OSWER 9240.1-45
EPA 540-R-04-004
October 2004
USEPA CONTRACT LABORATORY PROGRAM
NATIONAL FUNCTIONAL GUIDELINES
FOR
INORGANIC DATA REVIEW
FINAL
Office of Superfund Remediation and Technology Innovation (OSRTI)
U.S. Environmental Protection Agency
Washington, DC 20460
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NOTICE
The policies and procedures set forth here are intended as guidance to the United States Environmental
Protection Agency (hereafter referred to as USEPA) and other governmental employees. They do not
constitute rule making by USEPA, 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 USEPA's Contract Laboratory Program (CLP) Web site at:
http://www.epa.gov/superfund/programs/clp/guidance.htm
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TABLE OF CONTENTS
INTRODUCTION 1
DATA QUALIFIER DEFINITIONS 2
DATA PACKAGE INSPECTION 2
PRELIMINARY REVIEW 2
DATA REVIEW NARRATIVE 3
ICP-AES DATA REVIEW 4
An Example Analytical Sequence for ICP-AES 5
I. Preservation and Holding Times 6
II. Calibration 8
III. Blanks 14
IV. Inductively Coupled Plasma - Interference Check Sample (1CP-ICS) 18
V. Laboratory Control Sample (LCS) 22
VI. Duplicate Sample Analysis 25
VII. Spike Sample Analysis 28
VIII. ICP Serial Dilution 32
IX. Field Duplicates 34
X. Overall Assessment 35
Calculations for ICP-AES 37
ICP-MS DATA REVIEW 39
An Example Analytical Sequence for ICP-MS 40
I. Preservation and Holding Times 41
II. ICP-MS Tune Analysis 43
III. Calibration 46
IV. Blanks 52
V. Inductively Coupled Plasma-Interference Check Sample (ICP-ICS) 56
VI. Laboratory Control Sample (LCS) 59
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TABLE OF CONTENTS
VII. Duplicate Sample Analysis 61
VIII. Spike Sample Analysis 64
IX. ICP Serial Dilution 68
X. ICP-MS Internal Standards 70
XI. Field Duplicates 73
XII. Overall Assessment 74
Calculations for ICP-MS 76
MERCURY DATA REVIEW 77
An Example Analytical Sequence for Mercury 78
I. Preservation and Holding Times 79
II. Calibration 81
III. Blanks 86
IV. Laboratory Control Sample (LCS) 90
V. Duplicate Sample Analysis 93
VI. Spike Sample Analysis 96
VII. Field Duplicates 99
VIII. Overall Assessment 100
Calculations for Mercury 102
CYANIDE DATA REVIEW 103
An Example Analytical Sequence for Cyanide 104
I. Preservation and Holding Times 105
II. Calibration 107
III. Blanks 113
IV. Laboratory Control Sample (LCS) 117
V. Duplicate Sample Analysis 119
VI. Spike Sample Analysis 122
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TABLE OF CONTENTS
VII. Field Duplicates 126
VIII. Overall Assessment 127
Calculations for Cyanide 129
APPENDIX A: GLOSSARY 132
APPENDIX B: INORGANIC DATA REVIEW SUMMARY 136
LIST OF TABLES
Table 1. Technical Holding Time Actions for ICP-AES Analysis 7
Table 2. Acceptance Criteria for ICVs, CCVs, and CRIs 9
Table 3. Calibration Actions for ICP-AES Analysis 13
Table 4. Blank Actions for ICP-AES Analysis 17
Table 5. Interference Check Actions for ICP-AES Analysis 21
Table 6. LCS Actions for ICP-AES Analysis 24
Table 7. Duplicate Sample Actions for ICP-AES Analysis 27
Table 8. Spike Sample Actions for ICP-AES Analysis 31
Table 9. Serial Dilution Actions for ICP-AES Analysis 33
Table 10. Technical Holding Time Actions for ICP-MS Analysis 42
Table 11. ICP-MS Tune Actions for ICP-MS Analysis 45
Table 12. Acceptance Criteria for ICV, CCV, and CRI Standards 47
Table 13. Calibration Actions for ICP-MS Analysis 50
Table 14. Blank Actions for ICP-MS Analysis 55
Table 15. Interference Check Actions for ICP-MS Analysis 58
Table 16. LCS Actions for ICP-MS Analysis 60
Table 17. Duplicate Sample Actions for ICP-MS Analysis 63
Table 18. Spike Sample Actions for ICP-MS Analysis 67
Table 19. Serial Dilution Actions for ICP-MS Analysis 69
Table 20. Internal Standard Actions for ICP-MS Analysis 72
Table 21. Technical Holding Time Actions for Mercury Analysis 80
Table 22. Acceptance Criteria for ICVs, CCVs, and CRIs 82
Table 23. Calibration Actions for Mercury Analysis 85
Table 24. Blank Actions for Mercury Analysis 89
Table 25. LCS Actions for Mercury Analysis 92
Table 26. Duplicate Sample Actions for Mercury Analysis 95
Table 27. Spike Sample Actions for Mercury Analysis 98
Table 28. Technical Holding Time Actions for Cyanide Analysis 106
Table 29. Acceptance Criteria for ICVs, CCVs, and CRIs 108
Table 30. Calibration Actions for Cyanide Analysis 112
Table 31. Blank Actions for Cyanide Analysis 116
Table 32. LCS Actions for Cyanide Analysis 118
Table 33. Duplicate Sample Actions for Cyanide Analysis 121
Table 34. Spike Sample Actions for Cyanide Analysis 125
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ACRONYMS
AA Atomic Absorption
ASB Analytical Services Branch
CADRE Computer-Aided Data Review and Evaluation
CCB Continuing Calibration Blank
CCS Contract Compliance Screening
CCV Continuing Calibration Verification
CLP Contract Laboratory Program
CO Contracting Officer
CRI CRQL Check Standard
CRQL Contract Required Quantitation Limit
CSF Complete SDG File
CVAA Cold Vapor AA
DART Data Assessment Rapid Transmittal
DAT Data Assessment Tool
DF Dilution Factor
DQO Data Quality Objective
ICB Initial Calibration Blank
ICP Inductively Coupled Plasma
ICP-AES Inductively Coupled Plasma - Atomic Emission Spectroscopy
ICP-MS Inductively Coupled Plasma - Mass Spectrometry
ICS Interference Check Sample
ICV Initial Calibration Verification
LCS Laboratory Control Sample
LRS Linear Range Sample
MDL Method Detection Limit
NIST National Institute of Standards and Technology
OSRTI Office of Superfund Remediation and Technology Innovation
OSWER Office of Solid Waste and Emergency Response
PB Preparation Blank
PE Performance Evaluation
%D Percent Difference
%R Percent Recovery
%RI Percent Relative Intensity
%RSD Percent Relative Standard Deviation
%S Percent Solids
PO Project Officer
QA Quality Assurance
QAPP Quality Assurance Project Plan
QC Quality Control
RPD Relative Percent Difference
RSCC Regional Sample Control Center
SDG Sample Delivery Group
SMO Sample Management Office
SOP Standard Operating Procedure
SOW Statement of Work
TAL Target Analyte List
TR/COC Traffic Report/Chain of Custody Documentation
USEPA United States Environmental Protection Agency
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TARGET ANALYTE LIST
Al Aluminum
Sb Antimony
As Arsenic
Ba Barium
Be Beryllium
Cd Cadmium
Ca Calcium
Cr Chromium
Co Cobalt
Cu Copper
CN Cyanide
Fe Iron
Pb Lead
Mg Magnesium
Mn Manganese
Hg Mercury
Ni Nickel
K Potassium
Se Selenium
Ag Silver
Na Sodium
Tl Thallium
V Vanadium
Zn Zinc
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INTRODUCTION
This document is designed to offer the data reviewer guidance in determining the usability of analytical
data generated through the USEPA Contract Laboratory Program (CLP) multi-media Inorganic Statement
of Work (SOW), ILM05.X (ILM05.3 and any future editorial revisions of ILM05.3). This guidance is
somewhat limited in scope and is intended to be used as an aid in the formal technical review process. It
should not be used to establish specific contract compliance (use of this document to evaluate data
generated under Inorganic SOWs other than ILM05.X is cautioned). Definitive guidance is provided
where performance should be fully under a Laboratory's control [e.g., blanks, calibration verification
standards, Interference Check Samples (ICSs), Quality Control (QC) audit samples, and instrument
performance checks (tuning)], while general guidance is provided for evaluating subjective data that is
affected by site conditions.
The guidelines presented in the document will aid the data reviewer in establishing (a) if data meets the
specific technical and QC criteria established in the SOW, and (b) the usability and extent of bias of any
data not meeting the specific technical and QC criteria established in the SOW. It must be understood by
the reviewer that acceptance of data not meeting technical requirements is based upon many factors,
including, but not limited to, site-specific technical requirements, the need to facilitate the progress of
specific projects, and availability for re-sampling. To make judgments at this level requires the reviewer
to have a complete understanding of the intended use of the data. The reviewer is strongly encouraged to
establish a dialogue with the user prior to, and after data review, to discuss usability issues and to answer
questions regarding the review. It should also be understood that in all Cases, data which do not meet
specified criteria are never to be fully acceptable without qualification.
The reviewer should note that while this document is to be used as an aid in the formal data review
process, other sources of guidance and information, as well as professional judgment, should also be used
to determine the ultimate usability of data, especially in those Cases where all data does not meet specific
technical criteria. The reviewer should also be aware that minor modifications to some of the analytical
methods may be made through the "Modified Analysis Request" to meet site-specific requirements, and
that these modifications could affect certain validation criteria such as Contract Required Quantitation
Limits (CRQLs) and Target Analyte Lists (TALs). A copy of any modification request made to the
analytical method should be included in the data package by the Laboratory.
Please visit the CLP Web site at http://www.epa.gov/superfund/programs/clp/index.htm for more
information on how to obtain service through the CLP.
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DATA QUALIFIER DEFINITIONS
The following definitions provide brief explanations of the national qualifiers assigned to results in the
data review process. If the Regions choose to use additional qualifiers, a complete explanation of those
qualifiers should accompany the data review.
U
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.
J+
The result is an estimated quantity, but the result may be biased high.
J-
The result is an estimated quantity, but the result may be biased low.
R
The data are unusable. The sample results are rejected due to serious deficiencies in meeting
Quality Control (QC) criteria. The analyte may or may not be present in the sample.
UJ
The analyte was analyzed for, but was not detected. The reported quantitation limit is
approximate and may be inaccurate or imprecise.
DATA PACKAGE INSPECTION
For data obtained from the Contract Laboratory Program (CLP), the Data Assessment Tool (DAT) reports
may be used as a tool in the validation process. The DAT report incorporates Contract Compliance
Screening (CCS) and Computer-Aided Data Review and Evaluation (CADRE) results, and is transmitted
via the Data Assessment Rapid Transmittal (DART) system. For more information about DAT, please
refer to the following CLP Web site:
http://www.epa.gov/superfund/programs/clp/dat.htm
The DAT report will identify any missing and/or incorrect information in the data package. The CLP
Laboratory may submit a reconciliation package for any missing items or to correct data.
To obtain the DAT report and/or the reconciliation package, or if there are any other concerns regarding
the data package, contact the CLP Project Officer (CLP PO) from the Region where the samples were
taken. Please refer to the following CLP Web site for the most recent list of Regional CLP POs:
http://www.epa.gov/superfund/programs/clp/contacts.htm
PRELIMINARY REVIEW
This document is for the review of analytical data generated through the USEPA CLP Inorganic
Statement of Work (SOW), ILM05.X (ILM05.3 and any future editorial revisions of ILM05.3). To use
this document effectively, the reviewer should have a general overview of the Sample Delivery Group
(SDG) or sample Case at hand. The exact number of samples, their assigned numbers, their matrix, and
the number of Laboratories involved in the analysis are essential information.
It is suggested that an initial review of the data package be performed taking into consideration all
information specific to the sample data package (e.g., flexible analysis approval notices, Traffic
Report/Chain of Custody (TR/COC) documentation, SDG Narratives, etc.).
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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. The reviewer should contact the appropriate
Regional CLP PO to obtain copies of the QAPP and relevant site information. This information is
necessary in determining the final usability of the analytical data.
The SDGs or Cases routinely have unique samples that require special attention by the reviewer.
These include field blanks, field duplicates, and performance audit samples which must be identified.
The sampling records (e.g., TR/COC documentation, field logs, and/or contractor tables) should identify:
1. The Region where the samples were taken, and
2. The complete list of samples with information on:
a. Sample matrix;
b. Field blanks*;
c. Field duplicates*;
d. Field spikes*;
e. Quality Control (QC) audit samples*;
f Shipping dates;
g. Preservatives;
h. Types of analysis; and
i. Laboratories involved.
* If applicable.
The TR/COC documentation includes sample descriptions and date(s) of sampling. The reviewer must
consider lag times between sampling and start of analysis when assessing technical sample holding times.
The Laboratory's SDG Narrative is another source of general information. Notable problems
with matrices, insufficient sample volume for analysis or reanalysis, samples received in broken
containers, preservation, and unusual events should be documented in the SDG Narrative. The reviewer
should also inspect any telephone or communication logs detailing any discussion of sample or analysis
issues between the Laboratory, the CLP Sample Management Office (SMO), and the USEPA Region.
DATA REVIEW NARRATIVE
A Data Review Narrative, including the Inorganic Data Review Summary form (see Appendix B), must
accompany the Laboratory data forwarded to the intended data recipient (client) or user to promote
communication. A copy of the Data Review Narrative should be submitted to the CLP PO assigned
oversight responsibility for the Laboratory producing the data.
The Data Review Narrative should include comments that clearly identify the problems associated with a
Case or SDG and state the limitations of the data. Documentation should also include the Sample
Number, analytical method, extent of the problem, and assigned qualifiers.
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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:
I. Preservation and Holding Times
II. Calibration
A. Initial
B. Initial and Continuing Calibration Verification (ICV/CCV)
C. Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
III. Blanks
IV. Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)
V. Laboratory Control Sample (LCS)
VI. Duplicate Sample Analysis
VII. Spike Sample Analysis
VIII. ICP Serial Dilution
IX. Field Duplicates
X. Overall Assessment
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Inorganic Data Review ICP-AES
An Example Analytical Sequence for ICP-AES
SO
s
ICV
ICB
CRI
ICSA
ICSAB
CCV
CCB
ten samples
CCV
CCB
seven samples
CRI
ICSA
ICSAB
CCV
CCB
ten samples, etc.
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Inorganic Data Review ICP-AES
I. Preservation and Holding Times
A. Review Items:
Form IA-IN, Form IB-IN, Form XII-IN, Form XIII-IN, Traffic Report/Chain of Custody
(TR/COC) documentation, Form DC-1, raw data, and the Sample Delivery Group (SDG)
Narrative checking for: pH; cooler temperature; holding time; and other sample conditions.
B. Objective:
The objective is to ascertain the validity of the analytical results based on the sample condition,
and the holding time of the sample from the date of collection to the date of analysis.
C. Criteria:
1. Technical requirements for sample holding times have only been established for aqueous
matrices. The addition of nitric acid to adjust the pH is only required for aqueous samples.
2. The technical holding time criteria for aqueous metal samples is 180 days, preserved (with
nitric acid) to pH <2.
3. Aqueous samples shall be maintained at 4°C ±2°C until preparation and analysis to allow for
re-preparation and for the direct analysis of dissolved metals.
4. Soil/sediment samples shall be maintained at 4°C ±2°C until preparation and analysis.
D. Evaluation:
Technical holding times are established by comparing the sampling date(s) on the TR/COC
documentation with the dates of analysis on Form XIII-IN, and the raw data. Information
contained in the Complete SDG File (CSF) should also be considered in the determination of
holding times. Verify that the analysis dates on the Form XIIIs 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 that there were problems with the samples, the integrity of the
samples may be compromised and professional judgment should be used to evaluate the effect of
the problem on the sample results.
E. Action:
NOTE: Apply the action to each sample for which the preservation or holding time criteria was
not met.
1. If the pH of aqueous metal samples was >2 at the time of sample receipt, use professional
judgment to qualify the samples based on the pH of the sample and the chemistry of the
metal(s) of interest. Qualify results that are > Method Detection Limit (MDL) as estimated
low (J-), and qualify non-detects as unusable (R).
2. If technical holding times were 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
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Inorganic Data Review
ICP-AES
would be low. Qualify results that are >MDL as estimated low (J-), and qualify non-detects
as unusable (R).
3. Due to limited information concerning holding times for soil samples, it is left to the
discretion of the data reviewer whether to apply water holding time criteria to soil samples. If
they are applied, it must be clearly documented in the Data Review Narrative.
4. When the holding times are exceeded, the reviewer should comment in the Data Review
Narrative on any possible consequences for the analytical results.
5. When holding times are grossly exceeded, note it for Contract Laboratory Program Project
Officer (CLP PO) action.
Table 1. Technical Holding Time Actions for ICP-AES Analysis
Preservation & Holding Time Results
Aqueous metals samples received with pH >2
Technical Holding Time exceeded:
Metals > 180 days
Action for Samples
Use professional judgment
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
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Inorganic Data Review ICP-AES
II. Calibration
A. Review Items:
Form II-IN (Parts A & B), Form XI-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data.
B. Objective:
Method requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data for the metals on the Inorganic
Target Analyte List (TAL). Initial Calibration Verification (ICV) demonstrates that the
instrument is capable of acceptable performance at the beginning of the analytical run.
Continuing Calibration Verification (CCV) demonstrates that the initial calibration is still valid
by checking the performance of the instrument on a continuing basis.
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.
a. A blank and at least one calibration standard shall be used to establish each analytical
curve. All measurements shall be within the instrument linear working range where the
interelement correction factors are valid. A minimum of two replicate exposures are
required for standardization, all Quality Control (QC), and sample analyses. The average
result of the multiple exposures for the standardization, QC, and sample analyses shall be
used.
b. The instrumental calibration near the Contract Required Quantitation Limit (CRQL) must
be verified for each analyte. A CRQL Check Standard (CRI) solution shall be prepared
and analyzed at the beginning and end of each sample analysis run and every 20
analytical samples, immediately preceding the Interference Check Sample (ICS) analyses,
but not before ICV analysis. The CRI at the beginning of the run must immediately
follow the ICV/ICB analyses.
c. The CRI shall be run per Inductively Coupled Plasma (ICP) for every wavelength used
for analysis, and for all analytes except for Al, Ba, Ca, Fe, Mg, Na, and K. All results
and Percent Recoveries (%R) shall be reported on Form IIB-IN. If the results for the CRI
do not fall within the fixed acceptance limits, the Laboratory shall immediately reanalyze
the CRI for those analytes. If the results of the reanalysis do not fall within the
acceptance limits, the analysis should be terminated, the problem corrected, the
instrument recalibrated, and the new calibration then reverified.
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Inorganic Data Review
2. Initial and Continuing Calibration Verification (ICV and CCV)
The acceptance criteria for the ICVs, CCVs, and CRIs are presented in Table 2:
Table 2. Acceptance Criteria for ICVs, CCVs, and CRIs
ICP-AES
Analytical
Method
ICP-AES
Inorganic
Analytes
Metals
ICV/CCV
Low Limit
(% of True
Value)
90
ICV/CCV
High Limit
(% of True
Value)
110
CRI
Low Limit
(% of True
Value)
70 (50 for Sb,
Pb, Tl)
CRI
High Limit
(% of True
Value)
130 (150 for
Sb, Pb, Tl)
a. Initial Calibration Verification (ICV)
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 %R falls outside of the control limits, the analysis
should be terminated, the problem corrected, the instrument recalibrated, and all
affected samples reanalyzed.
2) If the ICV solution is not available from USEPA, or where a certified solution of an
analyte is not available from any source, analyses shall be conducted on an
independent standard at a concentration level other than that used for instrument
calibration (or the CRI), but within the calibrated range.
3) The ICV solution shall be run at each analytical wavelength used for analysis.
b. Continuing Calibration Verification (CCV)
1) To ensure accuracy during the course of each analytical run, the CCV shall be
analyzed and reported for each wavelength used for the analysis of each analyte.
2) The CCV standard shall be analyzed at a frequency of 10% or every two hours
during an analytical run, whichever is more frequent. The CCV standard shall also
be analyzed at the beginning of the run, 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 shall be one of the following solutions at, or
near, the mid-range levels of the calibration curve:
A. USEPA solutions;
B. National Institute of Standards and Technology (NIST) standards; or
C. A Laboratory-prepared standard solution (self-prepared or commercially
available).
4) The same CCV standard solution shall be used throughout the analysis runs for a
Sample Delivery Group (SDG).
5) The CCV shall be analyzed in the same fashion as an actual sample. Operations such
as the number of replicate analyses, the number and duration of the instrument rinses,
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Inorganic Data Review ICP-AES
etc., affect the measured CCV result and are not to be applied to the CCV to an extent
greater than was applied to the associated analytical samples. If the %R of the CCV
was outside of the control limits, the analysis should be terminated, the problem
corrected, the instrument recalibrated, and the preceding 10 analytical samples or all
analytical samples analyzed since the last compliant calibration verification
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 one calibration standard.
2. Confirm that the measurements were within the documented linear working range, and
were the average result of at least two replicate exposures.
3. Evaluate the reported CRI to confirm that it was analyzed at the proper concentration,
frequency, and location within the analytical run sequence. Verify that acceptable %R
results were obtained.
4. Verify that the ICV and CCV standards were analyzed for each analyte at the proper
frequency (10%) and at the appropriate concentration. Verify that acceptable %R results
were obtained.
5. Recalculate one or more of the ICV, CCV, and CRI %R using the following equation and
verify that the recalculated value agrees with the Laboratory-reported values on Forms II
(A & B)-IN.
%R =
True(value)
Where,
Found(value) = Concentration (in (ig/L) of each analyte measured in the analysis
of the ICV, CCV, or CRI solution
True(value) = Concentration (in (ig/L) of each analyte in the ICV, CCV, or CRI
source
NOTE: For data obtained from the Contract Laboratory Program (CLP), the above
criteria are evaluated as part of the Contract Compliance Screening (CCS)
process. Information regarding the Laboratory's compliance with these criteria
can be obtained from the Data Assessment Tool (DAT) reports, and may be used
as part of the evaluation process.
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Inorganic Data Review
E. Action:
NOTES:
ICP-AES
For initial calibrations or ICVs that do not meet the technical criteria, apply the
action to all samples reported from the analytical run.
For CCVs or CRIs 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 run.
1. If the instrument was not calibrated daily and each time the instrument was set up,
qualify the data 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), use professional judgment to qualify results
that are > Method Detection Limit (MDL) as estimated (J) or unusable (R), and non-
detects as estimated (UJ) or unusable (R).
2. If the CRIs are outside the acceptance criteria, use professional judgment to qualify
all associated data. If possible, indicate the bias in the review. The following
guidelines are recommended:
a. If the CRI %R is <50% (<30% for Sb, Pb, Tl), qualify all sample results that are
>MDL but < two times (2x) the CRQL and all non-detects as unusable (R).
Qualify detects that are >2x the CRQL as estimated (J).
b. If the CRI %R falls within the range of 50-69% (30-49% for Sb, Pb, Tl), qualify
all sample results that are >MDL but <2x the CRQL as estimated low (J-), and
all non-detects as estimated (UJ). Detects >2x the CRQL should not be qualified
based on this criterion.
c. If the CRI %R is >130% but < 180% (>150% but <200 for Sb, Pb, Tl), qualify all
sample results that are >MDL but <2x the CRQL as estimated high (J+). Non-
detects and detects >2x the CRQL should not be qualified based on this criterion.
d. If the CRI %R is >180% (>200% for Sb, Pb, Tl), qualify all sample results that
are >MDL as unusable (R).
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%, qualify non-detects as unusable (R). Use
professional judgment to qualify all results that are >MDL as estimated low (J-)
or unusable (R).
b. If the ICV or CCV %R falls within the range of 75-89%, qualify sample results
that are >MDL as estimated low (J-), and qualify non-detects as estimated (UJ).
c. If the ICV or CCV %R falls within the range of 111-125%, qualify sample
results that are >MDL as estimated high (J+).
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d. If the ICV or CCV %R is within the range of 111-125%, non-detects should not
be qualified.
e. If the ICV or CCV %R is >125%, use professional judgment to qualify results
that are >MDL as estimated high (J+) or unusable (R). Non-detects should not
be qualified.
f If the %R is >160%, qualify all results that are >MDL as unusable (R).
4. If the Laboratory failed to provide adequate calibration information, the Region's
designated representative should contact the Laboratory and request the necessary
information. If the information is not available, the reviewer must use professional
judgment to assess the data.
5. Note 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 CLP Project Officer (CLP
PO) 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.
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ICP-AES
Table 3. Calibration Actions for ICP-AES Analysis
Calibration Result
Calibration not performed
Calibration incomplete
CRI %R <50% (<30% for Sb, Pb, Tl)
CPJ %R 50-69% (30-49% for Sb, Pb, Tl)
CRI %R >130% but < 180% (>150% but <200%
for Sb, Pb, Tl)
CRI %R >180% (>200% for Sb, Pb, Tl)
ICV/CCV%R<75%
ICV/CCV %R 75-89%
ICV/CCV %R 1 1 1-125%
ICV/CCV %R> 125%
ICV/CCV %R> 160%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated (J) or
unusable (R)
Qualify non-detects as estimated (UJ) or unusable
(R)
Qualify results that are >MDL but <2x the CRQL
and all non-detects as unusable (R)
Qualify all results that are >2x the CRQL as
estimated (J)
Qualify results that are >MDL but <2x the CRQL
as estimated low (J-)
Qualify non-detects as estimated (UJ)
Results that are >2x the CRQL are not qualified
Qualify results that are >MDL but <2x the CRQL
as estimated high (J+)
Non-detects and results that are >2x the CRQL are
not qualified
Qualify results that are >MDL as unusable (R)
Qualify results that are >MDL as estimated low
(J-) or unusable (R)
Qualify all non-detects as unusable (R)
Qualify results that are >MDL as estimated low
(J-)
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated (J)
Qualify results that are >MDL as estimated high
(J+) or unusable (R)
Qualify results that are >MDL as unusable (R)
October 2004
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III. Blanks
A. Review Items:
Form I-IN, Form III-IN, Form XII-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, and raw data.
B. Objective:
The objective of blank analysis results assessment is to determine the existence and magnitude of
contamination resulting from Laboratory (or field) activities. The criteria for evaluation of blanks
applies to any blank associated with the samples (e.g., method blanks, calibration blanks, field
blanks, etc.). If problems with any blank exist, all associated data must be carefully evaluated to
determine whether or not there is an inherent variability in the data, or if the problem is an
isolated occurrence not affecting other data.
C. Criteria:
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed after the analytical standards, but not
before analysis of the Initial Calibration Verification (ICV) during the initial calibration of
the instrument (see Section II.C.I).
3. A Continuing Calibration Blank (CCB) shall be analyzed at each wavelength used for the
analysis, immediately after every ICV and Continuing Calibration Verification (CCV). The
CCB shall be analyzed at a frequency of 10% or every two hours during the run, whichever
is more frequent. The CCB shall be analyzed at the beginning of the run, and again after
the last CCV that was analyzed after the last analytical sample of the run. The CCB result
(absolute value) shall not exceed the Contract Required Quantitation Limit (CRQL) of each
analyte for which analysis is performed.
4. At least one Preparation Blank (PB) shall be prepared and analyzed for each matrix, with
every Sample Delivery Group (SDG), or with each batch of samples digested, whichever is
more frequent. The PB consists of reagent water processed through the appropriate sample
preparation and analysis procedure.
5. If any analyte concentration in the PB is >CRQL, the lowest concentration of that analyte
in the associated samples must be 10 times (lOx) the PB concentration. Otherwise, all
samples associated with that PB with the analyte's concentration <10x the PB
concentration, and >CRQL, should be redigested and reanalyzed for that analyte (except for
an identified field blank). The Laboratory is not to correct the sample concentration for the
blank value.
6. If the concentration of the PB for a certain analyte is <(-CRQL), all samples reported <10x
the CRQL (associated with that analyte in that blank), should be redigested and reanalyzed.
October 2004 14 Final
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Inorganic Data Review
D. Evaluation:
ICP-AES
E.
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the proper
frequency and location during the run, and PBs 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, as well as the raw data (e.g., instrument printouts, strip charts,
printer tapes, bench sheets, etc.) 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 target
analytes were present in a PB, or if a concentration was <(-CRQL), the affected samples
were redigested and reanalyzed. Verify that if target analytes were present 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.
NOTE:
For data obtained from the Contract Laboratory Program (CLP), many of the above
criteria are evaluated as part of the Contract Compliance Screening (CCS) process.
Information regarding the Laboratory's compliance with these criteria can be obtained
from the Data Assessment Tool (DAT) reports, and may be used as part of the
evaluation process.
Action:
NOTES: For ICBs that do not meet the technical criteria, apply the action to all samples reported
from the analytical run.
For CCBs that do not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the CCB and a
subsequent technically acceptable analysis of the CCB in the analytical run.
For PBs that do not meet the technical criteria, apply the action to all samples prepared
in the same preparation batch.
1. If the appropriate blanks were not analyzed with the correct frequency, the data reviewer
should use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the Laboratory. The
situation should then be recorded in the Data Review Narrative, and noted for CLP Project
Officer (PO) action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the
blank. The reviewer should note that 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.
October 2004
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Inorganic Data Review ICP-AES
3. Some general "technical" review actions include:
a. Any blank (including PB) reported with a negative result, whose value is <(-MDL) but
>(-CRQL), should be carefully evaluated to determine its effect on the sample data. The
reviewer shall then use professional judgment to assess the data. For any blank
(including PB) reported with a negative result, whose value is <(-CRQL), qualify results
that are >CRQL as estimated low (J-) and non-detects as estimated (UJ).
b. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil sample results reported on Form I-IN will not be
on the same basis (units, dilution) as the calibration blank data reported on Form III-IN.
The reviewer may find it easier to work with the raw data.
4. Specific "method" actions include:
a. If the absolute value of an ICB or a CCB result is >CRQL, the analysis should be
terminated. If the analysis was not terminated and the affected samples were not
reanalyzed, report non-detects and results that are >MDL, but CRQL but < Blank Result, use professional judgment to qualify the data
as unusable (R) or to report the results at the level of the blank with a "U" qualifier. Use
professional judgment to qualify results that are > Blank Result. Note this situation for
CLP PO action and record it in the Data Review Narrative.
b. If the absolute value of the concentration of the PB is MDL but CRQL.
c. If any analyte concentration in the PB is >CRQL, the lowest concentration of that analyte
in the associated samples must be lOx the PB concentration. Otherwise, all samples
associated with that blank with concentrations <10x the PB concentration and >CRQL
should be redigested and reanalyzed. Raise the CRQL to the concentration found in the
PB and report those samples that do not require redigestion (that are >MDL but
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Inorganic Data Review
ICP-AES
Table 4. Blank Actions for ICP-AES Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
PB
PB
PB
Blank Result
>MDL but
CRQL
<(-MDL) but
>(-CRQL)
<(-CRQL)
>CRQL
>MDL but
MDL but < CRQL
>CRQL
>MDL but < CRQL
>CRQL but Blank Result
>MDL, or non-detect
<10xtheCRQL
>MDL but < CRQL
>CRQL but <10x the Blank
Result
>1 Ox the Blank Result
Non-detect
>MDL but < CRQL
>CRQL
<10xtheCRQL
Action for Samples
No action
Report CRQL value with a"U"
Use professional judgment
Report CRQL value with a "U"
Report at level of Blank Result
with a "U" or qualify data as
unusable (R)
Use professional judgment
Use professional judgment
Qualify results that are >CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
Report CRQL value with a "U"
Qualify results as unusable (R) or
estimated high (J+)
No action
No action
Report CRQL value with a "U"
Use professional judgment
Qualify results that are >CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
October 2004
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IV. Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)
A. Review Items:
Form IVA-IN, Form IVB-IN, Form XIII-IN, instrument printouts, and raw data.
B. Objective:
The Inductively Coupled Plasma (ICP) Interference Check Sample (ICS) verifies the analytical
instrument's ability to overcome interferences typical of those found in samples.
NOTE: The Laboratory should have analyzed and reported ICS results for all elements being
reported from the analytical run and for all interferents (target and non-target) for these
reported elements.
C. Criteria:
1. The 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 Inductively Coupled Plasma - Atomic
Emissions Spectroscopy (ICP-AES).
2. An ICS must be run at the beginning and end of each sample analysis run and every 20
analytical samples. The ICS is not to be run prior to the Initial Calibration Verification
(ICV), and is to be immediately followed by a Continuing Calibration Verification (CCV),
which will be followed by a Continuing Calibration Blank (CCB).
3. Results for the analysis of ICS Solution A must fall within the control limits of ± two times
(2x) the Contract Required Quantitation Limit (CRQL), or ±20% of the true value (whichever
is greater) for the analytes and interferents.
4. Results forthe analysis of ICS Solution AB must fall within the control limits of ±2xthe
CRQL, or ±20% of the true value (whichever is greater) forthe 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 the affected samples reanalyzed.
6. The ICS should be obtained from USEPA if available, and analyzed according to the
instructions supplied with the solutions. The ICS may be prepared with the interferents at 2x
the level specified in the Statement of Work (SOW) if high levels of interferents are found in
the field samples. If the ICS is not available from USEPA, an independent ICS solution shall
be prepared with the interferent and analyte concentrations at the levels specified in the
method.
October 2004 18 Final
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Inorganic Data Review
D. Evaluation:
ICP-AES
1. Verify using the raw data (ICP instrumental printout) that the ICS was analyzed at the proper
frequency and location during the analytical run.
2. Evaluate the ICS raw data for results with an absolute value that is > Method Detection Limit
(MDL) for those analytes which are not present in the ICS solution.
3. Recalculate using the raw data and the following equation, one or more of the analyte Percent
Recoveries (%R), and verify that the recalculated value agrees with the Laboratory- reported
values on Form IV-IN.
%R =
True(value)
Where,
Found(value) =
True (value) =
Concentration (in (ig/L) of each analyte interferent measured in
the analysis of ICS Solution A or ICS Solution AB
Concentration (in (ig/L) of each analyte or interferent in ICS
Solution A or ICS Solution AB
E.
4. If the value of an ICS result exceeds the ±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 Contract Laboratory Project Officer (CLP PO) action and
record in the Data Review Narrative. Use professional judgment to assess the data.
NOTE:
Action:
NOTE:
For data obtained from the CLP, the above criteria are evaluated as part of the Contract
Compliance Screening (CCS) process. Information regarding the Laboratory's
compliance with these criteria can be obtained from the Data Assessment Tool (DAT)
reports, and may be used as part of the evaluation process.
For an ICS that does not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the ICS and a
subsequent technically acceptable analysis of the ICS in the analytical run.
1. The raw data should, but may not, contain results for interferents. If not, the reviewer shall
use professional judgment to qualify the data. If the data does contain results for interferents,
the reviewer should apply the following actions to samples with concentrations of interferents
that are comparable to, or greater than, their respective levels in the ICS:
a. If the ICS %R for an analyte or interferent is >120% (or greater than the true value + 2x
the CRQL, as applicable) and the sample results are non-detects, the data should not be
qualified.
b. If the ICS %R for an analyte or interferent is >120% (or greater than the true value + 2x
the CRQL, as applicable) qualify sample results that are >MDL as estimated high (J+). If
October 2004
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Inorganic Data Review ICP-AES
the ICS %R (or true value) grossly exceeds the limits, use professional judgment to
qualify the data.
c. If the ICS %R for an analyte or interferent falls within the range of 50-79% (or less than
the true value - 2x the CRQL, as applicable) qualify sample results that are >MDL as
estimated low (J-).
d. If the ICS recovery for an analyte falls within the range of 50-79% (or less than the true
value - 2x the CRQL, as applicable), the possibility of false negatives exists. Qualify
sample non-detects as estimated (UJ).
e. If the ICSAB %R for an analyte or interferent is <50%, qualify all sample results that are
>MDL as estimated low (J-) and all sample non-detects as unusable (R).
2. If results that are >MDL 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 elements 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 sample results that are >MDL as estimated high (J+). Non-detects should not be
qualified.
3. If negative results are observed for analytes that are not present in the ICS solution, and their
absolute value is >MDL, 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 comparable or higher levels of interferents, qualify non-detects for the affected
analytes as estimated (UJ), and results that are >MDL but <10x the absolute value of the
negative result as estimated low (J-).
4. In general, ICP-AES sample data can be accepted if the concentrations of Al, Ca, Fe, and 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, the reviewer should 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 XA-IN and XB-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-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).
5. If the raw data does not contain results for the interferents, note it in the Data Review
Narrative.
6. 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. The reviewer may need to obtain
additional information from the Laboratory. All interpretive situations should then be
recorded in the Data Review Narrative.
7. If the ICS acceptance criteria are grossly exceeded, note the specifics for CLP PO action.
October 2004 20 Final
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ICP-AES
Table 5. Interference Check Actions for ICP-AES Analysis
Interference Check Sample Results
ICS %R >120% (or greater than true value + 2x
the CRQL)
ICS %R 50-79% (or less than true value - 2x the
CRQL)
ICSAB%R<50%
Potential false positives in field samples with
interferents
Potential false negatives in field samples with
interferents
Action for Samples
Qualify results that are >MDL as estimated high
(J+)
Qualify results that are >MDL as estimated low
(J-)
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated low
(J-)
Qualify non-detects as unusable (R)
Qualify results that are >MDL as estimated high
(J+)
Qualify results that are >MDL but <10x( negative
value |) as estimated low (J-)
Qualify non-detects as estimated (UJ)
October 2004
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Inorganic Data Review ICP-AES
V. Laboratory Control Sample (LCS)
A. Review Items:
Form VII-IN, Form XII-IN, preparation logs, instrument printouts, and raw data.
B. Objective:
The Laboratory Control Sample (LCS) serves as a monitor of the overall performance of each
step during the analysis, including the sample preparation.
C. Criteria:
1. Aqueous and solid 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. The aqueous LCS solution shall be obtained from
USEPA, if available. However, if the LCS is unavailable from USEPA, the Initial
Calibration Verification (ICV) solution(s) may be used.
a. One aqueous LCS shall be prepared and analyzed for every group of aqueous samples in
a Sample Delivery Group (SDG), or with each batch of aqueous samples digested,
whichever is more frequent.
b. All aqueous LCS Percent Recoveries (%R) must fall within the control limits of 80-
120%, except for Sb and Ag which have no fixed control limits. If the %R for the
aqueous LCS falls outside of the control limits (except for Ag and Sb), the analysis
should be terminated, the problem corrected, and the samples prepared with that LCS
redigested and reanalyzed.
c. A solid LCS shall be prepared and analyzed utilizing each of the preparation and
analytical procedures applied to the soil/sediment samples received, with one exception:
the Percent Solids (%S) determination is not required. If the solid LCS is not available
from USEPA, other USEPA QA samples or certified materials may be used.
d. One solid LCS shall be prepared and analyzed for each group of soil sediment samples in
an SDG, for each batch of samples digested or distilled, whichever is more frequent.
e. All solid LCS results shall fall within the control limits reported on Form VII-IN. If the
results for the solid LCS fall outside of the control limits, the analyses should be
terminated, the problem corrected, and the samples prepared with that LCS redigested
and reanalyzed.
D. Evaluation:
1. Verify using Form VII-IN, Form XII-IN, and raw data that the appropriate number of
required LCSs were prepared and analyzed for the SDG.
2. Evaluate Form VII-IN and verify that all results for each analyte fall within the established
control limits.
October 2004 22 Final
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Inorganic Data Review ICP-AES
NOTE: Certain elements have only advisory limits for the LCS. Professional judgment should
be used when evaluating these elements.
3. Check the raw data (e.g., instrument printouts, strip charts, bench sheets, etc.) to verify that
the %Rs on Form VII-IN were accurately transcribed. Recalculate one or more of the
reported %Rs using the following equation:
True(value)
Where,
Found(value) = Concentration of each analyte (in (ig/L or mg/kg) measured in the
analysis of the LCS
True(value) = Concentration of each analyte (in (ig/L or mg/kg) in the LCS
4. Verify that the LCS was prepared at the same time as the associated samples using the same
procedures.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with these criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
E. Action:
If the LCS criteria are not met, the Laboratory performance and method accuracy are in question.
Professional judgment should be used 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. Aqueous LCS:
a. If the LCS %R falls within the range of 50-79%, qualify sample results that are > Method
Detection Limit (MDL) as estimated low (J-). If the LCS %R is >120%, qualify sample
results that are >MDL as estimated high (J+).
b. If the LCS recovery is >120% and the sample results are non-detects, the data should not
be qualified.
c. If the LCS recovery falls within the range of 50-79%, qualify non-detects as estimated
(UJ).
d. If LCS %R is <50%, qualify all results that are >MDL as estimated low (J-) and all non-
detects as unusable (R).
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ICP-AES
e. If the LCS %R is >150%, qualify all affected data (both detects and non-detects) as
unusable (R).
2. Solid LCS:
a. If the LCS results are greater than the reported control limits, qualify sample results that
are >MDL as estimated high (J+). If the LCS results are less than the reported control
limits, qualify sample results that are >MDL as estimated low (J-).
b. If the LCS results are greater than the reported control limits and the sample results are
non-detects, the data should not be qualified.
c. If the LCS results are less than the reported control limits, qualify non-detects as
estimated (UJ).
3. If a Laboratory fails to analyze an LCS with each SDG, or if a Laboratory consistently fails to
generate acceptable LCS recoveries, note this for CLP Project Officer (CLP PO) action.
4. Whenever possible, the potential effects on the data due to out-of-control LCS results should
be noted in the Data Review Narrative.
Table 6. LCS Actions for ICP-AES Analysis
LCS Result
Aqueous %R 50-79%
Aqueous %R> 120%
Aqueous %R <50%
Aqueous %R> 150%
Soil result > upper limit
Soil result < lower limit
Action for Samples
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated high (J+)
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Qualify all results as unusable (R)
Qualify results that are >MDL as estimated high (J+)
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
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Inorganic Data Review ICP-AES
VI. Duplicate Sample Analysis
A. Review Items:
Cover Page, Form VI-IN, Form XII-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. Duplicate analyses are also performed to generate data that
determines the long-term precision of the analytical method on various matrices. Non-
homogenous samples can impact the apparent method precision. However, aqueous samples are
generally homogenous and most soil samples are homogenous within a factor of two or three.
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 Sample Delivery Group (SDG).
Duplicates cannot be averaged for reporting on Form I-IN. Additional duplicate sample
analyses may be required by USEPA Regional request. Alternately, the Region may require
that a specific sample be used for the duplicate sample analysis.
3. Duplicate sample analyses are required for Percent Solids (%S) determination.
4. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original
and duplicate sample values > five times (5x) the Contract Required Quantitation Limit
(CRQL).
5. 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 VI-IN. If both samples are non-detects, the RPD is not calculated for
Form VI-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, Form XII-IN, and the raw data that the appropriate number of
required duplicate samples were prepared and analyzed for the SDG.
2. Evaluate Form VI-IN and the raw data to verify that all duplicate results for each analyte and
method fall within the established control limits.
October 2004 25 Final
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Inorganic Data Review ICP-AES
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 VI-IN:
RPD =
(S+D)/2
x 100
E.
Where,
RPD =
S =
D =
Relative Percent Difference
Sample Result (original)
Duplicate Result
NOTE:
For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with the above criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
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 reviewer considers the samples to be
sufficiently similar. The reviewer will need to exercise professional judgment in
determining sample similarity. The reviewer should make use of all available data
when determining similarity, 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 (TSSs), Total Dissolved Solids (TDSs), Total Organic Carbon
(TOC), alkalinity or buffering capacity, reactive sulfide, anions]. The reviewer should
also use the sample data (e.g., similar concentrations of analytes) in determining
similarity between samples in the SDG. The reviewer may determine that only some of
the samples in the SDG are similar to the duplicate sample, and that only these samples
should be qualified. Or, the reviewer may determine that no samples are sufficiently
similar to the sample used for the duplicate, and thus that 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. The reviewer may need to obtain additional information from the
Laboratory. Note the situation in the Data Review Narrative, and for CLP Project Officer
(CLP PO) action.
2. If the results from a duplicate analysis for a particular analyte fall outside the appropriate
control limits, qualify sample results that are >MDL as estimated (J) and non-detects as
estimated (UJ).
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3. If a field blank or PE sample was used for the duplicate sample analysis, note this for CLP
PO action. All of the other Quality Control (QC) data must then be carefully checked, and
professional judgment exercised by the data reviewer when evaluating the data.
4. Note the potential effects on the data due to out-of-control duplicate sample results in the
Data Review Narrative.
Table 7. Duplicate Sample Actions for ICP-AES Analysis
Duplicate Sample Results
Both original sample and duplicate sample >5x
the CRQL and RPD >20%*
Original sample or duplicate sample <5x the
CRQL (including non-detects) and absolute
difference between sample and duplicate
>CRQL*
Action for Samples
Qualify those results that are >MDL that
professional judgment determines to be affected
as estimated (J) and non-detects as estimated (UJ)
Qualify those results that are >MDL that
professional judgment determines to be affected
as estimated (J) and non-detects as estimated (UJ)
*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.
October 2004
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Inorganic Data Review ICP-AES
VII. Spike Sample Analysis
A. Review Items:
Cover Page, Form V-IN (Part A & B), Form XII-IN, instrument printouts, and raw data.
B. Objective:
The spiked sample analysis is designed to provide information about the effect of each sample
matrix on the sample preparation procedures and the measurement methodology. Non-
homogenous samples can impact the apparent method recovery. However, aqueous samples are
generally homogenous and most soil samples are homogenous within a factor of two or three. If
the spike is added to the sample prior to the digestion (e.g., prior to the addition of other
reagents), it is referred to as a spiked sample, pre-digestion, or Matrix Spike. If the spike is added
to the sample after the completion of the digestion procedures, it is referred to as a post-digestion
spike, or analytical spike.
C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (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 Sample Delivery Group
(SDG).
3. When the pre-digestion spike recovery falls outside of the control limits and the sample result
is < four times (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 Contract Required Quantitation Limit
(CRQL), whichever is greater.
NOTE: Post-digestion spikes are not required for Ag.
4. The spike Percent Recovery (%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 Statement of Work (SOW).
D. Evaluation:
1. Verify using the Cover Page, Form VA-IN, Form XII-IN, and raw data, that the appropriate
number of required spiked samples were prepared and analyzed for the SDG.
October 2004 28 Final
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Inorganic Data Review ICP-AES
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Evaluate Form VA-IN and the raw data to verify that all pre-digestion spiked sample results
for each required analyte fall within the established control limits. If not, verify that a post-
digestion/post-distillation 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 V(A
& B)-IN:
% Recovery =
SA
x 100
E.
Where,
SSR
SR
SA
NOTES:
Spiked Sample Result
Sample Result
Spike Added
When the sample concentration is < Method Detection Limit (MDL), 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
VA-IN and VB-IN.
For data obtained from the Contract Laboratory Program (CLP), the above
criteria are evaluated as part of the Contract Compliance Screening (CCS)
process. Information regarding the Laboratory's compliance with the above
criteria can be obtained from the Data Assessment Tool (DAT) reports, and may
be used as part of the evaluation process.
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 reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make 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 (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are
similar to the Matrix Spike sample, and that only these samples should be qualified.
Or, the reviewer may determine that no samples are sufficiently similar to the sample
used for the Matrix Spike, and thus that 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
October 2004
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Inorganic Data Review ICP-AES
should be qualified. The reviewer may need to obtain additional information from the
Laboratory. Note the situation in the Data Review Narrative, and for CLP Project Officer
(CLP PO) action.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked, and
professional judgment exercised by the data reviewer when evaluating the data.
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-
digestion spike was not performed, note this for CLP PO action.
4. If the Matrix Spike %R is <30%, verify that a post-digestion spike was analyzed if required.
If the post-digestion spike %R is <75% or is not performed, qualify sample results that are >
Method Detection Limit (MDL) as estimated low (J-) and non-detects as unusable (R). If the
post-digestion spike %R is >75%, qualify sample results that are >MDL as estimated (J) and
non-detects as estimated (UJ).
5. If the Matrix Spike %R is 30-74% and the sample results are >MDL, verify that a post-
digestion spike was analyzed if required. If the %R for the post-digestion is also <75% or is
not performed, qualify the affected data as estimated low (J-). If the %R for the post-
digestion spike is >75%, qualify the affected data as estimated (J).
6. If the Matrix Spike %R falls within the range of 30-74% and the sample results are non-
detects, qualify the affected data as estimated (UJ).
7. If the Matrix Spike %R is >125% and the reported sample results are non-detects, the sample
data should not be qualified.
8. If the Matrix Spike %R is > 125% and the sample results are >MDL, verify that a post-
digestion spike was analyzed if required. If the %R for the post-digestion spike is also
>125% or is not performed, qualify the affected data as estimated high (J+). If the %R for the
post-digestion spike is < 125%, qualify the affected data as estimated (J).
9. Note the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.
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Table 8. Spike Sample Actions for ICP-AES Analysis
Spike Sample Results
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 >125%
No post-digestion spike performed (e.g., not
required for Ag)
Action for Samples
Qualify affected results that are >MDL as estimated low
(J-) and affected non-detects as unusable (R)
Qualify affected results that are >MDL as estimated (J)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as estimated low
(J-) and affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as estimated (J)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as estimated
high (J+)
Qualify affected results that are >MDL as estimated (J)
Qualify affected results that are >MDL as estimated low
(J-) and affected non detects as unusable (R)
Qualify affected results that are >MDL as estimated low
(J-) and non-detects as estimated (UJ)
Qualify affected results that are >MDL as estimated
high (J+)
Non-detects are not qualified
October 2004
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VIII. ICP Serial Dilution
A. Review Items:
Form I-IN, Form VIII-IN, instrument printouts, and raw data.
B. Objective:
The serial dilution of samples quantitated by Inductively Coupled Plasma - Atomic Emission
Spectroscopy (ICP-AES) determines 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 Sample Delivery Group (SDG),
whichever is more frequent.
2. Samples identified as field blanks or Performance Evaluation (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 >50
times (5 Ox) the Method Detection Limit (MDL)], the serial dilution analysis (a five-fold
dilution) shall then agree within a 10 Percent Difference (%D) of the original determination
after correction for dilution. Note that serial dilutions of soil samples are reported in (ig/L,
but the MDL is in mg/kg. The units will need to be adjusted.
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 VIII-IN:
% Difference = I J ~ S I x 100
Where,
I = Initial Sample Result (instrument reading)
S = Serial Dilution Result (instrument reading x5)
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.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
October 2004 32 Final
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E.
regarding the Laboratory's compliance with the above criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
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 reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make 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 (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are
similar to the serial dilution sample, and that only these samples should be qualified.
Or, the reviewer may determine that no samples are sufficiently similar to the sample
used for serial dilution, and thus that only the field sample used to prepare the serial
dilution sample should be qualified.
1. If the required %D criteria are not met, qualify all affected results that are >MDL as
estimated (J) and all affected non-detects as estimated (UJ).
2. If evidence of positive or negative interference is found, use professional judgment to qualify
the associated sample data. Note the potential effects on the reported data in the Data Review
Narrative.
3. It should be noted for CLP Project Officer (CLP PO) action and in the Data Review Narrative
if a field blank or PE sample was used for the serial dilution analysis.
Table 9. Serial Dilution Actions for ICP-AES Analysis
Serial Dilution Result
Sample concentration >50x MDL and %D >10
Interferences present
Action for Samples
Qualify affected results that are >MDL as
estimated (J)
Qualify affected non-detects as estimated (UJ)
Use professional judgment
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IX. Field Duplicates
A. Review Items:
Form I-IN, instrument printouts, and raw data.
B. Objective:
Field duplicate samples may be collected and analyzed as an indication of overall precision.
These analyses measure both field and Laboratory precision. The results, therefore, may have
more variability than Laboratory duplicates that measure only Laboratory performance. It is also
expected that soil duplicate results will have a greater variance than water matrices due to
difficulties associated with collecting identical field samples.
C. Criteria:
There are no "required" review criteria for determining comparability of field duplicate analyses.
D. Evaluation:
Identify samples that are field duplicates using Traffic Report/Chain of Custody (TR/COC)
documentation or sample field sheets. Compare the results reported for each sample and calculate
the Relative Percent Difference (RPD), if appropriate.
E. Action:
Provide any evaluation of the field duplicates in the Data Review Narrative.
October 2004 34 Final
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Inorganic Data Review ICP-AES
X. Overall Assessment
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 ensure that the reported sample quantitation results are accurate. It is
appropriate for the data reviewer to make professional judgments and express concerns, as well as
to comment on the validity of the overall data for a Case. This is particularly appropriate when
there are several Quality Control (QC) criteria that are outside of the specification parameters.
The additive nature of QC factors that fall outside of specification parameters is difficult to
objectively assess. The reviewer has a responsibility to inform the user of data quality and data
limitations to help the user to avoid inappropriate use of the data, while not precluding any
consideration of the data. If qualifiers other than those used in this document are necessary to
describe or qualify the data, it is necessary to thoroughly document/explain the additional
qualifiers used. The data reviewer would be greatly assisted in this endeavor if the acceptance or
performance criteria were provided. The Inorganic Review Summary (see Appendix B) and
supplementary documentation must be included with the review.
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.
D. Evaluation:
Examine the raw data to verify that correct calculations of the sample results were reported by the
Laboratory. Digestion and distillation logs, instrument printouts, strip charts, etc., should be
compared to the reported sample results recorded on the appropriate Inorganic Summary Forms
(Form I-IN through Form XIII-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.
4. Verify that there are no transcription or reduction errors [e.g., dilutions, Percent Solids (%S),
sample weights, etc.] on one or more samples.
5. Verify that results fall within the linear range(s) of the Inductively Coupled Plasma (ICP)
instrument(s) (Form XI).
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Inorganic Data Review ICP-AES
6. If appropriate information is available, the reviewer may 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 Standard Operating Procedure(s) (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. Write a brief Data Review Narrative to give the user an indication of the analytical limitations
of the data. Note any discrepancies between the data and the SDG Narrative for Contract
Laboratory Program Project Officer (CLP PO) action. If sufficient information on the
intended use and required quality of the data are available, the reviewer should include an
assessment of the data usability within the given context.
3. If any discrepancies are found, the Laboratory may be contacted by the Region's designated
representative to obtain additional information for resolution. If a discrepancy remains
unresolved, the reviewer may determine that qualification of the data is warranted.
October 2004 36 Final
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Inorganic Data Review ICP-AES
Calculations for ICP-AES
Aqueous Samples by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES):
The concentrations determined in the digestate are to be reported in units of (ig/L:
Vf
Concentration (ng/L)= C x — x DF
V,
Where,
C = Instrument value in (ig/L
Vf = Final digestion volume (mL)
Vj = Initial digestion volume (mL)
DF = Dilution Factor
Soil Samples by ICP-AES:
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:
Concentration (dry wt.) (mg/kg) = x DF
Vv X IS
Where,
C = Concentration (mg/L)
V = Final sample volume in Liters (L)
W = Wet sample weight (kg)
S = % Solids/100 (see SOW ILM05.3 Exhibit D-Introduction to
Analytical Methods, Section 1.6)
DF = Dilution Factor
Adjusted Method Detection Limit (MDL)/Adjusted Contract Required Quantitation Limit (CRQL)
Calculation:
To calculate the adjusted MDL or adjusted CRQL for water/aqueous 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 samples as follows:
October 2004 37 Final
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Inorganic Data Review ICP-AES
WM VR i
Adjusted Concentration (dry wt.)(mg/kg) = C x —- x —- x — x DF
Where,
C = MDL or CRQL concentration (mg/kg)
WM = Minimum method required wet sample weight (g)
WR = Reported wet sample weight (g)
VM = Method required final sample volume (mL)
VR = Reported final sample volume (mL)
S = % Solids/100 (see Exhibit D - Introduction to Analytical
Methods, Section 1.6)
DF = Sample Dilution Factor
October 2004 38 Final
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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:
I. Preservation and Holding Times
II. ICP-MS Tune Analysis
III. Calibration
A. Initial
B. Initial and Continuing Calibration Verification (ICV/CCV)
C. Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
IV. Blanks
V. Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)
VI. Laboratory Control Sample (LCS)
VII. Duplicate Sample Analysis
VIII. Spike Sample Analysis
IX. ICP Serial Dilution
X. ICP-MS Internal Standards
XI. Field Duplicates
XII. Overall Assessment
NOTE: At this time, the ICP-MS method in SOW ILM05 .X is for water samples only. If soil samples
are analyzed by a modified version of this method, the reviewer must use professional judgment
to modify the review criteria [e.g., for duplicate sample analyses, spike sample analyses, serial
dilution analyses, Laboratory Control Samples (LCSs), and internal standards]. These
modifications must be detailed in the Data Review Narrative.
October 2004 39 Final
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Inorganic Data Review ICP-MS
An Example Analytical Sequence for ICP-MS
Tune(s)
SO
S
ICV
ICB
CRI
ICSA
ICSAB
CCV
CCB
ten samples
CCV
CCB
seven samples
CRI
CCV
CCB
ten samples, etc.
October 2004 40 Final
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Inorganic Data Review ICP-MS
I. Preservation and Holding Times
A. Review Items:
Form IA-IN, Form IB-IN, Form XII-IN, Form XIII-IN, Traffic Report/Chain of Custody
(TR/COC) documentation, Form DC-1, raw data, and the Sample Delivery Group (SDG)
Narrative checking for: pH; cooler temperature; holding time; and other sample conditions.
B. Objective:
The objective is to determine the validity of the analytical results based on the sample condition,
and the holding time of the sample from the date of collection to the date of analysis.
C. Criteria:
1. The technical holding time criteria for aqueous metal samples is 180 days; preserved (with
nitric acid) to pH <2.
2. Aqueous samples shall be maintained at 4°C ±2°C until preparation and analysis to allow for
re-preparation and for the direct analysis of dissolved metals.
D. Evaluation:
Technical holding times are established by comparing the sampling date(s) on the TR/COC
documentation with the dates of analysis on Form XIII-IN, and the raw data. Information
contained in the Complete SDG File (CSF) should also be considered in the determination of
holding times. Verify that the analysis dates on the Form XIIIs 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 that there were problems with the samples, the integrity of the
samples may be compromised and professional judgment should be used to evaluate the effect of
the problem on the sample results.
E. Action:
NOTE: Apply the action to each sample for which the preservation or holding time criteria was
not met.
1. If the pH of aqueous metals samples is >2 at the time of sample receipt, use professional
judgment to qualify the samples based on the pH of the sample and the chemistry of the
metal(s) of interest. Qualify results that are > Method Detection Limit (MDL) as estimated
low (J-), and qualify non-detects as unusable (R).
2. 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. Qualify results that are >MDL as estimated low (J-), and qualify non-detects as
unusable (R).
3. When the holding times are exceeded, the reviewer should comment in the Data Review
Narrative on any possible consequences for the analytical results.
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4. When holding times are grossly exceeded, note this for Contract Laboratory Program Project
Officer (CLP PO) action.
Table 10. Technical Holding Time Actions for ICP-MS Analysis
Preservation & Holding Time Results
Aqueous metals samples received with pH >2
Technical Holding Time exceeded:
Metals >180 days.
Action for Samples
Use professional judgment
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
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II. ICP-MS Tune Analysis
A. Review Items:
Form XIV-IN, instrument printouts, and raw data.
B. Objective:
The Inductively Coupled Plasma-Mass Spectrometry (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 at least
five times (5x) consecutively. The tuning solution contains 100 (ig/L of Be, Mg, Co, In, and
Pb. The solution shall contain all required isotopes of the above elements. The Laboratory
shall make any adjustments necessary to bring peak width within the instrument and to bring
mass resolution to within 0.1 amu over manufacturer's specifications the range of 6-210 amu.
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 XIV-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 XIV-IN that the mass calibration falls within the limits
for each isotope of each analyte.
3. Verify using the raw data and Form XIV-IN that the %RSD is <5% for each isotope of each
analyte.
4. Check the raw data to verify that the reported average mass and %RSD on Form XIV-IN
were accurately calculated. Recalculate one or more of the average masses and %RSDs for
an isotope using the following equations:
Mean = -^-
Where,
x = Mass from analysis
n = Number of analyses
on, x 100
Percent Relative Standard Deviation =
October 2004 43 Final
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Inorganic Data Review
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NOTE:
Where,
x = Mean
a n_] = Standard Deviation
For data obtained from the Contract Laboratory Program (CLP), many of the above
criteria are evaluated as part of the Contract Compliance Screening (CCS) process.
Information regarding the Laboratory's compliance with the above criteria can be
obtained from the Data Assessment Tool (DAT) reports and may be used as part of the
evaluation process.
E.
Action:
NOTE:
For ICP-MS tunes that does not meet the technical criteria, apply the action to all
samples reported from the analytical run.
1. If the ICP-MS instrument was not tuned prior to calibration, the sample data should be
qualified as unusable (R).
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, the reviewer
should use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the Laboratory. The
situation should be recorded in the Data Review Narrative and noted for CLP Project Officer
(CLP PO) action.
3. If the mass calibration is not within 0.1 amu for any isotope in the tuning solution, qualify all
analyte results that are >MDL associated with that isotope as estimated (J), and all non-
detects associated with that isotope as estimated (UJ). The situation should be recorded in the
Data Review Narrative and noted for CLP PO action.
4. If the %RSD exceeds 5% for any isotope in the tuning solution, qualify all sample results that
are >MDL associated with that tune as estimated (J), and all non-detects associated with that
tune as estimated (UJ). The situation should be recorded in the Data Review Narrative and
noted for CLP PO action.
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Table 11. ICP-MS Tune Actions for ICP-MS Analysis
ICP-MS Tune Results
Tune not performed
Tune not performed properly
Mass calibration not within 0. 1 amu
%RSD >5%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated (J)
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated (J)
Qualify non-detects as estimated (UJ)
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III. Calibration
A. Review Items:
Form II-IN (Parts A & B), Form XI-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data.
B. Objective:
Method requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data for the metals on the Inorganic
Target Analyte List (TAL). Initial Calibration Verification (ICV) demonstrates that the
instrument is capable of acceptable performance at the beginning of the analytical run.
Continuing Calibration Verification (CCV) demonstrates that the initial calibration is still valid
by checking the performance of the instrument on a continual basis.
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.
a. A blank and at least one calibration standard shall be used to establish each analytical
curve. All measurements shall be within the instrument linear working range. A
minimum of three replicate scans are required for standardization and all Quality Control
(QC) and sample analyses. The average result of the multiple scans for the
standardization, QC, and sample analyses shall be used.
b. The instrumental calibration near the Contract Required Quantitation Limit (CRQL) must
be verified for each analyte. A CRQL Check Standard (CRI) solution shall be prepared
and analyzed at the beginning and end of each sample analysis run and every 20
analytical samples, but not before the ICV analysis. The initial CRI shall immediately
precede the Interference Check Sample (ICS) analyses, and immediately follow the
ICV/ICB analyses.
c. The CRI shall be run by ICP-MS for every mass used for analysis. All results and
Percent Recoveries (%Rs) shall be reported on Form IIB-IN. If the results for the CRI do
not fall within the fixed acceptance limits, the Laboratory shall immediately reanalyze the
CRI for those analytes. If the results of the reanalysis do not fall within the acceptance
limits, the analysis should be terminated, the problem corrected, the instrument
recalibrated, and the new calibration then reverified.
2. Initial and Continuing Calibration Verification (ICV and CCV)
The acceptance criteria for the ICVs, CCVs, and CRIs are presented in Table 12:
October 2004 46 Final
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Inorganic Data Review
Table 12. Acceptance Criteria for ICV, CCV, and CRI Standards
ICP-MS
Analytical
Method
ICP-MS
Inorganic
Analytes
Metals
ICV/CCV
Low Limit
(% of True
Value)
90
ICV/CCV
High Limit
(% of True
Value)
110
CRI
Low Limit
(% of True
Value)
70 (50 for Co,
Mn, Zn)
CRI
High Limit
(% of True
Value)
130 (150 for
Co, Mn, Zn)
a. Initial Calibration Verification (ICV)
1) Immediately after each ICP-MS 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) If the ICV is not available from USEPA, or where a certified solution of an
analyte is not available from any source, analyses shall be conducted on an
independent standard at a concentration level other than that used for instrument
calibration (or the CRI), but within the calibrated range.
3) The ICV solution shall be run at each analytical mass used for analysis.
b. Continuing Calibration Verification (CCV)
1) To ensure accuracy during the course of each analytical run, 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 10% or every two hours
during an analytical run, whichever is more frequent. The CCV standard shall
also be analyzed at the beginning of the run, 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 shall be one of the following solutions at, or
near, the mid-range levels of the calibration curve:
A. USEPA solutions;
B. National Institute of Standards and Technology (NIST) standards; or
C. A Laboratory-prepared standard solution (self-prepared or commercially
available).
4) The same CCV standard solution shall be used throughout the analysis runs for a
Sample Delivery Group (SDG).
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5) The CCV shall be analyzed in the same fashion as an actual sample. Operations
such as the number of replicate analyses, the number and duration of the
instrument rinses, etc., affect the measured CCV result and are not to be applied
to the CCV to an extent greater than was applied to the associated analytical
samples. If the %R of the CCV was outside of the control limits, the analysis
should be terminated, the problem corrected, the instrument recalibrated, and the
preceding 10 analytical samples or all analytical samples analyzed since the last
compliant calibration verification 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 one calibration standard.
2. Confirm that the measurements were within the documented linear working range, and were
the average result of at least three replicate exposures.
3 . Evaluate the reported CRI to confirm that it was analyzed at the proper concentration,
frequency, and location within the analytical run sequence. Verify that acceptable %R results
were obtained.
4. Verify that the ICV and CCV standards were analyzed for each analyte at the proper
frequency (10%) and at the appropriate concentration. Verify that acceptable %R results
were obtained.
5. Recalculate one or more of the ICV, CCV, and CRI %Rs using the following equation and
verify that the recalculated value agrees with the Laboratory-reported values on Forms II (A
& B)-IN.
%R =
True(value)
Where,
Found(value) = Concentration (in (ig/L) of each analyte measured in the analysis
of the ICV, CCV, or CRI solution
True(value) = Concentration (in (ig/L) of each analyte in the ICV, CCV, or CRI
source
NOTE: For data obtained from the Contract Laboratory Program (CLP), the above
criteria are evaluated as part of the Contract Compliance Screening (CCS)
process. Information regarding the Laboratory's compliance with these criteria
can be obtained from the Data Assessment Tool (DAT) reports, and may be used
as part of the evaluation process.
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E. Action:
NOTE: For initial calibrations or ICVs that does not meet the technical criteria, apply the
action to all samples reported from the analytical run.
For CCVs or CRIs that does 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 run.
1. If the instrument was not calibrated daily and each time the instrument was set up, qualify the
data 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), use professional judgment to qualify results that are >MDL as estimated (J) or
unusable (R), and non-detects as estimated (UJ) or unusable (R).
2. If the CRIs are outside the acceptance criteria, use professional judgment to qualify all
associated data. If possible, indicate the bias in the review. The following guidelines are
recommended:
a. If the CRI %R is <50% (<30% for Co, Mn, Zn), qualify all sample results that are >MDL
but < two times (2x) the CRQL and all non-detects as unusable (R). Qualify detects that
are >2xthe CRQL as estimated (J).
b. If the CRI %R falls within the range of 50-69% (30-49% for Co, Mn, Zn), qualify all
sample results that are >MDL but <2x the CRQL as estimated low (J-), and all non-
detects as estimated (UJ). Detects that are >2x the CRQL should not be qualified based
on this criterion.
c. If the CRI %R is >130% but < 180% (>150% but <200% for Co, Mn, Zn), qualify all
sample results that are >MDL but <2x the CRQL as estimated high (J+). Non-detects
and detects that are >2x the CRQL should not be qualified based on this criterion.
d. If the CRI %R is >180% (>200% for Co, Mn, Zn), qualify all sample results that are
>MDL as unusable (R).
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%, qualify non-detects as unusable (R). Use professional
judgment to qualify all results that are >MDL as estimated low (J-) or unusable (R).
b. If the ICV or CCV %R falls within the range of 75-89%, qualify sample results that are
>MDL as estimated low (J-), and qualify non-detects as estimated (UJ).
c. If the ICV or CCV %R falls within the range of 111-125%, qualify sample results that are
>MDL as estimated high (J+).
d. If the ICV or CCV %R falls within the range of 111-125%, non-detects should not be
qualified.
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e. If the ICV or CCV %R is >125%, use professional judgment to qualify results that are
>MDL as estimated high (J+) or unusable (R). Non-detects should not be qualified.
f If the %R is >160%, qualify all results that are >MDL as unusable (R).
4. If the Laboratory failed to provide adequate calibration information, the USEPA Region's
designated representative should contact the Laboratory and request the necessary
information. If the information is not available, the reviewer must use professional judgment
to assess the data.
5. Note 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 CLP Project Officer (CLP PO)
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 13. Calibration Actions for ICP-MS Analysis
Calibration Result
Calibration not performed
Calibration incomplete
CRI %R <50% (<30% for Co, Mn, Zn)
CRI %R 50-69% (30-49% for Co, Mn,
Zn)
CRI %R >130% but < 180% (>150% but
< 200% for Co, Mn,Zn)
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated (J) or
unusable (R)
Qualify non-detects as estimated (UJ) or unusable (R)
Qualify all results that are >MDL but <2x the CRQL and
all non-detects as unusable (R)
Qualify all results that are >2x the CRQL as estimated (J)
Qualify results that are >MDL but <2x the CRQL as
estimated low (J-)
Qualify non-detects as estimated (UJ)
Results that are >2x the CRQL are not qualified
Qualify results that are >MDL but <2x the CRQL as
estimated high (J+)
Non-detects and results that are >2x the CRQL are not
qualified
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Table 13. Calibration Actions for ICP-MS Analysis (Con't)
Calibration Result
CRI %R >180% (>200% for Co, Mn, Zn)
ICV/CCV%R<75%
ICV/CCV %R 75-89%
ICV/CCV %R 1 1 1-125%
ICV/CCV %R> 125%
ICV/CCV %R> 160%
Action for Samples
Qualify all results that are >MDL as unusable (R)
Qualify results that are >MDL as estimated low (J-) or
unusable (R)
Qualify all non-detects as unusable (R)
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated (J)
Qualify results that are >MDL as estimated high (J+) or
unusable (R)
Qualify results that are >MDL as unusable (R)
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IV. Blanks
A. Review Items:
Form I-IN, Form III-IN, Form XII-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, and raw data.
B. Objective:
The objective of blank analysis results assessment is to determine the existence and magnitude of
contamination resulting from Laboratory (or field) activities. The criteria for evaluation of blanks
applies to any blank associated with the samples (e.g., method blanks, calibration blanks, field
blanks, etc.). If problems with any blank exist, all associated data must be carefully evaluated to
determine whether or not there is an inherent variability in the data, or if the problem is an
isolated occurrence not affecting other data.
C. Criteria:
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed after the analytical standards, but not
before analysis of the Initial Calibration Verification (ICV) during the initial calibration of
the instrument (see Section II.C.I).
3. A Continuing Calibration Blank (CCB) shall be analyzed at each mass used for the analysis,
immediately after every ICV and Continuing Calibration Verification (CCV). The CCB shall
be analyzed at a frequency of 10% or every two hours during the run, whichever is more
frequent. The CCB shall be analyzed at the beginning of the run, and again after the last
CCV that was analyzed after the last analytical sample of the run. The CCB result (absolute
value) shall not exceed the Contract Required Quantitation Limit (CRQL) of each analyte for
which analysis is performed.
4. At least one Preparation Blank (PB) shall be prepared and analyzed, with every Sample
Delivery Group (SDG), or with each batch of samples digested, whichever is more frequent.
The PB consists of reagent water processed through the appropriate sample preparation and
analysis procedure.
5. If any analyte concentration in the PB is >CRQL, the lowest concentration of that analyte in
the associated samples must be 10 times (lOx) the PB concentration. Otherwise, all samples
associated with that PB with the analyte's concentration <10x the PB concentration, and
>CRQL, should be redigested and reanalyzed for that analyte (except for an identified field
blank). The Laboratory is not to correct the sample concentration for the blank value.
6. If the concentration of the PB for a certain analyte is <(- CRQL), all samples reported <10x
the CRQL (associated with that analyte in that blank), should be redigested and reanalyzed.
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D. Evaluation:
ICP-MS
E.
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the proper
frequency and location during the run, and PBs 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 the Blank Summary (Form III-IN), as well as the raw data
(e.g., instrument printouts, strip charts, printer tapes, bench sheets, etc.) 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 target
analytes were present in a PB, or if a concentration was <(-CRQL), the affected samples
were redigested and reanalyzed. Verify that if target analytes were present 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.
NOTE:
For data obtained from the Contract Laboratory Program (CLP), many of the above
criteria are evaluated as part of the Contract Compliance Screening (CCS) process.
Information regarding the Laboratory's compliance with these criteria can be obtained
from the Data Assessment Tool (DAT) reports, and may be used as part of the
evaluation process.
Action:
NOTES: For ICBs that does not meet the technical criteria, apply the action to all samples
reported from the analytical run.
For CCBs that does not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the CCB and a
subsequent technically acceptable analysis of the CCB in the analytical run.
For PBs that does not meet the technical criteria, apply the action to all samples
prepared in the same preparation batch.
1. If the appropriate blanks were not analyzed with the correct frequency, the data reviewer
should use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the Laboratory. The
situation should then be recorded in the Data Review Narrative, and noted for CLP Project
Officer (CLP PO) action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the
blank. The reviewer should note that 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.
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3. Some general "technical" review actions include:
a. Any blank (including PB) reported with a negative result, whose value is <(-Method
Detection Limit) (MDL) but >(-CRQL), should be carefully evaluated to determine its
effect on the sample data. The reviewer shall then use professional judgment to assess
the data. For any blank (including PB) reported with a negative result, whose value is
<(-CRQL), qualify results that are >CRQL as estimated low (J-) and non-detects as
estimated (UJ).
4. Specific "method" actions include:
a. If the absolute value of an ICB or a CCB result >CRQL, the analysis should be
terminated. If the analysis was not terminated and the affected samples were not
reanalyzed, report non-detect and results that are >MDL but CRQL but < Blank Result, use professional judgment to qualify the data
as unusable or to report the results at the level of the blank with a "U" qualifier. Use
professional judgment to qualify results that are > Blank Result. Note this situation for
CLP PO action and record it in the Data Review Narrative.
b. If the absolute value of the concentration of the PB is MDL but CRQL.
c. If any analyte concentration in the PB is >CRQL, the lowest concentration of that analyte
in the associated samples must be lOx the PB concentration. Otherwise, all samples
associated with that blank with concentrations <10x the PB concentration and >CRQL
should be redigested and reanalyzed. Raise the CRQL to the concentration found in the
PB and report those samples that does not require redigestion (that are >MDL but
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Table 14. Blank Actions for ICP-MS Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
PB
PB
PB
Blank Result
>MDL but
CRQL
<(-MDL),
but >(-CRQL)
<(-CRQL)
>CRQL
>MDL but
MDL but < CRQL
>CRQL
>MDL but < CRQL
>CRQL but Blank Result
>MDL, or non-detect
<10x CRQL
>MDL but < CRQL
>CRQL but <10x the Blank
Result
>1 Ox the Blank Result
Non-detect
>MDL but < CRQL
>CRQL
<1 Ox CRQL
Action for Samples
No action
Report CRQL value with a "U"
Use professional judgment
Report CRQL value with a "U"
Report at level of Blank Result
with a "U" or qualify data as
unusable (R)
Use professional judgment
Use professional judgment
Qualify results that are >CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
Report CRQL value with a "U"
Qualify results as unusable (R) or
estimated high (J+)
No action
No action
Report CRQL value with a "U"
Use professional judgment
Qualify results that are >CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
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V. Inductively Coupled Plasma-Interference Check Sample (ICP-ICS)
A. Review Items:
Form IVA-IN, Form IVB-IN, Form XIII-IN, instrument printouts, and raw data.
B. Objective:
The Inductively Coupled Plasma-Interference Check Sample (ICP-ICS) verifies the analytical
instrument's ability to overcome isobaric interferences typical of those found in samples.
C. Criteria:
1. The 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 Inductively Coupled Plasma-Mass
Spectrometry (ICP-MS).
2. An ICS must be run at the beginning of each analysis run. The ICS is not to be run prior to
the Initial Calibration Verification (ICV), and shall be immediately followed by a Continuing
Calibration Verification/Continuing Calibration Blank (CCV/CCB).
3. Results for the ICP-MS analysis of the ICS Solution A shall fall within the control limits of
±3x the CRQL, or ±20% of the true value (whichever is greater) for the analytes included in
the solution.
4. Results for the ICP-MS analysis of the ICS Solution AB must fall within the control limits of
±3x the CRQL, or ±20% of the true value (whichever is greater) for the analytes included in
the solution.
5. If the value of an ICS result exceeds ±3x 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 USEPA, if available, and analyzed according to the
instructions supplied with the solutions. If the ICS is not available from USEPA, an
independent ICS solution shall be prepared with the interferent and analyte concentrations at
the levels specified in the method.
D. Evaluation:
1. Verify using the raw data (ICP instrumental printout) that the ICS was analyzed at the proper
frequency and location during the analytical run.
2. Evaluate the ICS raw data for results with an absolute value that is > Method Detection Limit
(MDL) for those analytes that are not present in the ICS solution.
October 2004 56 Final
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3. Recalculate using the raw data and the following equation, one or more of the analyte Percent
Recoveries (%R), and verify that the recalculated value agrees with the Laboratory- reported
values on Form IV-IN.
True(value)
Where,
Found(value) =
True (value) =
Concentration (in (ig/L) of each analyte interferent measured in
the analysis of ICS Solution A or ICS Solution AB
Concentration (in (ig/L) of each analyte or interferent in ICS
Solution A or ICS Solution AB
E.
4. If the value of an ICS result exceeds ±3x 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 Contract Laboratory Program Project Officer (CLP PO) action
and record in the Data Review Narrative. Use professional judgment to assess the data.
NOTE:
Action:
NOTE:
For data obtained from the CLP, the above criteria are evaluated as part of the Contract
Compliance Screening (CCS) process. Information regarding the Laboratory's
compliance with these criteria can be obtained from the Data Assessment Tool (DAT)
reports, and may be used as part of the evaluation process.
For an ICS for ICP-MS that does not meet the technical criteria, apply the action to all
samples reported from the analytical run.
1 . The raw data may not contain results for interferents. In this case, the reviewer shall use
professional judgment to qualify the data. If the data does contain results for interferents, the
reviewer should apply the following actions to samples with concentrations of interferents
that are comparable to, or greater than, their respective levels in the ICS:
a. If the ICS %R for an analyte is >120% (or greater than the true value + 3x the CRQL as
applicable) and the sample results are non-detects, the data should not be qualified.
b. If the ICS %R for an analyte is >120% (or greater than the true value + 3x the CRQL as
applicable) qualify sample results that are >MDL as estimated high (J+). If the ICS %R
(or true value) grossly exceeds the limits, use professional judgment to qualify the data.
c. If the ICS %R for an analyte falls within the range of 50-79% (or less than the true value
- 3x the CRQL as applicable) qualify sample results that are >MDL as estimated low
(J-).
d. If the ICS recovery for an analyte falls within the range of 50-79% (or less than the true
value - 3x the CRQL as applicable), the possibility of false negatives exists. Qualify
sample non-detects as estimated (UJ).
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e. If the ICSAB %R for an analyte or interferent is <50%, qualify all sample results that are
>MDL and all sample non-detects as unusable (R).
2. If results that are >MDL 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 elements 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 sample results that are >MDL as estimated high (J+). Non-detects should not be
qualified.
3. If negative results are observed for analytes that are not present in the ICS solution, and their
absolute value is >MDL, 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 comparable or higher levels of interferents, qualify non-detects for the affected
analytes as estimated (UJ), and results that are >MDL but <10x the absolute value of the
negative result as estimated low (J-).
4. If the raw data does not contain results for the interferents, note this in the Data Review
Narrative.
5. 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. The reviewer may need to obtain
additional information from the Laboratory. All interpretive situations should then be
recorded in the Data Review Narrative.
6. If the ICS acceptance criteria are grossly exceeded, note the specifics for CLP PO action.
Table 15. Interference Check Actions for ICP-MS Analysis
Interference Check Sample Results
ICS %R >120% (or > true value + 3x the
CRQL)
ICS %R 50-79% (or < true value - 3x the
CRQL)
ICSAB %R<50%
Potential false positives in field samples with
interferents
Potential false negatives in field samples with
interferents
Action for Samples
Qualify results that are >MDL as estimated high (J+)
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify all sample data as unusable (R)
Qualify results that are >MDL as estimated high (J+)
Qualify results that are >MDL but <10x( negative
value ) as estimated low (J-)
Qualify non-detects as estimated (UJ)
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VI. Laboratory Control Sample (LCS)
A. Review Items:
Form VII-IN, Form XII -IN, preparation logs, instrument printouts, and raw data.
B. Objective:
The Laboratory Control Sample (LCS) serves as a monitor of the overall performance of each
step during the analysis, including the sample preparation.
C. Criteria:
1 . Aqueous 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. The aqueous LCS solution shall be obtained from USEPA if
available. However, if the LCS is unavailable from USEPA, the Initial Calibration
Verification (ICV) solution(s) may be used.
a. One aqueous LCS shall be prepared and analyzed for every group of aqueous samples in
a Sample Delivery Group (SDG), or with each batch of aqueous samples digested,
whichever is more frequent.
b. All aqueous LCS Percent Recoveries (%R) must fall within the control limits of 80-
120%. If the %R for the aqueous 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 VII-IN, Form XII-IN, and raw data that the appropriate number of
required LCSs were prepared and analyzed for the SDG.
2. Evaluate Form VII-IN and verify that all results for each analyte fall within the established
control limits.
3. Check the raw data (e.g., instrument printouts, strip charts, bench sheets, etc.) to verify that
the %Rs on Form VII-IN were accurately transcribed. Recalculate one or more of the
reported %Rs using the following equation:
%R = x 100
True(value)
Where,
Found(value) = Concentration of each analyte (in (ig/L) measured in the
analysis of the LCS
True (value) = Concentration of each analyte (in (ig/L) in the LCS
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4. Verify that the LCS was prepared at the same time as the associated samples using the same
procedures.
E.
NOTE:
For data obtained from the Contract Laboratory Program (CLP), the above
criteria are evaluated as part of the Contract Compliance Screening (CCS)
process. Information regarding the Laboratory's compliance with these criteria
can be obtained from the Data Assessment Tool (DAT) reports, and may be used
as part of the evaluation process.
Action:
If the LCS criteria are not met, the Laboratory performance and method accuracy are in question.
Professional judgment should be used 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 LCS %R falls within the range of 50-79%, qualify sample results that are > Method
Detection Limit (MDL) as estimated low (J-). If the LCS %R is >120%, qualify sample
results that are >MDL as estimated high (J+).
2. If the LCS recovery is >120% and the sample results are non-detects, the data should not be
qualified.
3. If the LCS recovery falls within the range of 50-79%, qualify non-detects as estimated (UJ).
4. If LCS %R is <50%, qualify all results that are >MDL as estimated low (J-) and all non-
detects as unusable (R).
5. If the LCS %R is >150%, qualify all affected data (both detects and non-detects) as unusable
(R).
6. If a Laboratory fails to analyze an LCS with each SDG, or if a Laboratory consistently fails to
generate acceptable LCS recoveries, note this for CLP Project Officer (PO) action
7. Whenever possible, the potential effects on the data due to out-of-control LCS results should
be noted in the Data Review Narrative.
Table 16. LCS Actions for ICP-MS Analysis
LCS Result
Aqueous %R 50-79%
Aqueous %R> 120%
Aqueous %R <50%
Aqueous %R> 150%
Action for Samples
Qualify results that are >MDL as estimated
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated
Qualify results that are >MDL as estimated
Qualify non-detects as unusable (R)
low (J-)
high (J+)
low (J-)
Qualify all results as unusable (R)
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VII. Duplicate Sample Analysis
A. Review Items:
Cover Page, Form VI-IN, Form XII-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. Duplicate analyses are also performed to generate data that
determines the long-term precision of the analytical method on various matrices. Non-
homogenous samples can impact the apparent method precision. However, aqueous samples are
generally homogenous and most soil samples are homogenous within a factor of two or three.
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 or for each Sample Delivery Group (SDG). Duplicates cannot be
averaged for reporting on Form I-IN. Additional duplicate sample analyses may be required
by USEPA Regional request. Alternately, the Region may require that a specific sample be
used for the duplicate sample analysis.
3. Duplicate sample analyses are required for Percent Solids (%S) determination.
4. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original
and duplicate sample values > five times (5x) the Contract Required Quantitation Limit
(CRQL).
5. 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 VI-IN. If both samples are non-detects, the RPD is not calculated for
Form VI-IN.
D. Evaluation:
1. Verify from the Cover Page, Form XII-IN, and the raw data that the appropriate number of
required duplicate samples were prepared and analyzed for the SDG.
2. Evaluate Form VI-IN and the raw data to verify that all duplicate results for each analyte and
method 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 VI-IN:
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RPD =
| S - D |
(S+D)/2
x 100
E.
Where,
RPD
S
D
Relative Percent Difference
Sample Result (original)
Duplicate Result
NOTE:
For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with the above criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
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 reviewer considers the samples
sufficiently similar. The reviewer will need to exercise professional judgment in
determining sample similarity. The reviewer should make use of all available data,
including: site and sampling documentation (e.g., location and type of sample,
descriptive data); field test data (e.g., pH, Eh, conductivity, chlorine); and Laboratory
data for other parameters [e.g., Total Suspended Solids (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are
similar to the duplicate sample, and that only these samples should be qualified. Or,
the reviewer may determine that 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, use professional judgment
to determine if the associated sample data should be qualified. The reviewer may need to
obtain additional information from the Laboratory. Note the situation in the Data Review
Narrative, and for CLP Project Officer (PO) action.
2. If the results from a duplicate analysis for a particular analyte fall outside the appropriate
control limits, qualify sample results that are >MDL as estimated (J) and non-detects as
estimated (UJ).
3. If a field blank or PE sample was used for the duplicate sample analysis, note this for CLP
PO action. All of the other Quality Control (QC) data must then be carefully checked, and
professional judgment exercised by the data reviewer when evaluating the data.
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4. Note the potential effects on the data due to out-of-control duplicate sample results in the
Data Review Narrative.
Table 17. Duplicate Sample Actions for ICP-MS Analysis
Duplicate Sample Results
Both original sample and duplicate sample >5x
the CRQL and RPD>20%
Original sample or duplicate sample <5x the
CRQL (including non-detects) and absolute
difference between sample and duplicate >CRQL
Action for Samples
Qualify those results that are >MDL that
professional judgment determines to be affected
as estimated (J) and non-detects as estimated (UJ)
Qualify those results that are >MDL that
professional judgment determines to be affected
as estimated (J) and non-detects as estimated (UJ)
*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, 2xthe CRQL) to be assessed against duplicate soil
samples.
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VIII. Spike Sample Analysis
A. Review Items:
Cover Page, Form V-IN (Part A & B), Form XII-IN, instrument printouts, and raw data.
B. Objective:
The spiked sample analysis is designed to provide information about the effect of each sample
matrix on the sample preparation procedures and the measurement methodology. Non-
homogenous samples can impact the apparent method recovery. However, aqueous samples are
generally homogenous. If the spike is added to the sample before the digestion (e.g., prior to the
addition of other reagents), it is referred to as a spiked sample, pre-digestion spike, or Matrix
Spike. If the spike is added to the sample after the completion of the digestion procedures, it is
referred to as a post-digestion spike, or analytical spike.
C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used
for spiked sample analysis.
2. At least one spiked sample shall be prepared and analyzed for each Sample Delivery Group
(SDG).
3. When the Matrix Spike recovery falls outside of the control limits and the sample result is <
four times (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 Contract Required Quantitation Limit (CRQL),
whichever is greater.
4. The spike Percent Recovery (%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 Statement of Work (SOW).
D. Evaluation:
1. Verify using the Cover Page, Form VA-IN, Form XII-IN, and raw data that the appropriate
number of required spiked samples were prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
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3. Evaluate Form VA-IN and the raw data to verify 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 V(A
& B)-IN:
% Recovery =
SSR - SR
SA
x 100
Where,
SSR
SR
SA
Spiked Sample Result
Sample Result
Spike Added
NOTES: When the sample concentration is < Method Detection Limit (MDL), use SR = 0 only
for the purposes of calculating the %R. The actual spiked sample results, sample
results, and %R (positive or negative) shall still be reported on Form V (A & B)-IN.
For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with the above criteria can be obtained from
the Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
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 reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data, including: site and
sampling documentation (e.g., location and type of sample, descriptive data); field test
data (e.g., pH, Eh, conductivity, chlorine); and Laboratory data for other parameters
[e.g., Total Suspended Solids (TSSs), Total Dissolved Solids (TDSs), Total Organic
Carbon (TOC), alkalinity or buffering capacity, reactive sulfide, anions], in
determining similarity. The reviewer should also use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. The
reviewer may determine that only some of the samples in the SDG are similar to the
Matrix Spike sample, and that only these samples should be qualified. Or, the reviewer
may determine that no samples are sufficiently similar to the sample used for the
Matrix Spike, and thus that 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, use professional
judgment to determine if the associated sample data should be qualified. The reviewer may
need to obtain additional information from the Laboratory. Note the situation in the Data
Review Narrative, and for CLP Project Officer (CLP PO) action.
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2. If a field blank or PE sample was used for the spiked sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked, and
professional judgment exercised by the data reviewer when evaluating the data.
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-
digestion spike was not performed, note this for CLP PO action.
4. If the Matrix Spike %R is <30%, verify that a post-digestion spike was analyzed if required.
If the post-digestion spike %R is <75% or is not performed, qualify sample results that are
>MDL as estimated low (J-) and non-detects as unusable (R). If the post-digestion spike %R
is >75%, qualify sample results that are >MDL as estimated (J) and non-detects as estimated
(UJ).
5. If the Matrix Spike %R is 30-74% and the sample results are >MDL, verify that a post-
digestion spike was analyzed, if required. If the %R for the post-digestion spike is also <75%
or is not performed, qualify the affected data as estimated low (J-). If the %R for the post-
digestion spike is >75%, qualify the affected data as estimated (J).
6. If the Matrix Spike %R falls within the range of 30-74% and the sample results are non-
detects, qualify the affected data as estimated (UJ).
7. If the Matrix Spike %R is >125% and the reported sample results are non-detects, the sample
data should not be qualified.
8. If the Matrix Spike %R is > 125% and the sample results are >MDL, verify that a post-
digestion spike was analyzed, if required. If the %R for the post-digestion spike is also
>125% or is not performed, qualify the affected data as estimated high (J+). If the %R for the
post-digestion spike is < 125%, qualify the affected data as estimated (J).
9. Note the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.
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Table 18. Spike Sample Actions for ICP-MS Analysis
Spike Sample Results
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 >125%
No post-digestion spike performed
Action for Samples
Qualify affected results that are >MDL as
estimated low (J-)
Qualify affected non-detects as unusable (R)
Qualify affected results that are >MDL as
estimated (J)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as
estimated low (J-)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as
estimated (J)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as
estimated high (J+)
Qualify affected results that are >MDL as
estimated (J)
Qualify affected results that are >MDL as
estimated low (J-) and affected non-detects as
unusable (R)
Qualify affected results that are >MDL as
estimated low (J-) and affected non-detects as
estimated (UJ)
Qualify affected results that are >MDL as
estimated high (J+)
Non-detects are not qualified
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Inorganic Data Review ICP-MS
IX. ICP Serial Dilution
A. Review Items:
Form I-IN, Form VIII-IN, instrument printouts, and raw data.
B. Objective:
The serial dilution of samples quantitated by Inductively Coupled Plasma-Mass Spectrometry
(ICP-MS) determines 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 for each Sample Delivery
Group (SDG), whichever is more frequent.
2. Samples identified as field blanks or Performance Evaluation (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 >50
times (5 Ox) the Method Detection Limit (MDL)], the serial dilution analysis (a five-fold
dilution) shall then agree within a 10 Percent Difference (%D) of the original determination
after correction for dilution.
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 VIII-IN:
% Difference = I J ~ S I x 100
Where,
I = Initial sample result (instrument reading)
S = Serial dilution result (instrument reading x 5)
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.
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NOTE:
E.
For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with the above criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
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 reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data, including: site and
sampling documentation (e.g., location and type of sample, descriptive data); field test
data (e.g., pH, Eh, conductivity, chlorine); and Laboratory data for other parameters
[e.g., Total Suspended Solids (TSSs), Total Dissolved Solids (TDSs), Total Organic
Carbon (TOC), alkalinity or buffering capacity, reactive sulfide, anions], in
determining similarity. The reviewer should also use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. The
reviewer may determine that only some of the samples in the SDG are similar to the
serial dilution sample, and that only these samples should be qualified. Or, the
reviewer may determine that 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.
1. If the required %D criteria are not met, qualify all affected results that are >MDL as
estimated (J) and all affected non-detects as estimated (UJ).
2. If evidence of positive or negative interference is found, use professional judgment to qualify
the associated sample data. Note the potential effects on the reported data in the Data Review
Narrative.
3. It should be noted for CLP Project Officer (CLP PO) action and in the Data Review Narrative
if a field blank or PE sample was used for the serial dilution analysis.
Table 19. Serial Dilution Actions for ICP-MS Analysis
Serial Dilution Result
Sample concentration >50x MDL and %D >10
Interferences present
Action for Samples
Qualify affected results that are >MDL as
estimated (J)
Qualify affected non-detects as estimated (UJ)
Use professional judgment
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X. ICP-MS Internal Standards
A. Review Items:
Form XIII-IN, Form XV-IN, instrument printouts, and raw data.
B. Objective:
The analysis of Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) internal standards
determines the existence and magnitude of instrument drift and physical interferences. The
criteria for evaluation of internal standard results applies to all analytical and Quality Control
(QC) samples analyzed during the run, beginning with the calibration.
C. Criteria:
1. All samples analyzed during a run, with the exception of the ICP-MS 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 (the In115 isotope); Tb; Ho; Lu; and
Bi. If the Laboratory uses lithium as an internal standard, the Laboratory shall use an Li6-
enriched standard. The masses of the internal standards shall bracket the masses of the target
analytes. The laboratory shall monitor the same internal standards throughout the entire
analytical run.
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.
D. Evaluation:
1. Verify using Form XV-IN and the raw data that a minimum of five internal standards from
the specified list were used for the analysis, that the masses of the internal standards bracket
the masses of the target analytes, and that the same internal standards were monitored for the
entire run.
2. Verify using Form XV-IN and the raw data that these internal standards were added to each
sample in the run, including calibrations, samples, and QC samples (except tune).
3. Verify using Form XV-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 XIII-IN, Form XV-IN, and the raw data that if the %RI for a sample was
outside the limits (60-125%), the sample was reanalyzed of a 2X dilution.
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NOTE: For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with the above criteria can be obtained from the Data
Assessment Tool (DAT) reports and may be used as part of the evaluation process.
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 run, the sample data should be qualified as
unusable (R). Record this in the Data Review Narrative and note for CLP Project Officer
(CLP PO) action.
2. If less than five of the required internal standards were analyzed with the run, or the masses
of the internal standards does not bracket the masses of the target analytes, the analyte sample
data not bracketed by the internal standard masses should be qualified as unusable (R).
Record this in the Data Review Narrative and note for CLP PO action.
3. If the %RIs for all internal standards in a sample are within the 60-125% limit, the sample
data should not be qualified.
4. If the %RI for an internal standard in a sample is not within the 60-125% limit, qualify the
data for those analytes with atomic masses that fall between the atomic mass of the internal
standard lighter than the affected internal standard, and the atomic mass of the internal
standard heavier than the affected internal standard, or between the limit (upper or lower) of
the mass range and the nearest unaffected internal standard, as follows:
a. If the sample was reanalyzed at a two-fold dilution with internal standard %RI within the
limits, report the result of the diluted analysis without qualification. If the %RI of the
diluted analysis was not within the 60-125% limit, report the results of the original
undiluted analyses and qualify the data for all analytes that are > Method Detection Limit
(MDL) in the sample associated with the internal standard as estimated (J), and non-
detected analytes associated with the internal standard as estimated (UJ).
b. If the sample was not reanalyzed at a two-fold dilution, the reviewer should use
professional judgment to determine the reliability of the data. The reviewer may
determine that the results are estimated (J) or unusable (R).
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Table 20. Internal Standard Actions for ICP-MS Analysis
Internal Standard Results
No internal standards
<5 of the required internal standards
Masses of internal standards do not bracket
masses of target analytes
%RI <60% or >125%, and original sample
reanalyzed at 2-fold dilution
Original sample not reanalyzed at 2-fold dilution
Action for Samples
Qualify all results as unusable (R)
Qualify all analyte results not bracketed by
internal standard masses as unusable (R)
Qualify all analyte results not bracketed by
internal standard masses as unusable (R)
If %RI of diluted sample analysis 60-125%, do
not qualify the data
If the %RI of the diluted sample analysis is
outside the 60-125% limit, qualify results that are
>MDL as estimated (J) and qualify non-detects as
estimated (UJ)
Use professional judgment
Qualify sample results as estimated (J) or
unusable (R)
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XL Field Duplicates
A. Review Items:
Form I-IN, instrument printouts, and raw data.
B. Objective:
Field duplicate samples may be collected and analyzed as an indication of overall precision.
These analyses measure both field and Laboratory precision. The results, therefore, may have
more variability than Laboratory duplicates that measure only Laboratory performance. It is also
expected that soil duplicate results will have a greater variance than water matrices due to
difficulties associated with collecting identical field samples.
C. Criteria:
There are no "required" review criteria for determining comparability of field duplicate analyses.
D. Evaluation:
Identify samples that are field duplicates using Traffic Report/Chain of Custody (TR/COC)
documentation or sample field sheets. Compare the results reported for each sample and calculate
the Relative Percent Difference (RPD), if appropriate.
E. Action:
Provide any evaluation of the field duplicates in the Data Review Narrative.
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Inorganic Data Review ICP-MS
XII. Overall Assessment
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 ensure that the reported sample quantitation results are accurate. It is
appropriate for the data reviewer to make professional judgments and express concerns, as well as
to comment on the validity of the overall data for a Case. This is particularly appropriate when
there are several Quality Control (QC) criteria that are outside of the specification parameters.
The additive nature of QC factors that fall outside of specification parameters is difficult to assess
in an objective manner, but the reviewer has a responsibility to inform the user concerning data
quality and data limitations to assist that user in avoiding inappropriate use of the data, while not
precluding any consideration of the data at all. If qualifiers other than those used in this
document are necessary to describe or qualify the data, it is necessary to thoroughly
document/explain the additional qualifiers used. The data reviewer would be greatly assisted in
this endeavor if the acceptance or performance criteria were provided. The Inorganic Review
Summary (see Appendix B) and supplementary documentation must be included with the review.
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.
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, strip charts, etc., should be compared to the
reported sample results recorded on the appropriate Inorganic Summary Forms (Form I-IN
through Form XV-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 volumes were used in preparing the samples for analysis.
Verify that the turbidity was measured prior to method selection. If reduced volumes were
used, verify that the Laboratory had received Contract Laboratory Program Project Officer
(CLP PO) approval for the use of the reduced volume.
4. Verify that there are no transcription or reduction errors [e.g., dilutions, Percent Solids (%S),
sample weights, etc.] on one or more samples.
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Inorganic Data Review ICP-MS
5. Verify that results fall within the linear range(s) of the Inductively Coupled Plasma (ICP)
instrument(s) (Form XI).
6. If appropriate information is available, the reviewer may 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 Standard Operating Procedure(s) (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. Write a brief Data Review Narrative to give the user an indication of the analytical limitations
of the data. Note any discrepancies between the data and the Sample Delivery Group (SDG)
Narrative for CLP PO action. If sufficient information on the intended use and required
quality of the data are available, the reviewer should include an assessment of the data
usability within the given context.
3. If any discrepancies are found, the Laboratory may be contacted by the Region's designated
representative to obtain additional information for resolution. If a discrepancy remains
unresolved, the reviewer may determine that qualification of the data is warranted.
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Calculations for ICP-MS
Prepared Sample Concentration (Method HW2):
V V
Concentration (ug/L) = C x — x — x DF
V. 20
Where,
C = Instrument value in iig/L (the average of all replicate
integrations)
Vf = Final digestion volume (50 mL)
Vj = Initial digestion volume (100 mL)
DF = Dilution Factor
Prepared Sample Concentration (Method HW3):
Concentration (p,g/L) = C x DF
Where,
C = Instrument value in (ig/L (the average of all replicate
integrations)
DF = Dilution Factor
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Inorganic Data Review Mercury
MERCURY DATA REVIEW
The inorganic data requirements for mercury data review to be reviewed during validation are listed
below:
I. Preservation and Holding Times
II. Calibration
A. Initial
B. Initial and Continuing Calibration Verification (ICV/CCV)
C. Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
III. Blanks
IV. Laboratory Control Sample (LCS)
V. Duplicate Sample Analysis
VI. Spike Sample Analysis
VII. Field Duplicates
VIII. Overall Assessment
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Inorganic Data Review Mercury
An Example Analytical Sequence for Mercury
SO
S0.2
S0.5
Sl.O
S5.0
S10.0
ICV
ICB
CRI
CCV
CCB
ten samples
CCV
CCB
nine samples
CRI
CCV
CCB
ten samples, etc.
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Inorganic Data Review Mercury
I. Preservation and Holding Times
A. Review Items:
Form IA-IN, Form IB-IN, Form XII-IN, Form XIII-IN, Traffic Report/Chain of Custody
(TR/COC) documentation, Form DC-1, raw data, and the Sample Delivery Group (SDG)
Narrative checking for: pH; cooler temperature; holding time; and other sample conditions.
B. Objective:
The objective is to ascertain the validity of the analytical results based on the sample condition,
and the holding time of the sample from the date of collection to the date of analysis.
C. Criteria:
1. Technical requirements for sample holding times have only been established for aqueous
matrices. The addition of nitric acid to adjust the pH is only required for aqueous samples.
2. The technical holding time criteria for aqueous mercury samples is 28 days; preserved (with
nitric acid) to pH<2.
3. Aqueous samples shall be maintained at 4°C ±2°C until preparation and analysis to allow for
re-preparation and for the direct analysis of dissolved metals.
4. The preservation for soil/sediment samples is maintenance at 4°C ±2°C until preparation and
analysis.
D. Evaluation:
Technical holding times are established by comparing the sampling date(s) on the TR/COC
documentation with the dates of analysis on Form XIII-IN, and the raw data. Information
contained in the Complete SDG File (CSF) should also be considered in the determination of
holding times. Verify that the analysis dates on the Form XIIIs 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 that there were problems with the samples, the integrity of the
samples may be compromised and professional judgment should be used to evaluate the effect of
the problem on the sample results.
E. Action:
NOTE: Apply the action to each sample for which the preservation or holding time criteria was
not met.
1. If the pH of aqueous metals samples is >2 at the time of sample receipt, use professional
judgment to qualify the samples based on the pH of the sample and the chemistry of the
metal(s) of interest. Qualify results that are >MDL as estimated low (J-), and qualify non-
detects as unusable (R).
2. 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
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requirement and whether the samples were properly preserved. The expected bias would be
low. Qualify results that are >MDL as estimated low (J-), and non-detects as unusable (R).
3. Due to limited information concerning holding times for soil samples, it is left to the
discretion of the data reviewer whether to apply water holding time criteria to soil samples. If
they are applied, it must be clearly documented in the Data Review Narrative.
4. When the holding times are exceeded, the reviewer should comment in the Data Review
Narrative on any possible consequences for the analytical results.
5. When holding times are grossly exceeded, note this for Contract Laboratory Program Project
Officer (CLP PO) action.
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 for CLP PO action.
Table 21. Technical Holding Time Actions for Mercury Analysis
Preservation & Holding Time Results
Aqueous metals samples received with pH >2
Technical holding time exceeded:
mercury >28 days
Action for Samples
Use professional judgment
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
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II. Calibration
A. Review Items:
Form II-IN (Parts A & B), Form XI-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data.
B. Objective:
Method requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data for mercury. Initial Calibration
Verification (ICV) demonstrates that the instrument is capable of acceptable performance at the
beginning of the analytical run. Continuing Calibration Verification (CCV) demonstrates that the
initial calibration is still valid by checking the performance of the instrument on a continuing
basis.
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.
a. Cold Vapor Mercury Analysis
1) A blank and at least four calibration standards shall be employed to establish the
analytical curve. One of the calibration standards shall be at the Contract Required
Quantitation Limit (CRQL). The calibration curves for mercury shall possess a
correlation coefficient of > 0.995 to ensure the linearity over the calibrated range. All
sample results shall be reported from an analysis within the calibrated range.
2) The linearity of the analytical curve shall be verified near the CRQL. A CRQL
Check Standard (CRI) solution shall be prepared and analyzed at the beginning and
end of each sample analysis run and every 20 analytical samples, but not before the
ICV analysis. The CRI at the beginning of the run must immediately follow the
ICV/ICB analyses.
3) Analysis of the CRI for mercury is required for both the manual and automated cold
vapor methods, and the results and Percent Recovery (%R) are to be reported on
Form IIB-IN.
4) If the results for the CRI do not fall within the fixed acceptance limits, the Laboratory
shall reanalyze a CRI. If the results of the reanalysis do not fall within the
acceptance limits, the analysis should be terminated, the problem corrected, the
instrument recalibrated, the CRI and associated samples redigested if necessary, and
the new calibration then reverified.
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2. Initial and Continuing Calibration Verification (ICV and CCV)
The acceptance criteria for the ICVs, CCVs, and CRIs are presented in Table 22. These
standards shall be prepared by the same method used to prepare the samples for analysis.
Table 22. Acceptance Criteria for ICVs, CCVs, and CRIs
Analytical
Method
Cold Vapor AA
Inorganic
Analyte
Mercury
ICV/CCV
Low Limit
(% of True
Value)
80
ICV/CCV
High Limit
(% of True
Value)
120
CRI
Low Limit
(% of True
Value)
70
CRI
High Limit
(% of True
Value)
130
a. Initial Calibration Verification (ICV)
1) Immediately after each Atomic Absorption (AA) system has been calibrated, the
accuracy of the initial calibration must be verified and documented for mercury by
the analysis of an ICV solution(s). If the ICV %R falls outside of the control limits,
the analysis should be terminated, the problem corrected, the instrument recalibrated,
and all affected samples reanalyzed.
2) If the ICV is not available from USEPA, or where a certified solution of the analyte
is not available from any source, analyses shall be conducted on an independent
standard at a concentration level other than that used for instrument calibration (or
the CRI), but within the calibrated range.
b. Continuing Calibration Verification (CCV)
1) To ensure accuracy during the course of each analytical run, the CCV shall be
analyzed and reported.
2) The CCV standard shall be analyzed at a frequency of 10% or every two hours
during an analytical run, whichever is more frequent. The CCV standard shall also
be analyzed at the beginning of the run, and again after the last analytical sample.
3) The analyte concentration in the CCV standard shall be different than the
concentration used for the ICV, and shall be one of the following solutions at, or
near, the mid-range levels of the calibration curve:
A. USEPA solutions;
B. National Institute of Standards and Technology (NIST) standards; or
C. A Laboratory-prepared standard solution (self-prepared or commercially
available).
4) The same CCV standard solution shall be used throughout the analysis runs for a
Sample Delivery Group (SDG).
5) The CCV shall be analyzed in the same fashion as an actual sample. Operations such
as the number of replicate analyses, the number and duration of the instrument rinses,
etc., affect the measured CCV result and are not to be applied to the CCV to an extent
greater than was applied to the associated analytical samples. If the %R of the CCV
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D.
was outside of the control limits, the analysis should be terminated, the problem
corrected, the instrument recalibrated, and the preceding 10 analytical samples (or all
analytical samples analyzed since the last compliant CCV) reanalyzed.
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 four calibration standards. Confirm that
one of the calibration standards was analyzed at the CRQL.
2. Evaluate the reported CRI to confirm that it was analyzed at the proper frequency,
concentration, and location within the analytical run sequence. Verify that acceptable %R
results were obtained.
3. Verify that the ICV and CCV standards were analyzed for mercury at the proper frequency
(10%) and at the appropriate concentration. Verify that acceptable %R results were obtained.
4. Recalculate one or more of the ICV, CCV, or CRI %R using the following equation and
verify that the recalculated value agrees with the Laboratory-reported values on Forms II (A
& B)-IN.
%R = Found(value) x 10Q
True(value)
Where,
Found(value) =
True (value) =
Concentration (in (ig/L) of mercury measured in the
analysis of the ICV, CCV, or CRI solution
Concentration (in (ig/L) of mercury in the ICV, CCV, or
CRI source
E.
NOTE:
Action:
For data obtained from the Contract Laboratory Program (CLP), the above criteria
are evaluated as part of the Contract Compliance Screening (CCS) process.
Information regarding the Laboratory's compliance with these criteria can be
obtained from the Data Assessment Tool (DAT) reports, and may be used as part of
the evaluation process.
NOTES: For initial calibrations or ICVs that do not meet the technical criteria, apply the action
to all samples reported from the analytical run.
For CCVs or CRIs 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 run.
1. If the instrument was not calibrated daily and each time the instrument was set up, qualify the
data 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
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(e.g., a blank, or a standard at the CRQL), use professional judgment to qualify results that
are > Method Detection Limit (MDL) as estimated (J) or unusable (R), and non-detects as
estimated (UJ) or unusable (R).
2. If the correlation coefficient is <0.995, qualify sample results that are >MDL as estimated (J),
and non-detects as estimated (UJ). Depending on the degree of the deviation from linearity,
further qualification of the data may be required depending on the professional judgment of
the reviewer [e.g., unusable data (R)].
3. If the CRIs are outside the acceptance criteria, use professional judgment to qualify all
associated data. If possible, indicate the bias in the review. The following guidelines are
recommended:
a. If the CRI %R is <50%, qualify all sample results that are >MDL but < two times (2x)
the CRQL and all non-detects as unusable (R). Qualify detects that are >2x the CRQL as
estimated (J).
b. If the CRI %R falls within the range of 50-69%, qualify all sample results that are >MDL
but <2x the CRQL as estimated low (J-), and all non-detects as estimated (UJ). Detects
that are >2x the CRQL should not be qualified based on this criterion.
c. If the CRI %R is >130% but < 180%, qualify all sample results that are >MDL but <2x
the CRQL as estimated high (J+). Non-detects and detects that are >2x the CRQL should
not be qualified based on this criterion.
d. If the CRI %R is >180%, qualify all sample results that are >MDL as unusable (R).
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 <65%, qualify non-detects as unusable (R). Use professional
judgment to qualify all results that are >MDL as estimated low (J-) or unusable (R).
b. If the ICV or CCV %R falls within the range of 65-79%, qualify sample results that are
>MDL as estimated low (J-) and qualify non-detects as estimated (UJ).
c. If the ICV or CCV %R falls within the range of 121-135%, qualify sample results that are
>MDL as estimated high (J+).
d. If the ICV or CCV %R falls within the range of 121-135%, non-detects should not be
qualified.
e. If the ICV or CCV %R is >135%, use professional judgment to qualify results that are
>MDL as estimated high (J+) or unusable (R). Non-detects should not be qualified.
f If the %R is >170%, qualify all results that are >MDL as unusable (R).
5. If the Laboratory failed to provide adequate calibration information, the Region's designated
representative should contact the Laboratory and request the necessary information. If the
information is not available, the reviewer must use professional judgment to assess the data.
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6. Note 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 CLP Project Officer (CLP PO)
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 23. Calibration Actions for Mercury Analysis
Calibration Result
Calibration not performed
Calibration incomplete
Correlation coefficient <0.995
CRI%R<50%
CRI %R 50-69%
CRI %R >130% but < 180%
CRI%R>180%
ICV/CCV%R<65%
ICV/CCV %R 65-79%
ICV/CCV %R 121-135%
ICV/CCV%R>135%
ICV/CCV %R> 170%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated (J) or
unusable (R)
Qualify non-detects as estimated (UJ) or unusable (R)
Qualify results that are >MDL as estimated (J)
Qualify non-detects as estimated (UJ)
Qualify all results that are >MDL but <2x the CRQL
and all non-detects as unusable (R)
Qualify all results that are >2x the CRQL as
estimated (J)
Qualify results that are >MDL but <2x the CRQL as
estimated low (J-)
Qualify non-detects as estimated (UJ)
Results that are >2x the CRQL are not qualified
Qualify results that are >MDL but <2x the CRQL as
estimated high (J+)
Non-detects and results that are >2x the CRQL are
not qualified
Qualify all results that are >MDL as unusable (R)
Qualify results that are >MDL as estimated low (J-)
or unusable (R)
Qualify all non-detects as unusable (R)
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated (J)
Qualify results that are >MDL as estimated high (J+)
or unusable (R)
Qualify results that are >MDL as unusable (R)
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III. Blanks
A. Review Items:
Form I-IN, Form III-IN, Form XII-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, and raw data.
B. Objective:
The objective of blank analysis results assessment is to determine the existence and magnitude of
contamination resulting from Laboratory (or field) activities. The criteria for evaluation of blanks
applies to any blank associated with the samples (e.g., method blanks, calibration blanks, field
blanks, etc.). If problems with any blank exist, all associated data must be carefully evaluated to
determine whether or not there is an inherent variability in the data, or if the problem is an
isolated occurrence not affecting other data.
C. Criteria:
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed after the analytical standards, but not
before analysis of the Initial Calibration Verification (ICV) during the initial calibration of
the instrument (see Section II.C. 1). 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 ICV and
Continuing Calibration Verification (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 10%,
or every two hours during the run, whichever is more frequent. The CCB shall be analyzed at
the beginning of the run, and again after the last CCV that was analyzed after the last
analytical sample of the run. The CCB result (absolute value) shall not exceed the Contract
Required Quantitation Limit (CRQL) for mercury.
4. At least one Preparation Blank (PB) shall be prepared and analyzed for each matrix, with
every Sample Delivery Group (SDG), or with each batch of samples digested, whichever is
more frequent. The PB consists of reagent water processed through the appropriate sample
preparation and analysis procedure.
5. If the mercury concentration in the PB is >CRQL, the lowest concentration of mercury in the
associated samples must be 10 times (lOx) the PB concentration. Otherwise, all samples
associated with that PB with a mercury concentration <10x the PB concentration, and
>CRQL, should be redigested and reanalyzed (except for an identified field blank). The
Laboratory is not to correct the sample concentration for the blank value.
6. If the concentration of the PB for mercury is <(-CRQL), all samples reported <10x the
CRQL (associated with that analyte in that blank), should be redigested and reanalyzed.
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D. Evaluation:
Mercury
E.
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the proper
frequency and location during the run, and PBs 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 the Blank Summary (Form III-IN), as well as the raw data
(e.g., instrument printouts, strip charts, printer tapes, bench sheets, etc.) for all blanks, and
verify that the results are accurately reported.
3. Evaluate all of the associated blanks for the presence of mercury. Verify that if mercury was
present in a PB, or if a concentration was <(-CRQL), the affected samples were redigested
and reanalyzed. Verify that if mercury was present 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.
NOTE:
For data obtained from the Contract Laboratory Program (CLP), many of the above
criteria are evaluated as part of the Contract Compliance Screening (CCS) process.
Information regarding the Laboratory's compliance with these criteria can be obtained
from the Data Assessment Tool (DAT) reports, and may be used as part of the
evaluation process.
Action:
NOTES: For ICBs that do not meet the technical criteria, apply the action to all samples reported
from the analytical run.
For CCBs that do not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the CCB and a
subsequent technically acceptable analysis of the CCB in the analytical run.
For PBs that do not meet the technical criteria, apply the action to all samples prepared
in the same preparation batch.
1. If the appropriate blanks are not analyzed with the correct frequency, the data reviewer
should use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the Laboratory. The
situation should then be recorded in the Data Review Narrative, and noted for CLP Project
Officer (PO) action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the
blank. The reviewer should note that 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.
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3. Some general "technical" review actions include:
a. Any blank (including PB) reported with a negative result, whose value is < [-Method
Detection Limit (MDL)] but >(-CRQL), should be carefully evaluated to determine its
effect on the sample data. The reviewer shall then use professional judgment to assess
the data. For any blank (including PB) reported with a negative result, whose value is
<(-CRQL), qualify results that are >CRQL as estimated low (J-) and non-detects as
estimated (UJ).
b. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil sample results reported on Form I-IN will not be
on the same basis (units, dilution) as the calibration blank data reported on Form III-IN.
The reviewer may find it easier to work with the raw data.
4. Specific "method" actions include:
a. If the absolute value of an ICB or a CCB result is >CRQL, the analysis should be
terminated. If the analysis was not terminated and the affected samples are not
reanalyzed, report non-detects and results that are >MDL but CRQL but < Blank Result, use professional judgment to qualify the data
as unusable (R), or to report the results at the level of the blank with a "U" qualifier. Use
professional judgment to qualify results that are > Blank Result. Note this situation for
CLP PO action and record it in the Data Review Narrative.
b. If the absolute value of the concentration of the PB is MDL but CRQL.
c. If the mercury concentration in the PB is >CRQL, the lowest concentration of mercury in
the associated samples must be lOx the PB concentration. Otherwise, all samples
associated with that blank with concentrations <10x the PB concentration and >CRQL
should be redigested and reanalyzed. Raise the CRQL to the concentration found in the
PB and report those samples that do not require redigestion (that are >MDL but
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Inorganic Data Review
Mercury
Table 24. Blank Actions for Mercury Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
PB
PB
PB
Blank Result
Absolute value is
>MDL but
CRQL
<(-MDL), but
>(-CRQL)
<(-CRQL)
>CRQL
>MDL but
MDL but < CRQL
>CRQL
>MDL but < CRQL
>CRQL but Blank Result
>MDL, or non-detect
<10xtheCRQL
>MDL but < CRQL
>CRQL but <10x the Blank
Result
>1 Ox the Blank Result
Non-detect
>MDL but < CRQL
>CRQL
<10xtheCRQL
Action for Samples
No action
Report CRQL value with a "U"
Use professional judgment
Report CRQL value with a "U"
Report at level of Blank Result
with a "U" or qualify data as
unusable (R)
Use professional judgment
Use professional judgment
Qualify results that are >CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
Report CRQL value with a "U"
Qualify results as unusable (R) or
estimated high (J+)
No action
No action
Report CRQL with a "U"
Use professional judgment
Qualify results that are >CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
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IV. Laboratory Control Sample (LCS)
A. Review Items:
Form VII-IN, Form XII-IN, preparation logs, instrument printouts, and raw data.
B. Objective:
The Laboratory Control Sample (LCS) serves as a monitor of the overall performance of each
step during the analysis, including the sample preparation.
C. Criteria:
1. Solid LCSs shall be analyzed utilizing the same sample preparations, analytical methods, and
Quality Assurance/Quality Control (QA/QC) procedures as employed for the samples.
a. A solid LCS shall be prepared and analyzed utilizing each of the preparation and
analytical procedures applied to the soil/sediment samples received, with one exception:
The Percent Solids (%S) determination is not required. If the solid LCS is not available
from USEPA, other USEPA QA samples or certified materials may be used.
b. One solid LCS shall be prepared and analyzed for each group of soil sediment samples in
an Sample Delivery Group (SDG), or for each batch of samples digested, whichever is
more frequent.
c. All solid LCS results shall fall within the control limits reported on Form VII-IN. If the
results for the solid LCS fall outside of the control limits, the analyses should be
terminated, the problem corrected, and the samples prepared with that LCS redigested
and reanalyzed.
D. Evaluation:
1. Verify using Form VII-IN, Form XII-IN, and raw data that the appropriate number of
required LCSs were prepared and analyzed for the SDG.
2. Evaluate Form VII-IN and verify that all results for mercury fall within the established
control limits.
3. Check the raw data (e.g., instrument printouts, strip charts, bench sheets, etc.) to verify that
the Percent Recoveries (%Rs) on Form VII-IN were accurately transcribed. Recalculate one
or more of the reported %Rs using the following equation:
o/0R = Found(value) x 10Q
True(value)
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Where,
Found(value) = Concentration of mercury (in mg/kg) measured in the
analysis of the LCS
True(value) = Concentration of mercury (in mg/kg) in the LCS
4. Verify that the LCS was prepared at the same time as the associated samples using the same
procedures.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with these criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
E. Action:
If the LCS criteria are not met, the Laboratory performance and method accuracy are in question.
Professional judgment should be used 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. Solid LCS:
a. If the LCS results are greater than the reported control limits, qualify sample results that
are > Method Detection Limit (MDL) as estimated high (J+). If the LCS results are less
than the reported control limits, qualify sample results that are >MDL as estimated low
(J-).
b. If the LCS results are greater than the reported control limits and the sample results are
non-detects, the data should not be qualified.
c. If the LCS results are less than the reported control limits, qualify non-detects as
estimated (UJ).
d. If a Laboratory fails to analyze an LCS with each SDG, or if a Laboratory consistently
fails to generate acceptable LCS recoveries, note this for CLP Project Officer (PO)
action.
e. Whenever possible, the potential effects on the data due to out-of-control LCS results
should be noted in the Data Review Narrative.
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Table 25. LCS Actions for Mercury Analysis
LCS Result
Soil Result > upper limit
Soil Result < lower limit
Action for Samples
Qualify results that are >MDL as estimated high (J+)
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
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V. Duplicate Sample Analysis
A. Review Items:
Cover Page, Form VI-IN, Form XII-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. Duplicate analyses are also performed to generate data that
determines the long-term precision of the analytical method on various matrices. Non-
homogenous samples can impact the apparent method precision. However, aqueous samples are
generally homogenous and most soil samples are homogenous within a factor of two or three.
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 Sample Delivery Group (SDG).
Duplicates cannot be averaged for reporting on Form I-IN. Additional duplicate sample
analyses may be required by USEPA Regional request. Alternately, the Region may require
that a specific sample be used for the duplicate sample analysis.
3. Duplicate sample analyses are required for Percent Solids (%S) determination.
4. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original
and duplicate sample values > five times (5x) the Contract Required Quantitation Limit
(CRQL).
5. 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 VI-IN. If both samples are non-detects, the RPD is not calculated for
Form VI-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, Form XII-IN, and the raw data that the appropriate number of
required duplicate samples were prepared and analyzed for the SDG.
2. Evaluate Form VI-IN and the raw data to verify that all mercury duplicate results for each
method fall within the established control limits.
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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 VI-IN:
RPD =
(S+D)/2
x 100
E.
Where,
RPD
S
D
Relative Percent Difference
Sample Result (original)
Duplicate Result
NOTE:
For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with the above criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
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 reviewer considers the samples
sufficiently similar. The reviewer will need to exercise professional judgment in
determining sample similarity. The reviewer should make 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
(TSSs), Total Dissolved Solids (TDSs), Total Organic Carbon (TOC), alkalinity or
buffering capacity, reactive sulfide, anions], in determining similarity. The reviewer
should also use the sample data (e.g., similar concentrations of analytes) in determining
similarity between samples in the SDG. The reviewer may determine that only some of
the samples in the SDG are similar to the duplicate sample, and that only these samples
should be qualified. Or, the reviewer may determine that no samples are sufficiently
similar to the sample used for the duplicate, and thus that 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. The reviewer may need to obtain additional information from the
Laboratory. Note the situation in the Data Review Narrative, and for CLP Project Officer
(PO) action.
2. If the results from a duplicate analysis for mercury fall outside the appropriate control limits,
qualify sample results that are > Method Detection Limit (MDL) as estimated (J) and non-
detects as estimated (UJ).
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Mercury
3. If a field blank or PE sample was used for the duplicate sample analysis, note this for CLP
PO action. All of the other Quality Control (QC) data must then be carefully checked, and
professional judgment exercised by the data reviewer when evaluating the data.
4. Note the potential effects on the data due to out-of-control duplicate sample results in the
Data Review Narrative.
Table 26. Duplicate Sample Actions for Mercury Analysis
Duplicate Sample Results
Both original sample and duplicate sample >5x
the CRQL and RPD>20%*
Original sample or duplicate sample <5x the
CRQL (including non-detects) and absolute
difference between sample and duplicate
>CRQL*
Action for Samples
Qualify those results that are >MDL that
professional judgment determines to be affected
as estimated (J) and non-detects as estimated (UJ)
Qualify those results that are >MDL that
professional judgment determines to be affected
as estimated (J) and non-detects as estimated (UJ)
*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
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VI. Spike Sample Analysis
A. Review Items:
Cover Page, Form V-IN (Part A & B), Form XII-IN, instrument printouts, and raw data.
B. Objective:
The spiked sample analysis is designed to provide information about the effect of each sample
matrix on the sample preparation procedures and the measurement methodology. Non-
homogenous samples can impact the apparent method recovery. However, aqueous samples are
generally homogenous and most soil samples are homogenous within a factor of two or three. If
the spike is added to the sample before the digestion (e.g., prior to the addition of other reagents),
it is referred to as a spiked sample, pre-digestion spike, or Matrix Spike.
C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (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 Sample Delivery Group
(SDG).
3. The spike Percent Recovery (%R) shall be within the established acceptance limits.
However, spike recovery limits do not apply when the sample concentration is > four times
(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 concentrations required for mercury are presented in the method
described in the Statement of Work (SOW).
D. Evaluation:
1. Verify using the Cover Page, Form VA-IN, Form XII-IN, and raw data that the appropriate
number of required spiked samples were prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Evaluate Form VA-IN and the raw data to verify that all Matrix Spike sample results for
mercury fall within the established control limits.
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 V(A
& B)-IN:
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Mercury
% Recovery =
SSR - SR
SA
x 100
Where,
SSR
SR
SA
Spiked Sample Result
Sample Result
Spike Added
NOTES: When the sample concentration is < Method Detection Limit (MDL), use SR = 0
only for the purposes of calculating the %R. The actual spiked sample results,
sample results, and %R (positive or negative) shall still be reported on Form V (A &
For data obtained from the Contract Laboratory Program (CLP), the above criteria
are evaluated as part of the Contract Compliance Screening (CCS) process.
Information regarding the Laboratory's compliance with the above criteria can be
obtained from the Data Assessment Tool (DAT) reports, and may be used as part of
the evaluation process.
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 reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make 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 (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are
similar to the Matrix Spike sample, and that only these samples should be qualified.
Or, the reviewer may determine that no samples are sufficiently similar to the sample
used for the Matrix Spike, and thus that 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. The reviewer may need to obtain additional information from the
Laboratory. Note the situation in the Data Review Narrative, and for CLP Project Officer
(CLP PO) action.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked, and
professional judgment exercised by the data reviewer when evaluating the data.
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3.
Mercury
If the Matrix Spike %R is <30%, qualify affected results that are >MDL as estimated low
(J-). Qualify affected non-detects as unusable (R).
4. If the Matrix Spike %R falls within the range of 30-74% and the sample results are >MDL,
qualify the affected data as estimated low (J-).
5. If the Matrix Spike %R falls within the range of 30-74% and the sample results are non-
detects, qualify the affected data as estimated (UJ).
6. If the Matrix Spike %R is >125% and the reported sample results are non-detects, the
sample data should not be qualified.
7. If the Matrix Spike %R is >125% and the sample results are >MDL, qualify the affected
data as estimated high (J+).
8. Note 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
Spike Sample Results
Matrix Spike %R <30%
Matrix Spike %R 30-74%
Matrix Spike %R >125%
Action for Samples
Qualify affected results that are >MDL as
estimated low (J-) and affected non-detects as
unusable (R)
Qualify affected results that are >MDL as
estimated low (J-) and affected non-detects as
estimated (UJ)
Qualify affected results that are >MDL as
estimated high (J+)
Non-detects are not qualified
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VII. Field Duplicates
A. Review Items:
Form I-IN, instrument printouts, and raw data.
B. Objective:
Field duplicate samples may be collected and analyzed as an indication of overall precision.
These analyses measure both field and Laboratory precision. The results, therefore, may have
more variability than Laboratory duplicates that measure only Laboratory performance. It is also
expected that soil duplicate results will have a greater variance than water matrices due to
difficulties associated with collecting identical field samples.
C. Criteria:
There are no "required" review criteria for determining comparability of field duplicate analyses.
D. Evaluation:
Identify samples that are field duplicates using Traffic Report(s)/Chain of Custody (TR/COC)
documentation or sample field sheets. Compare the results reported for each sample and calculate
the Relative Percent Difference (RPD), if appropriate.
E. Action:
Provide any evaluation of the field duplicates in the Data Review Narrative.
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Inorganic Data Review Mercury
VIII. Overall Assessment
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 ensure that the reported sample quantitation results are accurate. It is
appropriate for the data reviewer to make professional judgments and express concerns, as well as
to comment on the validity of the overall data for a Case. This is particularly appropriate when
there are several Quality Control (QC) criteria that are outside of the specification parameters.
The additive nature of QC factors that fall outside of specification parameters is difficult to assess
in an objective manner, but the reviewer has a responsibility to inform the user concerning data
quality and data limitations to assist that user in avoiding inappropriate use of the data, while not
precluding any consideration of the data at all. If qualifiers other than those used in this
document are necessary to describe or qualify the data, it is necessary to thoroughly
document/explain the additional qualifiers used. The data reviewer would be greatly assisted in
this endeavor if the acceptance or performance criteria are provided. The Inorganic Review
Summary (see Appendix B) and supplementary documentation must be included with the review.
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.
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, strip charts, etc., should be compared to the
reported sample results recorded on the appropriate Inorganic Summary Forms (Form I-IN
through Form XV-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 had received Contract
Laboratory Program Project Officer (CLP PO) approval for the use of the reduced volume.
4. Verify that there are no transcription or reduction errors [e.g., dilutions, Percent Solids (%S),
sample weights, etc.] on one or more samples.
5. Verify that results fall within the calibrated range for mercury.
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Inorganic Data Review Mercury
6. If appropriate information is available, the reviewer may 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 Standard Operating Procedure(s) (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. Write a brief Data Review Narrative to give the user an indication of the analytical limitations
of the data. Note any discrepancies between the data and the SDG Narrative for CLP PO
action. If sufficient information on the intended use and required quality of the data are
available, the reviewer should include an assessment of the data usability within the given
context.
3. If any discrepancies are found, the Laboratory may be contacted by the Region's designated
representative to obtain additional information for resolution. If a discrepancy remains
unresolved, the reviewer may determine that qualification of the data is warranted.
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Inorganic Data Review Mercury
Calculations for Mercury
Aqueous Samples:
TT n *.. *• i n \ l^g He. curve 1000 mL
Hg Concentration (p.g/L) = ^—si x
aliquot volume, mL 1 L
Soil Samples:
Hg Concentration (mg/kg) = Hg ^ig/g = x (0.1L)
W x S
Where,
C = Concentration from curve ((ig/L)
W = Wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to Analytical Methods,
Section 1.6)
Adjusted Method Detection Limit (MDL)/Adjusted Contract Required Quantitation Limit (CRQL)
Calculation:
To calculate the adjusted MDL or adjusted CRQL for water/aqueous samples, multiply the value
of the MDL ((ig/L) or CRQL (ng/L) by the Dilution Factor (DF). Calculate the adjusted MDL or
adjusted CRQL for soil samples as follows:
WM i
Adjusted Concentration (dry wt.)(mg/kg) = C x —- x — x DF
WR S
Where,
C = MDL or CRQL concentration (mg/kg)
WM = Method required wet sample weight (g)
WR = Reported wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to Analytical
Methods, Section 1.6)
DF = Dilution Factor
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Inorganic Data Review Cyanide
CYANIDE DATA REVIEW
The inorganic data requirements for cyanide data review to be reviewed during validation are listed
below:
I. Preservation and Holding Times
II. Calibration
A. Initial
B. Initial and Continuing Calibration Verification (ICV/CCV)
C. Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
III. Blanks
IV. Laboratory Control Sample (LCS)
V. Duplicate Sample Analysis
VI. Spike Sample Analysis
VII. Field Duplicates
VIII. Overall Assessment
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An Example Analytical Sequence for Cyanide
SO
S10
S20
S50
S100
S200
S400
ICV (distilled)
ICB
CRI
CCV
CCB
MIDRANGE
nine samples
CCV
CCB
nine samples
CRI
CCV
CCB
ten samples, etc.
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Inorganic Data Review Cyanide
I. Preservation and Holding Times
A. Review Items:
Form IA-IN, Form IB-IN, Form XII-IN, Form XIII-IN, Traffic Report/Chain of Custody
(TR/COC) documentation, Form DC-1, raw data, and the Sample Delivery Group (SDG)
Narrative checking for: pH; cooler temperature; holding time; and other sample conditions.
B. Objective:
The objective is to ascertain the validity of the analytical results based on the sample condition,
and the holding time of the sample from the date of collection to the date of analysis.
C. Criteria:
1. Technical requirements for sample holding times have only been established for aqueous
matrices. The addition of sodium hydroxide to adjust the pH is only required for aqueous
samples.
2. The technical holding time criteria for aqueous cyanide samples are 14 days; oxidizing agents
removed, then preserved (with sodium hydroxide) to pH>12.
3. Aqueous samples shall be maintained at 4°C ±2°C until preparation and analysis to allow for
re-preparation and for the direct analysis of dissolved metals.
4. The preservation for soil/sediment samples is maintenance at 4°C ±2°C until preparation and
analysis.
D. Evaluation:
Technical holding times are established by comparing the sampling date(s) on the TR/COC
documentation with the dates of analysis on Form XIII-IN, and the raw data. Information
contained in the Complete SDG File (CSF) should also be considered in the determination of
holding times. Verify that the analysis dates on the Form XIIIs 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 that there are problems with the samples, the integrity of the
samples may be compromised and professional judgment should be used to evaluate the effect of
the problem on the sample results. For aqueous cyanide samples, the reviewer should look for
evidence that the samples were tested for the presence of sulfides or oxidizing agents, and
whether the appropriate preservation steps were taken.
E. Action:
NOTE: Apply the action to each sample for which the preservation or holding time criteria were
not met.
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Cyanide
1. If oxidizing agents are detected in aqueous cyanide samples at the time of sample preparation,
qualify results that are > Method Detection Limit (MDL) as estimated low (J-) and non-
detects as unusable (R). If sulfides are detected in aqueous cyanide samples at the time of
sample preparation and there is no evidence that the Laboratory removed the sulfides (using
precipitation and filtration), qualify results that are >MDL as estimated (J) and non-detects as
unusable (R). If the pH of aqueous cyanide samples is < 12 at the time of sample receipt, use
professional judgment to qualify the samples based on the pH of the sample. Qualify results
that are >MDL as estimated low (J-) and qualify non-detects as unusable (R).
2. 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. Qualify results that are >MDL as estimated low (J-) and non-detects as unusable (R).
3. Due to limited information concerning holding times for soil samples, it is left to the
discretion of the data reviewer whether to apply water holding time criteria to soil samples. If
they are applied, it must be clearly documented in the Data Review Narrative.
4. When the holding times are exceeded, the reviewer should comment in the Data Review
Narrative on any possible consequences for the analytical results.
5. When holding times are grossly exceeded, note this for Contract Laboratory Program Project
Officer (CLP PO) action.
Table 28. Technical Holding Time Actions for Cyanide Analysis
Preservation & Holding Time Results
Aqueous cyanide samples received with
oxidizing agents present.
Aqueous cyanide samples received with
sulfides present, and sulfides are not
removed
Aqueous cyanide samples received with
pH<12
Technical holding time exceeded:
Cyanide >14 days
Action for Samples
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Qualify results that are >MDL as estimated (J)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as unusable (R)
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II. Calibration
A. Review Items:
Form II-IN (Parts A & B), Form XI-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data.
B. Objective:
Method requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data for cyanide. Initial Calibration
Verification (ICV) demonstrates that the instrument is capable of acceptable performance at the
beginning of the analytical run. Continuing Calibration Verification (CCV) demonstrates that the
initial calibration is still valid by checking the performance of the instrument on a continuing
basis.
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.
a. A blank and at least three calibration standards, one of which shall be at the Contract
Required Quantitation Limit (CRQL), shall be employed to establish the analytical curve.
The calibration curve for cyanide shall possess a correlation coefficient of > 0.995 to
ensure the linearity over the calibrated range.
b. All sample results shall be reported from an analysis within the calibrated range.
c. At least one calibration standard (mid-level) shall be distilled and compared to similar
values on the curve to ensure that the distillation technique is reliable. The distilled
standard shall agree within ±15% of the undistilled standard. This mid-level standard
shall be prepared at least once for each distillation method used to prepare samples for
analysis. This standard shall be analyzed immediately following the first CCV/CCB
analyses.
d. The linearity of the analytical curve shall be verified near the CRQL. A CRQL Check
Standard (CRI) solution shall be prepared and analyzed at the beginning and end of each
sample analysis run and every 20 analytical samples, but not before the ICV analysis.
The CRI of the beginning of the run must immediately follow the ICV/ICB analyses.
e. Analysis of the CRI for cyanide is required for both the manual and semi-automated
spectrophotometric methods, and the results and Percent Recovery (%R) are to be
reported on Form IIB-IN.
f If the results for the CRI do not fall within the fixed acceptance limits, the Laboratory
must reanalyze the CRI. If the results of the reanalysis do not fall within the acceptance
limits, the analysis should be terminated, the problem corrected, the instrument
recalibrated, and the new calibration then reverified.
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2. Initial and Continuing Calibration Verification (ICV and CCV)
The acceptance criteria for the ICVs, CCVs, and CRIs are presented in Table 29:
Table 29. Acceptance Criteria for ICVs, CCVs, and CRIs
Cyanide
Analytical
Method
Other
Inorganic
Analyte
Cyanide
ICV/CCV
Low Limit
(% of True
Value)
85
ICV/CCV
High Limit
(% of True
Value)
115
CRI
Low Limit
(% of True
Value)
70
CRI
High Limit
(% of True
Value)
130
a. Initial Calibration Verification (ICV)
1) Immediately after each cyanide 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 %R falls outside of the control limits, the analysis should
be terminated, the problem corrected, the instrument recalibrated, and all affected
samples reanalyzed.
2) If the ICV is not available from USEPA, or where a certified solution of the
analyte is not available from any source, analyses shall be conducted on an
independent standard at a concentration level other than that used for instrument
calibration (or the CRI), but within the calibrated range.
3) For cyanide analysis, the ICV standard solution shall be distilled with each batch
of samples analyzed. An ICV distilled with a particular set of samples must be
analyzed only with that sample set.
b. Continuing Calibration Verification (CCV)
1) To ensure accuracy during the course of each analytical run, the CCV shall be
analyzed and reported.
2) The CCV standard shall be analyzed at a frequency of 10% or every two hours
during an analytical run, whichever is more frequent. The CCV standard shall
also be analyzed at the beginning of the run, 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 shall be one of the following solutions at, or
near, the mid-range levels of the calibration curve:
A. USEPA solutions;
B. National Institute of Standards and Technology (NIST) standards; or
C. A Laboratory-prepared standard solution (self-prepared or commercially
available).
4) The same CCV standard solution shall be used throughout the analysis runs for a
Sample Delivery Group (SDG).
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5) The CCV shall be analyzed in the same fashion as an actual sample. Operations
such as the number of replicate analyses, the number and duration of the
instrument rinses, etc., affect the measured CCV result and are not to be applied
to the CCV to an extent greater than was applied to the associated analytical
samples. If the %R of the CCV was outside of the control limits, the analysis
should be terminated, the problem corrected, the instrument recalibrated, and the
preceding 10 analytical samples or all analytical samples analyzed since the last
compliant calibration verification reanalyzed.
D. Evaluation:
1. Cyanide Analysis
a. 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 three calibration standards. Confirm
that one of the calibration standards was analyzed at the CRQL.
b. Check the distillation log and verify that a mid-level cyanide standard and the ICV were
distilled and analyzed. Verify that the distilled mid-level cyanide standard agrees within
±15% of the undistilled standard.
c. Evaluate the reported CRI to confirm that it was analyzed at the proper frequency,
concentration, and location within the analytical run sequence. Verify that acceptable
%R results were obtained.
d. Verify that the ICV and CCV standards were analyzed for cyanide at the proper
frequency (10%) and at the appropriate concentration. Verify that acceptable %R results
were obtained.
e. Recalculate one or more of the ICV, CCV, or CRI %R using the following equation and
verify that the recalculated value agrees with the Laboratory-reported values on Forms II
(A & B)-IN.
%R = Found(value) x 10Q
True(value)
Where,
Found(value) = Concentration (in (ig/L) of cyanide measured in
the analysis of the ICV, CCV, or CRI solution
True(value) = Concentration (in (ig/L) of cyanide in the ICV,
CCV, or CRI source
NOTE: For data obtained from the Contract Laboratory Program (CLP), the above
criteria are evaluated as part of the Contract Compliance Screening (CCS)
process. Information regarding the Laboratory's compliance with these criteria
can be obtained from the Data Assessment Tool (DAT) reports, and may be used
as part of the evaluation process.
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E. Action:
NOTES:
Cyanide
For initial calibrations or non-distilled ICVs that do not meet the technical
criteria, apply the action to all samples reported from the analytical run. For
distilled ICV, apply the action to all samples prepared in the same preparation
batch.
For CCVs or CRIs 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 run.
1. If the instrument was not calibrated daily and each time the instrument was set up,
qualify the data 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, or a standard at the CRQL), use professional
judgment to qualify results that are > Method Detection Limit (MDL) as estimated (J)
or unusable (R), and non-detects as estimated (UJ) or unusable (R).
2. If the correlation coefficient is <0.995, qualify sample results that are >MDL as
estimated (J), and non-detects as estimated (UJ). Depending on the degree of the
deviation from linearity, further qualification of the data may be required depending on
the professional judgment of the reviewer [e.g., unusable data (R)].
3. If one of the mid-range standards and the ICV are not distilled for cyanide, or the
distilled standard(s) does not agree with the undistilled standard (>±15% but <±30%)
qualify sample results that are >MDL as estimated (J). If the distilled standard
disagrees with the undistilled standard by more than 30%, qualify sample results that
are >MDL as unusable (R).
4. If the CRIs are outside the acceptance criteria, use professional judgment to qualify all
associated data. If possible, indicate the bias in the review. The following guidelines
are recommended:
a. If the CRI %R is <50%, qualify all sample results are >MDL but < two times (2x)
the CRQL and all non-detects as unusable (R). Qualify detects >2x the CRQL as
estimated (J).
b. If the CRI %R falls within the range of 50-69%, qualify all sample results that are
>MDL but <2x the CRQL as estimated low (J-) and all non-detects as estimated
(UJ). Detects that are >2x the CRQL should not be qualified based on this
criterion.
c. If the CRI %R is >130%, qualify all sample results that are >MDL but <2x the
CRQL as estimated high (J+). Non-detects and detects >2x the CRQL should not
be qualified based on this criterion.
d. If the CRI %R is >180%, qualify all sample results that are >MDL as unusable (R).
5. 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:
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a. If the ICV or CCV %R is <70%, qualify non-detects as unusable (R). Use
professional judgment to qualify all results that are >MDL as estimated low (J-) or
unusable (R).
b. If the ICV or CCV %R falls within the range of 70-84%, qualify sample results that
are >MDL as estimated low (J-), qualify non-detects as estimated (UJ).
c. If the ICV or CCV %R falls within the range of 116-13 0%, qualify sample results
that are >MDL as estimated high (J+).
d. If the ICV or CCV %R is within the range of 116-130%, non-detects should not be
qualified.
e. If the ICV or CCV %R is >130%, use professional judgment to qualify results that
are >MDL as estimated high (J+) or unusable (R). Non-detects should not be
qualified.
f If the %R is >165%, qualify all results that are >MDL as unusable (R).
6. If the Laboratory failed to provide adequate calibration information, the Region's
designated representative should contact the Laboratory and request the necessary
information. If the information is not available, the reviewer must use professional
judgment to assess the data.
7. Note the potential effects on the reported data due to exceeding the calibration criteria
in the Data Review Narrative.
8. If calibration criteria are grossly exceeded, note this for Contract Laboratory Program
Project Officer (CLP PO) 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.
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Cyanide
Table 30. Calibration Actions for Cyanide Analysis
Calibration Result
Calibration not performed
Calibration incomplete
Correlation coefficient <0.995
No distilled ICV or mid-range standard for
cyanide, or distilled standards do not agree
(>±15% but <±30%) with undistilled standard
Distilled standards do not agree (>±30%) with
undistilled standard
CRI%R<50%
CRI %R 50-69%
CRI %R >130% but < 165%
CRI%R>165%
ICV/CCV %R <70%
ICV/CCV %R 70-84%
ICV/CCV %R 116-130%
ICV/CCV %R> 130%
ICV/CCV %R> 165%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are >MDL as estimated (J) or
unusable (R)
Qualify non-detects as estimated (UJ) or unusable (R)
Qualify results that are >MDL as estimated (J)
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated (J)
Qualify results that are >MDL as unusable (R)
Qualify all results that are >MDL but <2x the CRQL
and all non-detects as unusable (R)
Qualify all results that are >2x the CRQL as
estimated (J)
Qualify results that are >MDL but <2x the CRQL as
estimated low (J-)
Qualify non-detects as estimated (UJ)
Results that are >2x the CRQL are not qualified
Qualify results that are >MDL but <2x the CRQL as
estimated high (J+)
Non-detects and results that are >2x the CRQL are
not qualified
Qualify all results that are >MDL as unusable (R)
Qualify results that are >MDL as estimated low (J-)
or unusable (R)
Qualify all non-detects as unusable (R)
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are >MDL as estimated (J)
Qualify results that are >MDL as estimated high (J+)
or unusable (R)
Qualify results that are >MDL as unusable (R)
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III. Blanks
A. Review Items:
Form I-IN, Form III-IN, Form XII-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, and raw data.
B. Objective:
The objective of blank analysis results assessment is to determine the existence and magnitude of
contamination resulting from Laboratory (or field) activities. The criteria for evaluation of blanks
applies to any blank associated with the samples (e.g., method blanks, calibration blanks, field
blanks, etc.). If problems with any blank exist, all associated data must be carefully evaluated to
determine whether or not there is an inherent variability in the data, or if the problem is an
isolated occurrence not affecting other data.
C. Criteria:
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed after the analytical standards, but not
before analysis of the Initial Calibration Verification (ICV) during the initial calibration of
the instrument (see Section II.C.I).
3. A Continuing Calibration Blank (CCB) shall be analyzed immediately after every ICV and
Continuing Calibration Verification (CCV). The CCB shall be analyzed at a frequency of
10% or every two hours during the run, whichever is more frequent. The CCB shall be
analyzed at the beginning of the run, and again after the last CCV that was analyzed after the
last analytical sample of the run. The CCB result (absolute value) shall not exceed the
Contract Required Quantitation Limit (CRQL) of cyanide.
4. At least one Preparation Blank (PB) shall be prepared and analyzed for each matrix, with
every Sample Delivery Group (SDG), or with each batch of samples distilled, whichever is
more frequent. The PB consists of reagent water processed through the appropriate sample
preparation and analysis procedure.
5. If the cyanide concentration in the PB is >CRQL, the lowest concentration of cyanide in the
associated samples must be 10 times (lOx) the PB concentration. Otherwise, all samples
associated with that PB with a cyanide concentration <10x the PB concentration, and
>CRQL, should be redistilled and reanalyzed cyanide (except for an identified field blank).
The Laboratory is not to correct the sample concentration for the blank value.
6. If the concentration of the PB for cyanide is <(-CRQL), all samples reported <10x the CRQL
(associated with that blank), should be redistilled and reanalyzed.
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D. Evaluation:
Cyanide
E.
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the proper
frequency and location during the run, and PBs 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 the Blank Summary (Form III-IN), as well as the raw data
(e.g., instrument printouts, strip charts, printer tapes, bench sheets, etc.) for all blanks, and
verify that the results were accurately reported.
3. Evaluate all of the associated blanks for the presence of cyanide. Verify that if cyanide was
present in a PB, or if a concentration was <(-CRQL), the affected samples were redistilled
and reanalyzed. Verify that if cyanide was present 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.
NOTE:
For data obtained from the Contract Laboratory Program (CLP), many of the above
criteria are evaluated as part of the Contract Compliance Screening (CCS) process.
Information regarding the Laboratory's compliance with these criteria can be obtained
from the Data Assessment Tool (DAT) reports, and may be used as part of the
evaluation process.
Action:
NOTES: For ICBs that do not meet the technical criteria, apply the action to all samples reported
from the analytical run.
For CCBs that do not meet the technical criteria, apply the action to all samples
analyzed between a previous technically acceptable analysis of the CCB and a
subsequent technically acceptable analysis of the CCB in the analytical run.
For PBs that do not meet the technical criteria, apply the action to all samples prepared
in the same preparation batch.
1. If the appropriate blanks are not analyzed with the correct frequency, the data reviewer
should use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the Laboratory. The
situation should then be recorded in the Data Review Narrative, and noted for CLP Project
Officer (PO) action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the
blank. The reviewer should note that 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.
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3. Some general "technical" review actions include:
a. Any blank (including PB) reported with a negative result, whose value is < [-Method
Detection Limit (MDL)] but >(-CRQL), should be carefully evaluated to determine its
effect on the sample data. The reviewer shall then use professional judgment to assess
the data. For any blank (including PB) reported with a negative result, whose value is
<(-CRQL), qualify results that are >CRQL as estimated low (J-) and non-detects as
estimated (UJ).
b. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil sample results reported on Form I-IN will not be
on the same basis (units, dilution) as the calibration blank data reported on Form III-IN.
The reviewer may find it easier to work with the raw data.
4. Specific "method" actions include:
a. If the absolute value of an ICB or a CCB result is >CRQL, the analysis should be
terminated. If the analysis was not terminated and the affected samples are not
reanalyzed, report non-detects and results that are >MDL but CRQL but < Blank Result, use professional judgment to qualify the data
as unusable (R), or report the results at the level of the blank with a "U" qualifier. Use
professional judgment to qualify results that are > Blank Result. Note this situation for
CLP PO action and record it in the Data Review Narrative.
b. If the absolute value of the concentration of the PB is MDL but CRQL.
c. If the cyanide concentration in the PB is >CRQL, the lowest concentration of cyanide in
the associated samples must be 1 Ox the PB concentration. Otherwise, all samples
associated with that blank with concentrations <10x the PB concentration and >CRQL
should be redistilled and reanalyzed. Raise the CRQL to the concentration found in the
PB and report those samples that do not require redigestion (>MDL but
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Cyanide
Table 31. Blank Actions for Cyanide Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
PB
PB
PB
Blank Result
Absolute value is
>MDL but
CRQL
<(-MDL),but
>(-CRQL)
<(-CRQL)
>CRQL
>MDL but
MDL but < CRQL
>CRQL
>MDL but < CRQL
>CRQL but Blank Result
>MDL, or non-detects
<10xtheCRQL
>MDL but < CRQL
>CRQL but <10x the Blank
Result
> lOx the Blank Result
Non-detect
>MDL but < CRQL
>CRQL
<10xtheCRQL
Action for Samples
No action
Report CRQL value with a"U"
Use professional judgment
Report CRQL value with a "U"
Report at level of Blank Result
with a "U" or qualify data as
unusable (R)
Use professional judgment
Use professional judgment
Qualify results that are >CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
Report CRQL value with a "U"
Qualify results as unusable (R) or
estimated high (J+)
No action
No action
Report CRQL value with a "U"
Use professional judgment
Qualify results that are >CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
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IV. Laboratory Control Sample (LCS)
A. Review Items:
Form VII-IN, Form XII -IN, preparation logs, instrument printouts, and raw data.
B. Objective:
The Laboratory Control Sample (LCS) serves as a monitor of the overall performance of each
step during the analysis, including the sample preparation.
C. Criteria:
1 . A solid LCS shall be prepared and analyzed utilizing each of the preparation and analytical
procedures applied to the soil/sediment samples received, with one exception: The Percent
Solids (%S) determination is not required. If the solid LCS is not available from USEPA,
other USEPA Quality Assurance (QA) samples or certified materials may be used.
2. One solid LCS shall be prepared and analyzed for each group of soil sediment samples in a
Sample Delivery Group (SDG), or for each batch of samples distilled, whichever is more
frequent.
3. All solid LCS results shall fall within the control limits reported on Form VII-IN. If the
results for the solid LCS fall outside of the control limits, the analyses should be terminated,
the problem corrected, and the samples prepared with that LCS redistilled and reanalyzed.
D. Evaluation:
1 . Verify using Form VII-IN, Form XII-IN, and raw data that the appropriate number of
required LCSs were prepared and analyzed for the SDG.
2. Evaluate Form VII-IN and verify that all results for cyanide fall within the established control
limits.
3. Check the raw data (e.g., instrument printouts, strip charts, bench sheets, etc.) to verify that
the Percent Recoveries ( %Rs) on Form VII-IN were accurately transcribed. Recalculate one
or more of the reported %Rs using the following equation:
%R = x 100
True(value)
Where,
Found(value) = Concentration of cyanide (in mg/kg) measured in the
analysis of the LCS
True(value) = Concentration of cyanide (in mg/kg) in the LCS
4. Verify that the LCS was prepared at the same time as the associated samples using the same
procedures
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NOTE: For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with these criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
E. Action:
If the LCS criteria are not met, the Laboratory performance and method accuracy are in question.
Professional judgment should be used 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 LCS results are greater than the reported control limits, qualify sample results that are >
Method Detection Limit (MDL) as estimated high (J+). If the LCS results are less than the
reported control limits, qualify sample results that are >MDL as estimated low (J-).
2. If the LCS results are greater than the reported control limits and the sample results are non-
detects, the data should not be qualified.
3. If the LCS results are less than the reported control limits, qualify non-detects as estimated
(UJ).
4. If a Laboratory fails to analyze an LCS with each SDG, or if a Laboratory consistently fails to
generate acceptable LCS recoveries, note this for CLP Project Officer (CLP PO) action.
5. Whenever possible, the potential effects on the data due to out-of-control LCS results should
be noted in the Data Review Narrative.
Table 32. LCS Actions for Cyanide Analysis
LCS Result
Soil Result > upper limit
Soil Result < lower limit
Action for Samples
Qualify results that are >MDL as estimated high (J+)
Qualify results that are >MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
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V. Duplicate Sample Analysis
A. Review Items:
Cover Page, Form VI-IN, Form XII-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. Duplicate analyses are also performed to generate data that
determines the long-term precision of the analytical method on various matrices. Non-
homogenous samples can impact the apparent method precision. However, aqueous samples are
generally homogenous and most soil samples are homogenous within a factor of two or three.
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 Sample Delivery Group (SDG).
Duplicates cannot be averaged for reporting on Form I-IN. Additional duplicate sample
analyses may be required by USEPA Regional request. Alternately, the Region may require
that a specific sample be used for the duplicate sample analysis.
3. Duplicate sample analyses are required for Percent Solids (%S) determination.
4. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original
and duplicate sample values > five times (5x) the Contract Required Quantitation Limit
(CRQL).
5. 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 VI-IN. If both samples are non-detects, the RPD is not calculated for
Form VI-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, Form XII-IN, and the raw data that the appropriate number of
required duplicate samples were prepared and analyzed for the SDG.
2. Evaluate Form VI-IN and the raw data to verify that all cyanide duplicate results for each
method fall within the established control limits.
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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 VI-IN:
RPD =
(S+D)/2
x 100
Where,
RPD
S
D
Relative Percent Difference
Sample result (original)
Duplicate result
NOTE: For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with the above criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
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 reviewer considers the samples
sufficiently similar. The reviewer will need to exercise professional judgment in
determining sample similarity. The reviewer should make 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
(TSSs), Total Dissolved Solids (TDSs), Total Organic Carbon (TOC), alkalinity or
buffering capacity, reactive sulfide, anions], in determining similarity. The reviewer
should also use the sample data (e.g., similar concentrations of analytes) in determining
similarity between samples in the SDG. The reviewer may determine that only some of
the samples in the SDG are similar to the duplicate sample, and that only these samples
should be qualified. Or, the reviewer may determine that no samples are sufficiently
similar to the sample used for the duplicate, and thus that 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. The reviewer may need to obtain additional information from the
Laboratory. Note the situation in the Data Review Narrative, and for CLP Project Officer
(PO) action.
2. If the results from a duplicate analysis for cyanide fall outside the appropriate control limits,
qualify sample results that are > Method Detection Limit (MDL) as estimated (J) and non-
detects as estimated (UJ).
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3. If a field blank or PE sample was used for the duplicate sample analysis, note this for CLP
PO action. All of the other Quality Control (QC) data must then be carefully checked, and
professional judgment exercised by the data reviewer when evaluating the data.
4. Note the potential effects on the data due to out-of-control duplicate sample results in the
Data Review Narrative.
Table 33. Duplicate Sample Actions for Cyanide Analysis
Duplicate Sample Results
Both original sample and duplicate sample >5x
the CRQL and RPD>20%*
Original sample or duplicate sample <5x the
CRQL (including non-detects) and absolute
difference between sample and duplicate
>CRQL*
Action for Samples
Qualify those results that are >MDL that
professional judgment determines to be affected
as estimated (J) and non-detects as estimated (UJ)
Qualify those results that are >MDL that
professional judgment determines to be affected
as estimated (J) and non-detects as estimated (UJ)
*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, 2xthe CRQL) to be assessed against duplicate soil
samples.
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VI. Spike Sample Analysis
A. Review Items:
Cover Page, Form V-IN (Part A & B), Form XII-IN, instrument printouts, and raw data.
B. Objective:
The spiked sample analysis is designed to provide information about the effect of each sample
matrix on the sample preparation procedures and the measurement methodology. Non-
homogenous samples can impact the apparent method recovery. However, aqueous samples are
generally homogenous and most soil samples are homogenous within a factor of two or three. If
the spike is added to the sample prior to any distillation steps (e.g., cyanide), it is referred to as a
spiked sample, pre-distillation spike, or Matrix Spike. If the spike is added to the sample after the
completion of the distillation procedures, it is referred to as a post-distillation spike, or analytical
spike.
C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (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 Sample Delivery Group
(SDG).
3. When the pre-distillation spike recovery falls outside of the control limits and the sample
result is < four times (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
Contract Required Quantitation Limit (CRQL), whichever is greater.
4. The spike Percent Recovery (%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 are presented in the method described in the
Statement of Work (SOW).
D. Evaluation:
1. Verify using the Cover Page, Form VA-IN, Form XII-IN, and raw data that the appropriate
number of required spiked samples were prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
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3. Evaluate Form VA-IN and the raw data to verify 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 %R using the following equation, and
verify that the recalculated value agrees with the Laboratory-reported values on Forms V(A
& B)-IN:
% Recovery =
SSR - SR
SA
x 100
Where,
SSR
SR
SA
Spiked Sample Result
Sample Result
Spike Added
NOTES: When the sample concentration is < Method Detection Limit (MDL), use SR = 0 only
for the purposes of calculating the %R. The actual spiked sample results, sample
results, and %R (positive or negative) shall still be reported on Form V(A & B)-IN.
For data obtained from the Contract Laboratory Program (CLP), the above criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information
regarding the Laboratory's compliance with the above criteria can be obtained from the
Data Assessment Tool (DAT) reports, and may be used as part of the evaluation
process.
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 reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make 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 (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are
similar to the Matrix Spike sample, and that only these samples should be qualified.
Or, the reviewer may determine that no samples are sufficiently similar to the sample
used for the Matrix Spike, and thus that 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. The reviewer may need to obtain additional information from the
Laboratory. Note the situation in the Data Review Narrative, and for CLP Project Officer
(CLP PO) action.
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2. If a field blank or PE sample was used for the spiked sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked, and
professional judgment exercised by the data reviewer when evaluating the data.
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-
distillation spike was not performed, note this for CLP PO action.
4. If the Matrix Spike %R is <30%, verify that a post-distillation spike was analyzed if required.
If the post-distillation spike %R is <75% or is not performed, qualify sample results that are
>MDL as estimated low (J-) and non-detects as unusable (R). If the post-distillation spike
%R is >75%, qualify sample results that are >MDL as estimated (J) and non-detects as
estimated (UJ).
5. If the Matrix Spike %R falls within the range of 30-74% and the sample results are >MDL,
verify that a post-distillation spike was analyzed if required. If the %R for the post-
distillation spike is also <75% or not performed, qualify the affected data as estimated low
(J-). If the %R for the post-distillation spike is >75%, qualify the affected data as estimated
(J).
6. If the Matrix Spike %R falls within the range of 30-74% and the sample results are non-
detects, qualify the affected data as estimated (UJ).
7. If the Matrix Spike %R is >125% and the reported sample results are non-detects, the sample
data should not be qualified.
8. If the Matrix Spike %R is > 125% and the sample results are >MDL, verify that a post-
distillation spike was analyzed if required. If the %R for the post-distillation spike is also
>125% or is not performed, qualify the affected data as estimated high (J+). If the %R for the
post-distillation spike is < 125%, qualify the affected data as estimated (J).
9. Note the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.
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Table 34. Spike Sample Actions for Cyanide Analysis
Spike Sample Results
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 %R >125%
No post-distillation spike performed
Action for Samples
Qualify affected results that are >MDL as
estimated low (J-)
Qualify affected non-detects as unusable (R)
Qualify affected results that are >MDL as
estimated (J)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as
estimated low (J-)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as
estimated (J)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are >MDL as
estimated high (J+)
Qualify affected results that are >MDL as
estimated (J)
Qualify affected results that are >MDL as
estimated low (J-) and affected non-detects as
unusable (R)
Qualify affected results that are >MDL as
estimated low (J-) and affected non-detects as
estimated (UJ)
Qualify affected results that are >MDL as
estimated high (J+)
Non-detects are not qualified
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Inorganic Data Review Cyanide
VII. Field Duplicates
A. Review Items:
Form I-IN, instrument printouts, and raw data.
B. Objective:
Field duplicate samples may be collected and analyzed as an indication of overall precision.
These analyses measure both field and Laboratory precision. The results, therefore, may have
more variability than Laboratory duplicates that measure only Laboratory performance. It is also
expected that soil duplicate results will have a greater variance than water matrices due to
difficulties associated with collecting identical field samples.
C. Criteria:
There are no "required" review criteria for determining comparability of field duplicate analyses.
D. Evaluation:
Identify samples that are field duplicates using Traffic Report/Chain of Custody (TR/COC)
documentation or sample field sheets. Compare the results reported for each sample and calculate
the Relative Percent Difference (RPD), if appropriate.
E. Action:
Provide any evaluation of the field duplicates in the Data Review Narrative.
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Inorganic Data Review Cyanide
VIII. Overall Assessment
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 ensure that the reported sample quantitation results are accurate. It is
appropriate for the data reviewer to make professional judgments and express concerns, as well as
to comment on the validity of the overall data for a Case. This is particularly appropriate when
there are several Quality Control (QC) criteria that are outside of the specification parameters.
The additive nature of QC factors that fall outside of specification parameters is difficult to assess
in an objective manner, but the reviewer has a responsibility to inform the user concerning data
quality and data limitations to assist that user in avoiding inappropriate use of the data, while not
precluding any consideration of the data at all. If qualifiers other than those used in this
document are necessary to describe or qualify the data, it is necessary to thoroughly
document/explain the additional qualifiers used. The data reviewer would be greatly assisted in
this endeavor if the acceptance or performance criteria were provided. The Inorganic Review
Summary (see Appendix B) and supplementary documentation must be included with the review.
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.
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, strip charts, etc., should be compared to
the reported sample results recorded on the appropriate Inorganic Summary Forms (Form I-IN
through Form XV-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 Contract Laboratory
Program Project Officer (CLP PO) approval for the use of the reduced volume.
4. Verify that there were no transcription or reduction errors [e.g., dilutions, Percent Solids
(%S), sample weights, etc.] on one or more samples.
5. Verify that results fall within the calibrated range for cyanide.
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Inorganic Data Review Cyanide
6. If appropriate information is available, the reviewer may 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 Standard Operating Procedure(s) (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. Write a brief Data Review Narrative to give the user an indication of the analytical limitations
of the data. Note any discrepancies between the data and the SDG Narrative for CLP PO
action. If sufficient information on the intended use and required quality of the data are
available, the reviewer should include an assessment of the data usability within the given
context.
3. If any discrepancies are found, the Laboratory may be contacted by the Region's designated
representative to obtain additional information for resolution. If a discrepancy remains
unresolved, the reviewer may determine that qualification of the data is warranted.
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Inorganic Data Review
Cyanide
Calculations for Cyanide
Aqueous Sample Concentration (Manual):
r-xr ^ +, +- / n \
CN Concentration (p,g/L) =
A x
B
50 mL
Where,
A
B
C
50mL
= (ig cyanide read from standard curve (per 250 mL)
= mL of original sample for distillation (see Exhibit D - Analytical
Methods for Total Cyanide Analysis, Section 10.2.2.1.1)
= mL taken for colorimetric analysis (see Exhibit D - Analytical
Methods for Total Cyanide Analysis, Section 10.3.1.1)
= Standard volume taken for colorimetric determination (see
Exhibit D - Analytical Methods for Total Cyanide Analysis,
Section 10.3.1.1)
1000 mL/L = Conversion mL to L
NOTE: The minimum value that can be substituted for A is the Method Detection
Limit (MDL) value adjusted for volume.
Soil Sample Concentration (Manual):
A x
CN Concentration (mg/kg) =
50 mL
B
C x
% solids
100
Where,
A
B
C
50 mL
% solids
= (ig cyanide read from standard curve (per 250 mL)
= mL of distillate taken for colorimetric determination (see Exhibit D -
Analytical Methods for Total Cyanide Analysis, Section 10.3.1.1)
= Wet weight of original sample in g (see Exhibit D - Analytical Methods
for Total Cyanide Analysis, Section 10.2.4.1.1)
= Standard volume taken for colorimetric determination (see Exhibit D -
Analytical Methods for Total Cyanide Analysis, Section 10.3.1.1)
= % Solids (see Exhibit D - Introduction to Analytical Methods, Section 1.6)
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Inorganic Data Review
Soil Sample Concentration (Semi-automated):
CN Concentration (mg/kg) =
Cyanide
A x .25
C x
% solids
100
Where,
A = (ig/L determined from standard curve
C = Wet weight of original sample in g (see Exhibit D - Analytical
Methods for Total Cyanide Analysis, Section 10.2.4.1.1)
.25 = Conversion factor for distillate final volume (see Exhibit D -
Analytical Methods for Total Cyanide Analysis, Section 10.2.2.1.5)
% Solids (see Exhibit D - Introduction to Analytical Methods,
Section 1.6)
% solids = % Solids (see Exhibit D - Introduction to Analytical Methods,
Section 1.6)
NOTE: The minimum value that can be substituted for A is the MDL value.
Calculations for Midi Distillation (Cyanide) of Waters and Soils:
Aqueous Sample Concentration (Midi):
A x D x F
CN Concentration (|ig/L) =
B
Where,
A
B
D
F
= (ig/L cyanide of sample from regression analysis
= Volume of original sample for distillation (0.050 L) (see Exhibit D -
Analytical Methods for Total Cyanide Analysis, Section 10.2.3.1.2)
= Any Dilution Factor (DF) necessary to bracket sample value within
standard values
= Sample receiving solution volume (0.050 L)
NOTE: The minimum value that can be substituted for A is the MDL value.
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Inorganic Data Review Cyanide
Soil Sample Concentration (Midi):
CN Concentration (mg/kg) =
B x E
Where,
A = (ig/L Cyanide of sample from regression analysis curve
B = Wet weight of original sample (see Exhibit D - Analytical Methods for Total
Cyanide Analysis, Section 10.2.4.2.2)
D = Any dilution factor necessary to bracket sample value within standard values
E = % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section
1.6)
F = Sample receiving solution volume (0.050 L)
NOTE: The minimum value that can be substituted for A is the MDL value.
Adjusted Method Detection Limit (MDL)/Adjusted Contract Required Quantitation Limit (CRQL)
Calculation:
To calculate the adjusted aqueous MDL or adjusted aqueous CRQL for the manual
colorimetric method, multiply the MDL ((ig/L) or CRQL ((ig/L) by 0.25 and substitute the
result for the "A" term in the appropriate equation above. To calculate the adjusted aqueous
MDL or adjusted aqueous CRQL for all other methods, follow the instructions in Exhibit D -
Data Analysis and Calculations, Section 11.1.1, or substitute the MDL ((ig/L) or CRQL
((ig/L) for the "A" term in the appropriate equation above.
The adjusted soil MDL or adjusted soil CRQL for all methods shall be calculated as follows:
WM i
Adjusted Concentration (mg/kg) = C x x —
WR S
Where,
C = MDL or CRQL concentration (mg/kg)
WM = Minimum method required wet sample weight (g)
WR = Reported wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to Analytical Methods,
Section 1.6)
NOTE: For the midi-distillation, multiply the adjusted concentration value (mg/kg)
obtained in the appropriate equation above by any applicable DF.
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Inorganic Data Review Appendix A
APPENDIX A: GLOSSARY
Analyte ~ The element of interest, ion, or parameter an analysis seeks to determine.
Analytical Services Branch (ASB) ~ Directs the Contract Laboratory Program (CLP) from within the
Office of Superfund Remediation and Technical Innovation (OSRTI) in the Office of Solid Waste and
Emergency Response (OSWER).
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), and Continuing Calibration Blank (CCB). Note
that the following are all defined as analytical samples: undiluted and diluted samples (USEPA and non-
USEPA); Matrix Spike samples; duplicate samples; serial dilution samples, analytical (post-
digestion/post-distillation) spike samples; Interference Check Samples (ICSs); Contract Required
Quantitation Limit (CRQL) Check Standards (CRIs); Laboratory Fortified Blanks (LFBs); Laboratory
Control Samples (LCSs); Preparation Blanks (PBs), and Linear Range Samples (LRSs).
Associated Samples ~ Any sample related to a particular Quality Control (QC) analysis. For example,
for Initial Calibration Verification (ICV), all samples run under the same calibration curve. For
duplicates, all Sample Delivery Group (SDG) samples digested/distilled of the same matrix.
Blank ~ A sample designed to assess specific sources of contamination. See individual definitions for
types of blanks.
Calibration ~ The establishment of an analytical curve based on the absorbance, emission intensity, or
other measured characteristic of known standards. The calibration standards are to 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 in the same concentration as those
used in the analytical sample preparation. This blank is not subject to the preparation method.
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 every ten samples and
designed to detect any carryover contamination.
Contract Compliance Screening (CCS) ~ A screening of electronic and hardcopy data deliverables for
completeness and compliance with the contract. This screening is performed under USEPA direction by
the Contract Laboratory Program (CLP) Sample Management Office (SMO) contractor.
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
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Inorganic Data Review Appendix A
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 run
every 10 analytical samples or every two hours, whichever is more frequent.
Contract Laboratory Program (CLP) ~ Supports the USEPA's Superfund effort by providing a range
of state-of-the-art chemical analytical services of known quality. This program is directed by the
Analytical Services Branch (ASB) of the Office of Superfund Remediation and Technical Innovation
(OSRTI)ofUSEPA.
Contract Laboratory Program Project Officer (CLP PO) ~ The Regional USEPA official responsible
for monitoring Laboratory performance and/or requesting analytical data or services from a CLP
Laboratory.
Contract Required Quantitation Limit (CRQL) ~ Minimum level of quantitation acceptable under the
contract Statement of Work (SOW).
CRQL Check Standard (CRI) ~ A single parameter or multi-parameter standard solution prepared at
the Contract Required Quantitation Limit (CRQL) and used to verify the instrument calibration at low
levels.
Duplicate ~ A second aliquot of a sample that is treated the same as the original sample in order to
determine the precision of the method.
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.
Holding Time ~ The maximum amount of time samples may be held before they are processed.
Contractual ~ 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.
Technical ~ The maximum amount of time that samples may be held from the collection date until
analysis.
Initial Calibration ~ Analysis of analytical standards for a series of different specified concentrations to
define the quantitative response, linearity, and dynamic range of the instrument to target analytes.
Initial Calibration Blank (ICB) ~ The first blank standard run to confirm the calibration curve.
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Inorganic Data Review Appendix A
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 USEPA ICV solutions are not available.
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.
Interference Check Sample (ICS) ~ Verifies the contract Laboratory's ability to overcome interferences
typical of those found in samples.
Laboratory Control Sample (LCS) ~ A control sample of known composition. LCSs are processed
using the same sample preparation, reagents, and analytical methods employed for the USEPA samples
received.
Linear Range, Linear Dynamic Range ~ The concentration range over which the instrument response
remains linear.
Matrix ~ The predominant material of which the sample to be analyzed is composed. For the purposes
of this document, the matrices are water and soil.
Matrix Spike ~ Introduction of a known concentration of analyte into a sample to provide information
about the effect of the sample matrix on the digestion and measurement methodology (also identified as a
pre-distillation/digestion spike).
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% probability that it is different from
the blank. For seven replicates of the sample, the mean value must be 3.14s above the blank, where "s" is
the standard deviation of the seven replicates.
Narrative (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.
Office of Solid Waste and Emergency Response (OSWER) - The USEPA office that provides policy,
guidance, and direction for the USEPA's solid waste and emergency response programs, including
Superfund.
Percent Difference (%D) ~ As used in this document and the Statement of Work (SOW), is used to
compare two values. The difference between the two values divided by one of the values.
Performance Evaluation (PE) Sample ~ A sample of known composition provided by USEPA for
contractor analysis. Used by USEPA to evaluate Contractor performance.
Post Digestion 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.
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Inorganic Data Review Appendix A
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).
Regional Sample Control Center (RSCC) ~ In USEPA Regions, coordinates sampling efforts and
serves as the central point-of-contact for sampling questions and problems. Also assists in coordinating
the level of Regional sampling activities to correspond with the monthly projected demand for analytical
services.
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:
a. Each Case of field samples received; or
b. Each 20 field samples [excluding Performance Evaluation (PE) samples] within a Case; or
c. 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).
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 samples in one SDG, all water samples in another) at the
discretion of the Laboratory.
Sample Management Office (SMO) ~ A contractor-operated facility operated under the SMO contract,
awarded and administered by the USEPA. Provides necessary management, operations, and
administrative support to the Contract Laboratory Program (CLP).
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.
Tune ~ Analysis of a solution containing a range of isotope masses to establish Inductively Coupled
Plasma - Mass Spectrometry (ICP-MS) mass-scale accuracy, mass resolution, and precision prior to
calibration.
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Inorganic Data Review Appendix B
APPENDIX B:
INORGANIC DATA REVIEW SUMMARY
CASE NO. SITE
LABORATORY NO. OF SAMPLES/MATRIX
SDGNO. SOW NO. REGION
REVIEWER NAME COMPLETION DATE
CLP PO: ACTION FYI
REVIEW CRITERIA METHOD/ANALYTE
ICP-AES ICP-MS Mercury Cyanide
1. Preservation/Holding Time
2. Calibration
3. Blanks
4. Interference Check Sample
5. Laboratory Control Sample
6. Duplicate Sample Analysis
7. Spike Sample Analysis
8. ICP Serial Dilution
9 ICP-MS Tune Analysis
10. ICP-MS Internal Standards
11. Field Duplicates
12. Overall Assessment
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