrative
The reviewer should complete a Data Review Narrative that includes comments that address the
problems identified during the review process and state the limitations of the data associated with a
Case or SDG. The CLP Sample Numbers, analytical methods, extent of the problem(s), and assigned
qualifiers should also be listed in the document.
The Data Review Narrative, including the Inorganic Data Review Summary form (see Appendix B),
must be provided together with the laboratory data to the appropriate recipient(s). A copy of the Data
Review Narrative should also be submitted to the Regional Laboratory COR assigned oversight
responsibility for the Contractor laboratory.
August 2014
-------
Inorganic Data Review
This page is intentionally left blank.
August 2014
-------
Inorganic Data Review
PART B: METHOD-SPECIFIC DATA REVIEW
August 2014
-------
Inorganic Data Review
This page is intentionally left blank.
August 2014 10
-------
Inorganic Data Review ICP-AES
ICP-AES DATA REVIEW
The inorganic data requirements for Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-
AES) to be reviewed during validation are listed below:
Example Analytical Sequence 13
I. Preservation and Holding Times 15
II. Calibration 17
III. Blanks 20
IV. Interference Check Sample 24
V. Laboratory Control Sample 27
VI. Duplicate Sample Analysis 30
VII. Spike Sample Analysis 33
VIII. Serial Dilution 36
IX. Regional Quality Assurance and Quality Control 38
X. Overall Assessment of Data 39
XI. Calculations 41
August 2014 11
-------
Inorganic Data Review ICP-AES
This page is intentionally left blank.
August 2014 12
-------
Inorganic Data Review ICP-AES
Example Analytical Sequence
This is an example of an analytical sequence:
S##
S##
s##
s##
s##
s##
ICV
ICB
ICSA
ICSAB
ccv###
CCB###
samples
ccv###
CCB###
samples
ccv###
CCB###, etc.
* Suffix ## and ### are as specified in Exhibit B of the Statement of Work (SOW).
August 2014 13
-------
Inorganic Data Review ICP-AES
This page is intentionally left blank.
August 2014 14
-------
Inorganic Data Review ICP-AES
I. Preservation and Holding Times
A. Review Items
Form 1-IN, Form 12-IN, Traffic Report/Chain of Custody (TR/COC) documentation, Form DC-1,
raw data, and the Sample Delivery Group (SDG) Narrative checking for: pH; shipping container
temperature; holding time; and other sample conditions.
B. Objective
The objective is to determine the validity of the analytical results based on the sample conditions and
the holding time of the sample.
C. Criteria
1. The technical holding time is determined from the date of collection, or the date Toxicity
Characteristic Leaching Procedure (TCLP) or Synthetic Precipitation Leaching Procedure (SPLP)
extraction is complete, to the date of analysis.
2. The technical holding time criteria for aqueous/water samples and leachate samples from TCLP
or SPLP is 180 days, preserved (with nitric acid) to pH < 2.
3. The technical holding time criteria for soil/sediment samples is 180 days, based on the technical
holding time criteria for aqueous/water samples.
4. The technical holding time criteria for wipe samples is 180 days, based on the technical holding
time criteria for aqueous/water samples.
5. Soil/sediment samples shall be maintained at < 6°C (but not frozen) from the time of collection
until receipt at the laboratory. All aqueous/water and soil/sediment samples must be stored at
< 6°C (but not frozen) from the time of sample receipt until digestion. The TCLP and SPLP
leachates must be stored at < 6°C (but not frozen) from the time of the leaching procedure
completion until digestion. Wipe samples should be maintained at room temperature until
preparation.
D. Evaluation
Establish technical holding times by comparing the sampling date(s) on the TR/COC documentation
with the dates of analysis on Form 12-IN and the raw data; also consider using information in the
Complete SDG File (CSF), as it may be helpful in the assessment. Verify that the analysis dates on
the Form 12-IN and the raw data are identical. Review the SDG Narrative and raw data preparation
logs to determine if samples were properly preserved. If there is an indication of problems with the
samples, the sample integrity may be compromised. Use professional judgment to evaluate the effect
of the problem on the sample results.
E. Action
NOTE: Apply the action to each field sample for which the preservation or holding time criteria
was not met.
1. If the pH of aqueous/water samples is > 2 at the time of sample receipt, determine if the
laboratory adjusted the pH of the sample to < 2 at the time of sample receipt. Also determine if
the laboratory adjusted the pH to < 2 for the TCLP and SPLP leachates after completion of the
leaching procedure. If not, use professional judgment to qualify the samples based on the pH of
the sample and the chemistry of the metal(s) of interest. Detects should be qualified as estimated
low (J-) and non-detects as unusable (R).
2. If soil/sediment samples are not maintained at < 6°C (but not frozen) from the time of collection
until receipt at the laboratory, detects should be qualified as estimated low (J-) and non-detects as
unusable (R).
August 2014 15
-------
Inorganic Data Review
ICP-AES
3. If technical holding times are exceeded, use professional judgment to determine the reliability of
the data, based on the magnitude of the additional time compared to the technical requirement and
whether the samples were properly preserved. The expected bias would be low. Detects should
be qualified as estimated low (J-) and non-detects as unusable (R).
4. Due to limited information concerning holding times for soil/sediment and wipe samples, use
discretion when deciding whether to apply the aqueous/water holding time criteria to
soil/sediment and wipe samples. If they are applied, document this action in the Data Review
Narrative.
5. If aqueous/water and soil/sediment samples are received with shipping container temperatures
> 10°C, use professional judgment to determine the reliability of the data, or qualify detects as
estimated (J) and non-detects as estimated (UJ).
6. When the holding times are exceeded, annotate any possible consequences for the analytical
results in the Data Review Narrative, and note it for Regional Laboratory Contracting Officer
Representative (COR) action.
Table 2. Preservation and Holding Time Actions for ICP-AES Analysis
Criteria
Aqueous/water samples received with pH > 2 and pH not
adjusted
TCLP/SPLP leachate samples with pH >2 and pH not adjusted
Soil/sediment samples not maintained at < 6°C (but not frozen)
from time of collection until receipt at the laboratory
Technical Holding Time:
Aqueous/water and TCLP/SPLP leachate samples > 180 days
Technical Holding Time:
Soil/sediment and wipe samples > 180 days
Samples received > 10°C*
Action
Detect
Use professional
judgment
J-
Use professional
judgment
J-
Use professional
judgment
J-
J-
J-
Use professional
judgment
J
Non-detect
Use professional
judgment
R
Use professional
judgment
R
Use professional
judgment
R
R
R
Use professional
judgment
UJ
* For samples received with shipping container temperatures > 10°C, Regional policy or project
Data Quality Objectives (DQO) may allow the use of higher temperature criteria before assessing
any actions for the affected samples.
August 2014
16
-------
Inorganic Data Review ICP-AES
II. Calibration
A. Review Items
Form 2-IN, Form 12-IN, Form 15-IN, Form 16-IN, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data.
B. Objective
The objective is to determine the validity of the analytical results based on initial calibration and
calibration verification.
C. Criteria
1. Initial Calibration
The instruments shall be successfully calibrated each time the instrument is set up and after
Continuing Calibration Verification (CCV) failure. The calibration date and time shall be
included in the raw data.
a. A blank and at least five calibration standards shall be used to establish each calibration
curve. At least one of these standards shall be at or below the Contract Required Quantitation
Limit (CRQL) but above the Method Detection Limit (MDL). All measurements shall be
within the instrument working range where the interelement correction factors are valid. A
minimum of three replicate exposures are required for standardization, for all Quality Control
(QC), and sample analyses. The average result of all the multiple exposures for the
standardization, QC, and sample analyses shall be used. The calibration curve shall be fitted
using linear regression or weighted linear regression. The curve may be forced through zero.
The curve must have a correlation coefficient > 0.995. The calculated percent differences
(%Ds) for all of the non-zero standards must be within ±30% of the true value of the
standard. The y-intercept of the curve must be less than the CRQL.
2. Initial and Continuing Calibration Verification
The acceptance criteria for the Initial Calibration Verification (ICV) and CCV standards are
presented in Table 3:
Table 3. Acceptance Criteria for ICV and CCV Standards for ICP-AES Analysis
Analytical Method
ICP-AES
Inorganic Analytes
Metals
ICV/CCV Low Limit
(% of True Value)
90
ICV/CCV High Limit
(% of True Value)
110
a. Initial Calibration Verification
1) Immediately after each system has been calibrated, the accuracy of the initial calibration
must be verified and documented for each target analyte by the analysis of an ICV
solution(s). If the ICV Percent Recovery (%R) falls outside of the control limits, the
analysis should be terminated, the problem corrected, the instrument recalibrated, and all
affected samples reanalyzed.
2) Only if the ICV is not available from the United States Environmental Protection Agency
(EPA), analyses shall be conducted using a certified solution of the analytes from an
independent commercial standard source, at a concentration level other than that used for
instrument calibration, but within the calibrated range.
3) The ICV solution shall be analyzed at each analytical wavelength used for analysis.
b. Continuing Calibration Verification
1) To ensure accuracy during the course of each analytical sequence, the CCV shall be
analyzed and reported for each wavelength used for the analysis of each analyte.
August 2014 17
-------
Inorganic Data Review ICP-AES
2) The CCV standard shall be analyzed at a frequency of every two hours during an
analytical sequence. The CCV standard shall also be analyzed at the beginning of the
analytical sequence, and again after the last analytical sample.
3) The analyte concentration(s) in the CCV standard(s) shall be different than the
concentration used for the ICV, and at a concentration equivalent to the mid-level of their
respective calibration curves.
4) The same CCV standard solution shall be used throughout the analysis for an SDG.
5) The CCV shall be analyzed in the same fashion as an actual sample. If the %R of the
CCV was outside of the control limits, the analysis should be terminated, the problem
corrected, the instrument recalibrated, and all analytical samples analyzed since the last
compliant CCV reanalyzed.
D. Evaluation
1. Verify that the instrument was calibrated each time the instrument was set up, utilizing a blank
and at least five calibration standards, one of which was at or below the CRQL but above the
MDL.
2. Confirm that the measurements were within the working calibration range, and were the average
result of at least three replicate exposures.
3. Verify that the ICV and CCV standards were analyzed for each analyte at the specified frequency
and at the appropriate concentration. Verify that acceptable %R results were obtained.
4. Recalculate one or more of the ICV and CCV %R(s) using the following equation and verify that
the recalculated value agrees with the laboratory-reported values on Form 2-IN.
Found (value)
%R = x 100
True (value)
Where,
, / i x Concentration (in ug/L) of each analyte measured in the analysis of the
Found (value) = T, ,, \ .. J J
ICV or CCV solution
True (value) = Concentration (in (ig/L) of each analyte in the ICV or CCV source
E. Action
NOTES: For initial calibrations or ICV standards that do not meet the technical criteria, apply the
action to all associated samples reported from the analytical sequence.
For CCV standards that do not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the QC sample and a
subsequent technically acceptable analysis of the QC sample in the analytical sequence.
1. If the instrument was not calibrated each time the instrument was set up, qualify detects and non-
detects as unusable (R). If the instrument was not calibrated with at least the minimum number of
standards, or if the calibration curve does not include standards at required concentrations (e.g., a
blank and at least one at or below CRQL but above the MDL), use professional judgment to
qualify detects as estimated (J) or unusable (R), and non-detects as estimated (UJ) or unusable
(R).
2. If the correlation coefficient is < 0.995, the %Ds are outside the ±30% limit, or the y-intercept >
CRQL, qualify detects as estimated (J) and non-detects as estimated (UJ).
3. If the ICV or CCV %R falls outside the acceptance windows, use professional judgment to
qualify all associated data. If possible, indicate the bias in the review. The following guidelines
are recommended:
a. If the ICV or CCV %R is < 75%, use professional judgment to qualify detects as estimated
low (J-) or unusable (R), and non-detects as unusable (R).
August 2014 18
-------
Inorganic Data Review
ICP-AES
b. If the ICV or CCV %R falls within the range of 75-89%, qualify detects as estimated low (J-)
and non-detects as estimated (UJ).
c. If the ICV or CCV %R falls within the range of 90-110%, detects and non-detects should not
be qualified.
d. If the ICV or CCV %R falls within the range of 111-125%, qualify detects as estimated high
(J+). Non-detects should not be qualified.
e. If the ICV or CCV %R is > 125%, use professional judgment to qualify detects as estimated
high (J+) or unusable (R). Non-detects should not be qualified.
4. If the laboratory failed to provide adequate calibration information, notify the Regional
Laboratory COR. The Regional Laboratory COR may contact the laboratory to request the
necessary information. If the information is unavailable, use professional judgment to assess the
data.
5. Annotate the potential effects on the reported data due to exceeding the calibration criteria in the
Data Review Narrative.
6. If calibration criteria are grossly exceeded, note this for Regional Laboratory COR action.
NOTE: For truly critical samples, a further in-depth evaluation of the calibration curve may be
warranted to determine if additional qualification is necessary.
Table 4. Calibration Actions for ICP-AES Analysis
Criteria
Calibration not performed
Calibration incomplete
Correlation coefficient < 0.995;
%D outside ±30%; y-intercept > CRQL
ICV/CCV%R<75%
ICV/CCV %R 75-89%
ICV/CCV%R90-110%
ICV/CCV %R 1 1 1-125%
ICV/CCV %R> 125%
Action
Detect
R
Use professional
judgment
JorR
J
Use professional
judgment
J-orR
J-
No qualification
J+
Use professional
judgment
J+orR
Non-detect
R
Use professional
judgment
UJorR
UJ
Use professional
judgment
R
UJ
No qualification
No qualification
No qualification
August 2014
19
-------
Inorganic Data Review ICP-AES
III. Blanks
A. Review Items
Form 1-IN, Form 3-IN, Form 12-IN, preparation logs, calibration standard logs, instrument logs, and
raw data.
B. Objective
The objective is to determine the validity of the analytical results based on the blank responses by
determining the existence and magnitude of contamination resulting from laboratory (or field)
activities or baseline drift during analysis.
C. Criteria
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed at each mass used for analysis after the
analytical standards, but not before analysis of the ICV during the initial calibration of the
instrument (see Section II.C.l).
3. A Continuing Calibration Blank (CCB) shall be analyzed at each wavelength used for the
analysis, immediately after every CCV. The CCB shall be analyzed at a frequency of every two
hours during the analytical sequence. The CCB shall be analyzed at the beginning of the
analytical sequence, and again after the last CCV that was analyzed after the last analytical
sample of the analytical sequence. The CCB result (absolute value) shall not exceed the CRQL
of each analyte for which analysis is performed.
4. At least one Preparation Blank shall be prepared and analyzed for each matrix, with every SDG,
or with each batch of samples digested, whichever is more frequent. The Preparation Blank
consists of reagent water or a clean wipe processed through the appropriate sample preparation
and analysis procedure.
5. If the concentration of any analyte in the Preparation Blank is > CRQL, the lowest concentration
of that analyte in the associated samples must be > lOx the Preparation Blank concentration.
Otherwise, all associated samples with the analyte's concentration < lOx the Preparation Blank
concentration and > CRQL, should be redigested and reanalyzed for that analyte. The laboratory
is not to correct the sample concentration for the blank value.
6. If the concentration of any analyte in the Preparation Blank is < (-CRQL), all associated samples
with the analyte's concentration < lOx the CRQL should be redigested and reanalyzed.
7. At least one Leachate Extraction Blank (LEB) shall be prepared and analyzed for each batch of
samples extracted by TCLP or SPLP. The LEB consists of reagent water processed through the
extraction procedure. Post-extraction, the LEB shall be processed through the appropriate sample
preparation and analysis procedure.
D. Evaluation
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the specified
frequency and sequence during the analysis, and Preparation Blanks were prepared and analyzed
as appropriate for the SDG (e.g., total number of samples, various types of matrices present,
number of digestion batches, etc.).
2. Review the results reported on Form 3-IN, as well as the raw data for all blanks, and verify that
the results were accurately reported.
3. Evaluate all of the associated blanks for the presence of target analytes. Verify that if the
concentration of any target analyte was > CRQL in a Preparation Blank, all associated samples
with the analyte's concentration > CRQL but < lOx the Preparation Blank concentration were
redigested and reanalyzed for that analyte. Verify that if a concentration was < (-CRQL) in a
Preparation Blank, all associated samples with the analyte's concentration < lOx CRQL were
August 2014 20
-------
Inorganic Data Review ICP-AES
redigested and reanalyzed. Verify that if the absolute value of any target analytes was > CRQL in
an ICB or a CCB, the analysis was terminated, the problem corrected, the instrument recalibrated,
and the preceding 10 analytical samples or all analytical samples analyzed since the last
compliant calibration blank reanalyzed.
E. Action
NOTES: For ICBs that do not meet the technical criteria, apply the action to all associated samples
reported from the analytical sequence.
For CCBs that do not meet the technical criteria, apply the action to all associated
samples analyzed between a previous technically acceptable analysis of the CCB and a
subsequent technically acceptable analysis of the CCB in the analytical sequence.
For Preparation Blanks that do not meet the technical criteria, apply the action to all
associated samples prepared in the same preparation batch. For LEBs that do not meet
the technical criteria, apply the action to all associated samples extracted in the same
extraction batch.
1. If the appropriate blanks were not analyzed with the specified frequency, use professional
judgment to determine if the associated sample data should be qualified; obtain additional
information from the laboratory, if necessary. Record the situation in the Data Review Narrative,
and note it for Regional Laboratory COR action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
In instances where more than one blank is associated with a given sample, qualification should be
based upon a comparison with the associated blank having the highest concentration of
contaminant.
3. Some general "technical" review actions include:
a. For any blank (including Preparation Blanks and LEBs) reported with detects < CRQLs,
report detects < CRQLs at the CRQLs and qualify as non-detect (U). For any blank
(including Preparation Blanks and LEBs) reported with detects < CRQLs, use professional
judgment to qualify the sample results > CRQLs. Non-detects should not be qualified.
b. For any blank (including Preparation Blanks and LEBs) reported with a negative result,
< (-MDL) but > (-CRQL), carefully evaluate and determine its effect on the sample data. Use
professional judgment to assess the data.
c. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil/sediment sample results reported on Form 1-IN will
not be on the same basis (units, dilution) as the calibration blank data reported on Form 3-IN.
It may be easier to work with the raw data and/or convert the ICB or CCB results to the same
units as the soil/sediment samples for comparison purposes.
4. Specific "method" actions include:
a. If an ICB or a CCB result is > CRQL, the analysis should be terminated. If the analysis was
not terminated and the associated samples were not reanalyzed, non-detects should not be
qualified. Report detects < CRQLs at the CRQLs and qualify as non-detect (U). Report
sample results that are > CRQLs but < ICB/CCB Results at ICB/CCB Results and use
professional judgment to qualify as non-detect (U) or unusable (R). Use professional
judgment to qualify sample results > ICB/CCB Results. Record the situation in the Data
Review Narrative, and note it for Regional Laboratory COR action.
b. If an ICB or a CCB result is < (-CRQL), the analysis should be terminated. If the analysis
was not terminated and the associated samples were not reanalyzed, use professional
judgment to qualify non-detects as estimated (UJ) or unusable (R). Use professional
judgment to qualify detects < CRQL, or qualify as estimated low (J-). Use professional
judgment to qualify sample results that are > CRQLs as estimated low (J-).
August 2014 21
-------
Inorganic Data Review
ICP-AES
c. If the concentration of any analyte in the Preparation Blank/LEB is > CRQL, the lowest
concentration of that analyte in the associated samples must be > lOx the Preparation
Blank/LEB concentration. All samples associated with the Preparation Blank with
concentrations < 1 Ox the Preparation Blank concentration and > CRQL should have been
redigested and reanalyzed. If the associated samples were not redigested and reanalyzed,
report the sample results at Preparation Blank Results; use professional judgment to qualify
the results as estimated high (J+) or unusable (R). Report results < lOx the LEB
concentration and > CRQL in the samples associated with the LEB at LEB Results; use
professional judgment to qualify the results as estimated high (J+) or unusable (R). Report
detects < CRQLs in the samples associated with the Preparation Blank/LEB at CRQLs and
qualify as non-detect (U). Non-detects and sample results that are > lOx the Preparation
Blank/LEB Results should not be qualified. If the laboratory failed to redigest and reanalyze
the samples associated with the Preparation Blank, record it in the Data Review Narrative,
and note it for Regional Laboratory COR action.
d. For any Preparation Blank or LEB reported with a negative result, < (-CRQL), use
professional judgment to qualify detects < CRQL, or qualify as estimated low (J-). Qualify
sample results that are > CRQLs as estimated low (J-), and qualify non-detects as estimated
(UJ). Sample results that are > lOx CRQLs should not be qualified.
Table 5. Blank Actions for ICP-AES Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
Blank Result
Detect < CRQL
< (-MDL) but
> (-CRQL)
>CRQL
< (-CRQL)
Sample Result
Non-detect
Detect < CRQL
>CRQL
Detect or non-detect
Non-detect
Detect < CRQL
> CRQL but
< ICB/CCB Result
> ICB/CCB Result
Non-detect
Detect < CRQL
>CRQL
Action
No qualification
Report at CRQL and qualify as non-
detect (U)
Use professional judgment
Use professional judgment
No qualification
Report at CRQL and qualify as non-
detect (U)
Report at ICB/CCB Result and
qualify as non-detect (U) or unusable
(R)
Use professional judgment
Use professional judgment to qualify
as estimated (UJ) or unusable (R)
Use professional judgment or (J-)
Use professional judgment to qualify
as estimated low (J-)
August 2014
22
-------
Inorganic Data Review
ICP-AES
Blank
Type
Preparation
Blank/LEB
Preparation
Blank/LEB
Preparation
Blank/LEB
Preparation
Blank/LEB
Blank Result
Detect < CRQL
< (-MDL) but
> (-CRQL)
>CRQL
< (-CRQL)
Sample Result
Non-detect
Detect < CRQL
>CRQL
Detect or non-detect
Non-detect
Detect < CRQL
> CRQL but
< 1 Ox the Preparation
Blank/LEB Result
> lOx the Preparation
Blank/LEB Result
Non-detect
Detect < CRQL
< lOx CRQL
> lOx CRQL
Action
No qualification
Report at CRQL and qualify as non-
detect (U)
Use professional judgment
Use professional judgment
No qualification
Report at CRQL and qualify as a non-
detect (U)
Report at Preparation Blank/LEB
Result and use professional judgment
to qualify results as estimated high
(J+) or unusable (R)
No qualification
Qualify as estimated (UJ)
Use professional judgment or (J-)
Qualify results that are > CRQL as
estimated low (J-)
No qualification
August 2014
23
-------
Inorganic Data Review ICP-AES
IV. Interference Check Sample
A. Review Items
Form 4-IN, Form 12-IN, instrument printouts, and raw data.
B. Objective
The objective is to determine the validity of the analytical results based on the instrument's ability to
overcome interferences typical of those found in samples.
C. Criteria
1. The Interference Check Sample (ICS) consists 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 of analyzing both solutions consecutively, starting with
Solution A, for all wavelengths used for each analyte reported by ICP-AES.
2. An ICS must be analyzed undiluted at the beginning of each sample analysis sequence. The ICS
is not to be analyzed prior to the ICV, and shall be immediately followed by a CCV, followed by
aCCB.
3. Results for the analysis of ICS Solution A must fall within the control limits of ± CRQL or ± 20%
of the true value (whichever is greater) for the analytes and interferents included in the solution.
4. Results for the analysis of ICS Solution AB must fall within the control limits of ± CRQL or ±
20% of the true value (whichever is greater) for the analytes and interferents included in the
solution.
5. If the value of an ICS result exceeds ± 2x the CRQL, or ± 20% of true value (whichever is
greater) criteria, the analysis shall be terminated, the problem corrected, the instrument
recalibrated, the new calibration then reverified, and all analytical samples since the last
compliant ICS reanalyzed.
6. The ICS should be obtained from the EPA, if available, and analyzed according to the
instructions supplied with the solutions. If the ICS is not available from the EPA, an independent
ICS solution shall be prepared using certified standards with the interferent and analyte
concentrations at the levels specified in the method.
D. Evaluation
1. Verify, using Form 12-IN and the raw data [Inductively Coupled Plasma (ICP) instrument
printout], that the ICS was analyzed at the specified frequency and sequence during the analytical
sequence.
2. Evaluate the ICS raw data for results with an absolute value that is > MDL for those analytes that
are not present in the ICS solution.
3. Recalculate, using the raw data and the following equation, one or more of the analyte %Rs, and
verify that the recalculated value agrees with the laboratory-reported values on Form 4-IN.
Found (value)
%R= x 100
True (value)
Where,
F , , , , _ Concentration (in (ig/L) of each analyte interferent measured in the
(value; - walysis of IC§ Solution A or ICS Solution AB
, , , _ Concentration (in (ig/L) of each analyte or interferent in ICS Solution
1 rue (value) - A or ICS Solutlon AB
August 2014 24
-------
Inorganic Data Review ICP-AES
4. If the value of an ICS result exceeds the ± CRQL or ± 20% of true value (whichever is greater)
criteria, and the laboratory failed to terminate the analysis and take the appropriate corrective
action, note this for Regional Laboratory COR action and record the situation in the Data Review
Narrative. Use professional judgment to assess the data.
E. Action
NOTE: For an ICS that does not meet the technical criteria, apply the action to all samples
reported from the analytical sequence.
1. If the ICS was not analyzed at the specified frequency, qualify detects and non-detects as
unusable (R). If the ICS was analyzed, but not in the proper sequence, use professional judgment
to qualify detects and non-detects.
2. The raw data may not contain results for interferents. In this case, use professional judgment to
qualify the data. If the data contains results for interferents, apply the following actions to
samples with concentrations of interferents that are within 10% of the levels of the interferents in
the ICS:
a. If the ICS Solution AB %R for an analyte or interferent is < 50%, qualify detects as estimated
low (J-) and non-detects as unusable (R).
b. If the ICS %R for an analyte or interferent falls within the range of 50-79% [or the ICS found
value is < (true value - CRQL), whichever is lower], qualify detects as estimated low (J-), and
non-detects as estimated (UJ).
c. If the ICS %R for an analyte or interferent falls within the range of 80-120%, detects and
non-detects should not be qualified.
d. If the ICS %R for an analyte or interferent is > 120% [or the ICS found value is > (true value
+ CRQL), whichever is greater], qualify detects as estimated high (J+). Non-detects should
not be qualified.
e. If the ICS %R for an analyte or interferent is above 150%, use professional judgment to
determine the qualifications of the associated sample data.
3. If sample results that are > MDLs are observed for analytes that are not present in the ICS
solution, the possibility of false positives exists. An evaluation of the associated sample data for
the affected analytes should be made. For samples with comparable or higher levels of
interferents and with analyte concentrations that approximate those levels found in the ICS,
qualify detects as estimated high (J+). Non-detects should not be qualified.
4. If negative sample results are observed for analytes that are not present in the ICS solution, and
their absolute values are > MDLs, the possibility of false negatives in the samples exists. An
evaluation of the associated sample data for the affected analytes should be made. For samples
with levels of interferents that are comparable to or higher than the levels found in the ICS,
qualify detects < lOx the absolute value of the negative result as estimated low (J-), and qualify
non-detects as estimated (UJ).
NOTE: The same result units should be used when comparing analyte results in samples to those
in the ICS. Unit conversion may be necessary when soil/sediment or wipe samples are
evaluated.
5. In general, ICP-AES sample data can be accepted if the concentrations of Aluminum (Al),
Calcium (Ca), Iron (Fe), and Magnesium (Mg) in the sample are found to be less than or equal to
their respective concentrations in the ICS. If these elements are present at concentrations greater
than the level in the ICS, or other elements are present in the sample at > 10 mg/L, investigate the
possibility of other interference effects as given in the ICP-AES method or as indicated by the
laboratory's interelement correction factors reported on Forms 10A-IN and 10B-IN for that
particular instrument. The analyte concentration equivalents presented in the method should be
considered only as estimated values since the exact value of any analytical system is instrument-
August 2014 25
-------
Inorganic Data Review
ICP-AES
specific. Therefore, estimate the concentration produced by an interfering element. If the
estimate is > 2xthe CRQL, and also > 10% of the reported concentration of the affected element,
qualify the affected results as estimated (J).
6. If the raw data does not contain results for the interferents, annotate this in the Data Review
Narrative.
7. Actions regarding the interpretation and/or the subsequent qualification of ICP data due to the
ICS analytical results can be extremely complex. Use professional judgment to determine the
need for the associated sample data to be qualified; obtain additional information from the
laboratory, if necessary. Record all interpretive situations in the Data Review Narrative.
8. If the ICS acceptance criteria are grossly exceeded, note the specifics for Regional Laboratory
COR action.
Table 6. Interference Check Actions for ICP-AES Analysis
Criteria
ICS not analyzed
ICS not analyzed in the proper sequence
ICSAB%R<50%
ICS %R 50-79% [or ICS found value is < (true
value - CRQL) whichever is lower]
ICS %R 80-120%
ICS %R > 120% (or ICS found value is > (true
value + CRQL) whichever is greater]
ICS%R>150%
Sample results > MDLs, but not present in ICS
Negative sample results, but not present in ICS
Action
Detect
R
Use professional
judgment
J-
J-
No qualification
J+
Use professional
judgment
J+
J-
for results <
lOx (negative sample
result)
Non- detect
R
Use professional
judgment
R
UJ
No qualification
No qualification
Use professional
judgment
No qualification
UJ
August 2014
26
-------
Inorganic Data Review ICP-AES
V. Laboratory Control Sample
A. Review Items
Form 7-IN, preparation logs, instrument printouts, and raw data.
B. Objective
The objective is to determine the validity of the analytical results based on the recovery of the
digested Laboratory Control Sample (LCS).
C. Criteria
1. Aqueous/water, soil/sediment and wipe LCSs shall be analyzed for each analyte utilizing the
same sample preparations, analytical methods, and Quality Assurance/Quality Control (QA/QC)
procedures as employed for the samples.
a. One LCS shall be prepared and analyzed for every group of aqueous/water or soil/sediment
samples in an SDG, or with each batch of samples digested, whichever is more frequent. The
LCS shall be spiked such that the final digestate contains each analyte at 2x the CRQL for the
associated matrix.
b. One LCS shall be prepared and analyzed for each group of wipe samples in an SDG, or with
each batch of wipe samples digested, whichever is more frequent. The wipe LCS shall be
spiked such that the final digestate contains each analyte at 2x the CRQL for the associated
matrix.
c. All LCS %Rs must fall within the control limits of 70-130%, except for Antimony (Sb) and
Silver (Ag) which must fall within the control limits of 50-150%. If the %R for the
aqueous/water and soil/sediment LCS falls outside of the control limits, the analysis should
be terminated, the problem corrected, and the samples prepared with that LCS redigested and
reanalyzed. No corrective actions are required for wipe LCSs when the %R is outside the
control limits.
D. Evaluation
1. Verify, using Form 7-IN, preparation logs, and raw data, that the appropriate number of required
LCSs were prepared and analyzed for the SDG.
2. Evaluate Form 7-IN and verify that all results for each analyte fall within the established control
limits.
a. Check the raw data to verify that the %Rs on Form 7-IN were accurately transcribed.
Recalculate one or more of the reported %Rs using the following equation:
Found (value)
%R=- -^-T xlOO
I rue (value)
Where,
1,1^ Concentration of each analyte (in ug/L, mg/kg, or ug) measured in the
Found (value) = , . ri, T j v n& , & &, \*&>
analysis or the LCS
True (value) = Concentration of each analyte (in (ig/L, mg/kg, or ug) in the LCS
3. Verify that the LCS was prepared at the same time as the associated samples using the same
procedures.
August 2014 27
-------
Inorganic Data Review ICP-AES
E. Action
NOTE: If the LCS criteria are not met, the laboratory performance and method accuracy are in
question. Use professional judgment to determine if the data should be qualified or
rejected. The following guidance is suggested for qualifying sample data associated with
an LCS that does not meet the required criteria.
For an LCS that does not meet the technical criteria, apply the action to all samples in the
same preparation batch.
1. If the required LCS was not analyzed at the specified frequency, use professional judgment to
determine if the associated sample results should be qualified; obtain additional information from
the laboratory, if necessary. If a laboratory fails to analyze a LCS with each SDG, or if a
laboratory consistently fails to generate acceptable LCS recoveries, record the situation in the
Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ).
2. Aqueous/Water and Soil/Sediment LCS:
a. If LCS %R is < 40% (< 20% for Ag and Sb), qualify detects as estimated low (J-) and non-
detects as unusable (R).
b. If the LCS %R falls within the range of 40-69% (20-49% for Ag and Sb), qualify detects as
estimated low (J-) and non-detects as estimated (UJ).
c. If the LCS %R falls within the range of 70-130%, detects and non-detects should not be
qualified.
d. If the LCS %R is > 130% (150% for Ag and Sb), qualify detects as estimated high (J+).
Non-detects should not be qualified.
e. If the LCS %R is > 150% (170% for Ag and Sb), qualify detects as unusable (R). Non-
detects should not be qualified.
3. Wipe LCS:
a. If the LCS %R is < 40%, qualify detects as estimated low (J-) and non-detects as unusable
(R).
b. If the LCS %R is in the range of 40-69%, qualify detects as estimated low (J-) and non-
detects as estimated (UJ).
c. If the LCS %R is within 70-130%, detects and non-detects should not be qualified.
d. If the LCS %R is > 130%, qualify detects as estimated high (J+). Non-detects should not be
qualified.
4. Annotate the potential effects on the data due to out-of-control LCS results in the Data Review
Narrative.
August 2014 28
-------
Inorganic Data Review
ICP-AES
Table 7. LCS Actions for ICP-AES Analysis
Criteria
Aqueous/Water and Soil/Sediment %R < 40%
(< 20% Ag, Sb)
Aqueous/Water and Soil/Sediment %R 40-69%
(20-69% Ag, Sb)
Aqueous/Water and Soil/Sediment %R 70-130%
Aqueous/Water and Soil/Sediment
%R > 130% (150% Ag, Sb)
Aqueous/Water and Soil/Sediment
%R > 150% (170% Ag, Sb)
Wipe%R<40%
Wipe %R 40-69%
Wipe %R 70- 130%
Wipe %R> 130%
Action
Detect
J-
J-
No qualification
J+
R
J-
J-
No qualification
J+
Non-detect
R
UJ
No qualification
No qualification
No qualification
R
UJ
No qualification
No qualification
August 2014
29
-------
Inorganic Data Review ICP-AES
VI. Duplicate Sample Analysis
A. Review Items
Cover Page, Form 6-IN, instrument printouts, and raw data.
B. Objective
The objective of duplicate sample analysis is to demonstrate acceptable method precision by the
laboratory at the time of analysis.
C. Criteria
1 . Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
duplicate sample analysis.
2. At least one duplicate sample shall be prepared and analyzed from each group of samples of a
similar matrix type (e.g., water or soil) or for each SDG. Duplicates are not required for wipe
samples. Duplicates cannot be averaged for reporting on Form 1-IN. Additional duplicate
sample analyses may be required by EPA Regional request. Alternately, the Region may require
that a specific sample be used for the duplicate sample analysis.
3 . A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original and
duplicate sample values > 5x the CRQL.
4. A control limit of the CRQL shall be used if either the sample or duplicate value is < 5x the
CRQL. The absolute value of the control limit (CRQL) shall be entered in the "Control Limit"
column on Form 6-IN. If both samples are non-detects, the RPD is not calculated for Form 6-IN.
NOTE: The above control limits are method requirements for duplicate samples, regardless of
the sample matrix type. However, it should be noted that laboratory variability arising
from the sub-sampling of non-homogenous soil samples is a common occurrence.
Therefore, for technical review purposes only, Regional policy or project DQOs may
allow the use of less restrictive criteria (e.g., 35% RPD, 2x the CRQL) to be assessed
against duplicate soil samples.
D. Evaluation
1 . Verify, using the Cover Page and the raw data, that the appropriate number of required duplicate
samples were prepared and analyzed for the SDG.
2. Verify, using Form 6-IN and the raw data, that all duplicate results for each analyte fall within the
established control limits.
3. Verify that a field blank or PE sample was not used for duplicate analysis.
4. Check the raw data and recalculate one or more of the RPD values using the following equation
to verify that the results were correctly reported on Form 6-IN:
IS-DI
Where,
RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
August 2014 30
-------
Inorganic Data Review ICP-AES
E. Action
NOTE: For a duplicate sample analysis that does not meet the technical criteria, apply the action
to all samples of the same matrix if the samples are considered sufficiently similar.
Exercise professional judgment in determining sample similarity when making use of all
available data, including: site and sampling documentation (e.g., location and type of
sample, descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity,
chlorine); and laboratory data for other parameters [e.g., Total Suspended Solids (TSS),
Total Dissolved Solids (TDS), Total Organic Carbon (TOC), alkalinity or buffering
capacity, reactive sulfide, anions]. Additionally, use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. Two
determinations are: 1) only some samples in the SDG are similar to the duplicate sample,
and that only these samples should be qualified; or 2) no samples are sufficiently similar
to the sample used for the duplicate, and thus only the field sample used to prepare the
duplicate sample should be qualified.
1. If the appropriate number of duplicate samples was not analyzed for each matrix using the correct
frequency, use professional judgment to determine if the associated sample data should be
qualified; obtain additional information from the laboratory, if necessary. Record the situation in
the Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ) if any of the frequency criteria is not
met.
2. If both original sample and duplicate sample results are > 5x the CRQL and the RPD is > 20%,
qualify detects as estimated (J) and non-detects as estimated (UJ).
3. If RPD > 100%, use professional judgment to determine if the associated sample data should be
qualified.
4. If both original sample and duplicate sample results are > 5x the CRQL and the RPD is < 20%,
detects and non-detects should not be qualified.
5. If the original sample or duplicate sample result is < 5x the CRQL (including non-detects) and the
absolute difference between sample and duplicate > CRQL, qualify detects as estimated (J) and
non-detects as estimated (UJ).
6. If the original sample or duplicate sample result is < 5x the CRQL (including non-detects) and the
absolute difference between sample and duplicate < CRQL, detects and non-detects should not be
qualified.
7. If a field blank or PE sample was used for the duplicate sample analysis, note this for Regional
Laboratory COR action. All of the other QC data must then be carefully checked. Use
professional judgment when evaluating the data.
8. Annotate the potential effects on the data due to out-of-control duplicate sample results in the
Data Review Narrative.
August 2014 31
-------
Inorganic Data Review
ICP-AES
Table 8. Duplicate Sample Actions for ICP-AES Analysis
Criteria
Both original sample and duplicate sample results are > 5x
the CRQL and RPD > 20%*
RPD > 100%
Both original sample and duplicate sample results are > 5x
the CRQL and RPD is < 20%
Original sample or duplicate sample result < 5x the CRQL
(including non-detects) and absolute difference between
sample and duplicate > CRQL*
Original sample or duplicate sample result < 5x the
CRQL (including non-detects) and absolute difference
between sample and duplicate < CRQL
Action
Detect
J
Use professional
judgment
No qualification
J
No qualification
Non-detect
UJ
Use professional
judgment
No qualification
UJ
No qualification
* The above control limits are method requirements for duplicate samples, regardless of the
sample matrix type. However, it should be noted that laboratory variability arising from the sub-
sampling of non-homogenous soil samples is a common occurrence. Therefore, for technical
review purposes only, Regional policy or project DQOs may allow the use of less restrictive
criteria (e.g., 35% RPD, 2xthe CRQL) to be assessed against duplicate soil samples.
August 2014
32
-------
Inorganic Data Review ICP-AES
VII. Spike Sample Analysis
A. Review Items
Cover Page, Form 5A-IN, Form 5B-IN, instrument printouts, and raw data.
B. Objective
The objective of the spiked sample analysis is to evaluate the effect of each sample matrix on the
sample preparation procedures and the measurement methodology.
C. Criteria
1. Samples identified as field blanks or PE samples cannot be used for spiked sample analysis.
2. At least one spiked sample (pre-digestion) shall be prepared and analyzed from each group of
samples with a similar matrix type (e.g., water or soil), or for each SDG. Matrix Spikes are not
required for wipe samples.
3. When the Matrix Spike recovery falls outside of the control limits and the sample result is < 4x
the spike added, a post-digestion spike shall be performed for those analytes that do not meet the
specified criteria. An aliquot of the remaining unspiked sample shall be spiked at 2x the
indigenous level or 2x the CRQL, whichever is greater.
NOTE: Post-digestion spikes are not required for Ag.
4. The spike %R shall be within the established acceptance limits. However, spike recovery limits
do not apply when the sample concentration is > 4x the spike added. In such an event, the data
shall be reported unflagged, even if the %R does not meet the acceptance criteria.
5. If the spiked sample analysis was performed on the same sample that was chosen for the duplicate
sample analysis, spike calculations shall be performed using the results of the sample designated
as the "original sample." The average of the duplicate results cannot be used for the purpose of
determining %R.
NOTE: The final spike concentrations required for the various target analytes are presented in the
methods described in the SOW.
D. Evaluation
1. Verify, using the Cover Page, Form 5 A-IN, and raw data, that the appropriate number of required
spiked samples was prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Verify, using Form 5A-IN, and the raw data, that all pre-digestion spiked sample results for each
required analyte fall within the established control limits. If not, verify that a post-digestion spike
was prepared and analyzed.
4. Recalculate, using the raw data, one or more of the %R using the following equation, and verify
that the recalculated value agrees with the laboratory-reported values on Forms 5A-IN & 5B-IN:
SSR-SR
%Recovery = x 100
SA
Where,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
August 2014 33
-------
Inorganic Data Review ICP-AES
NOTE: When the sample result is < MDL or reported as a non-detect, use SR = 0 only for the
purpose of calculating the %R. The actual spiked sample results, sample results, and %R
(positive or negative) shall still be reported on Forms 5A-IN & 5B-IN.
E. Action
NOTE: For a Matrix Spike that does not meet the technical criteria, apply the action to all
samples of the same matrix if the samples are considered sufficiently similar. Exercise
professional judgment in determining sample similarity when making use of all available
data, including: site and sampling documentation (e.g., location and type of sample,
descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity, chlorine);
and laboratory data for other parameters (e.g., TSS, TDS, TOC, alkalinity or buffering
capacity, reactive sulfide, anions). Additionally, use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. Two
determinations are: 1) only some of the samples in the SDG are similar to the Matrix
Spike sample, and that only these samples should be qualified; or 2) no samples are
sufficiently similar to the sample used for the Matrix Spike, and thus only the field
sample used to prepare the Matrix Spike sample should be qualified.
1. If the appropriate number of Matrix Spike samples was not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified; obtain additional information from the laboratory, if necessary. Record the situation in
the Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ) if any of the frequency criteria is not
met.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for Regional
Laboratory COR action. All of the other QC data must then be carefully checked. Use
professional judgment when evaluating the data. Detects should be qualified as estimated (J) and
non-detects qualified as estimated (UJ).
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-digestion
spike was not performed, note this for Regional Laboratory COR action.
4. If the Matrix Spike %R is < 30%, verify that a post-digestion spike was analyzed. If the post-
digestion spike %R is < 75% or the analysis was not performed, qualify detects as estimated low
(J-), and qualify non-detects as unusable (R). If the post-digestion spike %R is > 75%, qualify
detects as estimated (J) and qualify non-detects as estimated (UJ).
5. If the Matrix Spike %R falls within the range of 30-74%, verify that a post-digestion spike was
analyzed (if required when sample concentration is < 4x spike added). If the post-digestion spike
%R < 75% or the analysis was not performed, qualify detects as estimated low (J-) and non-
detects as estimated (UJ). If the post-digestion spike %R> 75%, qualify detects as estimated (J)
and non-detects as estimated (UJ).
6. If the Matrix Spike %R falls within the range of 75-125%, no post-digestion spike is required.
Detects and non-detects should not be qualified.
7. If the Matrix Spike %R is > 125%, verify that a post-digestion spike was analyzed (if required
when sample concentration is < 4x spike added). If the post-digestion spike %R > 125% or the
analysis was not performed, qualify detects as estimated high (J+); non-detects should not be
qualified. If the post-digestion spike %R< 125%, qualify detects as estimated (J); non-detects
should not be qualified.
8. Annotate the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.
August 2014 34
-------
Inorganic Data Review
ICP-AES
Table 9. Spike Sample Actions for ICP-AES Analysis
Criteria
Matrix Spike %R < 30%
Post-digestion spike %R < 75%
Matrix Spike %R < 30%
Post-digestion spike %R> 75%
Matrix Spike %R 30-74%
Post-digestion Spike %R < 75%
Matrix Spike %R 30-74%
Post-digestion spike %R> 75%
Matrix Spike %R> 125%
Post-digestion spike %R> 125%
Matrix Spike %R> 125%
Post-digestion spike %R< 125%
Matrix Spike %R < 30%
No post-digestion spike performed
(e.g., not required for Ag)
Matrix Spike %R 30-74%
No post-digestion spike performed
(e.g., not required for Ag)
Matrix Spike %R 75-125%
Post-digestion spike not required
Matrix Spike %R> 125%
No post-digestion spike performed
(e.g., not required for Ag)
Action
Detect
J-
J
J-
J
J+
J
J-
J-
No qualification
J+
Non- detect
R
UJ
UJ
UJ
No qualification
No qualification
R
UJ
No qualification
No qualification
NOTE: The above control limits are method requirements for spike samples, regardless of the
sample matrix type. However, it should be noted that laboratory variability arising from
the sub-sampling of non-homogenous soil samples is a common occurrence. Therefore,
for technical review purposes only, Regional policy or project DQOs may allow the use
of less restrictive criteria (e.g., 10 %R and 150 %R for the lower and upper limits) to be
assessed against spike and post-digestion spike soil samples.
August 2014
35
-------
Inorganic Data Review ICP-AES
VIII. Serial Dilution
A. Review Items
Form 1-IN, Form 8 -IN, instrument printouts, and raw data.
B. Objective
The objective of the serial dilution analysis is to determine whether or not significant physical or
chemical interferences exist due to sample matrix.
C. Criteria
1 . An ICP Serial Dilution analysis shall be performed on a sample from each group of samples with
a similar matrix type (e.g., water, soil or wipe) or for each SDG, whichever is more frequent.
2. Samples identified as field blanks or PE samples cannot be used for the ICP Serial Dilution
analysis.
3. If the analyte concentration is sufficiently high (concentration in the original sample is > 5 Ox the
MDL), the %D between the original determination and the serial dilution analysis (a five-fold
dilution) after correction for dilution (concentration in the serial dilution sample is > CRQL) shall
be < 10%.
NOTE: The above criteria are method requirements for serial dilution samples, regardless of the
sample matrix type. However, for technical review purposes only, Regional policy or
project DQOs may allow the use of less restrictive criteria (e.g., %D > 15%) to be
assessed against serial dilution soil samples.
D. Evaluation
1 . Verify that a field blank or PE sample was not used for the serial dilution analysis.
2. Check the raw data and recalculate the %D using the following equation. Verify that the serial
dilution analysis results and the calculated %D results agree with the values reported by the
laboratory on Form 8 -IN:
%Difference = - - - x 100
Where,
I = Initial Sample Result
S = Serial Dilution Result
3. Check the raw data for any evidence of positive or negative interference (results from the diluted
sample which are significantly different than the original sample), possibly due to high levels of
dissolved solids in the sample, ionization effects, etc.
E. Action
NOTE: For a serial dilution that does not meet the technical criteria, apply the action to all
samples of the same matrix if the samples are considered sufficiently similar. Exercise
professional judgment in determining sample similarity when making use of all available
data, including: site and sampling documentation (e.g., location and type of sample,
descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity, chlorine);
and laboratory data for other parameters (e.g., TSS, TDS, TOC, alkalinity or buffering
capacity, reactive sulfide, anions). Additionally, use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. Two
determinations are: 1) only some of the samples in the SDG are similar to the serial
dilution sample, and that only these samples should be qualified; or, 2) no samples are
sufficiently similar to the sample used for serial dilution, and thus only the field sample
used to prepare the serial dilution sample should be qualified.
August 2014 36
-------
Inorganic Data Review
ICP-AES
1. If the appropriate number of serial dilution samples was not analyzed for each matrix, use
professional judgment to determine if the associated sample data should be qualified; obtain
additional information from the laboratory, if necessary. If a field blank or PE sample was used
for the serial dilution analysis, record the situation in the Data Review Narrative, and note it for
Regional Laboratory COR action. Detects should be qualified as estimated (J) and non-detects as
estimated (UJ).
2. If the analyte concentration in the original sample is > 5 Ox the MDL, its concentration in the
serial dilution sample is > CRQL, and the %D > 10%, qualify detects as estimated (J) and non-
detects as estimated (UJ).
3. If the analyte concentration in the original sample is > 5 Ox the MDL, its concentration in the
serial dilution sample is > CRQL, and the %D is < 10%, detects and non-detects should not be
qualified.
4. If the analyte concentration in the original sample is > 5 Ox the MDL, its concentration in the
serial dilution sample is > CRQL, and %D is > 100%, use professional judgment to determine if
the associated sample data should be qualified.
5. If the analyte concentration in the original sample is > 5x the CRQL and its concentration in the
serial dilution sample is < CRQL, detects and non-detects should not be qualified.
6. If evidence of positive or negative interference is found, use professional judgment to qualify the
associated sample data. Annotate the potential effects on the reported data in the Data Review
Narrative.
Table 10. Serial Dilution Actions for ICP-AES Analysis
Criteria
Sample concentration
> 5 Ox MDL, serial dilution sample concentration >
CRQL, and %D > 10%*
Sample concentration
> 5 Ox MDL, serial dilution sample concentration >
CRQL, and %D < 10%
Sample concentration
> 5 Ox MDL, serial dilution sample concentration >
CRQL, and %D is > 100%
Sample concentration > 5x CRQL and serial dilution
sample concentration < CRQL
Interferences present
Action
Detect
J
No qualification
Use professional
judgment
No qualification
Use professional
judgment
Non- detect
UJ
No qualification
Use professional
judgment
No qualification
Use professional
judgment
The above criteria are method requirements for serial dilution samples, regardless of the sample
matrix type. However, for technical review purposes only, Regional policy or project DQOs
may allow the use of less restrictive criteria (e.g., %D > 15%) to be assessed against serial
dilution soil samples.
August 2014
37
-------
Inorganic Data Review ICP-AES
IX. Regional Quality Assurance and Quality Control
A. Review Items
Form 1-IN, instrument printouts, and raw data.
B. Objective
The objective is to use results from the analysis of Regional QA/QC samples such as field blanks, PE
samples, blind spikes, and blind blanks to determine the validity of the analytical results.
C. Criteria
Criteria are determined by each Region.
D. Evaluation
Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
review. Each Region will handle the evaluation of PE samples on an individual basis. Compare
results for PE samples to the acceptance criteria for the specific PE samples if possible.
Calculate the RPD between field duplicates and provide this information in the Data Review
Narrative.
E. Action
Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
results. Note any unacceptable PE sample results for Regional Laboratory COR action.
August 2014 38
-------
Inorganic Data Review ICP-AES
X. Overall Assessment of Data
A. Review Items
Entire sample data package, data review results, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data (including any confirmation data).
B. Objective
The objective is to provide the overall assessment on data quality and usability.
C. Criteria
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
2. Reported analyte concentrations must be quantitated according to the appropriate analytical
method, as listed in the method. All sample results must be within the linear calibration ranges
per methods. Percent Solids (%Solids) must be properly used for all applicable matrix result
calculations.
D. Evaluation
Examine the raw data to verify that correct calculations of the sample results were reported by the
laboratory. Digestion logs, instrument printouts, etc., should be compared to the reported sample
results recorded on the appropriate Inorganic Summary Forms (Form 1-IN through Form 16-IN).
1. Evaluate any technical problems not previously addressed.
2. Examine the raw data for any anomalies (e.g., baseline shifts, negative absorbance, omissions,
illegibility, etc.).
3. Verify that appropriate methods and amounts were used in preparing the samples for analysis. If
reduced volumes were used, verify that the laboratory had received Regional Laboratory COR
approval for the use of the reduced volume.
4. Verify that there are no transcription or reduction errors (e.g., dilutions, %Solids, sample weights,
etc.) on one or more samples. Recalculate %Solids for at least 10% of the samples and verify that
the calculated %Solids agree with that reported by the laboratory.
5. Verify that MDLs are properly reported and that they are not greater than the respective CRQLs.
6. Verify that results fall within the calibrated range(s) of the ICP instrument(s) (Form 15-IN).
7. If appropriate information is available, assess the usability of the data to assist the data user in
avoiding inappropriate use of the data. Review all available information, including the Quality
Assurance Project Plan (QAPP), focusing specifically on the acceptance or performance criteria,
the SOPs, and communication with the user concerning the intended use and desired quality of
these data.
E. Action
1. Use professional judgment to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
2. Use professional judgment to qualify detects and non-detects if the MDL exceeds CRQL.
3. If a sample is not diluted properly when sample results exceed the upper limit of the calibration
range, qualify detects as estimated (J).
4. Write a brief Data Review Narrative to give the user an indication of the analytical limitations of
the data. Annotate any discrepancies between the data and the SDG Narrative for Regional
Laboratory COR action. If sufficient information on the intended use and required quality of the
data is available, include an assessment of the data usability within the given context.
August 2014 39
-------
Inorganic Data Review ICP-AES
5. If any discrepancies are found, notify the Regional Laboratory COR. The Regional Laboratory
COR may contact the laboratory to obtain additional information for resolution. If a discrepancy
remains unresolved, use professional judgment to determine if qualification of the data is
warranted.
August 2014 40
-------
Inorganic Data Review ICP-AES
XI. Calculations
Aqueous/Water Samples:
The concentrations determined in the digestate are to be reported in units of (ig/L:
Vf
Concentration (ug/L) = C x x DF
Where,
C = Instrument value in |o,g/L (the average of all replicate exposures)
Vf = Final digestion volume (mL)
V = Initial aliquot amount (mL)
DF = Dilution Factor
Soil/Sediment Samples:
The concentrations determined in the digestate are to be reported on the basis of the dry weight of the
sample, in units of mg/kg:
Vf
Concentration (mg/kg dry weight) = C x - x DF/1000
Where,
C - Instrument value in |o,g/L (the average of all replicate exposures)
Vf = Final digestion volume (mL)
W = Initial aliquot amount (g)
S = %Solids/100 (see Exhibit D - General Inorganic Analysis, Section 10.1.4)
DF = Dilution Factor
Wipe Mass:
Mass (ug) = C x Vf x DF/1000
Where,
C = Instrument value in |o,g/L (The average of all replicate exposures)
Vf = Final digestion volume (mL)
DF = Dilution Factor
Adjusted MDL/Adjusted CRQL Calculation:
To calculate the adjusted MDL or adjusted CRQL for aqueous/water samples, substitute the value of
the MDL ((ig/L) or CRQL ((ig/L) into the "C" term in the equation above.
Calculate the adjusted MDL or adjusted CRQL for soil/sediment samples as follows:
WM Vf
Adjusted MDL or CRQL (mg/kg) = C x ^- x 1 x DF
W x S VM
Where,
C = MDL or CRQL (mg/kg)
WM = Minimum method required aliquot amount (g) (1.00 g or 0.50 g)
W = Initial aliquot amount (g)
VM = Method required final sample digestion volume (mL) (100 mL or 50 mL)
Vf = Final digestion volume (mL)
S = % Solids/100 (see Exhibit D - General Inorganic Analysis, Section 10.1.4)
DF = Dilution Factor
August 2014 41
-------
Inorganic Data Review ICP-AES
Hardness (Total) in Aqueous/Water Samples:
Total Hardness is defined as the sum of calcium and magnesium concentration, expressed as calcium
carbonate in mg/L.
Calculate Total Hardness for Aqueous/Water samples as follows:
Hardness (mg/L) = [Cone. Ca (mg/L) x 2.497] + [Cone. Mg (mg/L) x 4.118]
Where,
Cone. Ca (mg/L) = Calcium concentration ((ig/L) / 1000
Cone. Mg (mg/L) = Magnesium concentration ((ig/L) / 1000
August 2014 42
-------
Inorganic Data Review ICP-MS
ICP-MS DATA REVIEW
The inorganic data requirements for Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) to be
reviewed during validation are listed below:
Example Analytical Sequence 45
I. Preservation and Holding Times 47
II. Tune Analysis 49
III. Calibration 51
IV. Blanks 54
V. Interference Check Sample 58
VI. Laboratory Control Sample 61
VII. Duplicate Sample Analysis 63
VIII. Spike Sample Analysis 66
IX. Serial Dilution 69
X. Internal Standards 71
XI. Regional Quality Assurance and Quality Control 73
XII. Overall Assessment of Data 74
XIII. Calculations 76
August 2014 43
-------
Inorganic Data Review ICP-MS
This page is intentionally left blank.
August 2014 44
-------
Inorganic Data Review ICP-MS
Example Analytical Sequence
The following is an example of an analytical sequence:
Tune
S##
S##
s##
s##
s##
s##
ICV
ICB
ICSA
ICSAB
ccv###
CCB ###
samples
ccv###
CCB###
samples
ccv###
CCB###, etc.
* Suffix ## and ### are as specified in Exhibit B of the Statement of Work (SOW).
August 2014 45
-------
Inorganic Data Review ICP-MS
This page is intentionally left blank.
August 2014 46
-------
Inorganic Data Review ICP-MS
I. Preservation and Holding Times
A. Review Items
Form 1-IN, Form 12-IN, Traffic Report/Chain of Custody (TR/COC) documentation, Form DC-1,
raw data, and the Sample Delivery Group (SDG) Narrative checking for: pH; shipping container
temperature; holding time; and other sample conditions.
B. Objective
The objective is to determine the validity of the analytical results based on sample conditions and the
technical holding time of the sample.
C. Criteria
1. The technical holding time is determined from the date of collection to the date of analysis.
2. The technical holding time criteria for aqueous/water samples is 180 days, preserved (with nitric
acid) to pH < 2. The addition of nitric acid to adjust the pH is only required for aqueous/water
samples.
3. The technical holding time criteria for soil/sediment samples is 180 days, based on the technical
holding time criteria for aqueous/water samples.
4. Soil/sediment samples shall be maintained at < 6°C (but not frozen) from the time of collection
until receipt at the laboratory. All aqueous/water and soil/sediment samples must be stored at
< 6°C (but not frozen) from the time of sample receipt until digestion.
D. Evaluation
Establish technical holding times by comparing the sampling date(s) on the TR/COC documentation
with the dates of analysis on Form 12-IN and the raw data; also consider using information in the
Complete SDG File (CSF), as it may be helpful in the assessment. Verify that the analysis dates on
the Form 12-IN and the raw data are identical. Review the SDG Narrative and raw data preparation
logs to determine if samples were properly preserved. If there is an indication of problems with the
samples, the sample integrity may be compromised. Use professional judgment to evaluate the effect
of the problem on the sample results.
E. Action
NOTE: Apply the action to each field sample for which the preservation or holding time criteria
was not met.
1. If the pH of aqueous/water metals samples is > 2 at the time of sample receipt, determine if the
laboratory adjusted the pH to < 2 at the time of sample receipt. If not, use professional judgment
to qualify the samples based on the pH of the sample and the chemistry of the metal(s) of interest.
Detects should be qualified as estimated low (J-) and non-detects as unusable (R).
2. If soil/sediment samples are not maintained at < 6°C (but not frozen) from the time of collection
until receipt at the laboratory, detects should be qualified as estimated low (J-) and non-detects as
unusable (R).
3. If technical holding times are exceeded, use professional judgment to determine the reliability of
the data based on the magnitude of the additional time compared to the technical requirement and
whether the samples were properly preserved. The expected bias would be low. Detects should
be qualified as estimated low (J-) and non-detects as unusable (R).
4. Due to limited information concerning holding times for soil/sediment samples, use discretion
when deciding whether to apply the aqueous/water holding time criteria to soil/sediment samples.
If they are applied, annotate this in the Data Review Narrative.
August 2014 47
-------
Inorganic Data Review
ICP-MS
5. If samples are received with shipping container temperatures > 10°C, use professional judgment
to determine the reliability of the data, or qualify detects as estimated (J) and non-detects as
estimated (UJ).
6. When the holding times are exceeded, annotate any possible consequences for the analytical
results in the Data Review Narrative, and note it for Regional Laboratory Contracting Officer
Representative (COR) action.
Table 11. Preservation and Holding Time Actions for ICP-MS Analysis
Criteria
Aqueous/water samples received with pH > 2 and pH not
adjusted
Soil/sediment samples not maintained at < 6°C (but not
frozen) from time of collection until receipt at laboratory
Technical Holding Time:
Aqueous/water samples > 180 days
Technical Holding Time:
Soil/sediment samples > 180 days
Samples received > 10°C*
Action
Detect
Use professional
judgment
J-
Use professional
judgment
J-
J-
J-
Use professional
judgment
J
Non-detect
Use professional
judgment
R
Use professional
judgment
R
R
R
Use professional
judgment
UJ
For samples received with shipping container temperatures > 10°C, Regional policy or project
Data Quality Objectives (DQO) may allow the use of higher temperature criteria before assessing
any actions for the affected samples.
August 2014
48
-------
Inorganic Data Review ICP-MS
II. Tune Analysis
A. Review Items
Form 13-IN, instrument printouts, and raw data.
B. Objective
The ICP-MS tune serves as an initial demonstration of instrument stability and precision.
C. Criteria
1. Prior to calibration, the laboratory shall analyze or scan the ICP-MS tuning solution, containing
100 (ig/L of Beryllium (Be), Magnesium (Mg), Cobalt (Co), Indium (In), and Lead (Pb), at least
5x consecutively. The solution shall contain all required isotopes of these elements. The
laboratory shall make any adjustments necessary to bring peak width within the instrument
manufacturer's specifications and adjust the resolution of the mass calibration to within 0.1 (i
over the range of 6-210 (i.
2. The Percent Relative Standard Deviation (%RSD) of the absolute signals for all analytes in the
tuning solution must be < 5%.
D. Evaluation
1. Verify, using the raw data and Form 13-IN, that the appropriate number of analyses or scans of
the ICP-MS tuning solution were performed, and that the appropriate analytes were present in the
solution.
2. Verify, using the raw data and Form 13-IN, that the resolution of the mass calibration falls within
the limits for each isotope of each analyte.
3. Verify, using the raw data and Form 13-IN, that the %RSD is < 5% for each isotope of each
analyte.
4. Verify, using the raw data, that the reported average mass and %RSD on Form 13-IN was
accurately calculated. Recalculate one or more of the average masses and %RSDs for an isotope
using the following equations:
Ix
Mean =
n
Where,
= Mass from analysis
= Number of analyses
n.
Percent Relative Standard Deviation =
x
Where,
x = Mean
on_i = Standard Deviation
E. Action
NOTE: For ICP-MS tunes that do not meet the technical criteria, apply the action to all samples
reported from the analytical sequence.
1. If the ICP-MS instrument was not tuned prior to calibration, all sample data should be qualified
as unusable (R).
August 2014 49
-------
Inorganic Data Review
ICP-MS
2. If the tuning solution was not analyzed or scanned at least 5x consecutively, or the tuning solution
does not contain the required analytes spanning the analytical range, use professional judgment to
determine if the associated sample data should be qualified; obtain additional information from
the laboratory, if necessary. Record the situation in the Data Review Narrative, and note it for
Regional Laboratory COR action.
3. If the resolution of the mass calibration is not within 0.1 u for any isotope in the tuning solution,
qualify the associated analytes that are detects as estimated (J) and non-detects as estimated (UJ).
Record the situation in the Data Review Narrative, and note it for Regional Laboratory COR
action.
4. If the %RSD > 5% for any isotope in the tuning solution, qualify detects as estimated (J) and non-
detects as estimated (UJ). Record the situation in the Data Review Narrative, and note it for
Regional Laboratory COR action.
Table 12. ICP-MS Tune Actions for ICP-MS Analysis
Criteria
Tune not performed
Tune not performed properly (Section II.E.2)
Resolution of mass calibration not within 0.1 u
%RSD > 5%
Action
Detect
R
Use professional
judgment
J
J
Non- detect
R
Use professional
judgment
UJ
UJ
August 2014
50
-------
Inorganic Data Review ICP-MS
III. Calibration
A. Review Items
Form 2-IN, Form 12-IN, Form 15-IN, Form 16-IN, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data.
B. Objective
The objective is to determine the validity of the analytical results based on initial calibration and
calibration verification.
C. Criteria
1. Initial Calibration
The instruments shall be successfully calibrated each time the instrument is set up and after
Continuing Calibration Verification (CCV) failure. The calibration date and time shall be
included in the raw data.
a. A blank and at least five calibration standards shall be used to establish each calibration
curve. At least one standard shall be at or below the Contract Required Quantitation Limit
(CRQL), but above the Method Detection Limit (MDL). All measurements shall be within
the instrument working range. A minimum of three replicate scans are required for
standardization for all Quality Control (QC) and sample analyses. The average result of all
the multiple scans for the standardization, QC, and sample analyses shall be used. The
calibration curve shall be fitted using linear regression or weighted linear regression. The
curve may be forced through zero. The curve must have a correlation coefficient of > 0.995.
The calculated percent differences (%Ds) for all of the non-zero standards must be within
±30% of the true value of the standard. The y-intercept of the curve must be less than the
CRQL.
2. Initial and Continuing Calibration Verification
The acceptance criteria for the Initial Calibration Verification (ICV) and CCV standards are
presented in Table 13:
Table 13. Acceptance Criteria for ICV and CCV Standards for ICP-MS Analysis
Analytical Method
ICP-MS
Inorganic Analytes
Metals
ICV/CCV Low Limit
(% of True Value)
90
ICV/CCV High Limit
(% of True Value)
110
a. Initial Calibration Verification
1) Immediately after each system has been calibrated, the accuracy of the initial calibration
must be verified and documented for each target analyte by the analysis of an ICV
solution(s). If the ICV Percent Recovery (%R) falls outside of the control limits, the
analysis should be terminated, the problem corrected, the instrument recalibrated, and all
affected samples reanalyzed.
2) Only if the ICV is not available from the United States Environmental Protection Agency
(EPA), analyses shall be conducted using a certified solution of the analytes from an
independent commercial standard source, at a concentration level other than that used for
instrument calibration, but within the calibrated range.
3) The ICV solution shall be analyzed at each analytical mass used for analysis.
August 2014 51
-------
Inorganic Data Review ICP-MS
b. Continuing Calibration Verification
1) To ensure accuracy during the course of each analytical sequence, the CCV shall be
analyzed and reported for each mass used for the analysis of each analyte.
2) The CCV standard shall be analyzed at a frequency of every two hours during an
analytical sequence. The CCV standard shall also be analyzed at the beginning of the
analytical sequence, and again after the last analytical sample.
3) The analyte concentration(s) in the CCV standard(s) shall be different than the
concentration used for the ICV, and at a concentration equivalent to the mid-level of their
respective calibration curves.
4) The same CCV standard solution shall be used throughout the analysis for an SDG.
5) The CCV shall be analyzed in the same fashion as an actual sample. If the %R of the
CCV was outside of the control limits, the analysis should be terminated, the problem
corrected, the instrument recalibrated, and all analytical samples analyzed since the last
compliant CCV reanalyzed.
D. Evaluation
1. Verify that the instrument was calibrated each time the instrument was set up, utilizing a blank
and at least five calibration standards, one of which was at or below the CRQL, but above the
MDL.
2. Confirm that the measurements were within the working calibration range, and were the average
result of at least three replicate exposures.
3. Verify that the ICV and CCV standards were analyzed for each analyte at the specified frequency
and at the appropriate concentration. Verify that acceptable %R results were obtained.
4. Recalculate one or more of the ICV and CCV %Rs using the following equation and verify that
the recalculated value agrees with the laboratory-reported values on Form 2-IN.
Found (value)
%R=-TT^XIO°
I rue (value)
Where,
j / i x Concentration (in ug/L) of each analyte measured in the analysis of the ICV or
Found (value) = ,, i *
v ' CCV solution
True (value) = Concentration (in (ig/L) of each analyte in the ICV or CCV source
E. Action
NOTE: For initial calibrations or ICV standards that do not meet the technical criteria, apply the
action to all associated samples reported from the analytical sequence.
For CCV standards that do not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the QC sample and a
subsequent technically acceptable analysis of the QC sample in the analytical sequence.
1. If the instrument was not calibrated each time the instrument was set up, qualify detects and non-
detects as unusable (R). If the instrument was not calibrated with at least the minimum number of
standards, or if the calibration curve does not include standards at required concentrations (e.g., a
blank and at least one at or below CRQL but above MDL), use professional judgment to qualify
detects as estimated (J) or unusable (R), and non-detects as estimated (UJ) or unusable (R).
2. If the correlation coefficient is < 0.995, the %Ds are outside the ±30% limit, or the y-intercept >
CRQL, qualify detects as estimated (J), and non-detects as estimated (UJ).
August 2014 52
-------
Inorganic Data Review
ICP-MS
3. If the ICV or CCV %R falls outside the acceptance windows, use professional judgment to
qualify all associated data. If possible, indicate the bias in the review. The following guidelines
are recommended:
a. If the ICV or CCV %R is < 75%, use professional judgment to qualify detects as estimated
low (J-) or unusable (R), and non-detects as unusable (R).
b. If the ICV or CCV %R falls within the range of 75-89%, qualify detects as estimated low (J-)
and non-detects as estimated (UJ).
c. If the ICV or CCV %R falls within the range of 90-110%, detects and non-detects should not
be qualified.
d. If the ICV or CCV %R falls within the range of 111-125%, qualify detects as estimated high
(J+). Non-detects should not be qualified.
e. If the ICV or CCV %R is > 125%, use professional judgment to qualify detects as estimated
high (J+) or unusable (R). Non-detects should not be qualified.
4. If the laboratory failed to provide adequate calibration information, notify the Regional
Laboratory COR. The Regional Laboratory COR may contact the laboratory and request the
necessary information. If the information is unavailable, use professional judgment to assess the
data.
5. Annotate the potential effects on the reported data due to exceeding the calibration criteria in the
Data Review Narrative.
6. If calibration criteria are grossly exceeded, note this for Regional Laboratory COR action.
NOTE: For truly critical samples, a further in-depth evaluation of the calibration curve may be
warranted to determine if additional qualification is necessary.
Table 14. Calibration Actions for ICP-MS Analysis
Criteria
Calibration not performed
Calibration incomplete
Correlation coefficient < 0.995; %D
outside ±30%; y-intercept > CRQL
ICV/CCV%R<75%
ICV/CCV %R 75-89%
ICV/CCV%R90-110%
ICV/CCV %R 1 1 1-125%
ICV/CCV %R> 125%
Action
Detect
R
Use professional judgment
JorR
J
Use professional judgment
J-orR
J
No qualification
J+
Use professional judgment
J+orR
Non-detect
R
Use professional judgment
UJorR
UJ
R
UJ
No qualification
No qualification
No qualification
August 2014
53
-------
Inorganic Data Review ICP-MS
IV. Blanks
A. Review Items
Form 1-IN, Form 3-IN, Form 12-IN, preparation logs, calibration standard logs, instrument logs, and
raw data.
B. Objective
The objective is to determine the validity of the analytical results based on the blank responses by
determining the existence and magnitude of contamination resulting from laboratory (or field)
activities or baseline drift during analysis.
C. Criteria
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed at each mass used for analysis after the
analytical standards, but not before analysis of the ICV during the initial calibration of the
instrument (see Section III.C.I).
3. A Continuing Calibration Blank (CCB) shall be analyzed at each mass used for the analysis,
immediately after every CCV. The CCB shall be analyzed at a frequency of every two hours
during the analytical sequence. The CCB shall be analyzed at the beginning of the analytical
sequence, and again after the last CCV that was analyzed after the last analytical sample of the
analytical sequence. The CCB result (absolute value) shall not exceed the CRQL of each analyte
for which analysis is performed.
4. At least one Preparation Blank shall be prepared and analyzed for each matrix, with every SDG,
or with each batch of samples digested, whichever is more frequent. The Preparation Blank
consists of reagent water processed through the appropriate sample preparation and analysis
procedure.
5. If the concentration of any analyte in the Preparation Blank is > CRQL, the lowest concentration
of that analyte in the associated samples must be > lOx the Preparation Blank concentration.
Otherwise, all associated samples with the analyte's concentration < lOxthe Preparation Blank
concentration, and > CRQL, should be redigested and reanalyzed for that analyte. The laboratory
is not to correct the sample concentration for the blank value.
6. If the concentration of any analyte in the Preparation Blank is < (-CRQL), all associated samples
with the analyte's concentration < lOx the CRQL should be redigested and reanalyzed.
D. Evaluation
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the specified
frequency and sequence during the analytical sequence, and Preparation Blanks were prepared
and analyzed as appropriate for the SDG (e.g., total number of samples, various types of matrices
present, number of digestion batches, etc.).
2. Review the results reported on Form 3-IN, as well as the raw data for all blanks, and verify that
the results were accurately reported.
3. Evaluate all of the associated blanks for the presence of target analytes. Verify that if the
concentration of any target analyte was > CRQL in a Preparation Blank, all associated samples
with analyte concentration > CRQL but < lOx the Preparation Blank concentration were
redigested and reanalyzed for the analytes. Verify that if a concentration was < (-CRQL) in a
Preparation Blank, all associated samples with the analyte's concentration < lOx CRQL were
redigested and reanalyzed. Verify that if the absolute value of any target analytes was > CRQL in
an ICB or a CCB, the analysis was terminated, the problem corrected, the instrument recalibrated,
and the preceding 10 analytical samples or all analytical samples analyzed since the last
compliant calibration blank reanalyzed.
August 2014 54
-------
Inorganic Data Review ICP-MS
E. Action
NOTES: For ICBs that do not meet the technical criteria, apply the action to all associated samples
reported from the analytical sequence.
For CCBs that do not meet the technical criteria, apply the action to all associated
samples analyzed between a previous technically acceptable analysis of the CCB and a
subsequent technically acceptable analysis of the CCB in the analytical sequence.
For Preparation Blanks that do not meet the technical criteria, apply the action to all
associated samples prepared in the same preparation batch.
1. If the appropriate blanks were not analyzed with the correct frequency, use professional judgment
to determine if the associated sample data should be qualified; obtain additional information from
the laboratory, if necessary. Record the situation in the Data Review Narrative, and note it for
Regional Laboratory COR action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
In instances where more than one blank is associated with a given sample, qualification should be
based upon a comparison with the associated blank having the highest concentration of
contaminant.
3. Some general "technical" review actions include:
a. For any blank (including Preparation Blanks) reported with detects < CRQLs, report detects <
CRQLs at the CRQLs and qualify as non-detect (U). For any blank (including Preparation
Blanks) reported with detects < CRQLs, use professional judgment to qualify the sample
results > CRQL. Non-detects should not be qualified.
b. For any blank (including Preparation Blanks) reported with a negative result < (-MDL) but >
(-CRQL), carefully evaluate and determine its effect on the sample data. Use professional
judgment to assess the data.
c. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil/sediment sample results reported on Form 1-IN will
not be on the same basis (units, dilution) as the calibration blank data reported on Form 3-IN.
It may be easier to work with the raw data and/or convert the ICB or CCB results to the same
units as the soil/sediment samples for comparison purposes.
4. Specific "method" actions include:
a. If an ICB or a CCB result is > CRQL, the analysis should be terminated. If the analysis was
not terminated and the associated samples were not reanalyzed, non-detects should not be
qualified. Report detects < CRQLs at CRQLs and qualify as non-detect (U). Report sample
results that are > CRQLs but < ICB/CCB Results at ICB/CCB Results and use professional
judgment to qualify as non-detect (U) or unusable (R). Use professional judgment to qualify
sample results > ICB/CCB Results. Record the situation in the Data Review Narrative, and
note it for Regional Laboratory COR action.
b. If an ICB or a CCB result is < (-CRQL), the analysis should be terminated. If the analysis
was not terminated and the associated samples were not reanalyzed, use professional
judgment to qualify non-detects as estimated (UJ) or unusable (R). Use professional
judgment to qualify detects < CRQL, or qualify as estimated low (J-). Use professional
judgment to qualify sample results that are > CRQLs as estimated low (J-).
c. If the concentration of any analyte in the Preparation Blank is > CRQL, the lowest
concentration of that analyte in the associated samples must be > lOx the Preparation Blank
concentration. All samples associated with the Preparation Blank with concentrations < lOx
the Preparation Blank concentration and > CRQL should have been redigested and
reanalyzed. If the associated samples were not redigested and reanalyzed, report the sample
results at Preparation Blank Results; use professional judgment to qualify the results as
August 2014 55
-------
Inorganic Data Review
ICP-MS
estimated high (J+) or unusable (R). Report detects < CRQLs in the samples associated with
the Preparation Blank at CRQLs and qualify as non-detect (U). Non-detects and sample
results that are > lOx the Preparation Blank Results should not be qualified. If the laboratory
failed to redigest and reanalyze the samples associated with the Preparation Blank, record it
in the Data Review Narrative, and note it for Regional Laboratory COR action.
d. For any Preparation Blank reported with a negative result < (-CRQL), use professional
judgment to qualify detects < CRQLs or qualify as estimated low (J-). Qualify sample results
that are > CRQLs as estimated low (J-), and qualify non-detects as estimated (UJ). Sample
results that are > lOx CRQLs should not be qualified.
Table 15. Blank Actions for ICP-MS Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
Preparation
Blank
Preparation
Blank
Blank Result
Detect < CRQL
< (-MDL) but
> (-CRQL)
>CRQL
< (-CRQL)
Detect < CRQL
< (-MDL) but
> (-CRQL)
Sample Result
Non-detect
Detect < CRQL
>CRQL
Detect or non-detect
Non-detect
Detect < CRQL
> CRQL but < ICB/CCB
Result
> ICB/CCB Result
Non-detect
Detect < CRQL
>CRQL
Non-detect
Detect < CRQL
>CRQL
Detect or non-detect
Action
No qualification
Report at CRQL and qualify as non-
detect (U)
Use professional judgment
Use professional judgment
No qualification
Report at CRQL and qualify as non-
detect (U)
Report at ICB/CCB Result and
qualify as non-detect (U) or unusable
(R)
Use professional judgment
Use professional judgment to qualify
as estimated (UJ) or unusable (R)
Use professional judgment or (J-)
Use professional judgment to qualify
as estimated low (J-)
No qualification
Report at CRQL and qualify as non-
detect (U)
Use professional judgment
Use professional judgment
August 2014
56
-------
Inorganic Data Review
ICP-MS
Blank
Type
Preparation
Blank
Preparation
Blank
Blank Result
>CRQL
< (-CRQL)
Sample Result
Non-detect
Detect < CRQL
> CRQL but
< 1 Ox the Preparation Blank
Result
> 1 Ox the Preparation Blank
Result
Non-detect
Detect < CRQL
< lOx CRQL
> lOx CRQL
Action
No qualification
Report at CRQL and qualify as non-
detect (U)
Report at Preparation Blank Result
and use professional judgment to
qualify results as estimated high (J+)
or unusable (R)
No qualification
Qualify as estimated (UJ)
Use professional judgment or (J-)
Report results > CRQL as estimated
low (J-)
No qualification
August 2014
57
-------
Inorganic Data Review ICP-MS
V. Interference Check Sample
A. Review Items
Form 4-IN, Form 12-IN, instrument printouts, and raw data.
B. Objective
The objective is to determine the validity of the analytical results based on the instrument's ability to
overcome interferences typical of those found in samples.
C. Criteria
1. The Interference Check Sample (ICS) consists 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 of analyzing both solutions consecutively, starting with
Solution A, for all masses used for each analyte or interferent reported by ICP-MS.
2. An ICS must be analyzed undiluted at the beginning of each analysis sequence. The ICS is not to
be analyzed prior to the ICV, and shall be immediately followed by a CCV, followed by a CCB.
3. Results for the analysis of the ICS Solution A must fall within the control limits of ± 2x the
CRQL or ± 20% of the true value (whichever is greater) for the analytes and interferents included
in the solution.
4. Results for the analysis of the ICS Solution AB must fall within the control limits of ± 2x the
CRQL or ± 20% of the true value (whichever is greater) for the analytes and interferents included
in the solution.
5. If the value of an ICS result exceeds ± 2x the CRQL, or ± 20% of true value (whichever is
greater) criteria, the analysis shall be terminated, the problem corrected, the instrument
recalibrated, the new calibration then reverified, and all analytical samples analyzed since the last
compliant ICS reanalyzed.
6. The ICS should be obtained from the EPA, if available, and analyzed according to the
instructions supplied with the solutions. If the ICS is not available from the EPA, an independent
ICS solution shall be prepared using certified standards with the interferent and analyte
concentrations at the levels specified in the method.
D. Evaluation
1. Verify, using Form 12-IN and the raw data, that the ICS was analyzed at the specified frequency
and sequence during the analytical sequence.
2. Evaluate the ICS raw data for results with an absolute value that is > MDL for those analytes that
are not present in the ICS solution.
3. Recalculate, using the raw data and the following equation, one or more of the analyte %Rs, and
verify that the recalculated value agrees with the laboratory-reported values on Form 4-IN.
Found (value)
%R= / , / x 100
True (value)
Where,
, , , ^ Concentration (in ug/L) of each analyte interferent measured in the analysis
Found (value) = ,,Tr,c c , .. . T/c c , . AV>
of ICS Solution A or ICS Solution AB
, , , _ Concentration (in (ig/L) of each analyte or interferent in ICS Solution A or
1 rue (value) - ICS Solutlon AB
August 2014 58
-------
Inorganic Data Review ICP-MS
4. If the value of an ICS result exceeds ± 2x the CRQL, or ± 20% of true value (whichever is
greater) criteria, and the laboratory failed to terminate the analysis and take the appropriate
corrective action, note this for Regional Laboratory COR action and record the situation in the
Data Review Narrative. Use professional judgment to assess the data.
E. Action
NOTE: For an ICS that does not meet the technical criteria, apply the action to all samples
reported from the analytical sequence.
1. If the ICS was not analyzed at the specified frequency, qualify detects and non-detects as
unusable (R). If the ICS was analyzed, but not in the proper sequence, use professional judgment
to qualify detects and non-detects.
2. The raw data may not contain results for interferents. In this case, use professional judgment to
qualify the data. If the data contains results for interferents, apply the following actions to
samples with concentrations of interferents that are within 10% of the levels of the levels of
interferent in the ICS:
a. If the ICS Solution AB %R for an analyte or interferent is < 50%, qualify detects as estimated
low (J-) and non-detects as unusable (R).
b. If the ICS %R for an analyte or interferent falls within the range of 50-79% [or the ICS found
value is < (true value - 2x the CRQL), whichever is lower], qualify detects as estimated low
(J-), and non-detects as estimated (UJ).
c. If the ICS %R for an analyte or interferent falls within the range of 80-120%, detects and
non-detects should not be qualified.
d. The ICS %R for an analyte or interferent is > 120% [or the ICS found value is > (true value +
2x the CRQL), whichever is greater], qualify detects as estimated high (J+). Non-detects
should not be qualified.
e. If the ICS %R for an analyte or interferent is above 150%, use professional judgment to
determine the qualifications of the associated sample data.
3. If sample results that are > MDLs are observed for analytes which are not present in the ICS
solution, the possibility of false positives exists. An evaluation of the associated sample data for
the affected analytes should be made. For samples with comparable or higher levels of
interferents and with analyte concentrations that approximate those levels found in the ICS,
qualify detects as estimated high (J+). Non-detects should not be qualified.
4. If negative sample results are observed for analytes that are not present in the ICS solution, and
their absolute values are > MDLs, the possibility of false negatives in the samples exists. An
evaluation of the associated sample data for the affected analytes should be made. For samples
with levels of interferents that are comparable to or higher than the levels found in the ICS,
qualify detects < 1 Ox the absolute value of the negative result as estimated low (J-), and qualify
non-detects as estimated (UJ).
NOTE: The same result units should be used when comparing analyte results in samples to those
in the ICS. Unit conversion may be necessary when soil/sediment samples are evaluated.
5. If the raw data does not contain results for the interferents, annotate this in the Data Review
Narrative.
6. Actions regarding the interpretation and/or the subsequent qualification of Inductively Coupled
Plasma (ICP) data due to the ICS analytical results can be extremely complex. Use professional
judgment to determine the need for the associated sample data to be qualified; obtain additional
information from the laboratory, if necessary. Record all interpretive situations in the Data
Review Narrative.
August 2014 59
-------
Inorganic Data Review
ICP-MS
7. If the ICS acceptance criteria are grossly exceeded, note the specifics for Regional Laboratory
COR action.
Table 16. Interference Check Actions for ICP-MS Analysis
Criteria
ICS not analyzed
ICS not analyzed in proper sequence
ICSAB%R<50%
ICS %R 50-79% [or ICS found value is < (true
value - 2x CRQL), whichever is lower]
ICS %R 80-120%
ICS%R> 150%
ICS %R > 120% [or ICS true value is > (true
value + 2x CRQL), whichever is greater]
Sample results > MDLs, but not present in ICS
Negative sample results, but not present in ICS
Action
Detect
R
Use professional
judgment
J-
J-
No qualification
Use professional
judgment
J+
J+
J-
for results
< 10x( negative sample
result)
Non- detect
R
Use professional
judgment
R
UJ
No qualification
Use professional
judgment
No qualification
No qualification
UJ
August 2014
60
-------
Inorganic Data Review ICP-MS
VI. Laboratory Control Sample
A. Review Items
Form 7-IN, preparation logs, instrument printouts, and raw data.
B. Objective
The objective is to determine the validity of the analytical results based on the recovery of the
digested Laboratory Control Sample (LCS).
C. Criteria
1. Aqueous/water and soil/sediment LCSs shall be analyzed for each analyte utilizing the same
sample preparations, analytical methods, and Quality Assurance/Quality Control (QA/QC)
procedures as employed for the samples.
a. One LCS shall be prepared and analyzed for every group of aqueous/water or soil/sediment
samples in an SDG, or with each batch of samples digested, whichever is more frequent. The
LCS shall be spiked such that the final digestate contains each analyte at 2x the CRQL for the
associated matrix.
b. All LCS %Rs must fall within the control limits of 70-130%. If the %R for the LCS falls
outside of the control limits, the analysis should be terminated, the problem corrected, and the
samples prepared with that LCS redigested and reanalyzed.
D. Evaluation
1. Verify, using Form 7-IN, preparation logs, and raw data, that the appropriate number of required
LCSs were prepared and analyzed for the SDG.
2. Verify, using Form 7-IN, that all results for each analyte fall within the established control limits.
a. Check the raw data to verify that the %Rs on Form 7-IN were accurately transcribed.
Recalculate one or more of the reported %Rs using the following equation:
Found (value)
%R= xlOO
True (value)
Where,
j / i x Concentration of each analyte (in ug/L or mg/kg) measured in the analysis
Found (value) = ,,., T J \ rs 55; j
of the LCS
True (value) = Concentration of each analyte (in (ig/L or mg/kg) in the LCS
3. Verify that the LCS was prepared at the same time as the associated samples using the same
procedures.
E. Action
NOTE: If the LCS criteria are not met, the laboratory performance and method accuracy are in
question. Use professional judgment to determine if the data should be qualified or
rejected. The following guidance is suggested for qualifying sample data associated with
an LCS that does not meet the required criteria.
For an LCS that does not meet the technical criteria, apply the action to all samples in the
same preparation batch.
1. If the required LCS was not analyzed at the specified frequency, use professional judgment to
determine if the associated sample data should be qualified; obtain additional information from
the laboratory, if necessary. If a laboratory fails to analyze a LCS with each SDG, or if a
laboratory consistently fails to generate acceptable LCS recoveries, record the situation in the
August 2014 61
-------
Inorganic Data Review
ICP-MS
Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ).
2. LCS for all matrices:
a. If LCS %R is < 40%, qualify detects as estimated low (J-) and non-detects as unusable (R).
b. If the LCS %R falls within the range of 40-69%, qualify detects as estimated low (J-) and
non-detects as estimated (UJ).
c. If the LCS %R falls within the range of 70-130%, detects and non-detects should not be
qualified.
d. If the LCS %R is > 130%, qualify detects as estimated high (J+). Non-detects should not be
qualified.
e. If the LCS %R is > 150%, qualify detects as unusable (R). Non-detects should not be
qualified.
3. Annotate the potential effects on the data due to out-of-control LCS results in the Data Review
Narrative.
Table 17. LCS Actions for ICP-MS Analysis
Criteria
Aqueous/Water and Soil/Sediment %R < 40%
Aqueous/Water and Soil/Sediment %R 40-69%
Aqueous/Water and Soil/Sediment %R 70-130%
Aqueous/Water and Soil/Sediment %R > 130%
Aqueous/Water and Soil/Sediment %R > 150%
Action
Detect
J-
J-
No qualification
J+
R
Non- detect
R
UJ
No qualification
No qualification
No qualification
August 2014
62
-------
Inorganic Data Review ICP-MS
VII. Duplicate Sample Analysis
A. Review Items
Cover Page, Form 6-IN, instrument printouts, and raw data.
B. Objective
The objective of duplicate sample analysis is to demonstrate acceptable method precision by the
laboratory at the time of analysis.
C. Criteria
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
duplicate sample analysis.
2. At least one duplicate sample shall be prepared and analyzed from each group of samples of a
similar matrix type (e.g., water or soil) or for each SDG. Duplicates cannot be averaged for
reporting on Form 1-IN. Additional duplicate sample analyses may be required by EPA Regional
request. Alternately, the Region may require that a specific sample be used for the duplicate
sample analysis.
3. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original and
duplicate sample values > 5x the CRQL.
4. A control limit of the CRQL shall be used if either the sample or duplicate value is < 5x the
CRQL. The absolute value of the control limit (CRQL) shall be entered in the "Control Limit"
column on Form 6-IN. If both samples are non-detects, the RPD is not calculated for Form 6-IN.
NOTE: The above control limits are method requirements for duplicate samples, regardless of
the sample matrix type. However, it should be noted that laboratory variability arising
from the sub-sampling of non-homogenous soil samples is a common occurrence.
Therefore, for technical review purposes only, Regional policy or project DQOs may
allow the use of less restrictive criteria (e.g., 35% RPD, 2x the CRQL) to be assessed
against duplicate soil samples.
D. Evaluation
1. Verify, from the Cover Page and the raw data, that the appropriate number of required duplicate
samples were prepared and analyzed for the SDG.
2. Verify, using Form 6-IN and the raw data, that all duplicate results for each analyte fall within the
established control limits.
3. Verify that a field blank or PE sample was not used for duplicate analysis.
4. Check the raw data and recalculate one or more of the RPD values using the following equation
to verify that the results were correctly reported on Form 6-IN:
RPD
S-D
(S + D)/2
Where,
RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
100
August 2014 63
-------
Inorganic Data Review ICP-MS
E. Action
NOTE: For a duplicate sample analysis that does not meet the technical criteria, apply the action
to all samples of the same matrix if the samples are considered sufficiently similar.
Exercise professional judgment in determining sample similarity when making use of all
available data, including: site and sampling documentation (e.g., location and type of
sample, descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity,
chlorine); and laboratory data for other parameters [e.g., Total Suspended Solids (TSS),
Total Dissolved Solids (TDS), Total Organic Carbon (TOC), alkalinity or buffering
capacity, reactive sulfide, anions]. Additionally, use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG.
Possible determinations are: 1) only some of the samples in the SDG are similar to the
duplicate sample, and that only these samples should be qualified; or, 2) no samples are
sufficiently similar to the sample used for the duplicate, and thus only the field sample
used to prepare the duplicate sample should be qualified.
1. If the appropriate number of duplicate samples were not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified; obtain additional information from the laboratory, if necessary. Record the situation in
the Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ) if any of the frequency criteria is not
met.
2. If both original sample and duplicate sample results are > 5x the CRQL and the RPD is > 20%,
qualify detects as estimated (J), and qualify non-detects as estimated (UJ).
3. If RPD > 100%, use professional judgment to determine if the associated sample data should be
qualified.
4. If both original sample and duplicate sample results are > 5x the CRQL and the RPD is < 20%,
detects and non-detects should not be qualified.
5. If the original sample or duplicate sample result is < 5x the CRQL (including non-detects) and the
absolute difference between sample and duplicate > CRQL, qualify detects as estimated (J) and
non-detects as estimated (UJ).
6. If the original sample or duplicate sample result is < Sxthe CRQL (including non-detects) and
the absolute difference between sample and duplicate < CRQL, detects and non-detects should
not be qualified.
7. If a field blank or PE sample was used for the duplicate sample analysis, note this for Regional
Laboratory COR action. All of the other QC data must then be carefully checked. Use
professional judgment when evaluating the data.
8. Annotate the potential effects on the data due to out-of-control duplicate sample results in the
Data Review Narrative.
August 2014 64
-------
Inorganic Data Review
ICP-MS
Table 18. Duplicate Sample Actions for ICP-MS Analysis
Criteria
Both original sample and duplicate sample results are > 5x
the CRQL and RPD > 20%*
Both original sample and duplicate sample results are > 5x
the CRQL and RPD is < 20%
RPD > 100%
Original sample or duplicate sample result < 5x the CRQL
(including non-detects) and absolute difference between
sample and duplicate > CRQL*
Original sample or duplicate sample result < 5x the CRQL
(including non-detects) and absolute difference between
sample and duplicate < CRQL
Action
Detect
J
No qualification
Use professional
judgment
J
No qualification
Non-detect
UJ
No qualification
Use professional
judgment
UJ
No qualification
* The above control limits are method requirements for duplicate samples, regardless of the
sample matrix type. However, it should be noted that laboratory variability arising from the sub-
sampling of non-homogenous soil samples is a common occurrence. Therefore, for technical
review purposes only, Regional policy or project DQOs may allow the use of less restrictive
criteria (e.g., 35% RPD, 2xthe CRQL) to be assessed against duplicate soil samples.
August 2014
65
-------
Inorganic Data Review ICP-MS
VIII. Spike Sample Analysis
A. Review Items
Cover Page, Form 5A-IN, Form 5B-IN, instrument printouts, and raw data.
B. Objective
The objective of the spiked sample analysis is to evaluate the effect of each sample matrix on the
sample preparation procedures and the measurement methodology.
C. Criteria
1. Samples identified as field blanks or PE samples cannot be used for spiked sample analysis.
2. At least one spiked sample (pre-digestion) shall be prepared and analyzed from each group of
samples with a similar matrix type (e.g., water or soil), or for each SDG.
3. When the Matrix Spike recovery falls outside of the control limits and the sample result is < 4x
the spike added, a post-digestion spike shall be performed for those analytes that do not meet the
specified criteria. An aliquot of the remaining unspiked sample shall be spiked at 2x the
indigenous level or 2x the CRQL, whichever is greater.
4. The spike %R shall be within the established acceptance limits. However, spike recovery limits
do not apply when the sample concentration is > 4x the spike added. In such an event, the data
shall be reported unflagged, even if the %R does not meet the acceptance criteria.
5. If the spiked sample analysis was performed on the same sample that was chosen for the duplicate
sample analysis, spike calculations shall be performed using the results of the sample designated
as the "original sample." The average of the duplicate results cannot be used for the purpose of
determining %R.
NOTE: The final spike concentrations required for the various target analytes are presented in the
methods described in the SOW.
D. Evaluation
1. Verify, using the Cover Page, Form 5 A-IN, and raw data, that the appropriate number of required
spiked samples was prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Verify, using Form 5A-IN and the raw data, that all pre-digestion spiked sample results for each
required analyte fall within the established control limits. If not, verify that a post-digestion spike
was prepared and analyzed.
4. Recalculate using the raw data, one or more of the %R using the following equation, and verify
that the recalculated value agrees with the laboratory-reported values on Forms 5A-IN & 5B-IN:
SSR-SR
%Recovery= *100
Where,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
NOTE: When the sample result is < MDL or reported as a non-detect, use SR = 0 only for the
purpose of calculating the %R. The actual spiked sample results, sample results, and %R
(positive or negative) shall still be reported on Forms 5A-IN & 5B-IN.
August 2014 66
-------
Inorganic Data Review ICP-MS
E. Action
NOTE: For a Matrix Spike that does not meet the technical criteria, apply the action to all
samples of the same matrix, if the samples are considered sufficiently similar. Exercise
professional judgment in determining sample similarity when making use of all available
data, including: site and sampling documentation (e.g., location and type of sample,
descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity, chlorine);
and laboratory data for other parameters (e.g., TSS, TDS, TOC, alkalinity or buffering
capacity, reactive sulfide, anions). Additionally, use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG.
Possible determinations are: 1) only some of the samples in the SDG are similar to the
Matrix Spike sample, and that only these samples should be qualified; or, 2) no samples
are sufficiently similar to the sample used for the Matrix Spike, and thus only the field
sample used to prepare the Matrix Spike sample should be qualified.
1. If the appropriate number of Matrix Spike samples was not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified; obtain additional information from the laboratory, if necessary. Record the situation in
the Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ) if any of the frequency criteria is not
met.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for Regional
Laboratory COR action. All of the other QC data must then be carefully checked. Use
professional judgment when evaluating the data. Detects should be qualified as estimated (J) and
non-detects as estimated (UJ).
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-digestion
spike was not performed, note this for Regional Laboratory COR action.
4. If the Matrix Spike %R is < 30%, verify that a post-digestion spike was analyzed. If the post-
digestion spike %R is < 75% or the analysis was not performed, qualify detects as estimated low
(J-) and non-detects as unusable (R). If the post-digestion spike %R is > 75%, qualify detects as
estimated (J) and non-detects as estimated (UJ).
5. If the Matrix Spike %R falls within the range of 30-74%, verify that a post-digestion spike was
analyzed (if required when sample concentration is < 4x spike added). If the post-digestion spike
%R is < 75% or the analysis was not performed, qualify detects as estimated low (J-) and non-
detects as estimated (UJ). If the post-digestion spike %R for is > 75%, qualify detects as
estimated (J) and non-detects as estimated (UJ).
6. If the Matrix Spike %R falls within the range of 75-125%, no post-digestion spike is required.
Detects and non-detects should not be qualified.
7. If the Matrix Spike %R is > 125%, verify that a post-digestion spike was analyzed (if required
when sample concentration is < 4x spike added). If the post-digestion spike %R is also > 125%
or the analysis was not performed, qualify detects as estimated high (J+); non-detects should not
be qualified. If the post-digestion spike %R is < 125%, qualify detects as estimated (J); non-
detects should not be qualified.
8. Annotate the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.
August 2014 67
-------
Inorganic Data Review
ICP-MS
Table 19. Spike Sample Actions for ICP-MS Analysis
Criteria
Matrix Spike %R < 30%
Post-digestion spike %R < 75%
Matrix Spike %R < 30%
Post-digestion spike %R> 75%
Matrix Spike %R 30-74%
Post-digestion spike %R < 75%
Matrix Spike %R 30-74%
Post-digestion spike %R> 75%
Matrix Spike %R> 125%
Post-digestion spike %R> 125%
Matrix Spike %R> 125%
Post-digestion spike %R< 125%
Matrix Spike %R < 30%
No post-digestion spike performed
Matrix Spike %R 30-74%
No post-digestion spike performed
Matrix Spike %R 75-125%
No post-digestion spike is required
Matrix Spike %R> 125%
No post-digestion spike performed
Action
Detect
J-
J
J-
J
J+
J
J-
J-
No qualification
J+
Non- detect
R
UJ
UJ
UJ
No qualification
No qualification
R
UJ
No qualification
No qualification
NOTE: The above control limits are method requirements for spike samples, regardless of the
sample matrix type. However, it should be noted that laboratory variability arising from
the sub-sampling of non-homogenous soil samples is a common occurrence. Therefore,
for technical review purposes only, Regional policy or project DQOs may allow the use
of less restrictive criteria (e.g., 10 %R and 150 %R for the lower and upper limits) to be
assessed against spike and post-digestion spike soil samples.
August 2014
68
-------
Inorganic Data Review ICP-MS
IX. Serial Dilution
A. Review Items
Form 1-IN, Form 8 -IN, instrument printouts, and raw data.
B. Objective
The objective of the serial dilution analysis is to determine whether or not significant physical or
chemical interferences exist due to sample matrix.
C. Criteria
1 . An ICP Serial Dilution analysis shall be performed on a sample from each group of samples with
a similar matrix type (e.g., water or soil) or for each SDG, whichever is more frequent.
2. Samples identified as field blanks or PE samples cannot be used for the ICP Serial Dilution
analysis.
3. If the analyte concentration is sufficiently high (concentration in the original sample is > 5 Ox the
MDL), the %D between the original determination and the serial dilution analysis (a five-fold
dilution) after correction for dilution (concentration in the serial dilution sample is > CRQL) shall
be < 10%.
NOTE: The above criteria are method requirements for serial dilution samples, regardless of the
sample matrix type. However, for technical review purposes only, Regional policy or
project DQOs may allow the use of less restrictive criteria (e.g., %D > 15%) to be
assessed against serial dilution soil samples.
D. Evaluation
1 . Verify that a field blank or PE sample was not used for the serial dilution analysis.
2. Check the raw data and recalculate the %D using the following equation. Verify that the serial
dilution analysis results and the calculated %D results agree with the values reported by the
laboratory on Form 8 -IN:
-
%Difference =
Where,
I = Initial Sample Result
S = Serial Dilution Result
3. Check the raw data for any evidence of positive or negative interference (results from the diluted
sample which are significantly different than the original sample), possibly due to high levels of
dissolved solids in the sample, ionization effects, etc.
E. Action
NOTE: For a serial dilution that does not meet the technical criteria, apply the action to all
samples of the same matrix if the samples are considered sufficiently similar. Exercise
professional judgment in determining sample similarity when making use of all available
data, including: site and sampling documentation (e.g., location and type of sample,
descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity, chlorine);
and laboratory data for other parameters (e.g., TSS, TDS, TOC, alkalinity or buffering
capacity, reactive sulfide, anions). Additionally, use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. Two
determinations are: 1) only some of the samples in the SDG are similar to the serial
dilution sample, and that only these samples should be qualified; or, 2) no samples are
August 2014 69
-------
Inorganic Data Review
ICP-MS
sufficiently similar to the sample used for serial dilution, and thus only the field sample
used to prepare the serial dilution sample should be qualified.
1. If the appropriate number of serial dilution samples was not analyzed for each matrix, use
professional judgment to determine if the associated sample data should be qualified; obtain
additional information from the laboratory, if necessary. If a field blank or PE sample was used
for the serial dilution analysis, record the situation in the Data Review Narrative, and note it for
Regional Laboratory COR action. Detects should be qualified as estimated (J) and non-detects as
estimated (UJ).
2. If the analyte concentration in the original sample is > 5 Ox the MDL, its concentration in the
serial dilution sample is > CRQL, and the %D > 10%, qualify detects as estimated (J) and non-
detects as estimated (UJ).
3. If the analyte concentration in the original sample is > 5 Ox the MDL, its concentration in the
serial dilution sample is > CRQL, and the %D is < 10%, detects and non-detects should not be
qualified.
4. If the analyte concentration in the original sample is > 5 Ox the MDL, its concentration in the
serial dilution sample is > CRQL, and %D is > 100%, use professional judgment to determine if
the associated sample data should be qualified.
5. If the analyte concentration in the original sample is > 5x the CRQL and its concentration in the
serial dilution sample is < CRQL, detects and non-detects should not be qualified.
6. If evidence of positive or negative interference is found, use professional judgment to qualify the
associated sample data. Annotate the potential effects on the reported data in the Data Review
Narrative.
Table 20. Serial Dilution Actions for ICP-MS Analysis
Criteria
Sample concentration
> 5 Ox MDL, serial dilution sample
concentration > CRQL, and %D >
10%*
Sample concentration
> 5 Ox MDL, serial dilution sample
concentration > CRQL, and %D <
10%
Sample concentration
> 5 Ox MDL, serial dilution sample
concentration > CRQL, and %D >
100%
Sample concentration > 5x CRQL and
serial dilution sample concentration <
CRQL
Interferences present
Action
Detect
J
No qualification
Use professional
judgment
No qualification
Use professional
judgment
Non-detect
UJ
No qualification
Use professional
judgment
No qualification
Use professional
judgment
The above criteria are method requirements for serial dilution samples, regardless of the sample
matrix type. However, for technical review purposes only, Regional policy or project DQOs
may allow the use of less restrictive criteria (e.g., %D > 15%) to be assessed against serial
dilution soil samples.
August 2014
70
-------
Inorganic Data Review ICP-MS
X. Internal Standards
A. Review Items
Form 11-IN, Form 14-IN, instrument printouts, and raw data.
B. Objective
The objective of internal standard analysis is to determine the existence and magnitude of instrument
drift and physical interferences.
C. Criteria
1. All samples analyzed during an analytical sequence, with the exception of the tune, shall contain
internal standards. A minimum of five internal standards from the following list shall be added to
each sample: Li (the Li6 isotope); Sc; Y; Rh; In; Tb; Ho; Lu; and Bi. If the laboratory uses
lithium as an internal standard, the laboratory shall use an Li6-enriched standard. The laboratory
shall monitor the same internal standards throughout the entire analytical sequence and shall
assign each analyte to at least one internal standard.
2. The intensity of the internal standard response in a sample is monitored and compared to the
intensity of the response for that internal standard in the calibration blank. The Percent Relative
Intensity (%RI) in the sample shall fall within 60-125% of the response in the calibration blank.
3. If the %RI of the response in the sample falls outside of these limits, the laboratory shall
reanalyze the original sample at a two-fold dilution with internal standard added.
D. Evaluation
1. Verify, using Form 14-IN and the raw data, that a minimum of five internal standards from the
specified list were used for the analysis; that the same internal standards were monitored for the
entire analytical sequence; and that each analyte was associated to at least one internal standard.
2. Verify, using Form 14-IN and the raw data, that these internal standards were added to each
sample in the analytical sequence, including calibrations, samples, and QC samples (except tune).
3. Verify, using Form 14-IN, that the %RI between an internal standard in a sample and the internal
standard in the calibration blank was reported for each sample.
4. Verify, using Form 11-IN, Form 14-IN, and the raw data, that if the %RI for a sample was outside
the limits (60-125%), the sample was reanalyzed of a two-fold dilution with internal standard
added.
E. Action
NOTE: Apply the action to the affected analytes for each sample that does not meet the internal
standard criteria.
1. If no internal standards were analyzed with the analytical sequence, detects and non-detects
should be qualified as unusable (R). Record this issue in the Data Review Narrative, and note it
for Regional Laboratory COR action.
2. If less than five of the required internal standards were analyzed with the analytical sequence, or
(a) target analyte(s) is (are) not associated to an internal standard, the sample results, for the
analyte(s) not associated to an internal standard should be qualified as unusable (R). Record this
issue in the Data Review Narrative, and note it for Regional Laboratory COR action.
3. If the %RI for the internal standards in a sample falls within the range of 60-125%, the sample
results should not be qualified.
4. If the %RI for an internal standard in a sample is < 60% or > 125%, qualify the sample results of
the analytes associated with the non-compliant internal standard(s) as follows:
August 2014 71
-------
Inorganic Data Review
ICP-MS
b.
If the sample was reanalyzed at a two-fold dilution with internal standard %RIs within the
limits, report the result (for those analytes associated to the internal standard outside the
limits in the initial analysis) from the diluted analysis without qualification. If any of the
%RIs of the diluted analysis were < 60% or > 125%, report the results of the original
undiluted analysis and qualify the detects as estimated (J) and non-detects as estimated (UJ)
for the associated analytes.
If the sample was not reanalyzed at a two-fold dilution, use professional judgment to
determine the reliability of the data. Detects should be qualified as estimated (J) or unusable
(R) and non-detects as estimated (UJ) or unusable (R) for the associated analytes.
Table 21. Internal Standard Actions for ICP-MS Analysis
Criteria
No internal standards
< 5 of the required internal standards
Target analyte not associated with internal standard
%RI 60-125%
%RI < 60% or > 125% and original sample
reanalyzed at 2-fold dilution
Original sample not reanalyzed at 2-fold dilution
Action
Detect
R
R
R
No qualification
J
Use professional
judgment
JorR
Non-detect
R
R
R
No qualification
UJ
Use professional
judgment
UJorR
August 2014
72
-------
Inorganic Data Review ICP-MS
XI. Regional Quality Assurance and Quality Control
A. Review Items
Form 1 -IN, instrument printouts, and raw data.
B. Objective
The objective is to use results from the analysis of Regional QA/QC samples such as field blanks, PE
samples, blind spikes, and blind blanks to determine the validity of the analytical results.
C. Criteria
Criteria are determined by each Region.
D. Evaluation
Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
review. Each Region will handle the evaluation of PE samples on an individual basis. Compare
results for PE samples to the acceptance criteria for the specific PE samples if possible.
Calculate the RPD between field duplicates and provide this information in the Data Review
Narrative.
E. Action
Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
results. Note any unacceptable PE sample results for Regional Laboratory COR action.
August 2014 73
-------
Inorganic Data Review ICP-MS
XII. Overall Assessment of Data
A. Review Items
Entire sample data package, data review results, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data (including any confirmation data).
B. Objective
The objective is to provide the overall assessment on data quality and usability.
C. Criteria
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
2. Reported analyte concentrations must be quantitated according to the appropriate analytical
method, as listed in the method. All sample results must be within the linear calibration ranges
per methods. Percent Solids (%Solids) must be properly used for all applicable matrix result
calculations.
D. Evaluation
Examine the raw data to verify that the correct calculation of the sample results was reported by the
laboratory. Digestion logs, instrument printouts, etc., should be compared to the reported sample
results recorded on the appropriate Inorganic Summary Forms (Form 1-IN through Form 16-IN).
1. Evaluate any technical problems not previously addressed.
2. Examine the raw data for any anomalies (e.g., baseline shifts, negative response, mass dependent
drift, omissions, illegibility, etc.).
3. Verify that appropriate methods and volumes were used in preparing the samples for analysis. If
reduced volumes were used, verify that the laboratory had received Regional Laboratory COR
approval for the use of the reduced volume.
4. Verify that there are no transcription or reduction errors (e.g., dilutions, %Solids, sample weights,
etc.) on one or more samples. Recalculate %Solids for at least 10% of the samples and verify that
the calculated %Solids agree with that reported by the library.
5. Verify that MDLs are properly reported and that they are not greater than the respective CRQLs.
6. Verify that results fall within the calibrated range(s) of the instrument(s) (Form 15-IN).
7. If appropriate information is available, assess the usability of the data to assist the data user in
avoiding inappropriate use of the data. Review all available information, including the Quality
Assurance Project Plan (QAPP), focusing specifically on the acceptance or performance criteria,
the SOPs, and communication with the user concerning the intended use and desired quality of
these data.
E. Action
1. Use professional judgment to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
2. Use professional judgment to qualify detects and non-detects if the MDL exceeds CRQL.
3. If a sample is not diluted properly when sample results exceed the upper limit of the calibration
range, qualify detects as estimated (J).
4. Write a brief Data Review Narrative to give the user an indication of the analytical limitations of
the data. Annotate any discrepancies between the data and the SDG Narrative for Regional
Laboratory COR action. If sufficient information on the intended use and required quality of the
data is available, include an assessment of the data usability within the given context.
August 2014 74
-------
Inorganic Data Review ICP-MS
5. If any discrepancies are found, notify the Regional Laboratory COR. The Regional Laboratory
COR may contact the laboratory to obtain additional information for a resolution. If a
discrepancy remains unresolved, use professional judgment to determine if qualification of the
data is warranted.
August 2014 75
-------
Inorganic Data Review ICP-MS
XIII. Calculations
Aqueous/Water Sample Concentration by ICP-MS:
The concentrations determined in the digestate are to be reported in units of (ig/L:
Where,
. Vf
Concentration (ug/L) = C x x DF
C = Instrument value in |o,g/L (the average of all replicate integrations)
Vf = Final digestion volume (mL)
V = Initial Aliquot Amount (mL)
DF = Dilution Factor
Soil/Sediment Sample Concentration by ICP-MS:
The concentrations determined in the digestate are to be reported on the basis of the dry weight of the
sample, in units of mg/kg:
Vf
Concentration (mg/kg dry weight) = C x - x DF/1000
W x b
Where,
C = Instrument value in |o,g/L (the average of all replicate integrations)
Vf = Final digestion volume (mL)
W = Initial aliquot amount (g)
S = %Solids/100 (see Exhibit D - General Inorganic Analysis, Section 10.1.4)
DF = Dilution Factor
Adjusted MDL/Adjusted CRQL Calculation:
To calculate the adjusted MDL or adjusted CRQL for aqueous/water samples, substitute the value of
the MDL ((ig/L) or CRQL ((ig/L) into the "C" term in the equation above.
Calculate the adjusted MDL or adjusted CRQL for soil/sediment samples as follows:
WM Vf
Adjusted MDL or CRQL (mg/kg) = C x ^- x _i x DF
W x S V
Where,
C = MDL or CRQL (mg/kg)
WM = Minimum method required aliquot amount (g) (1 .OOg or 0.50g)
W = Initial aliquot amount (g)
VM = Method required final sample digestion volume (mL) (100 mL)
Vf = Final digestion volume (mL)
S = %Solids/100 (see Exhibit D - General Inorganic Analysis, Section 10.1.4)
DF = Dilution Factor
August 2014 76
-------
Inorganic Data Review Mercury
MERCURY DATA REVIEW
The inorganic data requirements for mercury to be reviewed during validation are listed below:
Example Analytical Sequence 79
I. Preservation and Holding Times 81
II. Calibration 83
III. Blanks 86
IV. Duplicate Sample Analysis 90
V. Spike Sample Analysis 93
VI. Regional Quality Assurance and Quality Control 95
VII. Overall Assessment of Data 96
VIII. Calculations 98
August 2014 77
-------
Inorganic Data Review Mercury
This page is intentionally left blank.
August 2014 78
-------
Inorganic Data Review Mercury
Example Analytical Sequence
This is an example of an analytical sequence:
S##
S##
s##
s##
s##
s##
ICV
ICB
ccv###
CCB###
samples
ccv###
CCB###
samples
ccv###
CCB###, etc.
*Suffix ## and ### are as specified in Exhibit B of the Statement of Work (SOW).
August 2014 79
-------
Inorganic Data Review Mercury
This page is intentionally left blank.
August 2014 80
-------
Inorganic Data Review Mercury
I. Preservation and Holding Times
A. Review Items
Form 1-IN, Form 12-IN, Traffic Report/Chain of Custody (TR/COC) documentation, Form DC-1,
raw data, and the Sample Delivery Group (SDG) Narrative checking for: pH; shipping container
temperature; holding time; and other sample conditions.
B. Objective
The objective is to determine the validity of the analytical results based on the sample conditions and
the holding time of the sample.
C. Criteria
1. The technical holding time is determined from the date of collection, or the date Toxicity
Characteristic Leaching Procedure (TCLP) or Synthetic Precipitation Leaching Procedure (SPLP)
extraction is complete, to the date of analysis.
2. The technical holding time criteria for aqueous/water samples and leachate samples from TCLP
or SPLP is 28 days, preserved (with nitric acid) to pH < 2.
3. The technical holding time criteria for soil/sediment samples is 28 days, based on the technical
holding time criteria for aqueous/water samples.
4. Soil/sediment samples shall be maintained at < 6°C (but not frozen) from the time of collection
until receipt at the laboratory. All aqueous/water and soil/sediment samples must be stored at
< 6°C (but not frozen) from the time of sample receipt until digestion. The TCLP and SPLP
leachates must be stored at < 6°C (but not frozen) from the time of the leaching procedure
completion until digestion.
5. Samples and standards shall be analyzed with 48 hours of preparation.
D. Evaluation
Establish technical holding times by comparing the sampling date(s) on the TR/COC documentation
with the dates of analysis on Form 12-IN and the raw data; also consider using information in the
Complete SDG File (CSF), as it may be helpful in the assessment. Verify that the analysis dates on
the Form 12-IN and the raw data are identical. Review the SDG Narrative and raw data preparation
logs to determine if samples were properly preserved. If there is an indication of problems with the
samples, the sample integrity may be compromised. Use professional judgment to evaluate the effect
of the problem on the sample results.
E. Action
NOTE: Apply the action to each field sample for which the preservation or holding time criteria
was not met.
1. If the pH of aqueous/water samples is > 2 at the time of sample receipt, determine if the
laboratory adjusted the pH to < 2 at the time of sample receipt. Also determine if the laboratory
adjusted the pH to < 2 for the TCLP and SPLP leachates after completion of the leaching
procedure. If not, use professional judgment to qualify the samples based on the pH of the
sample and the chemistry of Mercury (possible Methylation). Detects should be qualified as
estimated low (J-) and non-detects as unusable (R).
2. If soil/sediment samples are not maintained at < 6°C (but not frozen) from the time of collection
until receipt at the laboratory, detects should be qualified as estimated low (J-) and non-detects as
unusable (R).
3. If technical holding times are exceeded, use professional judgment to determine the reliability of
the data based on the magnitude of the additional time compared to the technical requirement and
whether the samples were properly preserved. The expected bias would be low. Detects should
be qualified as estimated low (J-) and non-detects as unusable (R).
August 2014 81
-------
Inorganic Data Review
Mercury
4. Due to limited information concerning holding times for soil/sediment samples, use professional
judgment when deciding whether to apply the aqueous/water holding time criteria to
soil/sediment samples. If they are applied, document this action in the Data Review Narrative.
5. If samples are received with shipping container temperatures > 10°C, use professional judgment
to determine the reliability of the data, or qualify detects as estimated (J) and non-detects as
estimated (UJ).
6. When shipping or storage temperatures grossly exceed the requirements, the loss of volatile
mercury compounds or metallic mercury is possible. The expected bias would be low. Use
professional judgment to qualify the samples and note it for Regional Laboratory Contracting
Officer Representative (COR) action.
7. When the holding times are exceeded, annotate any possible consequences for the analytical
results in the Data Review Narrative, and note it for Regional Laboratory COR action.
Table 22. Preservation and Holding Time Actions for Mercury Analysis
Criteria
Aqueous/water samples received with pH > 2 and pH
not adjusted
TCLP/SPLP leachate samples with pH > 2 and pH not
adjusted
Soil/sediment samples not maintained at < 6°C (but
not frozen) from time of collection until receipt at the
laboratory
Technical Holding Time:
Aqueous/water and TCLP/SPLP leachate samples >
28 days
Technical Holding Time:
Soil/sediment samples > 28 days
Samples received > 10°C*
Action
Detect
Use professional
judgment
J-
Use professional
judgment
J-
J-
J-
J-
Use professional
judgment
J
Non-detect
Use professional
judgment
R
Use professional
judgment
R
R
R
R
Use professional
judgment
UJ
For samples received with shipping container temperatures > 10°C, Regional policy or project
Data Quality Objectives (DQO) may allow the use of higher temperature criteria before assessing
any actions for the affected samples.
August 2014
82
-------
Inorganic Data Review Mercury
II. Calibration
A. Review Items
Form 2-IN, Form 12-IN, Form 15-IN, Form 16-IN, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data.
B. Objective
The objective is to determine the validity of the analytical results based on initial calibration and
calibration verification.
C. Criteria
1. Initial Calibration
The instruments shall be successfully calibrated daily (or once every 24 hours), and each time the
instrument is set up. The calibration date and time shall be included in the raw data. The
calibration curve shall be prepared by the same method used to prepare the samples for analysis.
The curve shall be prepared with the samples that will be analyzed using this calibration curve.
a. A blank and at least five calibration standards shall be used to establish the calibration curve.
At least one of the calibration standards shall be at or below the Contract Required
Quantitation Limit (CRQL) but above the Method Detection Limit (MDL). The calibration
curve shall be fitted using linear regression or weighted linear regression. The curve may be
forced through zero. The calibration curve must have a correlation coefficient > 0.995. The
calculated percent differences (%Ds) for all of the non-zero standards must fall within ±30%
of the true value of the standard. The y-intercept of the curve must be less than the CRQL.
2. Initial and Continuing Calibration Verification
The acceptance criteria for the Initial Calibration Verification (ICV) and Continuing Calibration
Verification (CCV) standards are presented in Table 23. These standards shall be prepared by the
same method used to prepare the samples for analysis.
Table 23. Acceptance Criteria for ICV and CCV Standards for Mercury Analysis
Analytical Method
Cold Vapor AA
Inorganic Analyte
Mercury
ICV/CCV Low Limit
(% of True Value)
85
ICV/CCV High Limit
(% of True Value)
115
a. Initial Calibration Verification
1) Immediately after the system has been calibrated, the accuracy of the initial calibration
must be verified and documented by the analysis of an ICV solution(s). If the ICV
Percent Recovery (%R) falls outside of the control limits, the analysis should be
terminated, the problem corrected, the instrument recalibrated, and all affected samples
reanalyzed.
2) Only if the ICV is not available from the United States Environmental Protection Agency
(EPA), analyses shall be conducted using a certified solution of the analyte from an
independent commercial standard source, at a concentration level other than that used for
instrument calibration, but within the calibrated range.
b. Continuing Calibration Verification
1) To ensure accuracy during the course of each analytical sequence, the CCV shall be
analyzed and reported.
2) The CCV standard shall be analyzed at a frequency of every hour during an analytical
sequence. The CCV standard shall also be analyzed at the beginning of the analytical
sequence, and again after the last analytical sample.
August 2014 83
-------
Inorganic Data Review Mercury
3) The analyte concentration in the CCV standard shall be different than the concentration
used for the ICV, and a concentration equivalent to the mid level of the calibration curve.
4) The same CCV standard solution shall be used throughout the analysis for an SDG.
5) The CCV shall be analyzed in the same fashion as an actual sample. If the %R of the
CCV was outside of the control limits, the analysis should be terminated, the problem
corrected, the instrument recalibrated, and all analytical samples analyzed since the last
compliant CCV reanalyzed.
D. Evaluation
1. Verify that the instrument was calibrated daily (once every 24 hours) and each time the
instrument was set up, utilizing a blank and at least five calibration standards. Confirm that at
least one of the calibration standards was analyzed at or below the CRQL, but above the MDL.
Confirm that calibration standards and samples were prepared at the same time.
2. Verify that the ICV and CCV standards were analyzed at the specified frequency and at the
appropriate concentration. Verify that acceptable %R results were obtained.
3. Recalculate one or more of the ICV or CCV %R using the following equation and verify that the
recalculated value agrees with the laboratory-reported values on Form 2-IN.
Found (value)
%R= / , / xlOO
True (value)
Where,
j / i x Concentration (in ug/L) of mercury measured in the analysis of the ICV or
Found (value) = ,, i *
v ' CCV solution
True (value) = Concentration (in (ig/L) of mercury in the ICV or CCV source
E. Action
NOTES: For initial calibrations or ICV standards that do not meet the technical criteria, apply the
action to the associated samples reported from the analytical sequence.
For CCV standards that do not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the Quality Control (QC)
sample and a subsequent technically acceptable analysis of the QC sample in the
analytical sequence.
1. If the instrument was not calibrated daily and each time the instrument was set up, qualify detects
and non-detects as unusable (R). If the instrument was not calibrated with at least the minimum
number of standards, or if the calibration curve does not include standards at required
concentrations (e.g., a blank, and at least one standard at or below the CRQL but above the
MDL), or if the instrument was not calibrated with standards prepared at the same time as the
samples, use professional judgment to qualify detects as estimated (J) or unusable (R), and non-
detects as estimated (UJ) or unusable (R).
2. If the correlation coefficient is < 0.995, the %D is outside the ±30% limit, or the y-intercept is >
CRQL, qualify detects as estimated (J) and non-detects as estimated (UJ).
3. If the ICV or CCV %R falls outside the acceptance windows, use professional judgment to
qualify all associated data. If possible, indicate the bias in the review. The following guidelines
are recommended:
a. If the ICV or CCV %R is < 70%, use professional judgment to qualify detects as estimated
low (J-) or unusable (R), and non-detects as unusable (R).
b. If the ICV or CCV %R falls within the range of 70-84%, qualify detects as estimated low (J-)
and non-detects as estimated (UJ).
August 2014 84
-------
Inorganic Data Review
Mercury
c. If the ICV or CCV %R falls within the range of 85-115%, detects and non-detects should not
be qualified.
d. If the ICV or CCV %R falls within the range of 116-130%, qualify detects as estimated high
(J+). Non-detects should not be qualified.
e. If the ICV or CCV %R is > 130%, use professional judgment to qualify detects as estimated
high (J+) or unusable (R). Non-detects should not be qualified.
f If the ICV or CCV %R is > 165%, qualify detects as unusable (R). Non-detects should not be
qualified.
4. If the laboratory failed to provide adequate calibration information, notify the Regional
Laboratory COR. The Regional Laboratory COR may contact the laboratory and request the
necessary information. If the information is unavailable, use professional judgment to assess the
data.
5. Annotate the potential effects on the reported data due to exceeding the calibration criteria in the
Data Review Narrative.
6. If calibration criteria are grossly exceeded, note this for Regional Laboratory COR action.
NOTE: For truly critical samples, a further in-depth evaluation of the calibration curve may be
warranted to determine if additional qualification is necessary.
Table 24. Calibration Actions for Mercury Analysis
Criteria
Calibration not performed
Calibration incomplete
Correlation coefficient < 0.995; %D outside
±30%; y-intercept > CRQL
ICV/CCV %R < 70%
ICV/CCV %R 70-84%
ICV/CCV %R 85-1 15%
ICV/CCV %R 116-130%
ICV/CCV %R> 130%
ICV/CCV %R> 165%
Action
Detect
R
Use professional
judgment
JorR
J
Use professional
judgment
J-orR
J-
No qualification
J+
Use professional
judgment
J+orR
R
Non- detect
R
Use professional
judgment
UJorR
UJ
R
UJ
No qualification
No qualification
No qualification
No qualification
August 2014
85
-------
Inorganic Data Review Mercury
III. Blanks
A. Review Items
Form 1-IN, Form 3-IN, Form 12-IN, preparation logs, calibration standard logs, instrument logs, and
raw data.
B. Objective
The objective is to determine the validity of the analytical results based on the blank responses by
determining the existence and magnitude of contamination resulting from laboratory (or field)
activities or baseline drift during analysis.
C. Criteria
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed at each mass used for analysis after the
analytical standards, but not before analysis of the ICV during the initial calibration of the
instrument (see Section II.C.l). The ICB shall be prepared by the same method used to prepare
the samples for analysis.
3. A Continuing Calibration Blank (CCB) shall be analyzed immediately after every CCV. The
CCB shall be prepared by the same method used to prepare the samples for analysis. The CCB
shall be analyzed at a frequency of every hour during the analytical sequence. The CCB shall be
analyzed at the beginning of the analytical sequence, and again after the last CCV that was
analyzed after the last analytical sample of the analytical sequence. The CCB result (absolute
value) shall not exceed the CRQL.
4. At least one Preparation Blank shall be prepared and analyzed for each matrix, with every SDG,
or with each batch of samples digested, whichever is more frequent. The Preparation Blank
consists of reagent water processed through the appropriate sample preparation and analysis
procedure.
5. If the analyte concentration in the Preparation Blank is > CRQL, the lowest concentration of the
analyte in the associated samples must be > lOx the Preparation Blank concentration. Otherwise,
all associated samples with the analyte's concentration < lOx the Preparation Blank
concentration, and > CRQL, should be redigested and reanalyzed. The laboratory is not to
correct the sample concentration for the blank value.
6. If the analyte concentration in the Preparation Blank is < (-CRQL), all associated samples with
the analyte's concentration < lOxthe CRQL, should be redigested and reanalyzed.
7. At least one Leachate Extraction Blank (LEB) shall be prepared and analyzed for each batch of
samples extracted by TCLP or SPLP. The LEB consists of reagent water processed through the
extraction procedure. Post-extraction, the LEB shall be processed through the appropriate sample
preparation and analysis procedure.
D. Evaluation
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the specified
frequency and sequence during the analytical sequence, and Preparation Blanks are prepared and
analyzed as appropriate for the SDG (e.g., total number of samples, various types of matrices
present, number of digestion batches, etc.).
2. Review the results reported on Form 3-IN, as well as the raw data for all blanks, and verify that
the results are accurately reported.
3. Evaluate all of the associated blanks for the presence of the target analyte. Verify that if the
concentration of the target analyte was > CRQL in a Preparation Blank, all associated samples
with analyte's concentration > CRQL but < lOx the Preparation Blank concentration were
redigested and reanalyzed for that analyte. Verify that if the concentration was < (-CRQL) in a
August 2014 86
-------
Inorganic Data Review Mercury
Preparation Blank, all associated samples with the analyte's concentration < lOx CRQL were
redigested and reanalyzed. Verify that if the absolute value of the target analyte was > CRQL in
an ICB or a CCB, the analysis was terminated, the problem corrected, the instrument recalibrated,
and the preceding 10 analytical samples or all analytical samples analyzed since the last
compliant calibration blank reanalyzed.
E. Action
NOTES: For ICBs that do not meet the technical criteria, apply the action to all associated samples
reported from the analytical sequence.
For CCBs that do not meet the technical criteria, apply the action to all associated
samples analyzed between a previous technically acceptable analysis of the CCB and a
subsequent technically acceptable analysis of the CCB in the analytical sequence.
For Preparation Blanks that do not meet the technical criteria, apply the action to all
associated samples prepared in the same preparation batch. For LEBs that do not meet
the technical criteria, apply the action to all associated samples extracted in the same
extraction batch.
1. If the appropriate blanks were not analyzed with the correct frequency, use professional judgment
to determine if the associated sample data should be qualified; obtain additional information from
the laboratory, if necessary. Record the situation in the Data Review Narrative, and note it for
Regional Laboratory COR action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
In instances where more than one blank is associated with a given sample, qualification should be
based upon a comparison with the associated blank having the highest concentration of
contaminant.
3. Some general "technical" review actions include:
a. For any blank (including Preparation Blanks and LEBs) reported with detects < CRQL, report
detects < CRQL at the CRQL and qualify as non-detect (U). For any blank (including
Preparation Blanks and LEBs) reported with a detect < CRQL, use professional judgment to
qualify the sample results > CRQL. Non-detects should not be qualified.
b. For any blank (including Preparation Blanks and LEBs) reported with a negative result
< (-MDL) but > (- CRQL), carefully evaluate it to determine its effect on the sample data.
Use professional judgment to assess the data.
c. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil/sediment sample results reported on Form 1-IN will not
be on the same basis (units, dilution) as the calibration blank data reported on Form 3-IN. It
may be easier to work with the raw data and/or convert the ICB or CCB results to the same
units as the soil/sediment samples for comparison purposes.
4. Specific "method" actions include:
a. If an ICB or a CCB result is > CRQL, the analysis should be terminated. If the analysis was
not terminated and the associated samples were not reanalyzed, non-detects should not be
qualified. Report detects < CRQL at CRQL and qualify as non-detect (U). Report sample
results that are > CRQL but < ICB/CCB Results at ICB/CCB Results and use professional
judgment to qualify as non-detect (U) or unusable (R). Use professional judgment to qualify
sample results > ICB/CCB Results. Record the situation in the Data Review Narrative, and
note it for Regional Laboratory COR action.
August 2014 87
-------
Inorganic Data Review Mercury
b. If an ICB or a CCB result is < (-CRQL), the analysis should be terminated. If the analysis
was not terminated and the associated samples were not reanalyzed, use professional
judgment to qualify non-detects as estimated (UJ) or unusable (R). Use professional
judgment to qualify detects < CRQL or qualify as estimated low (J-). Use professional
judgment to qualify sample results that are > CRQLs as estimated low (J-).
c. If the concentration of the analyte in the Preparation Blank/LEB is > CRQL, the lowest
concentration of that analyte in the associated samples must be > lOx the Preparation
Blank/LEB concentration. All samples associated with the Preparation Blank with
concentrations < 1 Ox the Preparation Blank concentration and > CRQL should have been
redigested and reanalyzed. If the associated samples were not redigested and reanalyzed,
report the sample results at Preparation Blank Results; use professional judgment to qualify
as estimated high (J+) or unusable (R). Report results <10x the LEB concentration and >
CRQL in the samples associated with the LEB at LEB Results; use professional judgment to
qualify the results as estimated high (J+) or unusable (R). Report detects < CRQLs in the
samples associated with the Preparation Blank/LEB at CRQLs and qualify as non-detect (U).
Non-detects and sample results that are > lOx Preparation Blank/LEB Results should not be
qualified. If the laboratory failed to redigest and reanalyze the samples associated with the
Preparation Blank, record it in the Data Review Narrative, and note it for Regional
Laboratory COR action.
d. For any Preparation Blank or LEB reported with a negative result, < (-CRQL), use
professional judgment to qualify detects < CRQL or qualify as estimated low (J-). Qualify
sample results that are > CRQLs as estimated low (J-), and qualify non-detects as estimated
(UJ). Sample results that are > lOx CRQLs should not be qualified.
August 2014 88
-------
Inorganic Data Review
Mercury
Table 25. Blank Actions for Mercury Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
Preparation
Blank/LEB
Preparation
Blank/LEB
Preparation
Blank/LEB
Preparation
Blank/LEB
Blank Result
Detect < CRQL
< (-MDL) but
> (-CRQL)
>CRQL
< (-CRQL)
Detect < CRQL
< (-MDL) but
> (-CRQL)
>CRQL
< (-CRQL)
Sample Result
Non-detect
Detect < CRQL
>CRQL
Detect or non-detect
Non-detect
Detect < CRQL
> CRQL but
< ICB/CCB Result
> ICB/CCB Result
Non-detect
Detect < CRQL
>CRQL
Non-detect
Detect < CRQL
>CRQL
Detect or non-detect
Non-detect
Detect < CRQL
> CRQL but
< 1 Ox the Preparation
Blank/LEB Result
> lOx the Preparation
Blank/LEB Result
Non-detect
Detect < CRQL
< lOx CRQL
> lOx CRQL
Action
No qualification
Report at CRQL and qualify as non-
detect (U)
Use professional judgment
Use professional judgment
No qualification
Report at CRQL and qualify as non-
detect (U)
Report at ICB/CCB Result as non-
detect (U) or unusable (R)
Use professional judgment
Use professional judgment to qualify
as estimated (UJ) or unusable (R)
Use professional judgment or (J-)
Use professional judgment to qualify
as estimated low (J-)
No qualification
Report at CRQL and qualify as non-
detect (U)
Use professional judgment
Use professional judgment
No qualification
Report at CRQL and qualify as non-
detect (U)
Report at Preparation Blank/LEB
Result and use professional judgment
to qualify results as estimated high
(J+) or unusable (R)
No qualification
Qualify as estimated (UJ)
Use professional judgment or (J-)
Report results > CRQL as estimated
low (J-)
No qualification
August 2014
89
-------
Inorganic Data Review Mercury
IV. Duplicate Sample Analysis
A. Review Items
Cover Page, Form 6-IN, instrument printouts, and raw data.
B. Objective
The objective of duplicate sample analysis is to demonstrate acceptable method precision by the
laboratory at the time of analysis.
C. Criteria
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
duplicate sample analysis.
2. At least one duplicate sample shall be prepared and analyzed from each group of samples of a
similar matrix type (e.g., water or soil) or for each SDG. Duplicates cannot be averaged for
reporting on Form 1-IN. Additional duplicate sample analyses may be required by EPA Regional
request. Alternately, the Region may require that a specific sample be used for the duplicate
sample analysis.
3. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original and
duplicate sample values > 5x the CRQL.
4. A control limit of the CRQL shall be used if either the sample or duplicate value is < 5x the
CRQL. The absolute value of the control limit (CRQL) shall be entered in the "Control Limit"
column on Form 6-IN. If both samples are non-detects, the RPD is not calculated for Form 6-IN.
NOTE: The above control limits are method requirements for duplicate samples, regardless of
the sample matrix type. However, it should be noted that laboratory variability arising
from the sub-sampling of non-homogenous soil samples is a common occurrence.
Therefore, for technical review purposes only, Regional policy or project DQOs may
allow the use of less restrictive criteria (e.g., 35% RPD, 2x the CRQL) to be assessed
against duplicate soil samples.
D. Evaluation
1. Verify, from the Cover Page and the raw data, that the appropriate number of required duplicate
samples were prepared and analyzed for the SDG.
2. Verify, using Form 6-IN and the raw data, that the duplicate results fall within the established
control limits.
3. Verify that a field blank or PE sample was not used for duplicate analysis.
4. Check the raw data and recalculate one or more of the RPD values using the following equation
to verify that the results were correctly reported on Form 6-IN:
IS-DI
RPD= x 100
(S + D)/2
Where,
RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
August 2014 90
-------
Inorganic Data Review Mercury
E. Action
NOTE: For a duplicate sample analysis that does not meet the technical criteria, apply the action
to all samples of the same matrix if the samples are considered sufficiently similar.
Exercise professional judgment in determining sample similarity when making use of all
available data, including: site and sampling documentation (e.g., location and type of
sample, descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity,
chlorine); and laboratory data for other parameters [e.g., Total Suspended Solids (TSS),
Total Dissolved Solids (TDS), Total Organic Carbon (TOC), alkalinity or buffering
capacity, reactive sulfide, anions]. Additionally, use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. Two
determinations are: 1) only some samples in the SDG are similar to the duplicate sample,
and that only these samples should be qualified; or 2) no samples are sufficiently similar
to the sample used for the duplicate, and thus only the field sample used to prepare the
duplicate sample should be qualified.
1. If the appropriate number of duplicate samples was not analyzed for each matrix using the correct
frequency, use professional judgment to determine if the associated sample data should be
qualified; obtain additional information from the laboratory, if necessary. Record the situation in
the Data Review Narrative, and note it for Regional Laboratory COR action. Associated samples
that are detects should be qualified as estimated (J) and non-detects as estimated (UJ) if any of the
frequency criteria is not met.
2. If both original sample and duplicate sample results are > 5x the CRQL and the RPD is > 20%,
qualify detects as estimated (J), and non-detects as estimated (UJ).
3. If both original sample and duplicate sample results are > 5x the CRQL and the RPD is < 20%,
detects and non-detects should not be qualified.
4. If RPD > 100%, use professional judgment to determine if the associated sample data should be
qualified.
5. If the original sample or duplicate sample result is < 5x the CRQL (including non-detects) and the
absolute difference between sample and duplicate > CRQL, qualify detects as estimated (J), and
non-detects as estimated (UJ).
6. If the original sample or duplicate sample result is < 5x the CRQL (including non-detects) and the
absolute difference between sample and duplicate < CRQL, detects and non-detects should not be
qualified.
7. If a field blank or PE sample was used for the duplicate sample analysis, note this for Regional
Laboratory COR action. All of the other QC data must then be carefully checked. Exercise
professional judgment when evaluating the data.
8. Annotate the potential effects on the data due to out-of-control duplicate sample results in the
Data Review Narrative.
August 2014 91
-------
Inorganic Data Review
Mercury
Table 26. Duplicate Sample Actions for Mercury Analysis
Criteria
Both original sample and duplicate sample results are > 5x
the CRQL and RPD > 20%*
Both original sample and duplicate sample results are > 5x
the CRQL and RPD is < 20%
RPD > 100%
Original sample or duplicate sample results < 5x the CRQL
(including non-detects) and absolute difference between
sample and duplicate > CRQL*
Original sample or duplicate sample result < 5x the CRQL
(including non-detects) and absolute difference between
sample and duplicate < CRQL
Action
Detect
J
No qualification
Use professional
judgment
J
No qualification
Non-detect
UJ
No qualification
Use professional
judgment
UJ
No qualification
* The above control limits are method requirements for duplicate samples, regardless of the
sample matrix type. However, it should be noted that laboratory variability arising from the sub-
sampling of non-homogenous soil samples is a common occurrence. Therefore, for technical
review purposes only, Regional policy or project DQOs may allow the use of less restrictive
criteria (e.g., 35% RPD, 2xthe CRQL) to be assessed against duplicate soil samples.
August 2014
92
-------
Inorganic Data Review Mercury
V. Spike Sample Analysis
A. Review Items
Cover Page, Form 5A-IN, instrument printouts, and raw data.
B. Objective
The objective of the spiked sample analysis is to evaluate the effect of each sample matrix on the
sample preparation procedures and the measurement methodology.
C. Criteria
1. Samples identified as field blanks or PE samples cannot be used for spiked sample analysis.
2. At least one spiked sample shall be prepared and analyzed from each group of samples with a
similar matrix type (e.g., water or soil), or for each SDG.
3. The spike %R shall be within the established acceptance limits. However, spike recovery limits
do not apply when the sample concentration is > 4x the spike added. In such an event, the data
shall be reported unflagged, even if the %R does not meet the acceptance criteria.
4. If the spiked sample analysis was performed on the same sample that was chosen for the duplicate
sample analysis, spike calculations shall be performed using the results of the sample designated
as the "original sample." The average of the duplicate results cannot be used for the purpose of
determining %R.
NOTE: The final spike concentration required is presented in the method described in the SOW.
D. Evaluation
1. Verify, using the Cover Page, Form 5 A-IN and raw data, that the appropriate number of required
spiked samples was prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Verify, using Form 5 A-IN and the raw data, that all Matrix Spike sample results fall within the
established control limits.
4. Recalculate, using the raw data, one or more of the %Rs using the following equation, and verify
that the recalculated value agrees with the laboratory-reported values on Form 5A-IN:
SSR-SR
%Recovery = x 100
oA.
Where,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
NOTE: When the sample result is < MDL or reported as a non-detect, use SR = 0 only for the
purpose of calculating the %R. The actual spiked sample result, sample result, and %R
(positive or negative) shall still be reported on Forms 5A-IN.
E. Action
NOTE: For a Matrix Spike that does not meet the technical criteria, apply the action to all
samples of the same matrix if the samples are considered sufficiently similar. Exercise
professional judgment in determining sample similarity when making use of all available
data, including: site and sampling documentation (e.g., location and type of sample,
descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity, chlorine);
and laboratory data for other parameters (e.g., TSS, TDS, TOC, alkalinity or buffering
capacity, reactive sulfide, anions). Additionally, use the sample data (e.g., similar
August 2014 93
-------
Inorganic Data Review
Mercury
concentrations of analytes) in determining similarity between samples in the SDG.
Possible determinations are: 1) only some of the samples in the SDG are similar to the
Matrix Spike sample, and that only these samples should be qualified; or, 2) no samples
are sufficiently similar to the sample used for the Matrix Spike, and thus only the field
sample used to prepare the Matrix Spike sample should be qualified.
1. If the appropriate number of Matrix Spike samples was not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified; obtain additional information from the laboratory, if necessary. Record the situation in
the Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ) if any of the frequency criteria is not
met.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for Regional
Laboratory COR action. All of the other QC data must then be carefully checked. Use
professional judgment when evaluating the data. Detects should be qualified as estimated (J) and
non-detects as estimated (UJ).
3. If the Matrix Spike %R is < 30%, qualify detects as estimated low (J-) and non-detects as
unusable (R).
4. If the Matrix Spike %R falls within the range of 30-74%, qualify detects as estimated low (J-) and
non-detects as estimated (UJ).
5. If the Matrix Spike %R falls with the range of 75-125%, detects and non-detects should not be
qualified.
6. If the Matrix Spike %R is > 125%, qualify detects as estimated high (J+). Non-detects should not
be qualified.
7. Annotate the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.
Table 27. Spike Sample Actions for Mercury Analysis
Criteria
Matrix Spike %R < 30%
Matrix Spike %R 30-74%
Matrix Spike %R75-125%
Matrix Spike %R > 125%
Action
Detect
J-
J-
No qualification
J+
Non- detect
R
UJ
No qualification
No qualification
NOTE: The above control limits are method requirements for spike samples, regardless of the
sample matrix type. However, it should be noted that laboratory variability arising from
the sub-sampling of non-homogenous soil samples is a common occurrence. Therefore,
for technical review purposes only, Regional policy or project DQOs may allow the use
of less restrictive criteria (e.g., 10 %R and 150 %R for the lower and upper limits) to be
assessed against spike soil samples.
August 2014
94
-------
Inorganic Data Review Mercury
VI. Regional Quality Assurance and Quality Control
A. Review Items
Form 1 -IN, instrument printouts, and raw data.
B. Objective
The objective is to use results from the analysis of Regional Quality Assurance/Quality Control
(QA/QC) samples such as field blanks, PE samples, blind spikes, and blind blanks to determine the
validity of the analytical results.
C. Criteria
Criteria are determined by the Region.
D. Evaluation
Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
review. Each Region will handle the evaluation of PE samples on an individual basis. Compare
results for PE samples with the acceptance criteria for the specific PE samples if possible.
Calculate the RPD between field duplicates and provide his information in the Data Review
Narrative.
E. Action
Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
results. Note any unacceptable PE sample results for Regional Laboratory COR action.
August 2014 95
-------
Inorganic Data Review Mercury
VII. Overall Assessment of Data
A. Review Items
Entire sample data package, data review results, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data (including any confirmation data).
B. Objective
The objective is to provide the overall assessment on data quality and usability.
C. Criteria
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
2. Reported analyte concentrations must be quantitated according to the appropriate analytical
method, as listed in the method. All sample results must be within the linear calibration ranges
per methods. Percent Solids (%Solids) must be properly used for all applicable matrix result
calculations.
D. Evaluation
Examine the raw data to verify that the correct calculation of the sample results was reported by the
laboratory. Digestion logs, instrument printouts, etc., should be compared to the reported sample
results recorded on the appropriate Inorganic Summary Forms (Form 1-IN through Form 16-IN).
1. Evaluate any technical problems not previously addressed.
2. Examine the raw data for any anomalies (e.g., baseline shifts, negative absorbance, omissions,
illegibility, etc.).
3. Verify that the appropriate methods and amounts were used to prepare samples and standards for
analysis. If reduced volumes are used, verify that the laboratory received Regional Laboratory
COR approval for the use of the reduced volume.
4. Verify that there are no transcription or reduction errors (e.g., dilutions, %Solids, sample weights,
etc.) on one or more samples. Recalculate %Solids for at least 10% of the samples and verify that
the calculated %Solids agree with that reported by the laboratory.
5. Verify that the MDL is properly reported and that it is not greater than the CRQL.
6. Verify that results fall within the calibrated range (Form 15-IN).
7. If appropriate information is available, assess the usability of the data to assist the data user in
avoiding inappropriate use of the data. Review all available information, including the Quality
Assurance Project Plan (QAPP), focusing specifically on the acceptance or performance criteria,
the SOPs, and communication with the user concerning the intended use and desired quality of
these data.
E. Action
1. Use professional judgment to determine if there is any need to qualify data which are not
qualified based on the QC criteria previously discussed.
2. Use professional judgment to qualify detects and non-detects if the MDL exceeds CRQL.
3. If a sample is not diluted properly when sample results exceed the upper limit of the calibration
range, qualify detects as estimated (J).
4. Write a brief Data Review Narrative to give the user an indication of the analytical limitations of
the data. Annotate any discrepancies between the data and the SDG Narrative for Regional
Laboratory COR action. If sufficient information on the intended use and required quality of the
data is available, include an assessment of the data usability within the given context.
August 2014 96
-------
Inorganic Data Review Mercury
5. If any discrepancies are found, notify the Regional Laboratory COR. The Regional Laboratory
COR may contact the laboratory to obtain additional information for resolution. If a discrepancy
remains unresolved, use professional judgment to determine if qualification of the data is
warranted.
August 2014 97
-------
Inorganic Data Review Mercury
VIII. Calculations
Aqueous/Water Samples:
Hg Concentration (ug/L) = C x DF
Where,
C = Instrument value in |o,g/L from the calibration curve
DF = Dilution Factor of the original sample
Soil/Sediment Samples:
Hg Concentration (mg/kg dry weight) = C x - x DF x 0.1
W x S
Where,
C = Instrument value in |o,g/L from the calibration curve
W = Initial aliquot amount (g)
S = %Solids/100 (see Exhibit D - General Inorganic Analysis, Section 10.1.4)
DF = Dilution Factor
Adjusted MDL/Adjusted CRQL Calculation:
To calculate the adjusted MDL or adjusted CRQL for aqueous/water samples, substitute the value of
the MDL ((ig/L) or CRQL ((ig/L) into the "C" term in the equation above.
Calculate the adjusted MDL or adjusted CRQL for soil/sediment samples as follows:
Wm
Adjusted MDL or CRQL (mg/kg) = C x - x DF
W x S
Where,
C = MDL or CRQL (mg/kg)
Wm = Method required minimum sample weight (g) (0.50 g)
W = Initial aliquot amount (g)
S = %Solids/100 (see Exhibit D - General Inorganic Analysis, Section 10.1.4)
DF = Dilution Factor
August 2014 98
-------
Inorganic Data Review Cyanide
CYANIDE DATA REVIEW
The inorganic data requirements for cyanide to be reviewed during validation are listed below:
Example Analytical Sequence 101
I. Preservation and Holding Times 103
II. Calibration 105
III. Blanks 109
IV. Duplicate Sample Analysis 113
V. Spike Sample Analysis 116
VI. Regional Quality Assurance and Quality Control 119
VII. Overall Assessment of Data 120
VIII. Calculations 122
August 2014 99
-------
Inorganic Data Review Cyanide
This page is intentionally left blank.
August 2014 100
-------
Inorganic Data Review Cyanide
Example Analytical Sequence
The following is an example of an analytical sequence:
S##
S##
s##
s##
s##
s##
ICV
ICB
ccv###
CCB###
samples
ccv###
CCB###
samples
ccv###
CCB###, etc.
* Suffix ## and ### are as specified in Exhibit B of the Statement of Work (SOW).
August 2014 101
-------
Inorganic Data Review Cyanide
This page is intentionally left blank.
August 2014 102
-------
Inorganic Data Review Cyanide
I. Preservation and Holding Times
A. Review Items
Form 1-IN, Form 12-IN, Traffic Report/Chain of Custody (TR/COC) documentation, Form DC-1,
raw data, and the Sample Delivery Group (SDG) Narrative checking for: pH; shipping container
temperature; holding time; and other sample conditions.
B. Objective
The objective is to determine the validity of the analytical results based on sample conditions and the
technical holding time of the sample.
C. Criteria
1. The technical holding time is determined from the date of collection, or the date Synthetic
Precipitation Leaching Procedure (SPLP) extraction is complete, to the date of analysis.
2. The technical holding time criteria for aqueous/water samples and leachate samples from SPLP is
14 days, preserved (with sodium hydroxide) to pH > 10.
3. The technical holding time criteria for soil/sediment samples is 14 days, based on the technical
holding time criteria for aqueous/water samples.
4. Aqueous/water and soil/sediment samples shall be maintained at < 6°C (but not frozen) from the
time of collection until preparation. The SPLP leachates must be stored at < 6°C (but not frozen)
from the time of the leaching procedure completion until preparation.
D. Evaluation
Establish technical holding times by comparing the sampling date(s) on the TR/COC documentation
with the dates of analysis on Form 12-IN and the raw data; also consider using information in the
Complete SDG File (CSF), as it may be helpful in the assessment. Verify that the analysis dates on
the Form 12-IN and the raw data are identical. Review the SDG Narrative and raw data preparation
logs to determine if samples were properly preserved. If there is an indication of problems with the
samples, the sample integrity may be compromised. Use professional judgment to evaluate the effect
of the problem on the sample results. For aqueous/water samples, look for evidence that the samples
were tested for the presence of sulfides, oxidizing agents, or nitrate/nitrite, and whether the
appropriate preservation steps were taken.
E. Action
NOTE: Apply the action to each field sample for which the preservation or holding time criteria
were not met.
1. If oxidizing agents were detected in aqueous/water samples at the time of sample preparation,
qualify detects as estimated low (J-) and non-detects as unusable (R). If sulfides were detected in
aqueous/water samples at the time of sample preparation, qualify detects as estimated (J) and
non-detects as unusable (R). If there is evidence that samples were not treated with sulfamic acid
prior to distillation for nitrate/nitrite interferences, qualify detects as estimated (J) and non-detects
as unusable (R). If the pH of aqueous/water samples was < 10 at the time of sample receipt, use
professional judgment to qualify the samples based on the pH of the sample. Detects should be
qualified as estimated low (J-) and non-detects as unusable (R).
2. If aqueous/water and soil/sediment samples are not maintained at < 6°C (but not frozen) from the
time of collection until receipt at the laboratory, detects should be qualified as estimated low (J-)
and non-detects as unusable (R).
3. If technical holding times are exceeded, use professional judgment to determine the reliability of
the data based on the magnitude of the additional time compared to the technical requirement and
whether the samples are properly preserved. The expected bias would be low. Detects should be
qualified as estimated low (J-) and non-detects as unusable (R).
August 2014 103
-------
Inorganic Data Review
Cyanide
4. Due to limited information concerning holding times for soil/sediment samples, use professional
judgment in deciding whether to apply the aqueous/water holding time criteria to soil/sediment
samples. If they are applied, document this in the Data Review Narrative.
5. When the holding times are exceeded, annotate any possible consequences for the analytical
results in the Data Review Narrative, and note it for Regional Laboratory Contracting Officer
Representative (COR) action.
Table 28. Preservation and Holding Time Actions for Cyanide Analysis
Criteria
Aqueous/water samples received with oxidizing agents
present
Aqueous/water samples received with sulfides present
Aqueous/water samples received with nitrate present and not
treated with sulfamic acid
Aqueous/water samples received with pH < 10
Aqueous/water and soil/sediment samples not maintained at
< 6°C (but not frozen) from time of collection until receipt at
the laboratory
Technical holding time:
Aqueous/water and SPLP leachate samples > 14 days
Technical holding time:
Soil/sediment samples > 14 days
Action
Detect
J-
J
J
Use professional
judgment
J-
Use professional
judgment
J-
J-
J-
Non- detect
R
R
R
Use professional
judgment
R
Use professional
judgment
R
R
R
August 2014
104
-------
Inorganic Data Review Cyanide
II. Calibration
A. Review Items
Form 2-IN, Form 12-IN, Form 15-IN, Form 16-IN, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data.
B. Objective
The objective is to determine the validity of the analytical results based on initial calibration and
calibration verification.
C. Criteria
1. Initial Calibration
The instruments shall be successfully calibrated daily (or once every 24 hours), and each time the
instrument is set up. The calibration date and time shall be included in the raw data. The
calibration curve standards shall be distilled by the same method used to prepare the samples for
analysis.
a. A blank and at least five calibration standards shall be employed to establish the calibration
curve. At least one of the calibration standards shall be at or below the Contract Required
Quantitation Limit (CRQL), but above the Method Detection Limit (MDL). The calibration
curve shall be fitted using linear regression or weighted linear regression. The curve may be
forced through zero. The calibration curve must have a correlation coefficient > 0.995. The
calculated percent differences (%Ds) for all of the non-zero standards must be within ±30%
of the true value of the standard. The y-intercept of the curve must be less than the CRQL.
2. Initial and Continuing Calibration Verification
The acceptance criteria for the Initial Calibration Verification (ICV) and Continuing Calibration
Verification (CCV) standards are presented in Table 29:
Table 29. Acceptance Criteria for ICV and CCV Standards for Cyanide Analysis
Analytical Method
Colorimetric
Inorganic Analyte
Cyanide
ICV/CCV Low Limit
(% of True Value)
85
ICV/CCV High Limit
(% of True Value)
115
a. Initial Calibration Verification
1) Immediately after each colorimetric system has been calibrated, the accuracy of the initial
calibration must be verified and documented by the analysis of an ICV solution(s). If the
ICV Percent Recovery (%R) falls outside of the control limits, the analysis should be
terminated, the problem corrected, the instrument recalibrated, and all affected samples
reanalyzed.
2) Only if the ICV is not available from the United States Environmental Protection Agency
(EPA), analyses shall be conducted using a certified solution of the analyte from an
independent commercial standard source, at a concentration level other than that used for
instrument calibration, but within the calibrated range.
3) The ICV standard solution shall be distilled by the same method used to prepare the
samples for analysis.
b. Continuing Calibration Verification
1) To ensure accuracy during the course of each analytical sequence, the CCV shall be
analyzed and reported.
August 2014 105
-------
Inorganic Data Review Cyanide
2) The CCV standard shall be analyzed at a frequency of every hour during an analytical
sequence. The CCV standard shall also be analyzed at the beginning of the analytical
sequence, and again after the last analytical sample.
3) The analyte concentration in the CCV standard shall be different from the concentration
used for the ICV, and at a concentration equivalent to the mid level of the calibration
curve.
4) The same CCV standard solution shall be used throughout the analysis for an SDG.
5) The CCV shall be processed and analyzed in the same fashion as an actual sample. If the
%R of the CCV was outside of the control limits, the analysis should be terminated, the
problem corrected, the instrument recalibrated, and all analytical samples analyzed since
the last compliant CCV reanalyzed.
6) The CCV standard solution shall be distilled by the same method used to prepare the
samples for analysis.
D. Evaluation
1. Verify that the instrument was calibrated daily (once every 24 hours) and each time the
instrument was set up, utilizing a blank and at least five calibration standards. Confirm that at
least one of the calibration standards was analyzed at or below the CRQL, but above the MDL.
2. Verify, using the distillation log, that the calibration standards, the ICV, and the CCV standards
were distilled and analyzed.
3. Verify that the ICV and CCV standards were analyzed at the specified frequency and at the
appropriate concentration. Verify that acceptable %R results were obtained.
4. Recalculate one or more of the ICV or CCV %R using the following equation and verify that the
recalculated value agrees with the laboratory-reported values on Form 2-IN.
Found (value)
%R = x 100
True (value)
Where,
j / i x Concentration (in ug/L) of cyanide measured in the analysis of the ICV or
Found (value) = ,, i *
v ' CCV solution
True (value) = Concentration (in (ig/L) of cyanide in the ICV or CCV source
E. Action
NOTES: For initial calibrations or ICV standards that do not meet the technical criteria, apply the
action to all associated samples reported from the analytical sequence.
For CCV standards that do not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the Quality Control (QC)
sample and a subsequent technically acceptable analysis of the QC sample in the
analytical sequence.
1. If the instrument was not calibrated daily and each time the instrument was set up, qualify detects
and non-detects as unusable (R). If the instrument was not calibrated with at least the minimum
number of standards, or if the calibration curve does not include standards at required
concentrations (e.g., a blank and a standard at or below the CRQL but above the MDL), use
professional judgment to qualify detects as estimated (J) or unusable (R), and non-detects as
estimated (UJ) or unusable (R).
2. If the correlation coefficient is < 0.995, the %D is outside the ±30% limit, or y-intercept > CRQL,
qualify detects as estimated (J) and non-detects as estimated (UJ).
August 2014 106
-------
Inorganic Data Review Cyanide
3. If the ICV or the CCV standards are not distilled, qualify detects as estimated (J) and non-detects
as estimated low (UJ-).
4. If the ICV or CCV %R falls outside the acceptance windows, use professional judgment to
qualify all associated data. If possible, indicate the bias in the review. The following guidelines
are recommended:
a. If the ICV or CCV %R is < 70%, qualify detects as estimated low (J-) or unusable (R) and
non-detects as unusable (R).
b. If the ICV or CCV %R falls within the range of 70-84%, qualify detects as estimated low (J-)
and non-detects as estimated (UJ).
c. If the ICV or CCV %R falls within the range of 85-115%, detects and non-detects should not
be qualified.
d. If the ICV or CCV %R falls within the range of 116-130%, qualify detects as estimated high
(J+). Non-detects should not be qualified.
e. If the ICV or CCV %R is > 130%, use professional judgment to qualify detects as estimated
high (J+) or unusable (R). Non-detects should not be qualified.
5. If the laboratory failed to provide adequate calibration information, notify the Regional
Laboratory COR. The Regional Laboratory COR may contact the laboratory and request the
necessary information. If the information is not available, use professional judgment to assess the
data.
6. Annotate the potential effects on the reported data due to exceeding the calibration criteria in the
Data Review Narrative.
7. If calibration criteria are grossly exceeded, note this for Regional Laboratory COR action.
NOTE: For truly critical samples, a further in-depth evaluation of the calibration curve may be
warranted to determine if additional qualification is necessary.
August 2014 107
-------
Inorganic Data Review
Cyanide
Table 30. Calibration Actions for Cyanide Analysis
Criteria
Calibration not performed
Calibration incomplete
Correlation coefficient < 0.995; %D outside ±30%;
y-intercept > CRQL
Standards and QC not distilled
ICV/CCV %R < 70%
ICV/CCV %R 70-84%
ICV/CCV %R 85-1 15%
ICV/CCV %R 116-130%
ICV/CCV %R> 130%
Action
Detect
R
Use professional
judgment
JorR
J
J
Use professional
judgment
J-orR
J-
No qualification
J+
Use professional
judgment
J+orR
Non-detect
R
Use professional
judgment
UJorR
UJ
UJ-
R
UJ
No qualification
No qualification
No qualification
August 2014
108
-------
Inorganic Data Review Cyanide
III. Blanks
A. Review Items
Form 1-IN, Form 3-IN, Form 12-IN, preparation logs, calibration standard logs, instrument logs, and
raw data.
B. Objective
The objective is to determine the validity of the analytical results based on the blank responses by
determining the existence and magnitude of contamination resulting from laboratory (or field)
activities or baseline drift during analysis.
C. Criteria
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed at each mass used for analysis after the
analytical standards, but not before analysis of the ICV during the initial calibration of the
instrument (see Section II.C.l).
3. A Continuing Calibration Blank (CCB) shall be analyzed immediately after every CCV. The
CCB shall be analyzed at a frequency of every hour during the analytical sequence. The CCB
shall be analyzed at the beginning of the analytical sequence, and again after the last CCV that
was analyzed after the last analytical sample of the analytical sequence. The CCB result
(absolute value) shall not exceed the CRQL.
4. At least one Preparation Blank shall be prepared and analyzed for each matrix, with every SDG,
or with each batch of samples distilled, whichever is more frequent. The Preparation Blank
consists of reagent water processed through the appropriate sample preparation and analysis
procedure.
5. If the analyte concentration in the Preparation Blank is > CRQL, the lowest concentration of the
analyte in the associated samples must be > lOx the Preparation Blank concentration. Otherwise,
all associated samples with the analyte's concentration < lOx the Preparation Blank
concentration, and > CRQL, should be redistilled and reanalyzed. The laboratory is not to correct
the sample concentration for the blank value.
6. If the analyte concentration in the Preparation Blank is < (-CRQL), all associated samples with
the analyte's concentration < lOxthe CRQL, should be redistilled and reanalyzed.
7. At least one Leachate Extraction Blank (LEB) shall be prepared and analyzed for each batch of
samples extracted by SPLP. The LEB consists of reagent water processed through the extraction
procedure. Post-extraction, the LEB shall be processed through the appropriate sample
preparation and analysis procedure.
D. Evaluation
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the specified
frequency and sequence during the analytical sequence, and Preparation Blanks and LEBs are
prepared and analyzed as appropriate for the SDG (e.g., total number of samples, various types of
matrices present, number of distillation batches, etc.).
2. Review the results reported Form 3-IN, as well as the raw data for all blanks, and verify that the
results were accurately reported.
3. Evaluate all of the associated blanks for the presence of the target analyte. Verify that if the
concentration of the target analyte was > CRQL in a Preparation Blank, all associated samples
with the analyte's concentration > CRQL but < lOx the Preparation Blank concentration were
redistilled and reanalyzed for the analyte. Verify that if a concentration was < (-CRQL) in a
Preparation Blank, all associated samples with the analyte's concentration < lOx CRQL were
redistilled and reanalyzed. Verify that if the absolute value of the target analyte was > CRQL in
August 2014 109
-------
Inorganic Data Review Cyanide
an ICB or a CCB, the analysis was terminated, the problem corrected, the instrument recalibrated,
and the preceding 10 analytical samples or all analytical samples analyzed since the last
compliant calibration blank reanalyzed.
E. Action
NOTES: For ICBs that do not meet the technical criteria, apply the action to all associated samples
reported from the analytical sequence.
For CCBs that do not meet the technical criteria, apply the action to all associated
samples analyzed between a previous technically acceptable analysis of the CCB and a
subsequent technically acceptable analysis of the CCB in the analytical sequence.
For Preparation Blanks that do not meet the technical criteria, apply the action to all
associated samples prepared in the same preparation batch. For LEBs that do not meet
the technical criteria, apply the action to all associated samples extracted in the same
extraction batch.
1. If the appropriate blanks were not analyzed with the correct frequency, use professional judgment
to determine if the associated sample data should be qualified; obtain additional information from
the laboratory, if necessary. Record the situation in the Data Review Narrative, and note it for
Regional Laboratory COR action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
In instances where more than one blank is associated with a given sample, qualification should be
based upon a comparison with the associated blank having the highest concentration of
contaminant.
3. Some general "technical" review actions include:
a. For any blank (including Preparation Blanks and LEBs) reported with detects < CRQL, report
detects < CRQL at the CRQL and qualify as a non-detect (U). For any blank (including
Preparation Blanks and LEBs) reported with a detect < CRQL, use professional judgment to
qualify the sample results > CRQLs. Non-detects should not be qualified.
b. For any blank (including Preparation Blanks and LEBs) reported with a negative result,
< (-MDL) but > (-CRQL), carefully evaluate and determine its effect on the sample data. Use
professional judgment to assess the data.
c. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil/sediment sample results reported on Form 1-IN will
not be on the same basis (units, dilution) as the calibration blank data reported on Form 3-IN.
It may be easier to work with the raw data and/or convert the ICB or CCB results to the same
units as the soil/sediment samples for comparison purposes.
4. Specific "method" actions include:
a. If an ICB or a CCB result is > CRQL, the analysis should be terminated. If the analysis was
not terminated and the associated samples were not reanalyzed, non-detects should not be
qualified. Report detects < CRQL at the CRQL and qualify as non-detect (U). Report
sample results that are > CRQL but < ICB/CCB Results at ICB/CCB Results and use
professional judgment to qualify as non-detect (U) or unusable (R). Use professional
judgment to qualify sample results that are > ICB/CCB Results. Record the situation in the
Data Review Narrative, and note it for Regional Laboratory COR action.
b. If an ICB or a CCB result is < (-CRQL), the analysis should be terminated. If the analysis
was not terminated and the associated samples were not reanalyzed, use professional
judgment to qualify non-detects as estimated (UJ) or unusable (R). Use professional
judgment to qualify detects < CRQL, or qualify as estimated low (J-). Use professional
judgment to qualify sample results that are > CRQLs as estimated low (J-).
August 2014 110
-------
Inorganic Data Review
Cyanide
c. If the concentration of any analyte in the Preparation Blank/LEB is > CRQL, the lowest
concentration of that analyte in the associated samples must be > lOx the Preparation
Blank/LEB concentration. Otherwise, all samples associated with that blank with
concentrations < 1 Ox the Preparation Blank concentration and > CRQL should have been
redistilled and reanalyzed. If the associated samples were not redistilled and reanalyzed,
report the sample results at Preparation Blank Results; use professional judgment to qualify
the results as estimated high (J+) or unusable (R). Report results < lOx the LEB
concentration and > CRQL in the samples associated with the LEB at LEB Results; use
professional judgment to qualify the results as estimated high (J+) or unusable (R). Report
detects < CRQLs in the samples associated with the Preparation Blank/LEB at CRQLs and
qualify as non-detect (U). Non-detects and sample results that are > lOx the Preparation
Blank/LEB Results should not be qualified. If the laboratory failed to redistill and reanalyze
the samples associated with the Preparation Blank, record it in the Data Review Narrative,
and note it for Regional Laboratory COR action.
d. For any Preparation Blanks or LEBs reported with a negative result < (-CRQL), use
professional judgment to qualify detects < CRQL, or qualify as estimated low (J-). Qualify
sample results that are > CRQLs as estimated low (J-), and non-detects as estimated (UJ).
Sample results that are > lOx CRQLs should not be qualified.
Table 31. Blank Actions for Cyanide Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
Preparation
Blank/LEB
Blank Result
Detect < CRQL
< (-MDL) but
> (-CRQL)
>CRQL
< (-CRQL)
Detect < CRQL
Sample Result
Non-detect
Detect < CRQL
>CRQL
Detect or non-detect
Non-detect
Detect < CRQL
> CRQL but
< ICB/CCB Result
> ICB/CCB Result
Non-detect
Detect < CRQL
>CRQL
Non-detect
Detect < CRQL
>CRQL
Action
No qualification
Report at CRQL and qualify as non-
detect (U)
Use professional judgment
Use professional judgment
No qualification
Report at CRQL and qualify as non-
detect (U)
Report at ICB/CCB Result and
qualify as non-detect (U) or unusable
(R)
Use professional judgment
Use professional judgment to qualify
as estimated (UJ) or unusable (R)
Use professional judgment or (J-)
Use professional judgment to qualify
as estimated low (J-)
No qualification
Report at CRQL and qualify as non-
detect (U)
Use professional judgment
August 2014
111
-------
Inorganic Data Review
Cyanide
Blank
Type
Preparation
Blank/LEB
Preparation
Blank/LEB
Preparation
Blank/LEB
Blank Result
< (-MDL) but
> (-CRQL)
>CRQL
< (-CRQL)
Sample Result
Detect or non-detect
Non-detect
Detect < CRQL
> CRQL but
< 1 Ox the Preparation
Blank/LEB Result
> lOx the Preparation
Blank/LEB Result
Non-detect
Detect < CRQL
< lOx CRQL
> lOx CRQL
Action
Use professional judgment
No qualification
Report at CRQL and qualify as non-
detect (U)
Report at Preparation Blank/LEB
Result and use professional judgment
to qualify results as estimated high
(J+) or unusable (R)
No qualification
Qualify as estimated (UJ)
Use professional judgment or (J-)
Qualify results that are > CRQL as
estimated low (J-)
No qualification
August 2014
112
-------
Inorganic Data Review Cyanide
IV. Duplicate Sample Analysis
A. Review Items
Cover Page, Form 6-IN, instrument printouts, and raw data.
B. Objective
The objective of duplicate sample analysis is to demonstrate acceptable method precision by the
laboratory at the time of analysis.
C. Criteria
1 . Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
duplicate sample analysis.
2. At least one duplicate sample shall be prepared and analyzed from each group of samples of a
similar matrix type (e.g., water or soil) or for each SDG. Duplicates cannot be averaged for
reporting on Form 1-IN. Additional duplicate sample analyses may be required by EPA Regional
request. Alternately, the Region may require that a specific sample be used for the duplicate
sample analysis.
3 . A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original and
duplicate sample values > 5x the CRQL.
4. A control limit of the CRQL shall be used if either the sample or duplicate value is < 5x the
CRQL. The absolute value of the control limit (CRQL) shall be entered in the "Control Limit"
column on Form 6-IN. If both samples are non-detects, the RPD is not calculated for Form 6-IN.
NOTE: The above control limits are method requirements for duplicate samples, regardless of
the sample matrix type. However, it should be noted that laboratory variability arising
from the sub-sampling of non-homogenous soil samples is a common occurrence.
Therefore, for technical review purposes only, Regional policy or project Data Quality
Objectives (DQOs) may allow the use of less restrictive criteria (e.g., 35% RPD, 2x the
CRQL) to be assessed against duplicate soil samples.
D. Evaluation
1 . Verify, from the Cover Page and the raw data, that the appropriate number of required duplicate
samples were prepared and analyzed for the SDG.
2. Verify, using Form 6-IN and the raw data, that the duplicate results fall within the established
control limits.
3. Verify that a field blank or PE sample was not used for duplicate analysis.
4. Check the raw data and recalculate one or more of the RPD values using the following equation
to verify that the results were correctly reported on Form 6-IN:
IS-DI
Where,
RPD = Relative Percent Difference
S = Sample result (original)
D = Duplicate result
August 2014 113
-------
Inorganic Data Review Cyanide
E. Action
NOTE: For a duplicate sample analysis that does not meet the technical criteria, apply the action
to all samples of the same matrix if the samples are considered sufficiently similar.
Exercise professional judgment in determining sample similarity when making use of all
available data, including: site and sampling documentation (e.g., location and type of
sample, descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity,
chlorine); and laboratory data for other parameters [e.g., Total Suspended Solids (TSS),
Total Dissolved Solids (TDS), Total Organic Carbon (TOC), alkalinity or buffering
capacity, reactive sulfide, anions]. Additionally, use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. The
determinations are: 1) only some of the samples in the SDG are similar to the duplicate
sample, and that only these samples should be qualified; or, 2) no samples are sufficiently
similar to the sample used for the duplicate, and thus only the field sample used to
prepare the duplicate sample should be qualified.
1. If the appropriate number of duplicate samples was not analyzed for each matrix using the correct
frequency, use professional judgment to determine if the associated sample data should be
qualified; obtain additional information from the laboratory, if necessary. Record the situation in
the Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ) if any of the frequency criteria is not
met.
2. If both original sample and duplicate sample results are > 5x the CRQL and the RPD is > 20%,
qualify detects as estimated (J), and qualify non-detects as estimated (UJ).
3. If RPD > 100%, use professional judgment to determine if the associated sample data should be
qualified.
4. If both original sample and duplicate sample results are > 5x the CRQL and the RPD is < 20%,
detects and non-detects should not be qualified.
5. If the original sample or duplicate sample result is < 5x the CRQL (including non-detects) and the
absolute difference between sample and duplicate > CRQL, qualify detects as estimated (J) and
non-detects as estimated (UJ).
6. If the original sample or duplicate sample result is < 5x the CRQL (including non-detects) and the
absolute difference between sample and duplicate < CRQL, detects and non-detects should not be
qualified.
7. If a field blank or PE sample was used for the duplicate sample analysis, note this for Regional
Laboratory COR action. All of the other QC data must then be carefully checked. Exercise
professional judgment when evaluating the data.
8. Annotate the potential effects on the data due to out-of-control duplicate sample results in the
Data Review Narrative.
August 2014 114
-------
Inorganic Data Review
Cyanide
Table 32. Duplicate Sample Actions for Cyanide Analysis
Criteria
Both original sample and duplicate sample results are > 5x
the CRQL and RPD > 20%*
RPD > 100%
Both original sample and duplicate sample results are > 5x
the CRQL and RPD is < 20%
Original sample or duplicate sample result < 5x the CRQL
(including non-detects) and absolute difference between
sample and duplicate > CRQL*
Original sample or duplicate sample result < 5x the CRQL
(including non-detects) and absolute difference between
sample and duplicate < CRQL
Action
Detect
J
Use professional
judgment
No qualification
J
No qualification
Non-detect
UJ
Use professional
judgment
No qualification
UJ
No qualification
* The above control limits are method requirements for duplicate samples, regardless of the
sample matrix type. However, it should be noted that laboratory variability arising from the sub-
sampling of non-homogenous soil samples is a common occurrence. Therefore, for technical
review purposes only, Regional policy or project DQOs may allow the use of less restrictive
criteria (e.g., 35% RPD, 2xthe CRQL) to be assessed against duplicate soil samples.
August 2014
115
-------
Inorganic Data Review Cyanide
V. Spike Sample Analysis
A. Review Items
Cover Page, Form 5A-IN, Form 5B-IN, instrument printouts, and raw data.
B. Objective
The objective of the spiked sample analysis is to evaluate the effect of each sample matrix on the
sample preparation procedures and the measurement methodology.
C. Criteria
1. Samples identified as field blanks or PE samples cannot be used for spiked sample analysis.
2. At least one spiked sample (pre-distillation) shall be prepared and analyzed from each group of
samples with a similar matrix type (e.g., water or soil), or for each SDG.
3. When the Matrix Spike recovery falls outside of the control limits and the sample result is < 4x
the spike added, a post-distillation spike shall be performed. An aliquot of the remaining
unspiked sample shall be spiked at 2x the indigenous level or 2x the CRQL, whichever is greater.
4. The spike %R shall be within the established acceptance limits. However, spike recovery limits
do not apply when the sample concentration is >4x the spike added. In such an event, the data
shall be reported unflagged, even if the %R does not meet the acceptance criteria.
5. If the spiked sample analysis was performed on the same sample that was chosen for the duplicate
sample analysis, spike calculations shall be performed using the results of the sample designated
as the "original sample." The average of the duplicate results cannot be used for the purpose of
determining %R.
NOTE: The final spike concentration required is presented in the method described in the SOW.
D. Evaluation
1. Verify, using the Cover Page, Form 5 A-IN and raw data, that the appropriate number of required
spiked samples was prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Verify, using Form 5 A-IN and the raw data, that all pre-distillation spiked sample results fall
within the established control limits. If not, verify that a post-distillation spike was prepared and
analyzed.
4. Recalculate, using the raw data, one or more of the %Rs using the following equation, and verify
that the recalculated value agrees with the laboratory-reported values on Forms 5A-IN & 5B-IN:
SSR-SR
%Recovery= x 100
oA.
Where,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
NOTE: When the sample result is < MDL or reported as a non-detect, use SR = 0 only for the
purpose of calculating the %R. The actual spiked sample results, sample results, and %R
(positive or negative) shall still be reported on Forms 5A-IN & 5B-IN.
August 2014 116
-------
Inorganic Data Review Cyanide
E. Action
NOTE: For a Matrix Spike that does not meet the technical criteria, apply the action to all
samples of the same matrix if the samples are considered sufficiently similar. Exercise
professional judgment in determining sample similarity when making use of all available
data, including: site and sampling documentation (e.g., location and type of sample,
descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity, chlorine);
and laboratory data for other parameters (e.g., TSS, TDS, TOC, alkalinity or buffering
capacity, reactive sulfide, anions). Also use the sample data (e.g., similar concentrations
of analytes) in determining similarity between samples in the SDG. The possible
determination are: 1) only some of the samples in the SDG are similar to the Matrix
Spike sample, and that only these samples should be qualified; or 2) no samples are
sufficiently similar to the sample used for the Matrix Spike, and thus only the field
sample used to prepare the Matrix Spike sample should be qualified.
1. If the appropriate number of Matrix Spike samples was not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified; obtain additional information from the laboratory, if necessary. Record the situation in
the Data Review Narrative, and note it for Regional Laboratory COR action. Detects should be
qualified as estimated (J) and non-detects as estimated (UJ) if any of the frequency criteria is not
met.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for Regional
Laboratory COR action. All of the other QC data must then be carefully checked. Use
professional judgment when evaluating the data. Detects should be qualified as estimated (J) and
non-detects as estimated (UJ).
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-distillation
spike was not performed, note this for Regional Laboratory COR action.
4. If the Matrix Spike %R is < 30%, verify that a post-distillation spike was analyzed (if required
when sample concentration is < 4x spike added). If the post-distillation spike %R is < 75% or the
analysis was not performed, qualify detects as estimated low (J-), and non-detects as unusable
(R). If the post-distillation spike %R is > 75%, qualify detects as estimated (J) and non-detects as
estimated (UJ).
5. If the Matrix Spike %R falls within the range of 30-74%, verify that a post-distillation spike was
analyzed (if required when sample concentration is < 4x spike added). If the post-distillation
spike %R is < 75% or the analysis was not performed, qualify detects as estimated low (J-), and
non-detects as estimated (UJ). If the post-distillation spike %R is > 75%, qualify detects as
estimated (J), and non-detects as estimated (UJ).
6. If the Matrix Spike %R falls within the range of 75-125%, no post-distillation spike is required.
Detects and non-detects should not be qualified.
7. If the Matrix Spike %R is > 125%, verify that a post-distillation spike was analyzed (if required
when sample concentration is < 4x spike added). If the post-distillation spike %R is > 125% or
the analysis was not performed, qualify detects as estimated high (J+); non-detects should not be
qualified. If the post-distillation spike %R is < 125%, qualify detects as estimated (J); non-
detects should not be qualified.
8. Annotate the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.
August 2014 117
-------
Inorganic Data Review
Cyanide
Table 33. Spike Sample Actions for Cyanide Analysis
Criteria
Matrix Spike %R < 30%
Post-distillation spike %R< 75%
Matrix Spike %R < 30%
Post-distillation spike %R> 75%
Matrix Spike %R 30-74%
Post-distillation spike %R< 75%
Matrix Spike %R 30-74%
Post-distillation spike %R> 75%
Matrix Spike %R > 125%
Post-distillation spike %R> 125%
Matrix Spike %R > 125%
Post-distillation spike %R< 125%
Matrix Spike %R < 30%
No post-distillation spike performed
Matrix Spike %R 30-74%
No post-distillation spike performed
Matrix Spike %R75-125%
Post-distillation not required
Matrix Spike %R > 125%
No post-distillation spike performed
Action
Detect
J-
J
J-
J
J+
J
J-
J-
No qualification
J+
Non-detect
R
UJ
UJ
UJ
No qualification
No qualification
R
UJ
No qualification
No qualification
NOTE: The above control limits are method requirements for spike samples, regardless of the
sample matrix type. However, it should be noted that laboratory variability arising from
the sub-sampling of non-homogenous soil samples is a common occurrence. Therefore,
for technical review purposes only, Regional policy or project DQOs may allow the use
of less restrictive criteria (e.g., 10 %R and 150 %R for the lower and upper limits) to be
assessed against spike soil samples.
August 2014
118
-------
Inorganic Data Review Cyanide
VI. Regional Quality Assurance and Quality Control
A. Review Items
Form 1 -IN, instrument printouts, and raw data.
B. Objective
The objective is to use results from the analysis of Regional Quality Assurance/Quality Control
(QA/QC) samples such as field blanks, PE samples, blind spikes, and blind blanks to determine the
validity of the analytical results.
C. Criteria
Criteria are determined by each Region.
D. Evaluation
Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
review. Each Region will handle the evaluation of PE samples on an individual basis. Compare
results for PE samples to the acceptance criteria for the specific PE samples if possible.
Calculate the RPD between field duplicates and provide this information in the Data Review
Narrative.
E. Action
Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
results. Note any unacceptable PE sample results for Regional Laboratory COR action.
August 2014 119
-------
Inorganic Data Review Cyanide
VII. Overall Assessment of Data
A. Review Items
Entire data package, data review results, preparation logs, calibration standard logs, instrument logs,
instrument printouts, and raw data (including any confirmation data).
B. Objective
The objective is to provide the overall assessment on data quality and usability.
C. Criteria
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
2. Reported analyte concentrations must be quantitated according to the appropriate analytical
method, as listed in the method. All sample results must be within the linear calibration ranges
per methods. Percent Solids (%Solids) must be properly used for all applicable matrix result
calculations.
D. Evaluation
Examine the raw data to verify that the correct calculation of the sample results was reported by the
laboratory. Distillation logs, instrument printouts, etc., should be compared to the reported sample
results recorded on the appropriate Inorganic Summary Forms (Form 1-IN through Form 16-IN).
1. Evaluate any technical problems not previously addressed.
2. Examine the raw data for any anomalies (e.g., baseline shifts, negative absorbance, omissions,
illegibility, etc.).
3. Verify that the appropriate methods and amounts were used to prepare samples for analysis. If
reduced volumes were used, verify that the laboratory had received Regional Laboratory COR
approval for the use of the reduced volume.
4. Verify that there were no transcription or reduction errors (e.g., dilutions, %Solids, sample
weights, etc.) on one or more samples. Recalculate %Solids for at least 10% of the samples and
verify that the calculated %Solids agree with that reported by the laboratory.
5. Verify that the MDL is properly reported and it is not greater than the CRQL.
6. Verify that results fall within the calibrated range (Form 15-IN).
7. If appropriate information is available, assess the usability of the data to assist the data user in
avoiding inappropriate use of the data. Review all available information, including the Quality
Assurance Project Plan (QAPP), focusing specifically on the acceptance or performance criteria,
the SOPs, and communication with user concerning the intended use and desired quality of these
data.
E. Action
1. Use professional judgment to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
2. Use professional judgment to qualify detects and non-detects if the MDL exceeds the CRQL.
3. If a sample is not diluted properly when sample results exceed the upper limit of the calibration
range, qualify detects as estimated (J).
4. Write a brief Data Review Narrative to give the user an indication of the analytical limitations of
the data. Annotate any discrepancies between the data and the SDG Narrative for Regional
Laboratory COR action. If sufficient information on the intended use and required quality of the
data is available, include an assessment of the data usability within the given context.
August 2014 120
-------
Inorganic Data Review Cyanide
5. If any discrepancies are found, notify the Regional Laboratory COR. The Regional Laboratory
COR may contact the laboratory to obtain additional information for resolution. If a discrepancy
remains unresolved, determine if qualification of the data is warranted.
August 2014 121
-------
Inorganic Data Review Cyanide
VIII. Calculations
Aqueous/Water Sample Concentration:
Vf
CN Concentration (ug/L) = C x -^ x DF
Where,
C = Instrument response in |og/L CN from the calibration curve
Vf = Final prepared (absorbing solution) volume (mL)
V = Initial aliquot amount (mL)
DF = Dilution Factor
Soil/Sediment Sample Concentration:
Vf
CN Concentration (mg/kg dry weight) = C x - x (1/1000) x DF
W x S
Where,
C = Instrument response in |og/L CN from the calibration curve
Vf = Final prepared (absorbing solution) volume (mL)
W = Initial aliquot amount (g)
S = %Solids/100 (see Exhibit D - General Inorganic Analysis, Section 10.1.4)
DF = Dilution Factor
Adjusted MDL/Adjusted CRQL Calculation:
To calculate the adjusted MDL or adjusted CRQL for aqueous/water samples, substitute the value of
the MDL ((ig/L) or CRQL ((ig/L) into the "C" term in the equation above.
Calculate the adjusted MDL or adjusted CRQL for all soil/sediment as follows:
WM
Adjusted MDL or CRQL (mg/kg) = C x ^- x DF
Where,
C = MDL or CRQL (mg/kg)
WM = Minimum method required aliquot amount (1.00 g for Midi or 0.50 g for Micro)
W = Initial aliquot amount (g)
S = %Solids/100 (see Exhibit D - General Inorganic Analysis, Section 10.1.4)
DF = Dilution Factor
August 2014 122
-------
Inorganic Data Review Appendix A
APPENDIX A: GLOSSARY
Analyte - The element or ion an analysis seeks to determine; the element of interest.
Analytical Sample - Any solution or media introduced into an instrument on which an analysis is
performed, excluding instrument calibration, Initial Calibration Verification (ICV), Initial Calibration
Blank (ICB), Continuing Calibration Verification (CCV), Continuing Calibration Blank (CCB), and
tunes. Note that the following are all defined as analytical samples: undiluted and diluted samples (EPA
and non-EPA); matrix spike samples; duplicate samples; serial dilution samples, analytical (post-
digestion/post-distillation) spike samples; Interference Check Samples (ICSs); Laboratory Control
Samples (LCSs); Performance Evaluation (PE) samples; and Preparation Blanks.
Analytical Services Branch (ASB) - The division of the United States Environmental Protection
Agency's (EPA) Office of Superfund Remediation and Technology Innovation (OSRTI) responsible for
the overall management of the Contract Laboratory Program (CLP).
Associated Samples - Any sample related to a particular Quality Control (QC) analysis. For example,
for Initial Calibration Verification (ICV), all samples analyzed under the same calibration curve. For
duplicates, all Sample Delivery Group (SDG) samples digested/distilled of the same matrix.
Blank - An analytical sample that has negligible or unmeasurable amounts of a substance of interest.
The blank is designed to assess specific sources of contamination. Types of blanks may include
calibration blanks, preparation blanks, and field blanks. See the individual definitions for types of blanks.
Calibration - A set of operations that establish under specific conditions, the relationship between values
indicated by a measuring instrument and the corresponding known values. The calibration standards must
be prepared using the same type of reagents or concentration of acids as used in the sample preparation.
Calibration Blank - A blank solution containing all of the reagents, and in the same concentration, as
those used in the analytical sample preparation. This blank is not subjected to the preparation method for
Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) and Inductively Coupled
Plasma-Mass Spectroscopy (ICP-MS), but is digested for mercury and cyanide. Calibration blanks are
used to verify that the instrument baseline is stable and the instrument is free of contamination.
Calibration Curve - A plot of instrument response versus concentration of standards.
Calibration Standards - A series of known standard solutions used by the analyst for calibration of the
instrument (i.e., preparation of the analytical curve). The solutions may or may not be subjected to the
preparation method, but contain the same matrix (i.e., the same amount of reagents and/or preservatives)
as the sample preparations to be analyzed.
Case - A finite, usually predetermined number of samples collected over a given time period from a
particular site. Case Numbers are assigned by the Sample Management Office (SMO). A Case consists
of one or more Sample Delivery Groups (SDGs).
Continuing Calibration Blank (CCB) - A reagent water sample that is run 2 hours (ICP-AES, ICP-MS)
or every hour (Hg, CN) and designed to detect any carryover contamination.
Continuing Calibration Verification (CCV) - A single parameter or multi-parameter standard solution
prepared by the analyst and used to verify the stability of the instrument calibration with time, and the
instrument performance during the analysis of samples. The CCV can be one of the calibration standards.
However, all parameters being measured by the particular system must be represented in this standard and
the standard must have the same matrix (i.e., the same amount of reagents and/or preservatives) as the
samples. The CCV should have a concentration in the middle of the calibration range and shall be
analyzed at the beginning of the day prior to the analysis of samples, and every 2 hours (1 hour for Hg
and CN).
August 2014 A-l
-------
Inorganic Data Review Appendix A
Contract Compliance Screening (CCS) - A screening of electronic and hardcopy data deliverables for
completeness and compliance with the contract. This screening is performed under EPA direction by the
Contract Laboratory Program (CLP) Sample Management Office (SMO) contractor.
Contract Laboratory Program (CLP) - Supports the EPA's Superfund effort by providing a range of
state-of-the-art chemical analytical services of known and documented quality. This program is directed
by the Analytical Services Branch (ASB) of the Office of Superfund Remediation and Technical
Innovation (OSRTI) of the EPA.
Contract Required Quantitation Limit (CRQL) - Minimum level of quantitation acceptable under the
contract Statement of Work (SOW).
Contractual Holding Time - The maximum amount of time that the Contract Laboratory Program
(CLP) laboratory may hold the samples from the sample receipt date until analysis and still be in
compliance with the terms of the contract, as specified in the CLP Analytical Services Statement of Work
(SOW). These times are the same or less than technical holding times to allow for sample packaging and
shipping.
Duplicate - A second aliquot of a sample that is treated the same as the original sample in order to
evaluate the precision.
Field Blank - Any sample that is submitted from the field and identified as a blank. A field blank is used
to check for cross-contamination during sample collection, sample shipment, and in the laboratory. A
field blank includes trip blanks, rinsate blanks, bottle blanks, equipment blanks, preservative blanks,
decontamination blanks, etc.
Field Duplicate - A duplicate sample generated in the field, not in the laboratory.
Initial Calibration - Analysis of analytical standards for a series of different specified concentrations;
used to define the quantitative response, linearity, and dynamic range of the instrument to target analytes.
Initial Calibration Blank (ICB) - The first blank standard analysis to confirm the calibration curve.
Initial Calibration Verification (ICV) - Solution(s) prepared from stock standard solutions, metals, or
salts obtained from a source separate from that utilized to prepare the calibration standards. The ICV is
used to verify the concentration of the calibration standards and the adequacy of the instrument
calibration. The ICV should be traceable to National Institute of Standards and Technology (NIST) or
other certified standard sources when EPA ICV solutions are not available.
Interference Check Sample (ICS) - A solution containing both interfering and analyte elements of
known concentration that can be used to verify background and interelement correction factors.
Internal Standard - A non-target element added to a sample at a known concentration after preparation
but prior to analysis. Instrument responses to internal standards are monitored as a means of assessing
overall instrument performance.
Laboratory Control Sample (LCS) - A matrix spiked at a known concentration. LCSs are analyzed
using the same sample preparation, reagents, and analytical methods employed for the EPA samples
received.
Matrix - The predominant material of which the sample to be analyzed is composed. For the purposes of
this document, the matrices are aqueous/water, soil/sediment, and wipe.
Matrix Spike - Aliquot of a sample (aqueous/water or soil/sediment) fortified (spiked) with known
quantities of specific compounds and subjected to the entire analytical procedure to indicate the
appropriateness of the method for the matrix by measuring recovery.
Method Detection Limit (MDL) - The concentration of a target parameter that, when a sample is
processed through the complete method, produces a signal with 99 percent probability that it is different
from the blank. For 7 replicates of the sample, the mean value must be 3.14s above the blank, where "s"
is the standard deviation of the 7 replicates.
August 2014 A-2
-------
Inorganic Data Review Appendix A
Percent Difference (%D) - As used in this document and the Statement of Work (SOW), is used to
compare two values. It is the difference between the two values divided by one of the values multiplied
by 100.
Performance Evaluation (PE) Sample - A sample of known composition to the EPA; however,
unknown to the Contractor that is provided to evaluate Contractor performance.
Post-Digestion Spike/Post-Distillation Spike - The addition of a known amount of standard after
digestion or distillation (also identified as an analytical spike).
Preparation Blank - An analytical control that contains reagent water and reagents, which is carried
through the entire preparation and analytical procedure.
Regional Laboratory Contracting Officer Representative (Regional Laboratory COR) - The EPA
official who monitors assigned CLP laboratories (either inside or outside of the Regional Laboratory
COR's respective Region), responds to and identifies problems in laboratory operations, and participants
in on-site laboratory programs.
Relative Percent Difference (RPD) - As used in this document and the Statement of Work (SOW) to
compare two values, the RPD is based on the mean of the two values, and is reported as an absolute value
(i.e., always expressed as a positive number or zero).
Relative Standard Deviation (RSD) - As used in this document and the Statement of Work (SOW), the
mean divided by the standard deviation, expressed as a percentage.
Sample - A single, discrete portion of material to be analyzed, which is contained in single or multiple
containers and identified by a unique Sample Number.
Sample Delivery Group (SDG) - A unit within a sample Case that is used to identify a group of samples
for delivery. An SDG is defined by the following, whichever is most frequent:
Each 20 field samples [excluding Performance Evaluation (PE) samples] within a Case; or
Each 7 calendar day period (3 calendar day period for 7-day turnaround) during which field
samples in a Case are received (said period beginning with the receipt of the first sample in the
SDG).
All samples scheduled with the same level of deliverables.
In addition, all samples and/or sample fractions assigned to an SDG must be scheduled under the
same contractual turnaround time. Preliminary Results have no impact on defining the SDG.
Samples may be assigned to SDGs by matrix (i.e., all soil/sediment samples in one SDG, all
aqueous/water samples in another) at the discretion of the laboratory. Laboratories shall take all
precautions to meet the 20 sample per SDG criteria.
Sample Management Office (SMO) - A contractor-operated facility operated under the SMO contract,
awarded and administered by the EPA. SMO provides necessary management, operations, and
administrative support to the Contract Laboratory Program (CLP).
SDG Narrative - Portion of the data package which includes laboratory, contract, Case, Sample Number
identification, and descriptive documentation of any problems encountered in processing the samples,
along with corrective action taken and problem resolution.
Serial Dilution - The dilution of a sample by a factor of five. When corrected by the Dilution Factor
(DF), the diluted sample must agree with the original undiluted sample within specified limits. Serial
dilution may reflect the influence of interferents [Inductively Coupled Plasma (ICP) only].
Statement of Work (SOW) - A document which specifies how laboratories analyze samples under a
particular Contract Laboratory Program (CLP) analytical program.
August 2014 A-3
-------
Inorganic Data Review Appendix A
Technical Holding Time - The maximum amount of time that samples may be held from the collection
date until analysis.
Tune - A solution containing a range of isotope masses to establish ICP-MS accuracy, resolution, and
precision prior to calibration. May also be called Instrument Performance Check sample (IPC).
August 2014 A-4
-------
Inorganic Data Review
Appendix B
CASE NO.
APPENDIX B: INORGANIC DATA REVIEW SUMMARY
SITE
LABORATORY.
MA NO.
SOW NO.
NO. OF SAMPLES/MATRIX
SDG NO.
REGION
REVIEWER NAME
COMPLETION DATE
REGIONAL LABORATORY COR
ACTION
REVIEW CRITERIA
1. Preservation and Holding
Time
2. Tune Analysis
3. Calibration
4. Blanks
5. Interference Check Sample
6. Laboratory Control Sample
7. Duplicate Sample Analysis
8. Spike Sample Analysis
9. Serial Dilution
10. Internal Standards
11. Regional Quality Assurance
and Quality Control
12. Overall Assessment of Data
FYI
METHOD/ANAL YTE
ICP-AES
ICP-MS
Mercury
Cyanide
August 2014
B-l
-------
Inorganic Data Review Appendix B
This page is intentionally left blank.
August 2014 B-2
------- |