NATIONALFUNCTIONALGUIDELINES
for High Resolution Superfund Methods Data Review
SEPA
Office of Superfund Remediation and Technology Innovation (OSRTI)
United States Environmental Protection Agency (EPA)
Washington, DC 20460
OLEM 9200.3-115
EPA 542-B-16-001
APRIL 2016
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NOTICE
The policies and procedures set forth here are intended as guidance to the United States Environmental
Protection Agency (EPA) and other governmental employees. They do not constitute rule-making by the
EPA, and may not be relied on to create a substantive or procedural right enforceable by any other person.
The Government may take action that is at a variance with the policies and procedures in this manual.
This document can be obtained from the EPA's Superfund Analytical Services and Contract Laboratory
Program website at:
http://www.epa.gov/clp/contract-laboratorv-program-national-functional-guidelines-data-review
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TABLE OF CONTENTS
LIST OF TABLES vii
ACRONYMS AND ABBREVIATIONS ix
I. Terminology ix
II. Target Analyte List xi
INTRODUCTION 1
I. Purpose of Document 1
II. Limitations of Use 1
III. Document Organization 1
IV. Additional Information 1
PART A: GENERAL DATA REVIEW 3
I. Preliminary Review 5
II. Data Qualifier Definitions 6
III. Data Review Narrative 7
PART B: METHOD-SPECIFIC DATA REVIEW 9
CHLORINATED DIBENZO-/7-DIOXIN/CHLORINATED DIBENZOFURAN (CDD/CDF)
DATA RE VIEW 11
I. Preservation and Holding Times 13
II. System Performance Checks 15
III. Initial Calibration 20
IV. Continuing Calibration Verification 23
V. Blanks 25
VI. Labeled Compounds 28
VII. Laboratory Control Sample/Laboratory Control Sample Duplicate 30
VIII. Target Analyte Identification 32
IX. Target Analyte Quantitation 35
X. Second Column Confirmation 37
XI. Estimated Detection Limit and Estimated Maximum Possible Concentration 38
XII. Toxic Equivalent Determination 39
XIII. Regional Quality Assurance and Quality Control 40
XIV. Overall Assessment of Data 42
CDD/CDF Tables 45
CHLORINATED BIPHENYL CONGENER (CBC) DATA REVIEW 55
I. Preservation and Holding Times 57
II. System Performance Checks 59
III. Initial Calibration 63
IV. Continuing Calibration Verification 66
V. Blanks 68
VI. Labeled Compounds 71
VII. Laboratory Control Sample/Laboratory Control Sample Duplicate 73
VIII. Target Analyte Identification 75
IX. Target Analyte Quantitation 78
X. Second Column Confirmation 80
XI. Estimated Detection Limit and Estimated Maximum Possible Concentration 81
XII. Toxic Equivalent Determination 82
XIII. Regional Quality Assurance and Quality Control 83
XIV. Overall Assessment of Data 85
CBC Tables 87
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APPENDIX A: GLOSSARY A-l
APPENDIX B: HIGH RESOLUTION DATA REVIEW SUMMARY B-l
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LIST OF TABLES
Table 1. Data Qualifiers and Definitions 6
Table 2. Technical Holding Times Actions for CDD/CDF Analysis 14
Table 3. System Performance Checks Actions for CDD/CDF Analysis 19
Table 4. Initial Calibration (ICAL) Actions for CDD/CDF Analysis 22
Table 5. Continuing Calibration Verification (CCV) Actions for CDD/CDF Analysis 24
Table 6. Blank Actions for CDD/CDF Analysis 27
Table 7. Labeled Compound Recovery Actions for CDD/CDF Analysis 29
Table 8. LCS/LCSD Recovery and RPD Actions for CDD/CDF Analysis 31
Table 9. PE Sample Data Actions for CDD/CDF Analysis 41
Table 10. Descriptors, Exact m/z Ratios, m/z Types, and m/z Formulas of the CDDs/CDFs 46
Table 11. Gas Chromatography RT WDM and ISC Standard for CDD/CDF Analysis 48
Table 12. RRTs and Quantitation References of the Native and Labeled CDDs/CDFs 49
Table 13. Theoretical lARs and QC Limits for CDD/CDF Analysis 50
Table 14. Concentration of CDDs/CDFs in Initial Calibration and CCV Solutions 51
Table 15. QC Limits for CDD/CDF in LCS/LCSD and Labeled Compounds in Samples 52
Table 16. CDD/CDF Toxic Equivalency Factors (TEFs) 53
Table 17. Technical Holding Times Actions for CBC Analysis 58
Table 18. System Performance Checks Actions for CBC Analysis 62
Table 19. Initial Calibration (ICAL) Actions for CBC Analysis 65
Table 20. Continuing Calibration Verification (CCV) Actions for CBC Analysis 67
Table 21. Blank Actions for CBC Analysis 70
Table 22. Labeled Compound Recovery Actions for CBC Analysis 72
Table 23. LCS/LCSD Recovery and RPD Actions for CBC Analysis 74
Table 24. PE Sample Data Actions for CBC Analysis 84
Table 25. Descriptors, Exact m/z Ratios, m/z Types, and m/z Formulas of the CBCs 88
Table 26. Gas Chromatography RT WDM for CBC Analysis 91
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs 92
Table 28. Theoretical lARs and QC Limits for CBC Analysis 100
Table 29. Concentration of CBCs in Initial Calibration and CCV Solutions 101
Table 30. QC Limits for CBC in CCV, LCS/LCSD, and Labeled Compounds in Samples 103
Table 31. CBC Toxic Equivalency Factors (TEFs) 105
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High Resolution Data Review
ACRONYMS AND ABBREVIATIONS
I. Terminology
The following acronyms and abbreviations may be found throughout this document. For definitions,
see Appendix A: Glossary at the end of the document.
CB
CBC
CCS
CCV
CDD
CDF
CLP
COR
CPS
CRQL
CS
CSF
CWA
DCDPE
DF
DQA
DQO
EDL
EDM
EMPC
EPA
EXES
GC
HpCDD
HpCDF
HpCDPE
HRGC
HRMS
HRSM
HxCDD
HxCDF
HxCDPE
IAR
ICAL
ISC
LCS
LCSD
LOC
Chlorinated Biphenyl
Chlorinated Biphenyl Congener
Contract Compliance Screening
Continuing Calibration Verification
Chlorinated Dibenzo-/>-Dioxin
Chlorinated Dibenzofuran
Contract Laboratory Program
Contracting Officer's Representative
Column Performance Solution
Contract Required Quantitation Limit
Calibration Standard
Complete Sample Deliverable Group (SDG) File
Clean Water Act
Decachlorodiphenyl ether
Dilution Factor
Data Quality Assessment
Data Quality Objective
Estimated Detection Limit
EXES Data Manager
Estimated Maximum Possible Concentration
United States Environmental Protection Agency
Electronic Data Exchange and Evaluation System
Gas Chromatography or Gas Chromatograph or Gas Chromatographic
Heptachlorinated Dibenzo-p-Dioxin
Heptachlorinated Dibenzofuran
Heptachlorodiphenyl ether
High Resolution Gas Chromatography or Fiigh Resolution Chromatograph
High Resolution Mass Spectrometry or High Resolution Mass Spectrometer
High Resolution Superfund Methods
Hexachlorinated Dibenzo-p-Dioxin
Hexachlorinated Dibenzofuran
Hexachlorodiphenyl ether
Ion Abundance Ratio
Initial Calibration
Isomer Specificity Check
Laboratory Control Sample
Laboratory Control Sample Duplicate
Level of Chlorination
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m/z
MDL
MQO
MS
NCDPE
NFG
OCDD
OCDF
OCDPE
OSRTI
%D
%R
%RSD
%Valley
PCB
PCDPE
PE
PeCDD
PeCDF
PFK
QA
QAPP
QATS
QC
RPD
RR
RR
RRF
RRF
RRT
RRT
RSD
RT
S/N
SAP
SDG
SEDD
SICP
SIM
SMO
SOP
SOW
TCDD
Mass-to-Charge Ratio
Method Detection Limit
Measurement Quality Objective
Mass Spectrometry or Mass Spectrometer
Nonachlorodiphenyl ether
National Functional Guidelines
Octachlorinated Dibenzo-p-Dioxin
Octachlorinated Dibenzofuran
Octachlorodiphenyl ether
Office of Superfund Remediation and Technology Innovation
Percent Difference
Percent Recovery
Percent Relative Standard Deviation
Percent Valley
Polychlorinated Biphenyl
Polychlorinated Diphenyl Ether
Performance Evaluation
Pentachlorinated Dibenzo-p-Dioxin
Pentachlorinated Dibenzofuran
Perfluorokerosene
Quality Assurance
Quality Assurance Project Plan
Quality Assurance Technical Support
Quality Control
Relative Percent Difference
Relative Response
Mean Relative Response
Relative Response Factor
Mean Relative Response Factor
Relative Retention Time
Mean Relative Retention Time
Relative Standard Deviation
Retention Time
Signal-to-Noise Ratio
Sampling and Analysis Plan
Sample Delivery Group
Staged Electronic Data Deliverable
Selected Ion Current Profile
Selected Ion Monitoring
Sample Management Office
Standard Operating Procedure
Statement of Work
Tetrachlorinated Dibenzo-p-Dioxin
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TCDF Tetrachlorinated Dibenzofuran
TAL Target Analyte List
TEF Toxic Equivalency Factor
TEQ Toxic Equivalent
TICP Total Ion Current Profile
TR/COC Traffic Report/Chain of Custody
WDM Window Defining Mixture
WHO World Health Organization
II. Target Analyte List
For a list of target analytes, refer to EPA Contract Laboratory Program (CLP) Statement of Work
(SOW)HRSM01.2.
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High Resolution Data Review Introduction
INTRODUCTION
I. Purpose of Document
This document contains guidance to aid the data reviewer in determining the usability of analytical
data generated using the United States Environmental Protection Agency (EPA) Contract Laboratory
Program (CLP) Statement of Work (SOW) for High Resolution Superfund Methods (Multi-Media,
Multi-Concentration) HRSM01.2. This SOW includes analytical methods for Chlorinated Dibenzo-
/>-Dioxins (CDDs), Chlorinated Dibenzofurans (CDFs), and Chlorinated Biphenyl Congeners
(CBCs).
The guidelines presented in this document are designed to assist the data reviewer in evaluating: (a)
whether the analytical data meet the technical and Quality Control (QC) criteria specified in the
SOW, and (b) the usability and extent of bias of any data not meeting these criteria. This document
contains definitive guidance in areas such as blanks, calibration standards, and instrument
performance checks in which performance is fully under a laboratory's control. General guidance is
provided to aid the reviewer in making subjective judgments regarding the use of data that are
affected by site conditions and do not meet SOW-specified requirements.
II. Limitations of Use
This guidance is specific to the review of analytical data generated using CLP SOW HRSM01.2. It
applies to the current version of the SOW, as well as future versions that contain editorial changes.
To use this document effectively, the reviewer should have an understanding of the analytical
methods and a general overview of the Sample Delivery Group (SDG) or Case at hand. This
guidance is not appropriate for use in conducting contract compliance reviews and should be used
with caution in reviewing data generated using methods other than SOW HRSM01.2, although the
general types of QC checks, the evaluation procedures, and the decisions made after consideration of
the evaluation criteria may be applicable to data for any similar method.
While this document is a valuable aid in the formal data review process, other sources of guidance
and information, along with professional judgment, are useful when determining the ultimate
usability of the data. This is particularly critical in those cases where all data do not meet SOW-
specific technical and QC criteria. To make the appropriate judgments, the reviewer needs to gain a
complete understanding of the intended use of the data, and is strongly encouraged to establish a
dialogue with the data user prior to and following data review, to discuss usability issues and to
resolve questions regarding the review.
Due to the toxicity of the analytes, the guidelines in this document have been designed to be
conservative in making decisions that affect the reporting of results as positive or negative. In other
words, any error associated with the decision to report a positive result vs. a non-detect should be
toward a false positive rather than a false negative. The importance of professional judgment to
determine the ultimate presentation and usability of the data cannot be overstated.
III. Document Organization
Following this introduction, the document is presented in two major parts: Part A - General Data
Review, which applies to all methods; and Part B - Method-Specific Data Review. In Part B, each
method is addressed individually in a stand-alone format. A complete list of acronyms used in this
document appears preceding this Introduction, and a Glossary is appended as Appendix A.
IV. Additional Information
For additional information regarding the CLP and the services it provides, refer to EPA's Superfund
Analytical Services and Contract Laboratory Program website at http://www.epa.gov/clp.
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High Resolution Data Review General
PART A: GENERAL DATA REVIEW
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High Resolution Data Review General
I. Preliminary Review
A preliminary review should be performed on the data, prior to embarking on the method-specific
review (see Part B). During this process, the reviewer should compile the necessary data package
elements to ensure that all of the information needed to determine data usability is available. The
preliminary review also allows the reviewer to obtain an overview of the Case or Sample Delivery
Group (SDG) under review.
This initial review should include, but is not limited to, verification of the exact number of samples,
their assigned number and matrices, and the Contractor laboratory name. It should take into
consideration all the documentation specific to the sample data package, which may include Modified
Analysis requests, the Traffic Report/Chain of Custody (TR/COC) Record, the SDG Narrative, and
other applicable documents.
The reviewer should be aware that minor modifications to the Statement of Work (SOW) that have
been made through a Modified Analysis request, to meet site-specific requirements, could affect
certain validation criteria such as Contract Required Quantitation Limits (CRQLs), Initial Calibration
(ICAL) levels, and Target Analyte Lists (TALs). Therefore, these modifications should be applied
during the method-specific review (Part B) process.
The Cases or SDGs routinely have unique field quality control (QC) samples that may affect the
outcome of the review. These include field blanks, field duplicates, and Performance Evaluation (PE)
samples which must be identified in the sampling records. The reviewer should verify that the
following information is identified in the sampling records (e.g., TR/COC Records, field logs, and/or
contractor tables):
1. The United States Environmental Protection Agency (EPA) Region where the samples were
collected, and
2. The complete list of samples with information on:
a. Sample matrix
b. Field blanks (if applicable)
c. Field duplicates (if applicable)
d. Field spikes (if applicable)
e. PE samples (if applicable)
f Sampling dates
g. Sampling times
h. Shipping dates
i. Preservatives
j. Types of analysis
k. Contractor laboratory
The laboratory's SDG Narrative is another source of general information which includes notable
problems with matrices; insufficient sample volume for analysis or reanalysis; samples received in
broken containers; preservation information; and unusual events. The reviewer should also inspect
any email or telephone/communication logs in the data package detailing any discussion of sample
logistics, preparation and/or analysis issues between the laboratory, the Contract Laboratory Program
(CLP) Sample Management Office (SMO), and the EPA Region.
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General
The reviewer should also have a copy of the Quality Assurance Project Plan (QAPP), or similar
document, for the project for which samples were analyzed, to assist in the determination of final
usability of the analytical data. The reviewer should contact the appropriate EPA Regional CLP
Contracting Officer's Representative (EPA Regional CLP COR) to obtain copies of the QAPP and
relevant site information.
For data obtained through the CLP, the Staged Electronic Data Deliverable (SEDD) generated by the
CLP laboratories is subjected to the following reviews via the Electronic Data Exchange and
Evaluation System (EXES): 1) automated data assessment for Contract Compliance Screening (CCS)
based on the technical and QC criteria in the CLP SOW HRSM01.2, and 2) automated data validation
based on the criteria in the EPA Contract Laboratory Program National Functional Guidelines for
High Resolution SuperfundMethods Data Review. In addition, completeness checks are manually
performed on the hardcopy data. The automated CCS results and hardcopy data issues are
subsequently included in a CCS defect report that is provided to the laboratory. The laboratory may
then submit a reconciliation package for any missing items, or to correct non-compliant data
identified in the report. The automated data validation results are summarized in criteria-based
National Functional Guidelines (NFG) reports that are provided to the EPA Regions. The data
reviewer can access the CCS and NFG reports through the EXES Data Manager (EDM) via the
Superfund Analytical Services SMO Portal and may use them in determining data usability.
For access to the Superfund Analytical Services SMO Portal, refer to the following EPA Superfund
Analytical Services and Contract Laboratory Program web page to contact the EPA Regional CLP
COR from the EPA Region where the data review is being performed and obtain the necessary
username and password information:
http://www.epa.gov/clp/foiTTLs/contact-us-about-superfund-analytical-services-or-contract-laboratory-
program#tab-3
For concerns or questions regarding the data package, contact the EPA Regional CLP COR from the
EPA Region where the samples were collected.
II. Data Qualifier Definitions
The following definitions provide brief explanations of the national qualifiers assigned to results
during the data review process. The reviewer should use these qualifiers as applicable. If the
reviewer chooses to use additional qualifiers, a complete explanation of those qualifiers should
accompany the data review.
Table 1. Data Qualifiers and Definitions
Data
Qualifier
U
J
J+
J-
UJ
R
Definition
The analyte
quantitation
was analyzed for, but was not detected above the level of the reported sample
limit.
The result is an estimated quantity. The associated numerical value is the approximate
concentration of the analyte in the sample.
The result is
The result is
an estimated quantity, but the result may be biased high.
an estimated quantity, but the result may be biased low.
The analyte was analyzed for, but was not detected. The reported quantitation limit is
approximate and may be inaccurate or imprecise.
The data are
meeting QC
unusable. The sample results are rejected due to serious deficiencies in
criteria. The analyte may or may not be present in the sample.
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III. Data Review Narrative
The reviewer should complete a Data Review Narrative that includes comments that address the
problems identified during the review process and states the limitations of the data associated with a
Case or SDG. The EPA CLP sample numbers, analytical methods, extent of the problem(s), and
assigned qualifiers should also be listed in the document.
The Data Review Narrative, including the High Resolution Data Review Summary form (see
Appendix B), should be provided together with the laboratory data to the appropriate recipient(s). A
copy of the Data Review Narrative should also be submitted to the EPA Regional CLP COR assigned
oversight responsibility for the Contractor laboratory.
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PART B: METHOD-SPECIFIC DATA REVIEW
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High Resolution Data Review CDD/CDF
CHLORINATED DIBENZO-p-DIOXIN/CHLORINATED DIBENZOFURAN (CDD/CDF)
DATA REVIEW
The high resolution CDD/CDF data requirements to be reviewed during validation are listed below:
I. Preservation and Holding Times 13
II. System Performance Checks 15
III. Initial Calibration 20
IV. Continuing Calibration Verification 23
V. Blanks 25
VI. Labeled Compounds 28
VII. Laboratory Control Sample/Laboratory Control Sample Duplicate 30
VIII. Target Analyte Identification 32
IX. Target Analyte Quantitation 35
X. Second Column Confirmation 37
XI. Estimated Detection Limit and Estimated Maximum Possible Concentration 38
XII. Toxic Equivalent Determination 39
XIII. Regional Quality Assurance and Quality Control 40
XIV. Overall Assessment of Data 42
CDD/CDF Tables 45
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High Resolution Data Review CDD/CDF
I. Preservation and Holding Times
A. Review Items
Form 1A-HR, Traffic Report/Chain of Custody (TR/COC) Record documentation, Form DC-1, raw
data, sample extraction sheets, and the Sample Delivery Group (SDG) Narrative checking for: pH,
shipping container temperature, holding time, and other sample conditions. (SOW HRSM01.2 -
Exhibit B, Section 3.4 and Exhibit D - CDD/CDF, Section 8.0)
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.
C. Criteria
1. The extraction technical holding time is determined from the date of sample collection to the date
of sample extraction for aqueous/water and non-aqueous [soil/sediment, sludge, tissue (non-
human), biosolids, ash, oil, filter] samples. The analysis technical holding time is determined
from the date of the start of the extraction to the date of sample analysis.
2. All aqueous/water and soil/sediment samples shall be stored at < 6°C, in the dark, from the time
of collection until extraction. If residual chlorine is present in aqueous/water samples, 80 mg of
sodium thiosulfate per liter of sample is to be added. If the aqueous/water sample pH is > 9, it
must be adjusted to pH 7-9 with sulfuric acid.
3. Tissue (non-human) samples should be received at the laboratory at < 6°C and shall be stored, in
the dark, at the laboratory at < -10°C until extraction.
4. All samples shall be extracted and analyzed within the time period specified during scheduling.
However, once thawed, tissue (non-human) samples must be extracted within 24 hours.
5. The extraction technical holding time for all properly preserved samples is one year.
6. The analysis technical holding time for all properly stored sample extracts is one year.
D. Evaluation
1. Review the SDG Narrative and the TR/COC Record documentation to verify that the samples
were received intact and iced at < 6°C. Use special consideration for samples delivered directly
from the field to the laboratory. If there is an indication of problems with the samples, the sample
integrity may be compromised. If the samples were not iced, if there were any problems with the
samples upon receipt, or if discrepancies in the sample condition could affect the data, record the
issue in the Data Review Narrative.
2. Verify that the extraction dates and analysis dates for samples on Form 1A-HR and the raw data
are identical.
3. Establish technical holding times for sample extraction and analysis by comparing the sampling
dates on the TR/COC Record documentation with the dates of extraction and analysis on Form
1A-HR.
E. Action
1. If a residual chlorine test was performed and found to be negative, detects and non-detects should
not be qualified. If sodium thiosulfate preservative was not added to aqueous/water samples with
a chlorine residual, qualify detects as estimated (J) and non-detects as unusable (R). If pH is > 9
and was not adjusted, qualify detects as estimated (J) and non-detects as estimated (UJ).
2. If shipment and storage conditions were not met, use professional judgment to determine if the
sample data are affected. Detects and non-detects may be qualified as estimated (J) and (UJ),
respectively.
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High Resolution Data Review
CDD/CDF
3. If extraction technical holding times are exceeded for aqueous/water or soil/sediment samples,
qualify detects as estimated (J) and non-detects as estimated (UJ) or unusable (R). If extraction
technical holding times are exceeded for tissue (non-human) samples, use professional judgment
to qualify detects and non-detects.
4. There is limited information concerning holding times for oily samples. Use professional
judgment to determine if the sample data are affected. It is recommended that the aqueous/water
sample technical holding time criteria be applied to oily samples.
5. For sample extracts that are not properly stored, but analyzed within the 1-year analysis technical
holding time, qualify detects as estimated (J) and non-detects as estimated (UJ).
6. For sample extracts that are analyzed outside the 1-year analysis technical holding time, use
professional judgment to qualify detects as estimated low (J-) and non-detects as estimated (UJ)
or unusable (R).
7. When holding times are exceeded, record the effect on sample data in the Data Review Narrative,
and note it for United States Environmental Protection Agency Regional Contract Laboratory
Program Contracting Officer's Representative (EPA Regional CLP COR) action.
Table 2. Technical Holding Times Actions for CDD/CDF Analysis
Criteria
Chlorine present in aqueous/water sample but
sodium thiosulfate not added
Aqueous/water sample pH > 9 but pH not adjusted
Aqueous/water and soil/sediment samples received
or stored at > 6°C
Tissue (non-human) samples received at > 6°C or
stored at > -10°C
Aqueous/water and soil/sediment samples properly
preserved but extracted outside 1-year technical
holding time
Tissue (non-human) samples properly preserved but
extracted outside 1-year technical holding time
Sample extract not properly stored but analyzed
within 1 -year technical holding time
Sample extract analyzed outside 1 -year technical
holding time
Action
Detect
J
J
Use professional
judgment
J
Use professional
judgment
J
J
Use professional
judgment
J
Use professional
judgment
J-
Non-detect
R
UJ
Use professional
judgment
UJ
Use professional
judgment
UJ
UJorR
Use professional
judgment
UJ
Use professional
judgment
UJorR
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High Resolution Data Review _ CDD/CDF
II. System Performance Checks
Prior to analyzing the calibration standards, blanks, samples, and Quality Control (QC) samples, the High
Resolution Gas Chromatograph (HRGC) and High Resolution Mass Spectrometer (HRMS) operating
conditions necessary to obtain optimum performance must be established. There are three fundamental
HRGC/HRMS system performance checks: Mass Calibration and Resolution, Mass Spectrometer (MS)
Selected Ion Monitoring (SIM) scan descriptor switching times, and Gas Chromatographic (GC)
resolution. Ion Abundance Ratio (IAR) and Signal-to-Noise (S/N) ratio (determined in the lowest initial
calibration standard) are pertinent in evaluating system performance.
1. Mass Calibration and Mass Spectrometer Resolution
A. Review Items
Peak profile raw data of the MS resolution. (SOW HRSM01.2 - Exhibit D - CDD/CDF, Sections
9.1.2, 9.2, and 9.3)
B. Objective
The objective is to ensure adequate mass resolution and to document this level of performance prior
to and after analyzing any sequence of standards or samples.
C. Criteria
Laboratories are required to demonstrate MS resolving power at > 10,000 and provide evidence of the
MS performance at the beginning and end of each 12-hour period during which samples or standards
are analyzed. Documentation of the instrument resolving power shall be completed by recording the
peak profiles of the reference peaks chosen for each descriptor using perfluorokerosene (PFK). While
generating the peak profiles, the detector zero shall be adjusted to allow presentation of the profile
shoulders on-scale so the resolution can be manually determined. The format of the peak profiles
shall show a horizontal axis calibrated in atomic mass units (u) or ppm, and a vertical scale in percent
maximum signal. The result of the peak width measurement [performed at 5% of the maximum,
which corresponds to the 10 Percent Valley (%Valley) definition] must appear on the profile, and
must not exceed 100 ppm [i.e., 0.038 u for a peak at mass-to-charge ratio (m/z) 380.9760]. This
documentation shall be provided for each check of the static resolving power of each instrument used,
and shall contain identifying information, including instrument ID, date, and time. The deviation
between the exact mass measured m/z (m/zmon) and the target m/z (m/Zth) shall be calculated using the
equation below and must be < 5 ppm (i.e., the value found for m/z 3 19.8645 must be accurate to
±0.0016 u)].
Resppm = r- - —, - r > 10,000
|m/zth- m/zmon|
D. Evaluation
Examine the raw data and verify that the MS has been tuned to a resolving power of > 10,000.
E. Action
In the event that MS resolution is < 10,000, the risk of false positive results may exist. If a
demonstration of the required mass resolution is not provided, carefully evaluate other factors to
determine whether or not there is sufficient evidence of adequate resolution to preclude interference
from other ions with similar m/z. This may include, but is not limited to: other tunes in the data
package for the same instrument; the quality and similarity of peak shapes between the calibrations
and the samples; and baseline noise in calibrations, blanks, and calibration performance. Consider
these factors when determining the appropriate course of action and use professional judgment to
qualify detects as unusable (R).
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2. Window Defining Mixture
A. Review Items
Form 5A-HR. (SOW HRSM01.2 - Exhibit B, Section 3.4.10 and Exhibit D - CDD/CDF, Sections
9.2 and 9.4)
B. Objective
The objective is to establish the appropriate switching times for the SIM descriptors by analyzing a
Window Defining Mixture (WDM) solution containing the first and last eluting isomers in each
homologous series and to document the accuracy of the switching times prior to and after analyzing
any sequence of standards or samples.
C. Criteria
1. The WDM is a commercially available, diluted 16-component solution that must contain (at a
minimum) the first and last eluting isomers in each homologous series listed in Table 11 (in the
CDD/CDF Tables section in this document). Mixtures are column-specific where the mixture for
the DB-5 (or equivalent) column may not be appropriate for the DB-225 or other columns. To
evaluate the MS SIM scan descriptor switching times, the WDM must be analyzed after the PFK
tune and before any calibration standards on each instrument and GC column used for analysis.
The WDM shall also be analyzed each time a new initial calibration is performed, regardless of
reason; once at the beginning and once at the end of each 12-hour period during which standards
or samples are analyzed; prior to the Continuing Calibration Verification (CCV); and whenever
adjustments or instrument maintenance activities that may affect Retention Times (RTs) are
performed.
2. The ions in each of the five recommended descriptors are arranged for minimal overlap between
the descriptors. The ions for Tetrachlorinated Dibenzo-/?-Dioxin (TCDD) and Tetracholorinated
Dibenzofuran (TCDF) isomers are in the first descriptor. The ions for Pentachlorinated Dibenzo-
/>-Dioxin (PeCDD) and Pentachlorinated Dibenzofuran (PeCDF) isomers, Hexachlorinated
Dibenzo-p-Dioxin (HxCDD) and Hexachlorinated Dibenzofuran (HxCDF) isomers,
Heptachlorinated Dibenzo-/?-Dioxin (HpCDD) and Heptachlorinated Dibenzofuran (HpCDF)
isomers, and Octachlorinated Dibenzo-/>-Dioxin (OCDD) and Octachlorinated Dibenzofuran
(OCDF) isomers are sequentially in the second through the fifth descriptors, respectively. In
some cases, TCDD/TCDF and PeCDD/PeCDF are combined in a single descriptor as described in
Table 10 (in the CDD/CDF Tables section in this document).
3. The descriptor switching times are set as such that the isomers eluting from the GC during a
given RT window will also be those isomers for which the ions are monitored. The switching
times are not to be set as such when a change in descriptors occurs at or near the expected RT of
any 2,3,7,8-substituted isomers.
4. If the laboratory uses a GC column that has a different elution order than the columns specified in
the SOW, the laboratory must ensure that there is no overlap of homologue groups between
descriptors, and that the first and last eluting isomers in each homologous series are represented
in the WDM used to evaluate that column. The concentrations of any additional isomers should
be approximately the same as those in WDM solutions intended for use with conventional
CDD/CDF GC columns.
5. Analysis on a single GC column (as opposed to situations requiring second column confirmation)
is acceptable if the required separation of all 2,3,7,8-substituted isomers is demonstrated and the
resolution criteria for both the DB-5 and DB-225 (or equivalent) columns are met (see Section
X - Second Column Confirmation in this document).
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High Resolution Data Review CDD/CDF
D. Evaluation
1. Verify that the WDM was analyzed at the required frequency and sequence.
2. Examine the WDM chromatograms to determine whether the switching times have been
optimized properly. Proper optimization is demonstrated by complete elution of the first and last
isomers in each homologous series.
3. Note the RT of each first and last eluting isomer in each homologous series on Form 5A-HR for
identification of switching times. Each positive dioxin and furan result (tetra- through hepta-)
must have an RT within the limits established by the WDM for the corresponding homologous
series. The 2,3,7,8-substituted dioxins and furans must also meet the Relative Retention Time
(RRT) limits in Table 12 (in the CDD/CDF Tables section in this document).
E. Action
1. If the WDM was not analyzed at the required frequency or sequence, or correct adjustments in
descriptor switching times are not evident, but the calibration standards met specifications for the
individual 2,3,7,8-substituted target analytes, detects and non-detects should not be qualified.
Qualify Homologue Totals detects as estimated (J) and non-detects as (UJ) since one or more
CDDs/CDFs may not have been detected.
2. If the chromatography for the calibration standards indicates that target analytes may have been
missed due to a significant problem with descriptor switching times, qualify detects and non-
detects as unusable (R). The EPA Regional CLP COR should be contacted to decide if sample
reanalysis is necessary.
3. Chromatographic Resolution
A. Review Items
Form 5B-HR and raw data. (SOW HRSMO1.2 - Exhibit B, Section 3.4.11 and Exhibit D -
CDD/CDF, Sections 9.2 and 9.4.5)
B. Objective
The objective is to evaluate the ability of the GC column to resolve the closely-e luting dioxin and
furan isomers and to document the resolution prior to and after analyzing any sequence of samples or
standards.
C. Criteria
1. Chromatographic resolution is verified by analyzing an Isomer Specificity Check (ISC) standard
solution. The WDM and ISC standards can be combined into a single Column Performance
Solution (CPS) at the discretion of the analyst. The ISC or CPS analysis shall be performed
before any initial calibration; on each instrument and HRGC column used for analysis; and at the
beginning and end of each 12-hour analytical sequence, or whenever adjustments or instrument
maintenance activities that may affect RTs are performed.
2. The resolution criteria must be evaluated using measurements made on the Selected Ion Current
Profiles (SICPs) for the appropriate ions for each isomer. Measurements are not to be performed
on Total Ion Current Profiles (TICPs).
a. For analyses on a DB-5 (or equivalent) GC column, the Chromatographic resolution is
evaluated by the analysis of the ISC standard prior to Initial Calibration and CCV procedures
for each instrument and GC column used for analysis. GC resolution criteria for DB-5 (or
equivalent) column: the Chromatographic peak separation between the 2,3,7,8-TCDD peak
and the 1,2,3,8-TCDD peak shall be resolved with a %Valley of < 25% when determined
using the equation in the SOW.
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High Resolution Data Review CDD/CDF
b. For the DB-5 (or equivalent) column, the 12-hour sample analysis period begins with
analyzing the WDM or CPS solution. The identical HRGC/HRMS conditions used for the
analysis of the WDM, ISC, and CPS solutions must also be used for the analysis of the initial
calibration and CCV standards.
3. The chromatographic resolution for analyses on the confirmation GC column (DB-225 or
equivalent) is evaluated using a DB-225 ISC standard containing the TCDF isomers that elute
most closely with 2,3,7,8-TCDF (1,2,3,9-TCDF and 2,3,4,7-TCDF).
a. GC resolution criteria for DB-225 (or equivalent) column: the chromatographic peak
separation between the 2,3,7,8-TCDF peak and the 2,3,4,7-TCDF peak must be resolved with
a %Valley < 25% when determined using the equation in the SOW.
b. Further analysis may not proceed until the GC resolution criteria have been met.
4. If the laboratory uses a GC column that is not one of those specified in the SOW, the laboratory
must ensure that it meets all specifications and requirements listed in the SOW, and all alternate
column performance criteria established by the laboratory must be thoroughly documented in the
SDG Narrative. The laboratory must ensure that the isomers eluting closest to 2,3,7,8-TCDD on
that column are used to evaluate GC column resolution. The chromatographic peak separation
between 2,3,7,8-TCDD and the peaks representing all other TCDD isomers must be resolved with
a %Valley < 25%.
D. Evaluation
1. Verify that the ISC standard or CPS was analyzed at the required frequency and sequence.
2. Verify that Form 5B-HR is included and examine the SICP raw data to verify that the %Valley is
< 25%.
3. Technical acceptance criteria must be met before any calibration standards, samples, QC samples,
and required blanks are analyzed. However, if the ISC standard or CPS analysis was not
analyzed, but a compliant calibration standard was analyzed, and chromatographic performance
in the samples does not indicate interference with any target analyte peaks, especially 2,3,7,8-
TCDD (or 2,3,7,8-TCDF on the confirmation column), the data may still be usable. In this case,
all SICPs must be carefully evaluated in order to verify that analyte and/or labeled analog peaks
are clearly within the expected RT window, and that no persistent interference is evident.
E. Action
1. If the ISC standard or CPS was not analyzed at the specified frequency and sequence, qualify
detects in TCDD/TCDF - HxCDD/HxCDF isomers as estimated (J). Non-detects are not
qualified.
2. If the GC resolution on the DB-5 (or equivalent) column does not meet the %Valley criteria for
TCDD, use professional judgment to evaluate the severity of the non-compliant chromatographic
resolution and qualify results as necessary. Qualify detects in TCDD/TCDF - HxCDD/HxCDF
and HpCDF congeners as estimated (J), and contact the EPA Regional CLP COR to arrange for
sample reanalysis. The resolution criteria should not affect HpCDD, OCDD, or OCDF congeners
since there is only one isomer in each group. These results and non-detects should not be
qualified.
3. If the ISC standard does not meet the %Valley criterion and calibration standards or samples
indicate poor resolution for 2,3,7,8-substituted congeners, qualify detects and non-detects as
unusable (R).
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CDD/CDF
Table 3. System Performance Checks Actions for CDD/CDF Analysis
Criteria
MS resolution > 10,000 not demonstrated
WDM analysis not performed at required frequency or
sequence, or WDM failed and adjustments not made, but
calibration standards performance is acceptable
WDM failed and adjustments not made, and calibration
standards indicate a problem in detecting 2,3,7,8-
substituted analytes
ISC standard or CPS analysis not performed at required
frequency or sequence, or ISC standard or CPS failed
(GC Resolution %Valley > 25%) and adjustments not
made, but calibration standards performance is
acceptable
ISC standard failed and adjustments not made, and
calibration standards or samples indicate a problem in
resolving 2,3,7,8-substituted analytes
Action1
Detect
Use professional
judgment
R
J
(Homologue Totals
Only)
R
Use professional
judgment
J
(Tetra - Hexa and
HpCDF congeners)
R
Non-detect
No qualification
UJ
(Homologue Totals
Only)
R
No qualification
R
1 In any case where data would be rejected by these rules, contact the EPA Regional CLP COR to request
that the laboratory reanalyze, or re-extract and reanalyze, the affected sample(s).
April 2016
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High Resolution Data Review CDD/CDF
III. Initial Calibration
A. Review Items
Form 6A-HR, Form 6B-HR, and raw data for all initial calibration standards. (SOW HRSM01.2 -
Exhibit B, Section 3.4.12 and Exhibit D - CDD/CDF, Section 9.5)
B. Objective
The objective is to establish a linear calibration range capable of producing acceptable qualitative and
quantitative data for the CDDs/CDFs.
C. Criteria
1. Once the PFK, WDM and ISC, or the PFK and CPS standards have been analyzed at the specified
frequency and sequence, and after the descriptor switching times have all been verified, five
initial calibration (ICAL) standards containing all required target analytes and labeled compounds
at the specified concentrations (Table 14 in the CDD/CDF Tables section in this document) must
be analyzed prior to any sample analysis. Initial calibration standard CS1 may be analyzed at
either the specified 0.5 ng/mL concentration or at a lower level (e.g., 0.1 ng/mL).
2. The Mean Relative Responses (RRs) of the applicable target analytes, Mean Relative Response
Factors (RRFs) for the non 2,3,7,8-substituted CDD/CDF analytes and labeled compounds, and
Percent Relative Standard Deviations (%RSDs) are determined from the five-point initial
calibration.
3. The initial calibration must be performed at the specified frequency and sequence whenever:
• The laboratory takes any corrective action that may change or affect the initial calibration
criteria.
• The CCV acceptance criteria cannot be met even after corrective action has been taken (see
Section IV - Continuing Calibration Verification in this document).
4. To achieve the acceptable GC resolutions, DB-5, DB-225, or equivalent columns must be used
for analysis.
5. The IAR for each target analyte and labeled compound in the ICAL standards must be within the
QC limits listed in Table 13 (in the CDD/CDF Tables section in this document). The lower and
upper limits of the lARs represent a ±15% window around the theoretical abundance ratio for
each pair of selected ions (see Table 10 for m/z types and Table 13 for m/z ratios in the
CDD/CDF Tables section in this document). The IAR criteria do not apply to the cleanup
standard compound 37Cl4-2,3,7,8-TCDD.
6. The RTs of the isomers in the ICAL standards must fall within the appropriate RT windows
established by the WDM analysis. In addition, the absolute RT of the internal standard
13Ci2-l,2,3,4-TCDD must be > 25 minutes on the DB-5 (or equivalent) column and > 15 minutes
on the DB-225 (or equivalent) column, to ensure adequate resolution between target analytes and
to separate known interfering substances.
7. The S/N must be > 10 for all analytes, including labeled compounds and internal standards, in the
ICAL standards.
8. The %RSD for the Relative Response (RR) must be < 20% and the %RSD for the Relative
Response Factor (RRF) must be < 35%.
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High Resolution Data Review CDD/CDF
D. Evaluation
1. Verify that the initial calibration was performed at the specified frequency and sequence. Verify
that all target analytes and labeled compounds are present at the correct concentrations in all
ICAL standards (Table 14 in the CDD/CDF Tables section in this document).
2. Verify that the IAR on Form 6B-HR for each target analyte and applicable labeled compound in
each calibration standard is within ±15% of the theoretical IAR values (Table 13 in the
CDD/CDF Tables section in this document).
3. Verify that the RT on Form 6A-HR for each target analyte and internal standard is within the
specified RT windows, if equivalent columns to those specified in the SOW are used. If this
cannot be verified in the documentation, the SICPs for each descriptor should be examined. All
analytes must be present in the proper descriptor.
4. Verify that RTs are consistent between the calibration standards, and between the calibration
standards and any subsequent samples.
• If an alternate column has been used, the laboratory should have included sufficient
information in the SDG Narrative to evaluate column performance, ideally a table of
descriptors with the first and last eluting congeners (similar to Table 11 in the CDD/CDF
Tables section in this document), as well as information on the optimum resolution of closely
eluting congeners, and a table of RRTs, similar to Table 12 (in the CDD/CDF Tables section
in this document).
• Be aware that slight changes in the GC temperature program may cause the actual RRTs to be
outside the range in Table 12 (in the CDD/CDF Tables section in this document), but that the
RRT limits in Table 12 should still be met.
5. Verify that the S/N ratio is > 10 in all SICPs.
6. Verify on Form 6A-HR that the %RSD of the RR for each applicable target analyte is < 20% and
that the %RSD of the RRF for each labeled compound is < 35%.
E. Action
1. If no initial calibration was performed, the data should not be considered definitive; qualify
detects and non-detects as unusable (R). If the specified calibration concentration levels were not
used, it may be necessary to modify the linear range for reporting (with approval of the data user).
If an otherwise compliant initial calibration was performed but not at the specified frequency,
qualify detects as estimated (J) and non-detects as estimated (UJ).
2. Non-compliant IAR for any analyte is cause for concern. It may indicate that the MS was not
tuned correctly, that the ion source was dirty, or that other electronic problems existed. If there
was a systemic problem resulting in failed ion ratios in the calibration, qualify detects and non-
detects in the associated samples as unusable (R).
3. If the RRTs are outside the specified windows, qualify detects and non-detects as unusable (R).
Contact the EPA Regional CLP COR to discuss the reanalysis of the initial calibration and all
associated samples. If RTs of internal standard 13Ci2-l,2,3,4-TCDD are < 25 minutes on the
DB-5 (or equivalent) column, or < 15 minutes on the DB-225 (or equivalent) column, qualify
detects and non-detects as unusable (R). If an alternate column was used and equivalent elution
data and limits were not provided, contact the EPA Regional CLP COR.
4. If the S/N ratio for any analyte in the CS1 standard is < 10, use professional judgment to increase
the reporting limit to the lowest calibration standard which meets the criteria (CS2 standard for
example) and qualify detects at concentration levels below the CS2 standard as estimated (J).
5. If the S/N ratio is < 10 due to a more systematic lack of sensitivity, qualify detects as estimated
(J) and non-detects as unusable (R).
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CDD/CDF
6. If the %RSD is > 20% for the RR or > 35% for the RRF, qualify detects as estimated (J) and non-
detects as estimated (UJ).
7. In the event that significant QC issues are evident with the initial calibration, which may show up
as poor compliance with IAR, Response Factor (RF), RRF, %RSD, or S/N requirements, the CS1
or the CSS standard value may be discarded from the initial calibration in an effort to salvage a
usable calibration. If this is done, calculate new response factors and %RSDs for the remaining
calibration levels. If discarding either of these points brings the calibration within the specified
criteria, qualify either the low-end or high-end results, based on the newly defined linear range. It
may be necessary to request reanalysis if either of these scenarios affects a majority of the data, or
if project-specific Data Quality Objectives (DQOs) are negatively impacted. Relying on
professional judgment, a more in-depth review may be performed to minimize the qualification of
data. To illustrate this approach, consider the following example:
• If the IAR is not within the limits for an analyte in the CS1 standard (Table 12 in the
CDD/CDF Tables section in this document), qualify the low-end results for that analyte
(below the CS2 standard concentration from Table 13 in the CDD/CDF Tables section in this
document) as unusable (R), or qualify as non-detect (U) and report at the level of the next
lowest standard (in this example, the CS2 standard).
The logic for allowing this flexibility is that system baseline noise near the lower limit of
detection may cause calibration peaks to fail even in an otherwise adequately performing system.
However, if the IAR is not within the limits or other quality problems persist for an analyte in
standards CS3 - CSS, qualify detects and non-detects as unusable (R).
Table 4. Initial Calibration (ICAL) Actions for CDD/CDF Analysis
Criteria
Initial calibration not performed
Initial calibration not performed at required frequency
(but other factors are acceptable)
IAR not within ±15% window
RRT not within specified windows, or absolute RT of
internal standard 13Ci2-l,2,3,4-TCDD < 25 minutes on
the DB-5 (or equivalent) column, or < 15 minutes on the
DB-225 (or equivalent) column
S/N ratio < 10 in the ICAL standard
RR %RSD > 20%
RRF %RSD > 35%
Action
Detect
R
J
R
R
J
J
Non-detect
R
UJ
R
R
R
UJ
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High Resolution Data Review CDD/CDF
IV. Continuing Calibration Verification
A. Review Items
Form 7A-HR, Form 7B-HR, and raw data for the CCV mid-point calibration standard (CSS). (SOW
HRSM01.2 - Exhibit B, Section 3.4.13 and Exhibit D - CDD/CDF, Section 9.6)
B. Objective
The objective is to ensure that the instrument continues to meet the sensitivity and linearity criteria to
produce acceptable qualitative and quantitative data throughout each analytical sequence.
C. Criteria
The laboratory shall proceed with sample analysis only when acceptable CS3 CCV analyses have
been performed at the specified frequency and sequence. The CCV shall be analyzed following the
HRMS system tune, the WDM and ICS standard, or the CPS, bracketing each 12-hour period.
Acceptable closing CCVs may also be used as the beginning of the subsequent 12-hour period.
1. The IAR for each target analyte and labeled compound in the CCV standard must be within the
QC limits listed in Table 13 (in the CDD/CDF Tables section in this document).
2. The absolute RT of the internal standard 13Ci2-l,2,3,4-TCDD must be > 25 minutes on the DB-5
(or equivalent) column and > 15 minutes on the DB-225 (or equivalent) column. In addition, if
the absolute RTs of the internal standards are not within ±15 seconds of the RTs obtained from
the initial calibration, the descriptor switching times may not be optimum for detecting all
homologues.
3. The RRTs of each target analyte and labeled compound shall be within the specified limits in
Table 12 (in the CDD/CDF Tables section in this document), and in agreement with the initial
calibration.
4. The S/N ratio must be > 10 for all analytes, including the labeled compounds and internal
standards, in the CCV standard.
5. The RR and RRF Percent Difference (%D) for each applicable target analyte and labeled
compound in the CCV standard must be calculated using the equations in the SOW.
6. The RR and RRF %D for each target analyte and labeled compound must be within the limits of
±25% and ±35%, respectively.
D. Evaluation
1. Verify that the CCV standard was analyzed at the required frequency and sequence, and that the
calibration verification was associated to the correct initial calibration.
2. Verify that the IAR on Form 7A-HR for each target analyte and labeled compound in the CCV
standard is within the limits of ±15% of the theoretical IAR listed in Table 13 (in the CDD/CDF
Tables section in this document).
3. Verify that the absolute RT of internal standard 13C12-1,2,3,4-TCDD is > 25 minutes on DB-5 (or
equivalent) column, or > 15 minutes on DB-225 (or equivalent) column.
4. Verify that the absolute RTs on Form 7B-HR of the internal standards are within ±15 seconds of
the RTs in the initial calibration. If any absolute RTs are outside this range, this may mean that
some homologues have been missed.
5. Verify that the RRT on Form 7B-HR of each target analyte and labeled compound is within the
limits specified in Table 12 (in the CDD/CDF Tables section in this document).
6. Verify that the S/N ratio is > 10 in all analytes.
April 2016 23
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High Resolution Data Review
CDD/CDF
7. Verify that the RR %D on Form 7A-HR is within the limits of ±25% and that the RRF %D is
within the limits of ±35% for each applicable analyte and labeled compound in the CCV standard.
E. Action
1. If the CCV standard was not analyzed at the specified frequency and sequence, use professional
judgment to qualify detects and non-detects. Contact the EPA Regional CLP COR to arrange for
sample reanalysis.
2. If the IAR of any target analyte and labeled compound in the CCV standard is not within the
limits of ±15% of the theoretical IAR values listed in Table 13 (in the CDD/CDF Tables section
in this document), qualify detects as estimated (J) and non-detects as unusable (R).
3. If the absolute RT of internal standard 13C12-1,2,3,4-TCDD is < 25 minutes on the DB-5 (or
equivalent) column, or < 15 minutes on the DB-225 (or equivalent) column, use professional
judgment to qualify detects and non-detects.
4. If the absolute RTs of the internal standards are outside ±15 seconds of the RT windows
established during initial calibration, use professional judgment to qualify detects and non-detects
for target analytes. Additionally, qualify Homologue Totals detects as estimated (J) and non-
detects as estimated (UJ).
5. If the RRT of any target analyte and labeled compound is outside the specified limits in Table 12
(in the CDD/CDF Tables section in this document), use professional judgment to qualify detects
and non-detects.
6. If the S/N ratio is < 10, qualify detects as estimated (J) and non-detects as unusable (R).
7. If the RR %D is outside the limits of ±25% or the RRF %D is outside the limits of ±35%, qualify
detects as estimated (J) and non-detects as estimated (UJ).
Table 5. Continuing Calibration Verification (CCV) Actions for CDD/CDF Analysis
Criteria
CCV analysis not performed at the specified frequency
and sequence
IAR not within the limits of ±15% of the theoretical IAR
values
Absolute RT of internal standard 13C12-1,2,3,4-TCDD
< 25 minutes on the DB-5 (or equivalent) column, or < 15
minutes on the DB-225 (or equivalent) column
Internal standards absolute RT not within ±15 seconds of
the RT in the initial calibration
RRT not within the specified QC limits
S/N ratio < 10 in the CCV standard
RR %D not within the limits of ±25%
RRF %D not within the limits of ±35%
Action
Detect
Use professional
judgment
J
Use professional
judgment
Use professional
judgment for target
analytes
J
Homologue Totals
Use professional
judgment
J
J
Non-detect
Use professional
judgment
R
Use professional
judgment
Use professional
judgment for target
analytes
UJ
Homologue Totals
Use professional
judgment
R
UJ
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High Resolution Data Review CDD/CDF
V. Blanks
A. Review Items
Form 1A-HR, Form 4-HR, preparation logs, instrument logs, and raw data. (SOW HRSM01.2 -
Exhibit B, Sections 3.4.2 and 3.4.9; and Exhibit D - CDD/CDF, Section 12.1)
B. Objective
The objective is to determine the existence and magnitude of contamination resulting from laboratory
(or field) activities.
C. Criteria
1. There must be at least one method blank for each batch of samples extracted. The method blank
shall be prepared with a reference matrix of an equivalent initial weight or volume, by the same
procedures including extract cleanup, and analyzed after the acceptable CCV standard on each
instrument used to analyze samples for every 12-hour analytical sequence, on a DB-5 primary
column (or equivalent) and DB-225 confirmatory column (or equivalent).
2. When there is not enough volume of the method blank available, an instrument blank, which is a
volume of clean solvent spiked with the required labeled compounds at the same spiking
concentrations as the method blank, shall be analyzed as part of each 12-hour analytical sequence.
3. The method blanks and instrument blanks must meet the technical acceptance criteria for sample
analysis specified in the SOW.
4. The method blanks and instrument blanks must not contain any target analyte (except
OCDD/OCDF) at or above one-half the Contract Required Quantitation Limit (CRQL). The
concentrations of OCDD/OCDF in the method or instrument blank(s) must be < 3x CRQLs.
5. If a group of samples and the associated method or instrument blank are contaminated, the blank
and the associated samples containing analyte peaks that meet the qualitative identification
criteria must be reanalyzed.
NOTE: The laboratory must report results for all peaks with an S/N ratio > 3, even if they are
< CRQLs.
D. Evaluation
1. Verify that each sample extract is included on Form 4-HR for the associated method blank.
Verify that a method blank was analyzed on each instrument used to analyze the samples at the
specified frequency and sequence.
2. Verify that the required instrument blanks were analyzed at the specified frequency. In addition,
blanks analyzed in the same analytical sequence and any blind Performance Evaluation (PE)
sample blanks submitted with the samples may be considered. Evaluation of field and equipment
blanks should be performed according to EPA Regional policy and the criteria established in the
project Quality Assurance Project Plan (QAPP). Use the highest blank contamination result from
the same column to make decisions about data qualification.
3. Verify that the method blank(s) and instrument blank(s) do not have any target analytes (except
OCDD/OCDF) detected at concentrations > l/2x CRQLs. The concentrations of OCDD/OCDF
in the method or instrument blank(s) must be < 3x CRQLs. Data users who require data reporting
down to the Estimated Detection Limit (EDL) or Estimated Maximum Possible Concentration
(EMPC) should consider any target analytes that are present, in addition to any chemical or
electronic interference, for data qualification. This may require examination of the raw data in
addition to the reported results.
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High Resolution Data Review CDD/CDF
4. For data users who use the EDL or EMPC to calculate the Toxic Equivalent (TEQ) for non-
detects, the issue of blank contamination is of particular significance. It is advisable to evaluate
as many factors as possible that indicate system stability and the possible sources of interference
for their contribution to positive interference in those analytes with the highest Toxic Equivalency
Factors (TEFs) [i.e., TCDD and PeCDD in the 2005 World Health Organization (WHO)
mammalian TEFs].
NOTE: If the EDL is < the Method Detection Limit (MDL), then the analyte/matrix/instrument-
specific MDL value, adjusted for sample mass or volume as specified in Exhibit D -
CDD/CDF of the SOW, is reported for the 2,3,7,8-substituted isomers.
5. The blank analyses may not include the same weights, volumes, or dilution factors as the
associated samples. In particular, aqueous blank results may be associated with soil/sediment
sample results. The total amount of contamination must be considered, and qualifiers applied
accordingly. It may be advantageous to use the raw data (i.e., instrument quantitation reports) to
compare soil sample data to aqueous blank data. Another approach would be to convert the
aqueous blank concentration to soil concentration by appropriate factors.
E. Action
1. If a method blank or an instrument blank was not prepared and analyzed at the specified
frequency, use professional judgment to determine if the associated sample data should be
qualified. It may be necessary to obtain additional information from the laboratory. Record the
situation in the Data Review Narrative and note it for EPA Regional CLP COR action.
2. For a method blank or an instrument blank reported with results > MDLs or EDLs but < l/2x
CRQLs (3x CRQLs for OCDD/OCDF), non-detects should not be qualified. Report sample
results that are > MDLs or EDLs but < CRQLs (3x CRQLs for OCDD/OCDF) at the CRQLs and
qualify as non-detect (U). Use professional judgment to qualify sample results > CRQLs
(3x CRQLs for OCDD/OCDF) or > Blank Results.
3. For a method blank or an instrument blank reported with results > l/2x CRQLs (3x CRQLs for
OCDD/OCDF), non-detects should not be qualified. Report sample results that are < CRQLs
(3x CRQLs for OCDD/OCDF) at the CRQLs and qualify as non-detect (U). Report sample
results that are > CRQLs (3x CRQLs for OCDD/OCDF) but < Blank Results at the blank results
and qualify as non-detect (U). Use professional judgment to qualify sample results that are
> CRQLs (3x CRQLs for OCDD/OCDF) and > Blank Results.
4. In the case where minimal contamination may exist, the reviewer may decide not to assign
qualification to sample results at considerably high concentrations. Alternatively, expanded
criteria may be applied when significant contamination occurs. For example, sample results that
are at 2x to 5x the results of the highest contaminated associated blank (lOx for OCDD/OCDF)
may be reported and qualified as non-detect (U). However, sample results greater than these
amounts may be reported without qualification. Using either approach requires careful
professional judgment when evaluating the effects of contamination to avoid reporting false
negatives.
5. There may be instances where little or no contamination was present in the associated blanks, but
qualification of the sample is deemed necessary. For example, an analyte in the method blank
was not reported as detected because it did not satisfy one of the identification criteria (either the
S/N ratio or the IAR), but in the associated sample, it met the IAR requirement, and/or had a
slightly higher S/N ratio than specified, and was detected at < 5x the blank concentration. Use
professional judgment to qualify sample results in these situations and provide an explanation of
the rationale used for data qualifications in the Data Review Narrative.
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6. Blanks or samples analyzed after a PE sample, Laboratory Control Sample (LCS), LCS Duplicate
(LCSD), or CCV should be carefully examined to determine the occurrence of instrument or
syringe carry-over. Use professional judgment to determine whether sample or blank results are
attributable to carry-over.
7. When there is convincing evidence that contamination is isolated to a particular instrument,
matrix, or concentration level, use professional judgment to determine if qualification should only
be applied to certain associated samples (as opposed to all of the associated samples).
8. If gross contamination exists (i.e., saturated peaks), qualify detects and non-detects as unusable
(R). The laboratory should have taken corrective action prior to reporting the data. Therefore,
report the situation to the EPA Regional CLP COR for resolution.
Table 6. Blank Actions for CDD/CDF Analysis
Blank Type
Method, Instrument,
Field, Equipment
Blank Result
> MDL or EDL but
< l/2x CRQL (3x
CRQLs for
OCDD/OCDF)
> l/2x CRQL (3x
CRQLs for
OCDD/OCDF)
Gross contamination
Sample Result
Non-detect
> MDL or EDL but
< CRQL (3x CRQLs for
OCDD/OCDF)
> CRQL (3x CRQLs for
OCDD/OCDF) or
> Blank Result
Non-detect
< CRQL (3x CRQLs for
OCDD/OCDF)
> CRQL (3x CRQLs for
OCDD/OCDF) and
< Blank Result
> CRQL (3x CRQLs for
OCDD/OCDF) and
> Blank Result
Non-detect and detect
Action
No qualification
Report at CRQL and
qualify as non-detect (U)
Use professional judgment
No qualification
Report at CRQL and
qualify as non-detect (U)
Report at Blank Result and
qualify as non-detect (U)
Use professional judgment
R
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High Resolution Data Review CDD/CDF
VI. Labeled Compounds
A. Review Items
Form 2-HR and raw data. (SOW HRSM01.2 - Exhibit B, Section 3.4.6 and Exhibit D - CDD/CDF,
Section 11.2.2)
B. Objective
The objective is to measure the extraction efficiency of the analytical method by the recovery of the
labeled compounds. These compounds are added to all samples prior to sample preparation and are
used to quantify the target analytes.
C. Criteria
1. A labeled compound spiking solution, that includes 15 labeled target analytes and the cleanup
standard, shall be added to each sample, blank, and LCS/LCSD at the concentrations specified in
the SOW.
2. The Percent Recovery (%R) of each labeled compound must be calculated according to the SOW
equation.
3. Each labeled compound must meet the IAR requirement specified in Table 13 (in the CDD/CDF
Tables section in this document). If the IAR for any labeled compound is outside the limits, the
sample extract shall be reanalyzed. If the problem corrects itself, the second analysis shall be
considered compliant. If the IAR fails in the second analysis, the extract shall be processed
through additional cleanup steps, or the sample re-extracted and reprocessed through sufficient
cleanup steps to remove the possible interferences.
4. If any labeled compound S/N ratio is < 10 at its m/z(s), the samples must be re-extracted and
reanalyzed.
5. If any labeled compound %R is < 100%, there may have been loss of the labeled compound and
target analyte during the analytical process. If any labeled compound %R is > 100%, there may
have been errors in the quantitation of the labeled compound or problems with the cleanup of the
sample extracts.
6. If the original sample, prior to any dilutions, has more than one labeled compound or cleanup
standard with a %Rthat is not within the limits specified in Table 15 (in the CDD/CDF Tables
section in this document), it shall be re-extracted and reanalyzed due to an efficiency issue with
the extract cleanup procedure.
D. Evaluation
1. Verify that a Form 2-HR is included for each sample, blank, and LCS/LCSD. Verify that the
required labeled compounds, internal standards, and cleanup standard are present in each sample,
blank, and LCS/LCSD, and that the %Rs for each labeled compound and cleanup standard are
calculated correctly.
2. Verify that the IAR of each labeled compound is within the limits in Table 13 (in the CDD/CDF
Tables section in this document).
3. Verify that the S/N ratio of each labeled compound is > 10.
4. Verify that the labeled compounds and cleanup standard %R values fall within the required limits
prior to any dilutions.
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E. Action
1. If the required labeled compounds, internal standards, and cleanup standard are not present in
each sample, blank, and LCS/LCSD, or the %Rs for each labeled compound and cleanup standard
are not calculated correctly, use professional judgment to evaluate the effect on the data.
2. If a labeled compound (exclusive of the cleanup standard) fails the IAR criteria in a sample but
the lARs for that labeled compound in all of the associated calibration standards are acceptable,
qualify detects as estimated (J) and non-detects as estimated (UJ). If the IAR for that labeled
compound also fails in any of the associated the calibration standards, qualify detects as estimated
(J) and non-detects as unusable (R).
3. If the %R for any labeled compound is < 10% and the S/N ratio > 10, qualify detects as estimated
low (J-) and non-detects as unusable (R).
4. If the %R for any labeled compound is < 10% and the S/N ratio < 10, qualify detects and non-
detects as unusable (R).
5. If the %R for any labeled compound is > 10% but < lower acceptance limit, qualify detects as
estimated low (J-) and non-detects as estimated (UJ).
6. If the %R for any labeled compound is > lower acceptance limit and < upper acceptance limit,
detects and non-detects should not be qualified.
7. If the %R for any labeled compound is > upper acceptance limit, qualify detects as estimated high
(J+) and non-detects as estimated (UJ).
8. If the %R of the cleanup standard is < lower acceptance limit, qualify detects as estimated (J) and
non-detects as estimated (UJ). If a wide range of cleanup standard %R is noted between samples,
use professional judgment to qualify sample results.
9. If the %Rs for the labeled compounds were not within the QC limits, and other identification
criteria and S/N ratio requirements were not met, the laboratory should have performed a
reanalysis. If the sample was not reanalyzed, contact the EPA Regional CLP COR to arrange for
reanalysis.
Table 7. Labeled Compound Recovery Actions for CDD/CDF Analysis
Criteria
IAR criteria not met in sample but met in all associated
calibration standards
IAR fails in sample and fails in any one of associated
calibration standards
%R < 10% and S/N ratio > 10
%R < 10% and S/N ratio < 10
%R > 10% but < Lower Acceptance Limit
Lower Acceptance Limit < %R < Upper Acceptance Limit
%R > Upper Acceptance Limit
%R of Cleanup Standard < Lower Acceptance Limit
Action
Detect
J
J
J-
R
J-
No qualification
J+
J
Non-detect
UJ
R
R
R
UJ
No qualification
UJ
UJ
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VII. Laboratory Control Sample/Laboratory Control Sample Duplicate
A. Review Items
Form 3A-HR, Form 3B-HR, preparation logs, instrument logs, and raw data. (SOW HRSM01.2 -
Exhibit B, Section 3.4.7 and Exhibit D - CDD/CDF, Section 12.2)
B. Objective
The objective is to evaluate the accuracy of the analytical method and laboratory performance.
C. Criteria
1. The laboratory shall prepare spiked LCS/LCSD samples for each matrix type that occurs in an
SDG by the same procedures used for the samples.
2. The LCS/LCSD shall meet the technical acceptance criteria for sample analysis.
3. The %R and Relative Percent Difference (RPD) of each spiked analyte shall be calculated
according to the SOW equations.
4. The %R of each spiked analyte must be within the QC limits in Table 15 (in the CDD/CDF
Tables section in this document).
5. The RPD of each spiked analyte must be within the QC limits specified in the SOW.
D. Evaluation
1. Verify that Form 3A-HR and Form 3B-HR are included for the LCS/LCSD. Verify that the LCS
and LCSD were prepared and analyzed at the required frequency.
2. Verify that the spiking solution was added to the LCS/LCSD, and that the target analytes were at
the correct concentrations.
3. Verify that calculations and transcriptions from raw data were performed correctly.
4. Verify that the %R of each spiked analyte is within the QC limits.
5. Verify that the RPD of each spiked analyte is within the QC limits.
E. Action
1. If the LCS and LCSD analyses were not performed, or not performed at the required frequency,
be sure to note this in the Data Review Narrative. Qualify detects as estimated (J) and use
professional judgment to qualify non-detects.
2. If the %R of any LCS/LCSD spiked analyte is < 10%, qualify detects as estimated low (J-) and
non-detects as unusable (R). Contact the EPA Regional CLP COR regarding samples associated
with a non-compliant LCS/LCSD to determine whether re-extraction and reanalysis are
necessary.
3. If the %R of any LCS/LCSD spiked analyte is > 10% but < lower acceptance limit, qualify
detects as estimated low (J-) and non-detects as estimated (UJ).
4. If the %R of any LCS/LCSD spiked analyte is > lower acceptance limit and < upper acceptance
limit, detects and non-detects should not be qualified.
5. If the %R of any LCS/LCSD spiked analyte is > upper acceptance limit, qualify detects as
estimated high (J+). Non-detects should not be qualified. Contact the EPA Regional CLP COR
regarding samples associated with a non-compliant LCS/LCSD to determine whether
re-extraction and reanalysis are necessary.
6. If the RPD of any LCS/LCSD spiked analyte is > 30%, use professional judgment to qualify
detects and non-detects. This limit is only advisory.
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7. %R and/or RPD failure, in conjunction with other performance factors, may indicate that the
laboratory performance is unacceptable. In this case, use professional judgment to qualify detects
and non-detects.
Table 8. LCS/LCSD Recovery and RPD Actions for CDD/CDF Analysis
Criteria
LCS/LCSD not performed
LCS/LCSD not performed at required frequency
%R< 10%
%R > 10% but < Lower Acceptance Limit
Lower Acceptance Limit < %R < Upper Acceptance Limit
%R > Upper Acceptance Limit
RPD > 30%
Action
Detect
J
J
J-
J-
No qualification
J+
Use professional
judgment
Non-detect
Use professional
judgment
Use professional
judgment
R
UJ
No qualification
No qualification
Use professional
judgment
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VIII. Target Analyte Identification
A. Review Items
Form 1A-HR, Form 2-HR, and raw data. (SOW HRSM01.2 - Exhibit D - CDD/CDF, Section 11.1)
B. Objective
The objective is to provide unambiguous identification of the target analyte.
C. Criteria
For a GC peak to be identified as a CDD/CDF target analyte, it must meet all of the following
criteria:
1. Retention Times (RTs) and Relative Retention Times (RRTs)
RTs are required for all chromatograms; scan numbers are optional. For positive identifications,
RTs for the two quantitation ions must maximize within 2 seconds, RTs must either be printed at
the apex of each peak on the chromatogram, or each peak must be unambiguously labeled with an
identifier that refers to the quantitation report. The chromatogram, the quantitation report, or a
combination of both must contain the RT of each peak and its area.
a. To make a positive identification of the target analytes, the RRT at the maximum peak height
of the analyte must be within the RRT window in Table 12 (in the CDD/CDF Tables section
in this document). The RRT must be calculated using the SOW equation.
b. To make a positive identification of the non-2,3,7,8-substituted analytes (tetra- through
hepta-), the RTs must be within the RT window established by the WDM for the
corresponding homologous series.
2. Peak Identification
For each target analyte, the two specified quantitation ions listed in Table 10 (in the CDD/CDF
Tables section in this document), and the RT reported on Form 1A-HR, must be present in the
raw data. The ion current responses for the two quantitation ions must maximize simultaneously
within the same 2 seconds. This requirement also applies to the labeled compounds and the
internal standards. For the cleanup standard, only one ion is monitored.
3. Ion Abundance Ratios (lARs)
The IAR for the target analytes, labeled compounds, and internal standards must be within the
limits specified in Table 13 (in the CDD/CDF Tables section in this document), or within ±15 of
the ratio in the most recent CCV midpoint calibration standard (CS3). The ratios shall be
calculated using peak areas. If interferences are present and lARs are not met using peak areas,
but all other qualitative identification criteria are met (RT, S/N, presence of both ions), the
laboratory may use peak heights to evaluate the ion ratio. The lARs for any target analytes and
the associated labeled compounds and/or internal standards may be determined using peak
heights instead of areas.
4. Signal-to-Noise (S/N) Ratio
The integrated ion current for each target analyte ion listed in Table 10 (in the CDD/CDF Tables
section in this document) must be at least 3x the background noise and must not have saturated
the detector (applies to sample extracts only). The labeled compound and internal standard ions,
however, must be at least lOx the background noise and must also not have saturated the detector.
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5. Polychlorinated Diphenyl Ether (PCDPE) Interferences
If PCDPE interferences are detected at S/N ratio > 3, as indicated by the presence of peaks at the
exact m/z(s) monitored for these interferents (see Table 10 in the CDD/CDF Tables section in this
document), their presence may interfere with quantitative determination of any of the furans.
Additional extract cleanup with clean glassware and reagents (florisil and/or alumina) can
eliminate these interferents.
6. Non-2,3,7,8-Substituted Analytes
Peaks are commonly found in each descriptor which pass all identification criteria for 2,3,7,8-
substituted analytes except retention time. These peaks represent the many less toxic non-2,3,7,8-
substituted analytes. These analytes do not have associated TEQs, but the total quantity of
CDDs/CDFs in each homologous series is required by certain data users. All peaks identified as
non-2,3,7,8 -substituted analytes must meet the same qualitative criteria as the 2,3,7,8-substituted
target analytes, except RT.
D. Evaluation
1. Evaluate chromatograms for each SICP to verify adequate system performance, proper scaling,
and adequate presentation. This evaluation allows a visual comparison of lock-mass trace and
PCDPE interference channel to the associated target ion channels for verifying positive
identifications.
2. Verify that the RRTs for the target analytes and labeled compounds are within the RRT windows
listed in Table 12 (in the CDD/CDF Tables section in this document).
3. Verify that the RTs for the non-2,3,7,8-substituted analytes are within the RT windows
established by the WDM for the corresponding homologues.
4. Verify that the lARs on Form 1A-HR and Form 2-HR are within the criteria listed in Table 13 (in
the CDD/CDF Tables section in this document), or within ±15% of the ratio in the most recent
CS3 CCV.
5. Verify that the SICPs of the two quantitation ions for each analyte maximize simultaneously
(within the same 2 seconds).
6. Verify that the S/N ratio is > 3 for each analyte and that the detector has not been saturated. If an
analyte is flagged with an asterisk (*), it means that the laboratory determined that the analyte
failed one or more qualitative identification criteria and an EMPC has been reported. Examine
the SICPs to determine whether there is some interference (i.e., PCDPEs) that could potentially
cause the ion ratio to fail.
7. Verify that no PCDPE interferences exist on chromatograms at the expected retention time of
each target analyte.
8. For non-2,3,7,8 results, verify that both ions are present and maximize within 2 seconds, and that
they meet the S/N and IAR requirements. If detector saturation occurs in a region of the SICP
that is clearly due to either a non-2,3,7,8-substituted analyte or to an interferent, it is normally not
interpreted as a positive result and no further action is required by the laboratory. EMPC, EDL,
or MDL should not be included in homologue calculation.
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E. Action
1. If the RRT for any of the target analytes or labeled compounds falls outside the limits listed in
Table 12 (in the CDD/CDF Tables section in this document) and the RT falls outside the WDM
windows, examine the SICP to evaluate whether there is a peak that meets the RRT and RT
criteria. If there is no peak, consider the analyte as a non-detect with the reported EDL and
qualify as non-detect (U).
2. If the RT for any of the non-2,3,7,8-substituted analytes falls outside the WDM windows, no
action shall be taken.
3. If the IAR criteria are not met, examine the other information provided to be sure the other
criteria have been met. Check the calculation of EMPC results and/or ask the laboratory to
recalculate and re-report these results. The isotope dilution method provides the ability to
calculate ion ratios for the two ions monitored. If the IAR is outside the criteria, it does not
unequivocally prove that dioxins/furans are not present; it indicates that either interference is
present for one of the ions, or that another compound may be present. Use professional judgment
to decide how to qualify EMPCs.
4. If the ion current responses for the two quantitation ions for an analyte fail to maximize
simultaneously (within 2 seconds), examine the SICP to evaluate whether there are peaks or
shoulders that do meet the 2-second criterion. If there are no peaks or shoulders that meet the
2-second criterion, consider the analyte as a non-detect. In a case where a peak is present but did
not meet all identification criteria, the analyte should be considered as detected and the result
should be reported as EMPC.
5. If the S/N criteria are not met, consider the analyte as a non-detect with the reported EDL and
qualify as non-detect (U). In cases where EDL < the adjusted MDL, the adjusted MDL is
reported and qualified as non-detect (U).
6. If PCDPE interferences are identified above the S/N ratio of 3, consider the magnitude of the
PCDPE and that of the target analytes. If the raw abundance of the PCDPE interference is
significant (i.e., > 10% of that for the associated target CDF analytes), use professional judgment
to qualify the affected target CDF analytes either as non-detects at an estimated reporting limit
(UJ) or unusable (R). If the interference is minor (i.e., < 10% of the associated target CDF
analytes), qualify detects as estimated (J) and non-detects as estimated (UJ).
7. In the event that any of the non-2,3,7,8-substituted analytes are improperly identified, it may be
necessary to re-evaluate the raw data, or forward a request through the EPA Regional CLP COR
for possible data resubmission from the laboratory.
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IX. Target Analyte Quantitation
A. Review Items
Form 1A-HR, Form 1D-HR, Form 2-HR, and raw data. (SOW HRSM01.2 - Exhibit B, Sections
3.4.2, 3.4.3, and 3.4.5; and Exhibit D - CDD/CDF, Section 11.2)
B. Objective
The objective is to verify that the reported target analyte and Homologue Totals results are accurately
calculated.
C. Criteria
1. For an isotope dilution method, known amounts of labeled compounds are added to the samples
to provide recovery corrections for the target analytes, and the concentrations of the labeled
compounds are used for quantitation of the associated target analytes except for 1,2,3,7,8,9-
HxCDD and OCDF.
2. The results for target analyte 1,2,3,7,8,9-HxCDD are determined using the average of the
responses of the labeled compounds 1,2,3,4,7,8-HxCDD and 1,2,3,6,7,8-HxCDD. The results for
target analyte OCDF are determined using the response of the labeled OCDD compound since the
labeled OCDF is not added to the samples due to interference concerns.
3. An estimate of quantitative results is determined for any peaks representing non-2,3,7,8-
substituted compounds using the average response factors from all of the labeled 2,3,7,8-isomers
at the same level of chlorination. The Homologue Totals concentrations are then determined by
summing the results of target and non-target analytes for each level of chlorination.
4. The RR values from the initial calibration are used to determine target analyte concentrations
using the equation for the specific matrix in the SOW.
5. The internal standard method is used to calculate the concentrations of target analytes 1,2,3,7,8,9-
HxCDD and OCDF, labeled compounds, and the cleanup standard using the RRFs from the initial
calibration using the equations in the SOW.
6. The amount of moisture in solid samples should not have an impact on the calculation of
quantitative results since the laboratory is required to prepare an equivalent of 10 grams dry-
weight of solid or aqueous samples containing > 1% solids. The CRQLs of the samples should
be equal to those listed in SOW HRSM01.2 Exhibit C, Table 1 - Chlorinated Dibenzo-/?-
Dioxins/Chlorinated Dibenzofurans Target Analyte List and Contract Required Quantitation
Limits, provided that sample volume or dry weight, extract final volume, and injection volume
are the same as in Exhibit D - CDD/CDF of the SOW. However, if any one of these factors is
different, the CRQL used for data qualification should be adjusted, using the equations for the
specific matrix in the SOW.
D. Evaluation
1. Use the raw data to verify the correct calculation of all sample results reported by the laboratory.
Before verifying calculations for solid samples, check whether the reported weight is a dry weight
or a total weight (including any moisture). Only the dry weight should be used in these
calculations. Each type of calculation should be verified, including those from the confirmation
column, if utilized.
2. Compare RTs, internal standard recoveries, ion ratios, S/N determination, positive results,
dilution results, EDLs and/or MDLs, EMPCs, and CRQLs in the processed raw data reports and
applicable forms (i.e., Form 1A-HR and Form 2-HR) with the reported detects and non-detects in
the sample results.
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High Resolution Data Review CDD/CDF
3. Check the reported CRQLs for accuracy and compliance with SOW HRSMO1.2 Exhibit C, Table
1 - Chlorinated Dibenzo-/>-Dioxins/Chlorinated Dibenzofurans Target Analyte List and Contract
Required Quantitation Limits. Verify that the CRQLs are adjusted based on sample volume or
weight.
4. Verify whether the reported results are < adjusted CRQLs. Check that the laboratory has
followed the requirements in SOW HRSMO 1.2 Exhibit B - Reporting and Deliverables
Requirements for reporting results on Form 1A-HR and Form 1D-HR.
5. The amount of moisture in a solid sample may have an impact on data representativeness. Due to
the extremely low solubility of dioxins and furans in water, they should be contained in the solid
phase. However, be aware of any EPA Regional Standard Operating Procedures (SOPs) and/or
concerns of the data user and evaluate the data accordingly.
E. Action
1. If any discrepancies are found, contact the EPA Regional CLP COR, who may contact the
laboratory to obtain additional information that could resolve any issues. If a discrepancy
remains unresolved, use professional judgment to decide which value is the most accurate and to
determine whether qualification of the data is required. Record the qualification applied to the
data and the reasons for the qualification in the Data Review Narrative.
2. Qualify target analyte results that are > the EDLs or the adjusted MDLs and < the adjusted
CRQLs as estimated (J).
3. Qualify Homologue Totals detects as estimated (J) and non-detects as estimated (UJ).
4. If numerous or significant failures occurred with the quantitation of the target analytes,
Homologue Totals, CRQLs, or TEQs, notify the EPA Regional CLP COR for appropriate action.
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X. Second Column Confirmation
A. Review Items
Form 1A-HR and raw data. (SOW HRSM01.2 - Exhibit B, Sections 2.4.5.1 and 3.4.2; and Exhibit
D - CDD/CDF, Section 11.1.1.5)
B. Objective
The objective is to confirm the presence of target analyte 2,3,7,8-TCDF in a sample, when the analyte
is detected on the DB-5 (or equivalent) column.
C. Criteria
1. Second column confirmation is required for any sample analyzed on a DB-5 (or equivalent)
column in which 2,3,7,8-TCDF is detected or where the result is reported as an EMPC.
2. One of the following options may be used to achieve better specificity than can be obtained on
the DB-5 (or equivalent) column:
a. The sample extract may be analyzed on a GC column capable of resolving all of the 2,3,7,8-
substituted target analytes from other isomers, but not necessarily capable of resolving all of
the non-2,3,7,8-substituted isomers from one another.
b. The sample extract may be reanalyzed on a DB-225 (or equivalent) column to achieve better
GC resolution for individual 2,3,7,8-substituted isomers.
3. Regardless of the GC column used, for a GC peak to be identified as 2,3,7,8-TCDF, it must meet
all of the criteria specified in Exhibit D - CDD/CDF (IAR, S/N ratio, RT, etc.) of the SOW. If
any GC columns other than those specified in the SOW are used, the laboratory shall clearly
document the elution order of all analytes of interest on any such column in the SDG Narrative.
D. Evaluation
1. Verify that a second column confirmation analysis is performed when 2,3,7,8-TCDF is detected
in any sample or when the result is reported as an EMPC on a DB-5 (or equivalent) column. The
confirmation analysis is not required when the GC column used for initial analysis meets the
isomer specificity requirements for both 2,3,7,8-TCDD and 2,3,7,8-TCDF.
2. Verify that quantitation is performed on both columns and that the results are reported on Form
1A-HR. The two concentrations should not be combined or averaged, especially if the second
column confirmation analysis is performed on a different instrument.
3. Verify that the second column confirmation analysis meets all criteria (initial calibration
requirements, linearity specifications, etc.).
E. Action
1. If second column confirmation was required but not performed, contact the EPA Regional CLP
COR to direct the laboratory to perform the analysis.
2. If a second column confirmation analysis was performed and the result is confirmed to be a
detect, report the result from the confirmation analysis. If the result from the confirmation
analysis is a non-detect, report the result at the EDL or adjusted MDL and qualify as non-detect
(U).
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XI. Estimated Detection Limit and Estimated Maximum Possible Concentration
A. Review Items
Form 1A-HR and raw data. (SOW HRSM01.2 - Exhibit D - CDD/CDF, Sections 11.2.5 and 11.2.6)
B. Objective
The objective is to verify that the sample-specific EDLs and EMPCs are accurately calculated and
reported.
C. Criteria
1. The EDL is an estimated concentration of a given analyte that must be present to produce a signal
with a peak height of at least 3x the background noise signal.
a. The EDL is calculated for each 2,3,7,8-substituted target analyte that is not positively
identified, regardless of whether or not any non-2,3,7,8-substituted target analytes are present
in that homologous series. If the EDL is less than the adjusted MDL, then the adjusted MDL
value shall be reported on Form 1A-HR with a "UM" qualifier.
b. The EDL must be calculated using the equation for the specific matrix in the SOW. The
background level (Hx) is determined by measuring the height of the noise at the expected RTs
of both of quantitation ions of the particular 2,3,7,8-substituted target analytes. The expected
RT is determined from the most recent analysis of the CCV midpoint standard (CS3)
performed on the same HRGC/HRMS system that was used for the analysis of the samples.
In addition, if there is an associated labeled compound present, the RT of the expected
analyte should be within ± 2 seconds of that of the labeled compound.
2. The EMPC is the estimated maximum possible concentration for analytes that do not meet all
technical acceptance criteria.
a. An EMPC is calculated for 2,3,7,8-substituted target analytes characterized by a response that
meets the RT requirement, with an S/N ratio of at least 3 for both quantitation ions, but does
not meet the IAR criteria.
b. The EMPC must be calculated using the equation for the specific matrix in the SOW.
D. Evaluation
1. Verify that an EDL or adjusted MDL is reported for each undetected 2,3,7,8-substituted target
analyte. The EDL must be < CRQL, except when increased due to dilution of the extract.
2. Verify that the analytes that were reported as EMPCs meet all of the identification criteria, except
for lARs.
3. Verify that the EDLs and EMPCs are calculated correctly.
E. Action
1. If the non-detects were not reported at the EDL or adjusted MDL, notify the EPA Regional CLP
COR of the deficiency.
2. Qualify target analyte results reported with EMPCs as estimated (J) or as non-detect (U), in
accordance with EPA Regional SOPs.
3. If calculations were not correctly performed by the laboratory, notify the EPA Regional CLP
COR of the deficiency.
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High Resolution Data Review CDD/CDF
XII. Toxic Equivalent Determination
A. Review Items
Form 1A-HR, Form 1B-HR, and raw data. (SOW HRSM01.2 - Exhibit B, Section 3.4.3 and Exhibit
D - CDD/CDF, Section 11.2.8)
B. Objective
The objective is to verify that the Total TEQs for the 2,3,7,8-substituted tetra- through octa- isomers
are accurately calculated and reported.
a. The exclusion of mono-, di-, tri-, and the non-2,3,7,8-chlorine substituted isomers in the
higher homologous series does not mean that they are not toxic. Their toxicity, as estimated
at this time, is relatively much less than the toxicity of the native 2,3,7,8-substituted isomers.
C. Criteria
1. The criteria for calculating the TEF-adjusted concentrations and the Total TEQs depend upon
EPA Regional policies. Two common approaches are outlined below:
a. The first approach is to include only the detected 2,3,7,8-substituted congeners that meet all
of the qualitative identification criteria and use a zero for any EMPC or EDL value in the
calculations. If confirmation analyses were performed, the lower of the two values reported
on Forms 1A-HR should be used in the calculations.
b. In the second approach, in addition to the results of any positively identified 2,3,7,8-
substituted congeners, the reported values of any EMPCs or EDLs are also used in the
calculations.
2. The laboratory shall perform the calculations (as specified in the SOW) and report the TEFs for
all three species (Mammal, Fish, and Bird). The results of the TEF and Total TEQ calculations
must be reported on Form 1B-HR.
NOTE 1: The TEFs used in these calculations are derived and published by WHO. Updates of
TEFs are published by WHO approximately every five years for mammalian toxicity.
The timetable has been longer for other types of organisms (i.e., birds and fish).
NOTE 2: The 2,3,7,8-TCDD TEF-adjusted concentration of a sample is often used by the
laboratory as an aid in determining when second column confirmation or re-extractions
and reanalyses are required.
D. Evaluation
1. Verify that the TEF and Total TEQ calculations were performed correctly.
2. In the determination of the Total TEQ for a sample, consider the impact of using estimated
quantities in the Total TEQ calculation.
E. Action
1. If the calculations were not correctly performed by the laboratory, notify the EPA Regional CLP
COR of the deficiency.
2. If any, or a portion, of the Total TEQ number has been derived from qualified results, use
professional judgment to decide whether or not to qualify the Total TEQ accordingly. For
example, if more than 10% of the total represents "J"-qualified values, then the total may also be
"J" qualified. Be sure to document these decisions in the Data Review Narrative.
April 2016 39
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High Resolution Data Review CDD/CDF
XIII. Regional Quality Assurance and Quality Control
A. Review Items
Form 1A-HR, Form 1B-HR, chromatograms, quantitation reports, TR/COC Record documentation,
and raw data. (SOW HRSM01.2 - Exhibit B, Sections 2.4 and 3.4)
B. Objective
The objective is to use results from the analysis of EPA Regional Quality Assurance/Quality Control
(QA/QC) samples, including PE samples, field duplicates, blind spikes, and blind blanks to assess the
impact on data quality and determine the validity of the analytical results.
C. Criteria
1. The frequency of EPA Regional QA/QC samples should be defined in the QAPP.
2. Performance criteria for EPA Regional QA/QC samples should also be defined in the QAPP.
3. The EPA Region may provide the laboratory with PE samples to be analyzed with each SDG.
These samples may include blind spikes and/or blind blanks. The laboratory must analyze a PE
sample when provided by the EPA Region.
4. The EPA Region may score the PE samples based on data provided by QATS.
D. Evaluation
1. Determine whether the results of EPA Regional QA/QC samples impact all samples in the project
or only those directly associated (i.e., in the same SDG, collected on the same day, prepared
together, or contained in the same analytical sequence).
2. If PE samples are included in the SDG, verify that the results are within the warning limits [95%
(2a) confidence interval] and action limits [99% (3a) confidence interval].
3. If a significant number (i.e., half or more) of the analytes in the PE samples fall outside of the
95% or 99% warning or action criteria, or if a number of false positive results are reported,
evaluate the overall impact on data.
4. If a blind blank is included in the SDG, verify that no target analytes are present in that sample.
The results of the blind blank analysis should be comparable to those in the associated method
blank (see Section V - Blanks in this document).
5 Equipment rinsate samples should not contain any target analyte contamination. Moreover, they
should be comparable to the associated method blank(s).
6 Evaluate field duplicates for comparability (i.e., precision).
7. Determine whether poor precision is the fault of the laboratory, or a result of sample non-
homogeneity in the field. Laboratory observations of sample appearance may become important
in these situations.
E. Action
Any action must be in accordance with EPA Regional specifications and criteria for acceptable
QA/QC sample results. Note in the Data Review Narrative any observations and the impact on data
quality of any QA/QC issues.
If a result is not within the acceptance criteria for any CDD/CDF congener, evaluate the other QC
samples in the SDG (e.g., LCS/LCSD, calibration, labeled standard recovery, internal standard
recovery, and cleanup standard recovery). In such situations, the PE sample may not be
representative of the field samples. PE samples are only one indicator of technical performance of the
laboratory.
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High Resolution Data Review
CDD/CDF
1. In general, if the PE sample analytes results are not within the 95% confidence interval or
warning performance window, but are within the 99% confidence interval, qualify detects as
estimated (J) and non-detects as estimated (UJ).
2. For data outside the 95% or 99% confidence interval and scored as "warning-high" or "action-
high", qualify detects as estimated (J). Non-detects should not be qualified.
3. If the results are scored as "action-low", qualify detects as estimated (J) and non-detects as
unusable (R). Contact the EPA Regional CLP COR if reanalysis of samples is required. For
example, if HxCDD was quantitated beyond the high end of the action limit and was not detected
in any of the samples, the usability of the data would not be affected. On the other hand, in the
situation described in Section D.3 above, it may be necessary to qualify all sample data, and not
only those analytes present in the PE samples.
4. In general, for EPA Regional QA/QC performance not within QAPP specification, qualify detects
as estimated (J) and non-detects as estimated (UJ). The impact on overall data quality should be
assessed after consultation with the data user and/or field personnel. Contact the EPA Regional
CLP COR if reanalysis of samples is required.
Table 9. PE Sample Data Actions for CDD/CDF Analysis
Criteria
Results are not within the 95% confidence interval (> 2a)
but inside the 99% interval (< 3 a), and are biased low
(Warning - Low)
Results are not within the 95% confidence interval (> 2a)
but inside the 99% interval (< 3 a), and are biased high
(Warning - High)
Results are outside the 99% confidence interval (> 3a) and
biased high (Action - High)
Results are outside the 99% confidence interval (> 3a) and
biased low (Action - Low)
Action
Detect
J
J
J
J
Non-detect
UJ
No qualification
No qualification
R
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High Resolution Data Review CDD/CDF
XIV. Overall Assessment of Data
A. Review Items
Entire data package, data review results, and (if available) the QAPP and Sampling and Analysis Plan
(SAP).
B. Objective
The objective is to provide an overall assessment of data quality and usability.
C. Criteria
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems. Contract compliance issues should be directed to the EPA
Regional CLP COR.
2. It is appropriate to make professional judgments and express concerns, as well as to comment on
the validity of the overall data for a Case, especially when there are several QC criteria that are
outside of the specification parameters.
3. Reported analyte concentrations must be quantitated according to the appropriate equations, as
listed in the method.
4. If the concentration for any target analyte (except OCDD and OCDF) exceeds the calibration
range, the laboratory must perform sample dilution to bring the analyte concentration within the
calibration range. The laboratory shall either dilute the sample extract (when the labeled
compounds in the extract meets the criteria) or re-extract the sample with a smaller or diluted
aliquot. The sample extract may be diluted with a solvent such as n-nonane as long as the 10:1
S/N criterion continues to be met for the labeled compounds. Otherwise, a smaller aliquot of the
original sample should be used for re-extraction and reanalysis.
5. If qualifiers other than those used in this document are needed to describe or qualify the data,
thoroughly document/explain the additional qualifiers.
D. Evaluation
1. Evaluate any technical problems which have not been previously addressed.
2. Review all available information including, but not limited to: the QAPP [specifically, the
Measurement Quality Objectives (MQOs)], the SAP, and any communications from the data user
that concern the intended use and desired quality of the data.
3. If appropriate information is available, assess the usability of the data to assist the data user.
4. Evaluate sample dilutions to determine the validity of sample results.
I. Extract dilution:
a. Verify that all target analyte concentrations (except OCDD or OCDF) in the diluted
sample are within the calibration range.
b. Examine the preparation and/or analysis logs to verify that a proper dilution scheme was
followed. Also examine the SICPs to determine whether any peaks saturated the
detector.
c. Verify that the internal standard calculations used to determine analyte concentrations in
the diluted sample extract were performed correctly. If the laboratory calculated or
reported the results incorrectly, it may be necessary to request a resubmission of the data.
NOTE: The laboratory should not correct the results of the diluted sample extract for the
labeled compounds recoveries determined from the initial analysis. However,
initial labeled compound recovery is a factor that should be considered
qualitatively during this evaluation.
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High Resolution Data Review CDD/CDF
d. Verify that a dilution factor of < 10 was used and correctly documented, or that prior
communication with the EPA Regional customer was documented.
II. Dilution by re-extraction and reanalysis:
a. Verify that all target analyte concentrations (except OCDD or OCDF) in the diluted
sample are within the calibration range. If substantial differences are noted between the
initial analysis and the diluted re-extraction/reanalysis, examine the preparation and/or
run logs to verify that a proper dilution scheme was followed. Also examine the SICPs to
determine whether any peaks saturated the detector. If the laboratory calculated or
reported the results incorrectly, it may be necessary to request a resubmission of the data.
Check the calculation of results from a diluted sample and a re-extracted sample (if
present) to verify correct determination of results.
E. Action
1. Use professional judgment to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
2. Use professional judgment to qualify sample results that are > adjusted MDLs or EDLs and non-
detects if the adjusted MDL or EDL exceeds adjusted CRQL.
3. If a sample was not diluted properly when sample results exceeded the upper limit of the
calibration range, qualify sample results that are > adjusted MDLs or EDLs as estimated (J).
4. If unexplained differences are identified between the initial and the diluted sample results, use
professional judgment to qualify sample results.
5. Include a summary of these observations in the Data Review Narrative to give the data user an
indication of any limitations on the use of the data. If sufficient information on the intended use
and required quality of the data is available, include an assessment of the data usability within the
given context. This may be used as part of the formal Data Quality Assessment (DQA).
6. If any discrepancies are found, the laboratory may be contacted by the EPA Regional CLP COR
to obtain additional information for resolution. If a discrepancy remains unresolved, use
professional judgment to determine if qualification of the data is warranted.
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April 2016 44
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High Resolution Data Review CDD/CDF
CDD/CDF Tables
The following tables are referenced in the preceding documentation for the CDD/CDF data review.
The table information is also available in SOW HRSM01.2, but the table titles may not be the same as
they are in this document.
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High Resolution Data Review
CDD/CDF
Table 10. Descriptors, Exact m/z Ratios, m/z Types, and m/z Formulas of the CDDs/CDFs
Descriptor
1
2
3
4
Exact m/z1
292.9825
303.9016
305.8987
315.9419
317.9389
319.8965
321.8936
327.8847
330.9792
331.9368
333.9339
375.8364
339.8597
341.8567
351.9000
353.8970
354.9792
355.8546
357.8516
367.8949
369.8919
409.7974
373.8208
375.8178
383.8639
385.8610
389.8157
391.8127
392.9760
401.8559
403.8529
430.9729
445.7555
407.7818
409.7789
417.8253
419.8220
423.7766
425.7737
430.9729
m/z Type
Lock
M
M+2
M
M+2
M
M+2
M
QC
M
M+2
M+2
M+2
M+4
M+2
M+4
Lock
M+2
M+4
M+2
M+4
M+2
M+2
M+4
M
M+2
M+2
M+4
Lock
M+2
M+4
QC
M+4
M+2
M+4
M
M+2
M+2
M+4
Lock
m/z Formula
C7Fn
Cu H4 35C14 O
C12 H4 35C13 37C1 O
13C12 H4 35C14 O
13C12 H4 35C13 37C1 O
C12 H4 35C14 O2
C12 H4 35C13 37C1 O2
Cl2 FLj C14 O2
C7F13
13C12 H4 35C14 O2
13C12 H4 35C13 37C1 O2
€12 H4 35C15 37C1 O
C12 H3 35C14 37C1 O
C12 H3 35C13 37C12 O
13C12 H3 35C14 37C1 O
13C12 H3 35C13 37C12 O
C9F13
€12 H3 35C14 37C1 O2
Cu H3 35C13 37C12 O2
13C12 H3 35C14 37C1 O2
13C12 H3 35C13 37C12 O2
€12 H3 35C16 37C1 O
€12 H2 35C15 37C1 O
Ci2 H2 35C14 37C12 O
13C12 H2 35C16 O
13C12 H2 35C15 37C1 O
C12 H2 35C15 37C1 O2
Ci2 H2 35C14 37C12 O2
C9F15
13C12 H2 35C15 37C1 O2
13C12 H2 35C14 37C12 O2
C9F17
€12 H2 35C16 37C12 O
C12 H 35C16 37C1 O
C12 H 35C15 37C12 O
13C12 H 35C17 O
13C12 H 35C16 37C1 O
C12 H 35C16 37C1 O2
€12 H 35C15 37C12 O2
C9F17
Substance2
PFK
TCDF
TCDF
TCDF3
TCDF3
TCDD
TCDD
TCDD4
PFK
TCDD3
TCDD3
HxCDPE
PeCDF
PeCDF
PeCDF
PeCDF3
PFK
PeCDD
PeCDD
PeCDD3
PeCDD3
HpCDPE
HxCDF
HxCDF
HxCDF3
HxCDF3
HxCDD
HxCDD
PFK
HxCDD3
HxCDD3
PFK
OCDPE
HpCDF
HpCDF
HpCDF3
HpCDF3
HpCDD
HpCDD
PFK
April 2016
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High Resolution Data Review
CDD/CDF
Table 10. Descriptors, Exact m/z Ratios, m/z Types, and m/z Formulas of the CDDs/CDFs (Con't)
Descriptor
5
Exact m/z1
435.8169
437.8140
479.7165
441.7428
442.9728
443.7399
457.7377
459.7348
469.7779
471.7750
513.6775
m/z Type
M+2
M+4
M+4
M+2
Lock
M+4
M+2
M+4
M+2
M+4
M+4
m/z Formula
13C12 H 35C16 37C1 O2
13C12 H 35C15 37C12 O2
€12 H 35C17 37C12 O
C12 35C17 37C1 O
CIQ FIV
Ciz 35C16 37C12 O
C12 35C17 37C1 O2
C12 35C16 37C12 O2
13C12 35C17 37C1 O2
13C12 35C16 37C12 O2
C12 35C18 37C12 O
Substance2
HpCDD3
HpCDD3
NCDPE
OCDF
PFK
OCDF
OCDD
OCDD
OCDD3
OCDD3
DCDPE
1 Nuclidic masses used:
H= 1.007825 C= 12.00000
0=15.994915 35C1 = 34.968853
2 Definition:
13C= 13.003355
37C1 = 36.965903
F= 18.9984
TCDD = Tetrachlorodibenzo-p-dioxin
TCDF = Tetrachlorodibenzofuran
PeCDD = Pentachlorodibenzo-/>-dioxin
PeCDF = Pentachlorodibenzofuran
HxCDD = Hexachlorodibenzo-p-dioxin
HxCDF = Hexachlorodibenzofuran
HpCDD = Heptachlorodibenzo-/>-dioxin
HpCDF = Heptachlorodibenzofuran
OCDD = Octachlorodibenzo-/>-dioxin
OCDF = Octachlorodibenzofuran
HxCDPE = Hexachlorodiphenyl ether
HpCDPE = Heptachlorodiphenyl ether
OCDPE = Octachlorodiphenyl ether
NCDPE = Nonachlorodiphenyl ether
DCDPE = Decachlorodiphenyl ether
PFK = Perfluorokerosene
3 Labeled compound.
4 There is only one m/z for 37Cl4-2,3,7,8,-TCDD (Cleanup Standard).
April 2016
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High Resolution Data Review
CDD/CDF
Table 11. Gas Chromatography RT WDM and ISC Standard for CDD/CDF Analysis
Analyte Name
TCDF
TCDD
PeCDF
PeCDD
HxCDF
HxCDD
HpCDF
HpCDD
First Eluted
1,3,6,8-
1,3,6,8-
1,3,4,6,8-
1,2,4,7,9-
1,2,3,4,6,8-
1,2,4,6,7,9-
1,2,3,4,6,7,8-
1,2,3,4,6,7,9-
Last Eluted
1,2,8,9-
1,2,8,9-
1,2,3,8,9-
1,2,3,8,9-
1,2,3,4,8,9-
1,2,3,4,6,7-
1,2,3,4,7,8,9-
1,2,3,4,6,7,8-
DB-5 Column TCDD Isomer Specificity Check Standard
1,2,3,7 and 1,2,3,8-TCDD
2,3,7,8-TCDD
1,2,3,9-TCDD
DB-225 Column TCDF Isomer Specificity Check Standard
2,3,4,7-TCDF
2,3,7,8-TCDF
1,2,3,9-TCDF
Sp-2331 Column TCDD Isomer Specificity Check Standard
2,3,7,8-TCDD
1,4,7,8-TCDD
1,2,3,7-TCDD
1,2,3,8-TCDD
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High Resolution Data Review
CDD/CDF
Table 12. RRTs and Quantitation References of the Native and Labeled CDDs/CDFs
Analyte Name
Retention Time and
Quantitation Reference
Relative Retention Time
Limits
Compounds using 13Ci2-l,2,3,4-TCDD as the internal standard
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
13C12-2,3,7,8-TCDF
13C12-2,3,7,8-TCDD
37Cl4-2,3,7,8-TCDD
13C12-l,2,3,7,8-PeCDF
13C12-2,3,4,7,8-PeCDF
13C12-l,2,3,7,8-PeCDD
13C12-2,3,7,8-TCDF
13C12-2,3,7,8-TCDD
13C12-l,2,3,7,8-PeCDF
13C12-2,3,4,7,8-PeCDF
13C12-l,2,3,7,8-PeCDD
13C12-1,2,3,4-TCDD
13C12-1,2,3,4-TCDD
13C12-1,2,3,4-TCDD
13C12-1,2,3,4-TCDD
13C12-1,2,3,4-TCDD
13C12-1,2,3,4-TCDD
0.999-1.003
0.999-1.002
0.999-1.002
0.999-1.002
0.999-1.002
0.923-1.103
0.976-1.043
0.989-1.052
1.000-1.425
1.011-1.526
1.000-1.567
Compounds using 13Ci2-l,2,3,7,8,9-HxCDD as the internal standard
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD1
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
13C12-l,2,3,4,7,8-HxCDF
13C12-l,2,3,6,7,8-HxCDF
13C12-l,2,3,7,8,9-HxCDF
13C12-2,3,4,6,7,8-HxCDF
13C12-l,2,3,4,7,8-HxCDD
13C12-l,2,3,6,7,8-HxCDD
13C12-l,2,3,4,6,7,8-HpCDF
13C12-l,2,3,4,7,8,9-HpCDF
13C12-l,2,3,4,6,7,8-HpCDD
13C12-OCDD
13C12-l,2,3,4,7,8-HxCDF
13C12-l,2,3,6,7,8-HxCDF
13C12-l,2,3,7,8,9-HxCDF
13C12-2,3,4,6,7,8-HxCDF
13C12-l,2,3,4,7,8-HxCDD
13C12-l,2,3,6,7,8-HxCDD
13C12-l,2,3,4,6,7,8-HpCDF
13C12-l,2,3,4,7,8,9-HpCDF
13C12-l,2,3,4,6,7,8-HpCDD
13C12-OCDD
13C12-OCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
13C12-l,2,3,7,8,9-HxCDD
0.999-1.001
0.997-1.005
0.999-1.001
0.999-1.001
0.999-1.001
0.998-1.004
1.000-1.019
0.999-1.001
0.999-1.001
0.999-1.001
0.999-1.008
0.999-1.001
0.944-0.970
0.949-0.975
0.977-1.047
0.959-1.021
0.977-1.000
0.981-1.003
1.043-1.085
1.057-1.151
1.086-1.110
1.032-1.311
1 The retention time reference for 1,2,3,7,8,9-HxCDD
quantified using the averaged responses of 13Ci2-l,2
is 13C12-l,2,3,6,7,8-HxCDD
,3,4,7,8-HxCDD
and 13C12-1
1,2,3,7,8,9-HxCDD is
2,3,6,7,8-HxCDD.
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CDD/CDF
Table 13. Theoretical lARs and QC Limits for CDD/CDF Analysis
Number of
Chlorine Atoms
42
5
6
63
7
74
8
m/z Forming Ratio
M/(M+2)
(M+2)/(M+4)
(M+2)/(M+4)
M/(M+2)
(M+2)/(M+4)
M/(M+2)
(M+2)/(M+4)
Theoretical Ratio
0.77
1.55
1.24
0.51
1.05
0.44
0.89
QC Limits1
Lower
0.65
1.32
1.05
0.43
0.88
0.37
0.76
Upper
0.89
1.78
1.43
0.59
1.20
0.51
1.02
1 QC limits represent ±15% windows around the theoretical ion abundance ratios.
2 Does not apply to 37Cl4-2,3,7,8-TCDD (Cleanup Standard).
Used for 13C12-HxCDF only.
Used for 1JC12-HpCDF only.
April 2016
50
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High Resolution Data Review
CDD/CDF
Table 14. Concentration of CDDs/CDFs in Initial Calibration and CCV Solutions
Analyte Name
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
13C12-2,3,7,8-TCDD
13C12-2,3,7,8-TCDF
13C12-l,2,3,7,8-PeCDD
13C12-l,2,3,7,8-PeCDF
13C12-2,3,4,7,8-PeCDF
13C12-l,2,3,4,7,8-HxCDD
13C12-l,2,3,6,7,8-HxCDD
13C12-l,2,3,4,7,8-HxCDF
13C12-l,2,3,6,7,8-HxCDF
13C12-l,2,3,7,8,9-HxCDF
13C12-2,3,4,6,7,8-HxCDF
13C12-l,2,3,4,6,7,8-HpCDD
13C12-l,2,3,4,6,7,8-HpCDF
13C12-l,2,3,4,7,8,9-HpCDF
13C12-OCDD
Solution Concentration (ng/mL)
CS1
0.5
0.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5.0
5.0
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
CS2
2
2
10
10
10
10
10
10
10
10
10
10
10
10
10
20
20
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
CS31
10
10
50
50
50
50
50
50
50
50
50
50
50
50
50
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
CS4
40
40
200
200
200
200
200
200
200
200
200
200
200
200
200
400
400
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
CSS
200
200
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
2000
2000
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
Cleanup Standard
37Cl4-2,3,7,8-TCDD
0.5
2
10
40
200
Internal Standards
13C12-1,2,3,4-TCDD
13C12-l,2,3,7,8,9-HxCDD
100
100
100
100
100
100
100
100
100
100
CCV solution.
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High Resolution Data Review
CDD/CDF
Table 15. QC Limits for CDD/CDF in LCS/LCSD and Labeled Compounds in Samples
Analyte Name
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
Test Cone
(ng/mL)
10
10
50
50
50
50
50
50
50
50
50
50
50
50
50
100
100
LCS/LCSD
%Recovery
67-158
75-158
70-142
80-134
68-160
70-164
76-134
64-162
72-134
84-130
78-130
70-156
70-140
82-132
78-138
78-144
63-170
Labeled Compound
%Recovery in Sample
N/A
Labeled Compound
13C12-2,3,7,8-TCDD
13C12-2,3,7,8-TCDF
13C12-l,2,3,7,8-PeCDD
13C12-l,2,3,7,8-PeCDF
13C12-2,3,4,7,8-PeCDF
13C12-l,2,3,4,7,8-HxCDD
13C12-l,2,3,6,7,8,-HxCDD
13C12-l,2,3,4,7,8-HxCDF
13C12-l,2,3,6,7,8-HxCDF
13C12-l,2,3,7,8,9-HxCDF
13C12-2,3,4,6,7,8,-HxCDF
13C12-l,2,3,4,6,7,8-HpCDD
13C12-l,2,3,4,6,7,8-HpCDF
13C12-l,2,3,4,7,8,9-HpCDF
13C12-OCDD
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
20-175
22-152
21-227
21-192
13-328
21-193
25-163
19-202
21-159
17-205
22-176
26-166
21-158
20-186
13-198
25-164
24-169
25-181
24-185
21-178
32-141
28-130
26-152
26-123
29-147
28-136
23-140
28-143
26-138
17-157
Cleanup Standard
37Cl4-2,3,7,8-TCDD
10
31-191
35-197
April 2016
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High Resolution Data Review
CDD/CDF
Table 16. CDD/CDF Toxic Equivalency Factors (TEFs)
Analyte Name
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDD
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDD
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
Source
Mammal
1
0.1
1
0.03
0.3
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.01
0.01
0.01
0.0003
0.0003
WHO* 2005
TEF
Fish
1
0.05
1
0.05
0.5
0.5
0.1
0.01
0.1
0.01
0.1
0.1
0.001
0.01
0.01
0.0001
0.0001
WHO
Bird
1
1
1
0.1
1
0.05
0.1
0.01
0.1
0.1
0.1
0.1
0.001
0.01
0.01
0.0001
0.0001
* 1998
*World Health Organization
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High Resolution Data Review CDD/CDF
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April 2016 54
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High Resolution Data Review CBC
CHLORINATED BIPHENYL CONGENER (CBC)
DATA REVIEW
The high resolution CBC data requirements to be reviewed during validation are listed below:
I. Preservation and Holding Times 57
II. System Performance Checks 59
III. Initial Calibration 63
IV. Continuing Calibration Verification 66
V. Blanks 68
VI. Labeled Compounds 71
VII. Laboratory Control Sample/Laboratory Control Sample Duplicate 73
VIII. Target Analyte Identification 75
IX. Target Analyte Quantitation 78
X. Second Column Confirmation 80
XI. Estimated Detection Limit and Estimated Maximum Possible Concentration 81
XII. Toxic Equivalent Determination 82
XIII. Regional Quality Assurance and Quality Control 83
XIV. Overall Assessment of Data 85
CBC Tables 87
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High Resolution Data Review CBC
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April 2016 56
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High Resolution Data Review CBC
I. Preservation and Holding Times
A. Review Items
Form 1A-HR, Traffic Report/Chain of Custody (TR/COC) Record documentation, Form DC-1, raw
data, sample extraction sheets, and the Sample Delivery Group (SDG) Narrative checking for: pH,
shipping container temperature, holding time, and other sample conditions. (SOW HRSM01.2 -
Exhibit B, Section 3.4 and Exhibit D - CBC, Section 8.0)
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.
C. Criteria
1. The extraction technical holding time is determined from the date of sample collection to the date
of sample extraction for aqueous/water and non-aqueous [soil/sediment, sludge, tissue (non-
human), biosolids, ash, oil, filter] samples. The analysis technical holding time is determined
from the date of the start of the extraction to the date of sample analysis.
2. All aqueous/water and soil/sediment samples shall be stored at < 6°C, in the dark, from the time
of collection until extraction. If residual chlorine is present in aqueous/water samples, 80 mg of
sodium thiosulfate per liter of sample is to be added.
3. Tissue (non-human) samples shall be received at the laboratory at < 6°C and shall be stored, in
the dark, at the laboratory at < -10°C until extraction.
4. All samples shall be extracted and analyzed within the time period specified during scheduling.
However, once thawed, tissue (non-human) samples must be extracted within 24 hours.
5. The extraction technical holding time for all properly preserved samples is one year.
6. The analysis technical holding time for all properly stored sample extracts is one year.
D. Evaluation
1. Review the SDG Narrative and the TR/COC Record documentation to verify that the samples
were received intact and iced at < 6°C. Use special consideration for samples delivered directly
from the field to the laboratory. If there is an indication of problems with the samples, the sample
integrity may be compromised. If the samples were not iced, if there were any problems with the
samples upon receipt, or if discrepancies in the sample condition could affect the data, record the
issue in the Data Review Narrative.
2. Verify that the extraction dates and analysis dates for samples on Form 1A-HR and the raw data
are identical.
3. Establish technical holding times for sample extraction and analysis by comparing the sampling
dates on the TR/COC Record documentation with the dates of extraction and analysis on Form
1A-HR.
E. Action
1. If a residual chlorine test was performed and found to be negative, detects and non-detects should
not be qualified. If sodium thiosulfate preservative was not added to aqueous/water samples with
a chlorine residual, qualify detects as estimated (J) and non-detects as unusable (R).
2. If shipment and storage conditions were not met, use professional judgment to determine if the
sample data are affected. Detects and non-detects may be qualified as estimated (J) and (UJ),
respectively.
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High Resolution Data Review
CBC
3. If extraction technical holding times are exceeded for aqueous/water or soil/sediment samples,
qualify detects as estimated (J) and non-detects as estimated (UJ) or unusable (R). If extraction
technical holding times are exceeded for tissue (non-human) samples, use professional judgment
to qualify detects and non-detects.
4. There is limited information concerning holding times for oily samples. Use professional
judgment to determine if the sample data are affected. It is recommended that the aqueous/water
sample technical holding time criteria be applied to oily samples.
5. For sample extracts that are not properly stored, but analyzed within the 1-year analysis technical
holding time, qualify detects as estimated (J) and non-detects as estimated (UJ).
6. For sample extracts that are analyzed outside the 1-year analysis technical holding time, use
professional judgment to qualify detects as estimated low (J-) and non-detects as estimated (UJ)
or unusable (R).
7. When holding times are exceeded, note the effect on sample data in the Data Review Narrative,
and note it for United States Environmental Protection Agency Regional Contract Laboratory
Program (CLP) Contracting Officer's Representative (EPA Regional CLP COR) action.
Table 17. Technical Holding Times Actions for CBC Analysis
Criteria
Chlorine present in aqueous/water sample but
sodium thiosulfate not added
Aqueous/water and soil/sediment samples received
or stored at > 6°C
Tissue (non-human) samples received at > 6°C or
stored at > -10°C
Aqueous/water and soil/sediment samples properly
preserved but extracted outside 1-year technical
holding time
Tissue (non-human) samples properly preserved but
extracted outside 1-year technical holding time
Sample extract not properly stored but analyzed
within 1 -year technical holding time
Sample extract analyzed outside 1 -year technical
holding time
Action
Detect
J
Use professional
judgment
J
Use professional
judgment
J
J
Use professional
judgment
J
Use professional
judgment
J-
Non-detect
R
Use professional
judgment
UJ
Use professional
judgment
UJ
UJorR
Use professional
judgment
UJ
Use professional
judgment
UJorR
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High Resolution Data Review _ CBC
II. System Performance Checks
Prior to analyzing the calibration standards, blanks, samples, and Quality Control (QC) samples, the High
Resolution Gas Chromatograph (HRGC) and High Resolution Mass Spectrometer (HRMS) operating
conditions necessary to obtain optimum performance must be established. There are three fundamental
HRGC/HRMS system performance checks: Mass Calibration and Resolution, Mass Spectrometer (MS)
Selected Ion Monitoring (SIM) scan descriptor switching times, and Gas Chromatographic (GC)
resolution. Ion Abundance Ratio (IAR) and Signal-to-Noise (S/N) ratio (determined in the lowest initial
calibration standard) are pertinent in evaluating system performance.
1. Mass Calibration and Mass Spectrometer Resolution
A. Review Items
Peak profile raw data of the MS resolution. (SOW HRSMO 1 .2 - Exhibit D - CBC, Sections 9. 1 .2,
9.2, and 9.3)
B. Objective
The objective is to ensure adequate mass resolution and to document this level of performance prior
to and after analyzing any sequence of standards or samples.
C. Criteria
Laboratories are required to demonstrate MS resolving power at > 10,000 and provide evidence of the
MS performance at the beginning and end of each 12-hour period during which samples or standards
are analyzed. Documentation of the instrument resolving power shall be completed by recording the
peak profiles of the reference peaks chosen for each descriptor using perfluorokerosene (PFK). While
generating the peak profiles, the detector zero shall be adjusted to allow presentation of the profile
shoulders on-scale so the resolution can be manually determined. The format of the peak profiles
shall show a horizontal axis calibrated in atomic mass units (u) or ppm, and a vertical scale in percent
maximum signal. The result of the peak width measurement [performed at 5% of the maximum,
which corresponds to the 10 Percent Valley (%Valley) definition] must appear on the profile, and
must not exceed 100 ppm [i.e., 0.038 u for a peak at mass-to-charge ratio (m/z) 380.9760]. This
documentation shall be provided for each check of the static resolving power of each instrument used,
and shall contain identifying information, including instrument ID, date, and time. The deviation
between the exact mass measured m/z (m/zmon) and the target m/z (m/Zth) shall be calculated using the
equation below and must be < 5 ppm (i.e., the value found for m/z 293.9165 must be accurate to
±0.0015 u).
Resppm = r- - —, - r > 10,000
|m/zth- m/zmon|
D. Evaluation
Examine the raw data and verify that the MS has been tuned to a resolving power of > 10,000.
E. Action
In the event that MS resolution is < 10,000, the risk of false positive results may exist. If a
demonstration of the required mass resolution is not provided, carefully evaluate other factors to
determine whether or not there is sufficient evidence of adequate resolution to preclude interference
from other ions with similar m/z. This may include, but is not limited to: other tunes in the data
package for the same instrument; the quality and similarity of peak shapes between the calibrations
and the samples; and baseline noise in calibrations, blanks, and calibration performance. Consider
these factors when determining the appropriate course of action and use professional judgment to
qualify defects as unusable (R).
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High Resolution Data Review CBC
2. Window Defining Mixture
A. Review Items
Form 5A-HR. (SOW HRSM01.2 - Exhibit B, Section 3.4.10 and Exhibit D - CBC, Sections 9.2 and
9.4)
B. Objective
The objective is to establish the appropriate switching times for the SIM descriptors by analyzing a
Window Defining Mixture (WDM) solution containing the first and last eluting isomers in each
homologous series and to document the accuracy of the switching times prior to and after analyzing
any sequence of standards or samples.
C. Criteria
1. The WDM solution must contain an appropriate amount of Labeled Toxic/Level of Chlorination
(LOC)AVindow-Defining congeners. Mixtures are available for various columns. Therefore, the
mixture for the SPB-Octyl (or equivalent) column may not be appropriate for the DB-1 or other
columns. In addition, the lowest initial calibration standard (CS1) or mid-point calibration
standard (CSS) may be used for this analysis. To evaluate the MS SIM scan descriptor switching
times, the WDM must be analyzed after the PFK tune and before any calibration standards on
each instrument and GC column used for analysis. The WDM shall also be analyzed each time a
new initial calibration is performed, regardless of reason; once at the beginning and once at the
end of each 12-hour period during which standards or samples are analyzed; prior to the
Continuing Calibration Verification (CCV); and whenever adjustments or instrument
maintenance activities that may affect Retention Times (RTs) are performed.
2. The ions in each of the six recommended descriptors are arranged for convenient RT switching
between the descriptors, while including labeled standards for each LOC in the descriptor. See
Table 25 (in the CBC Tables section in this document) for details.
3. The descriptor switching times are set as such that the isomers eluting from the GC during a
given RT window will also be those isomers for which the ions are monitored. Be aware that the
descriptors in the CBC analysis overlap levels of chlorination. The switching times are not to be
set as such when a change in descriptors occurs at or near the expected RT of any Chlorinated
Biphenyl (CB) congeners.
4. If the laboratory uses a GC column that has a different elution order than the columns specified in
the SOW, the laboratory must ensure that the first and last eluting congeners in each descriptor
window are represented in the WDM used to evaluate that column. The concentrations of any
additional congeners should be approximately the same as those in WDM solutions intended for
use with conventional CBC GC columns.
D. Evaluation
1. Verify that the WDM was analyzed at the required frequency and sequence.
2. Examine the WDM chromatograms to determine whether the switching times have been
optimized properly. Proper optimization is demonstrated by complete elution of the first and last
peaks in the window, and that no CB peaks are missing.
3. Note the RT of each first and last eluting isomer in each homologous series on Form 5 A-HR for
identification of switching times. Each positive CBC result must have an RT/Relative Retention
Time (RRT) within the limits in Table 27 (in the CBC Tables section in this document).
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High Resolution Data Review CBC
E. Action
1. If the WDM was not analyzed at the required frequency or sequence, or correct adjustments in
descriptor switching times are not evident, but the calibration standards met specifications for the
target analytes, detects and non-detects should not be qualified. Qualify Homologue Totals
detects as estimated (J) and non-detects as estimated (UJ) since one or more CBC target analytes
may not have been detected.
2. If the chromatography for the calibration standards indicates that target analytes may have been
missed due to a significant problem with descriptor switching times, qualify detects and non-
detects as unusable (R). The EPA Regional CLP COR should be contacted to decide if sample
reanalysis is necessary.
3. Chromatographic Resolution
A. Review Items
Form 5C-HR and raw data. (SOW HRSM01.2 - Exhibit B, Section 3.4.11 and Exhibit D - CBC,
Sections 9.2 and 9.4.5)
B. Objective
The objective is to evaluate the ability of the GC column to resolve the close ly-e luting congeners and
to document the resolution prior to and after analyzing any sequence of samples or standards.
C. Criteria
1. The Isomer Specificity Check (ISC) standard, a diluted combined 209-congener solution, shall be
analyzed after or simultaneously with the WDM, and before any initial calibration on each
instrument and HRGC column used for analysis. An ISC standard shall be analyzed at the
beginning and end of each 12-hour analytical sequence, or whenever adjustments or instrument
maintenance activities that may affect RTs are performed.
2. The resolution criteria must be evaluated using measurements made on the Selected Ion Current
Profiles (SICPs) for the appropriate ions for each isomer. Measurements are not to be performed
on Total Ion Current Profiles (TICPs).
3. For analyses on a SPB-Octyl column, the chromatographic peaks must be uniquely separated for
target analytes Polychlorinated Biphenyl (PCB)-34 from PCB-23 and PCB-187 from PCB-182;
peaks at the peak maximum for target analytes PCB-156 and PCB-157 must be co-eluted within
2 seconds. A %Valley < 40% of the shorter of the two peaks in the diluted combined
209-congener standard shall be achieved when calculated using the equation in the SOW.
4. If the laboratory uses a GC column that is not one of those specified in the SOW, the laboratory
must ensure that it meets all specifications and requirements listed in the SOW, and all alternate
column performance criteria established by the laboratory must be thoroughly documented in the
SDG Narrative.
D. Evaluation
1. Verify that the ISC standard was analyzed at the required frequency and sequence.
2. Verify that Form 5B-HR is included and examine the SICP raw data to verify that the %Valley is
< 40%.
3. Technical acceptance criteria must be met before any calibration standards, samples, QC samples,
and required blanks are analyzed. However, if the ISC standard was not analyzed, but a
compliant calibration standard was analyzed, and chromatographic performance in the samples
does not indicate interference with any target analyte peaks, the data may still be usable. In this
case, all SICPs must be carefully evaluated in order to verify that analyte and/or labeled analog
peaks are clearly within the expected RT window, and that no persistent interference is evident.
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High Resolution Data Review
CBC
E. Action
1. If the ISC standard was not analyzed at the required frequency and sequence, qualify detects as
estimated (J). Non-detects are not qualified.
2. If the GC resolution on the SPB-Octyl (or equivalent) column does not meet the %Valley criteria
for PCB-34 and PCB-23, and for PCB-187 and PCB-182, use professional judgment to evaluate
the severity of the non-compliant chromatographic resolution. Qualification may range from
qualifying detects as estimated (J) and not qualifying non-detects, to qualifying detects and non-
detects as unusable (R), if the resolution is very poor. Contact the EPA Regional CLP COR to
arrange for sample reanalysis.
Table 18. System Performance Checks Actions for CBC Analysis
Criteria
MS resolution > 10,000 not demonstrated
WDM analysis not performed at required frequency or
sequence, or WDM failed and adjustments were not
made, but calibration standard performance is acceptable
WDM failed and adjustments were not made, and
calibration standards indicate a problem in detecting the
analytes
ISC standard analysis not performed at required
frequency or sequence, or ISC standard failed (GC
Resolution %Valley > 40%) and adjustments were not
made, but calibration standards performance is
acceptable
ISC standard failed and adjustments were not made, and
calibration standards or samples indicate a problem in
resolving the specified congeners pairs
Action1
Detect
Use professional
judgment
R
J
(Homologue Totals
Only)
R
Use professional
judgment
J
R
Non-detect
No qualification
UJ
(Homologue Totals
Only)
R
No qualification
R
1 In any case where data would by rejected by these rules, contact the EPA Regional CLP COR to request
that the laboratory reanalyze, or re-extract and reanalyze, the affected sample(s).
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High Resolution Data Review CBC
III. Initial Calibration
A. Review Items
Form 6A-HR, Form 6B-HR, Form 6C-HR, and raw data for all initial calibration standards. (SOW
HRSM01.2 - Exhibit B, Section 3.4.12 and Exhibit D - CBC, Section 9.5)
B. Objective
The objective is to establish a linear calibration range capable of producing acceptable qualitative and
quantitative data for the CBCs.
C. Criteria
1. Once the PFK, WDM, and ISC standards have been analyzed at the specified frequency and
sequence, and after the descriptor switching times have all been verified, five initial calibration
(ICAL) standards containing all required target analytes and labeled compounds at the specified
concentrations (Table 29 in the CBC Tables section in this document) must be analyzed prior to
any sample analysis. For target analytes other than the World Health Organization (WHO)
Toxic/LOC Congener target analytes, initial calibration is established with a single point diluted
combined 209-congener standard. All initial calibration standards, including the five-point WHO
Toxic/LOC Congener standards and the single point diluted combined 209-congener standard,
must be analyzed at the concentrations described in SOW HRSMO1.2.
2. The Mean Relative Responses (RRs) of the WHO Toxic/LOC Congener target analytes, Mean
Relative Response Factors (RRFs) for the labeled compounds, and Percent Relative Standard
Deviations (%RSDs) are determined from the five-point initial calibration.
3. Initial calibration must be performed at the specified frequency and sequence whenever:
• The laboratory takes any corrective action that may change or affect the initial calibration
criteria.
• The CCV acceptance criteria cannot be met even after corrective action has been taken (see
Section IV- Continuing Calibration Verification in this document).
4. To achieve the acceptable GC resolutions, SPB-Octyl or equivalent columns must be used for
analysis.
5. The IAR for each target analyte and labeled compound in the ICAL standards must be within the
QC limits listed in Table 28 (in the CBC Tables section in this document). The lower and upper
limits of the lARs represent a ±15% window around the theoretical abundance ratio for each pair
of selected ions (see Table 25 for m/z types and Table 28 for m/z ratios in the CBC Tables section
in this document).
6. The %Valley for specific analytes PCB-34 and PCB-23, and for PCB-187 and PCB-182 must be
< 40% in the CS209 standard.
7. The RTs of each target analyte in the ICAL standards must fall within the appropriate RT
windows established by the WDM, CS1, or combined 209-congener standard analysis.
8. The S/N must be > 10 for all analytes, including labeled compounds and internal standards, in the
ICAL standards.
9. The %RSD for the Relative Response (RR) must be < 20% and the %RSD for the Relative
Response Factor (RRF) must be < 35%.
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D. Evaluation
1. Verify that the initial calibration was performed at the specified frequency and sequence. Verify
that all target analytes and labeled compounds are present at the correct concentrations in all
ICAL standards (Table 29 in the CBC Tables section in this document).
2. Verify that the IAR on Form 6B-HR and Form 6C-HR for each target analyte and labeled
compound in each calibration standard is within ±15% of the theoretical IAR values (Table 28 in
the CBC Tables section in this document).
3. Verify that the %Valley is < 40% in the CS209 standard.
4. Verify that the RT on Form 6A-HR for each target analyte and internal standard is within the
specified RT windows, if equivalent columns to those specified in the SOW are used. If this
cannot be verified in the documentation, the SICPs for each descriptor should be examined. All
analytes must be present in the proper descriptor.
5. Verify that RTs are consistent between the calibration standards, and between the calibration
standards and any subsequent samples.
• If an alternate column has been used, the laboratory should have included sufficient
information in the SDG Narrative to evaluate column performance, ideally a table of
descriptors with the first and last eluting congeners (similar to Table 26 in the CBC Tables
section in this document), as well as information on the optimum resolution of closely eluting
congeners, and a table of relative retention times, similar to Table 27 (in the CBC Tables
section in this document).
• Be aware that slight changes in the GC temperature program may cause the actual RRTs to be
outside the range in Table 27 (in the CBC Tables section in this document), but that the RRT
limits in Table 27 should still be met.
6. Verify that the S/N ratio is > 10 in all SICPs.
7. Verify on Form 6A-HR that the %RSD of the RR for each target analyte is < 20% and that the
%RSD of the RRF for each labeled compound is < 35%.
E. Action
1. If no initial calibration was performed, the data should not be considered definitive; qualify
detects and non-detects as unusable (R). If the specified calibration concentration levels were not
used, it may be necessary to modify the linear range for reporting (with approval of the data user).
If an otherwise compliant initial calibration was performed, but not at the specified frequency,
qualify detects as estimated (J) and non-detects as estimated (UJ).
2. Non-compliant IAR for any analyte is cause for concern. It may indicate that the MS was not
tuned correctly, that the ion source was dirty, or that other electronic problems existed. If there
was a systemic problem resulting in failed ion ratios in the calibration, qualify detects and non-
detects in the associated samples as unusable (R).
3. If the %Valley is > 40% in the CS209 standard, qualify detects as estimated (J) and non-detects
as estimated (UJ). The data user may request a reanalysis for all samples following a failed
resolution to ensure the qualitative and quantitative results.
4. If the RTs are outside the specified windows, qualify detects and non-detects as unusable (R).
Contact the EPA Regional CLP COR to discuss the reanalysis of the initial calibration and all
associated samples.
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5. If the RRTs are outside the specified windows, qualify detects and non-detects as unusable (R).
Contact the EPA Regional CLP COR to discuss the reanalysis of the initial calibration and all
associated samples. If the RTs do not meet the criteria in sample-specific, potentially matrix-
caused cases, the RRTs of the analytes and their respective labeled compound should still be
valid. In this case, identification can still be made although quantitative interferences may be
present.
6. Problems with the S/N ratio not being met usually occur in the CS1 standard. Use professional
judgment to increase the reporting limit to the lowest calibration standard which meets criteria
(CS2 standard for example), depending on data requirements. Qualify detects at concentration
levels below the CS2 standard as estimated (J).
7. If the S/N ratio is < 10 due to a more systematic lack of sensitivity, qualify detects as estimated
(J) and non-detects as unusable (R).
8. If the %RSD is > 20% for the RR or > 35% for the RRF, qualify detects as estimated (J) and non-
detects as estimated (UJ).
9. In the event that significant QC issues are evident with the initial calibration, which may show up
as poor compliance with IAR, RF, RRF, %RSD, or S/N requirements, the CS1 or the CSS
standard value may be discarded from the initial calibration in an effort to salvage a usable
calibration. If this is done, calculate new response factors and %RSDs for the remaining
calibration levels. If discarding either of these points brings the calibration within the specified
criteria, qualify either the low-end or high-end results, based on the newly defined linear range. It
may be necessary to request reanalysis if either of these scenarios affects a majority of the data, or
if project-specific Data Quality Objectives (DQOs) are negatively impacted. Relying on
professional judgment, a more in-depth review may be performed to minimize the qualification of
data. To illustrate this approach, consider the following example:
• If the IAR is not within the limits for an analyte in the CS 1 standard (Table 28 in the CBC
Tables section in this document), qualify the low-end results for that analyte (below the CS2
standard concentration from Table 29 in the CBC Tables section in this document) as
unusable (R), or qualify as non-detect (U) and report at the level of the next lowest standard
(in this example, the CS2 standard).
The logic for allowing this flexibility is that system baseline noise near the lower limit of
detection may cause calibration peaks to fail even in an otherwise adequately performing system.
However, if the IAR is not within the limits or other quality problems persist for an analyte in
standards CSS - CSS, qualify detects and non-detects as unusable (R).
Table 19. Initial Calibration (ICAL) Actions for CBC Analysis
Criteria
Initial calibration not performed
Initial calibration not performed at required frequency
(but other factors are acceptable)
IAR not within ±15% window
%Valley > 40% in CS209 standard
RT not within specified windows
RRT not within specified windows
S/N ratio < 10 in the ICAL standard
RR %RSD > 20%
RRF %RSD > 35%
Action
Detect
R
J
R
J
R
J
J
Non-detect
R
UJ
R
UJ
R
R
UJ
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IV. Continuing Calibration Verification
A. Review Items
Form 7A-HR, Form 7B-HR, and raw data for the CCV diluted combined 209-congener standard.
(SOW HRSM01.2 - Exhibit B, Section 3.4.13 and Exhibit D - CBC, Section 9.6)
B. Objective
The objective is to ensure that the instrument continues to meet the sensitivity and linearity criteria to
produce acceptable qualitative and quantitative data throughout each analytical sequence.
C. Criteria
The laboratory shall proceed with sample analysis only when acceptable CCV analyses have been
performed at the specified frequency and sequence. CS3 CCV standard analyses shall be associated
with sample analyses for the WHO Toxic Congeners and diluted combined 209-congener standard
(CS209) analyses shall be associated with sample analyses of the 209 congener target analytes. The
opening CCV (CS3 or CS209 standard) shall be analyzed after the PFK tune. The closing CCV (CS3
or CS209 standard) must also bracket the end of each 12-hour period and can be used as opening
CCV for the next 12-hour period.
1. The IAR for each target analyte and labeled compound in the CCV standard must be within the
QC limits listed in Table 28 (in the CBC Tables section in this document).
2. The absolute RTs of the internal standards in the CCV standard on column SPB-Octyl (or
equivalent) must be within ±15 seconds of the RTs obtained during the initial calibration.
3. The RRTs of each target analyte and labeled compound in the CCV standard shall be within the
specified limits in Table 27 (in the CBC Tables section in this document), and in agreement with
the initial calibration.
4. The S/N ratio must be > 10 for all analytes, including the labeled compounds and the internal
standards, in the CCV standard.
5. RR and RRF Percent Difference (%D) for each WHO Toxic/LOC Congener target analyte and
labeled compound in the CCV standard must be calculated using the equations in the SOW.
6. The RR %D must be within ±25% for each WHO Toxic/LOC Congener target analyte and the
RRF %D must be within the QC limit in Table 30 (in the CBC Tables section in this document)
for each labeled compound.
D. Evaluation
1. Verify that the CCV standards (CS3 or CS209) were analyzed at the required frequency and
sequence, and that the calibration verification was associated to the correct initial calibration.
2. Verify that the IAR on Form 7A-HR for each target analyte and labeled compound in the CCV
standards (CS3 and CS209) are within the limits listed in Table 28 (in the CBC Tables section in
this document).
3. Verify that the absolute RTs on Form 7B-HR of the internal standards are within ±15 seconds of
the RTs in the initial calibration. If any absolute RTs are outside this range, this may mean that
some homologues have been missed.
4. Verify that the RRT on Form 7B-HR of each target analyte and labeled compound is within the
limits specified in Table 27 (in the CBC Tables section in this document).
5. Verify that the S/N ratio is > 10 in all analytes.
6. Verify that the RR %D on Form 7A-HR is within ±25% for each WHO Toxic/LOC Congener
target analyte and that the RRF %D is within the QC limit in Table 30 (in the CBC Tables section
in this document) for each labeled compound.
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E. Action
1. If the CCV standard was not analyzed at the specified frequency and sequence, use professional
judgment to qualify detects and non-detects. Contact the EPA Regional CLP COR to arrange for
sample reanalysis.
2. If the IAR of any target analyte and labeled compound in the CCV standard is not within the QC
limits listed in Table 28 (in the CBC Tables section in this document), qualify detects as
estimated (J) and non-detects as unusable (R).
3. If the absolute RTs of the internal standards are outside ±15 seconds of the RT windows
established during initial calibration, use professional judgment to qualify detects and non-detects
for target analytes. Additionally, qualify Homologue Totals detects as estimated (J) and non-
detects as estimated (UJ).
4. If the RRT of each target analyte and labeled compound is outside the specified limits in Table 27
(in the CBC Tables section in this document), use professional judgment to qualify detects and
non-detects.
5. If the S/N ratio is < 10, qualify detects as estimated (J) and non-detects as unusable (R).
6. If the RR %D of an applicable analyte or the RRF %D of a labeled compound in the CCV
standard is not within QC limits, qualify detects as estimated (J) and non-detects as estimated
(UJ).
Table 20. Continuing Calibration Verification (CCV) Actions for CBC Analysis
Criteria
CCV analysis not performed at the specified frequency
and sequence
lARs not within the specified QC limits
Internal standards absolute RT not within ±15 seconds of
the RT in the initial calibration
RRT not within the specified QC limits
S/N ratio < 10 in the CCV standard
RR %D not within the limits of ±25%
RRF %D not within QC limits in Table 30 (in the CBC
Tables section in this document)
Action
Detect
Use professional
judgment
J
Use professional
judgment for target
analytes
J
Homologue Totals
Use professional
judgment
J
J
Non-detect
Use professional
judgment
R
Use professional
judgment for target
analytes
UJ
Homologue Totals
Use professional
judgment
R
UJ
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V. Blanks
A. Review Items
Form 1A-HR, Form 4-HR, preparation logs, instrument logs, and raw data. (SOW HRSM01.2 -
Exhibit B, Sections 3.4.2 and 3.4.9; and Exhibit D - CBC, Section 12.1)
B. Objective
The objective is to determine the existence and magnitude of contamination resulting from laboratory
(or field) activities.
C. Criteria
1. There must be at least one method blank for each batch of samples extracted. The method blank
shall be prepared with a reference matrix of an equivalent initial weight or volume, by the same
procedures including extract cleanup, and analyzed on each instrument used for sample analysis.
2. When there is not enough volume of the method blank available, an instrument blank, which is a
volume of clean solvent spiked with the required labeled compounds at the same spiking
concentrations as the method blank, shall be analyzed as part of each 12-hour analytical sequence.
3. The method blanks and instrument blanks must meet the technical acceptance criteria for sample
analysis specified in the SOW.
4. The method blanks and instrument blanks must not contain any chemical interference or
electronic noise at or above one-half the Contract Required Quantitation Limit (CRQL) at the m/z
of the specified CBC target analyte ions.
5. The concentration of any WHO Toxic/LOC Congener target analyte detected in the method blank
must not exceed l/2x CRQL.
6. If a group of samples and the associated method or instrument blank are contaminated, the blank
and the associated samples containing analyte peaks that meet the qualitative identification
criteria must be reanalyzed.
NOTE: The laboratory must report results for all peaks with an S/N ratio > 3, even if they are
< CRQLs.
D. Evaluation
1. Verify that each sample extract is included on Form 4-HR for the associated method blank.
Verify that a method blank was analyzed on each instrument used to analyze the samples at the
specified frequency and sequence.
2. Verify that the required instrument blanks were analyzed at the specified frequency. In addition,
blanks analyzed in the same analytical sequence and any blind Performance Evaluation (PE)
sample blanks submitted with the samples may be considered. Evaluation of field and equipment
blanks should be performed according to EPA Regional policy and the criteria established in the
project Quality Assurance Project Plan (QAPP). Use the highest blank contamination result from
the same column to make decisions about data qualification.
3. Verify that the method blank(s) and instrument blank(s) do not have any WHO Toxic/LOC
Congener target analytes detected at concentrations > l/2x CRQLs. Data users who require data
reporting down to the Estimated Detection Limit (EDL) or Estimated Maximum Possible
Contamination (EMPC) should consider any target analytes that are present, in addition to any
chemical or electronic interference, for data qualification. This may require examination of the
raw data in addition to reported results.
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4. For data users who use the EDL or EMPC to calculate the Toxic Equivalent (TEQ) for non-
detects, the issue of blank contamination is of particular significance. It is advisable to evaluate
as many factors as possible that indicate system stability and the possible sources of interference
for their contribution to positive interference in those analytes with the highest Toxic Equivalency
Factors (TEFs).
NOTE: If the EDL is < the Method Detection Limit (MDL), then the analyte/matrix/instrument-
specific MDL value, adjusted for sample mass or volume as specified in Exhibit D -
CBC of the SOW, is reported for WHO Toxic Congeners.
5. The blank analyses may not include the same weights, volumes, or dilution factors as the
associated samples. In particular, aqueous blank results may be associated with soil/sediment
sample results. The total amount of contamination must be considered, and qualifiers applied
accordingly. It may be advantageous to use the raw data (i.e., instrument quantitation reports) to
compare soil sample data to aqueous blank data. Another approach would be to convert the
aqueous blank concentration to soil concentration by appropriate factors.
NOTE: Each of the "Evaluation" steps above should also be applied to the non-toxic Homologue
Totals.
E. Action
1. If a method blank or an instrument blank was not prepared and analyzed at the specified
frequency, use professional judgment to determine if the associated sample data should be
qualified. It may be necessary to obtain additional information from the laboratory. Record the
situation in the Data Review Narrative, and note it for EPA Regional CLP COR action.
2. For a method blank or an instrument blank reported with non-WHO Toxic Congeners results
< l/2x CRQLs, non-detects should not be qualified. Report non-WHO Toxic Congeners sample
results that are < CRQLs at the CRQLs and qualify as non-detect (U). Use professional judgment
to qualify non-WHO Toxic Congeners sample results > CRQLs or > Blank Results.
3. For a method blank or an instrument blank reported with results > l/2x CRQLs, non-detects
should not be qualified. Report sample results that are < CRQLs at the CRQLs and qualify as
non-detect (U). Report sample results > CRQLs but < Blank Results at the blank results and
qualify as non-detect (U.). Use professional judgment to qualify sample results > CRQLs and
> Blank Results.
4. If method blanks or instrument blanks are reported with WHO Toxic Congeners results > MDLs
or EDLs but < l/2x CRQLs, non-detects should not be qualified. Report WHO Toxic Congeners
sample results that are > MDLs or EDLs but < CRQLs at the CRQLs and qualify as non-detect
(U). Use professional judgment to qualify WHO Toxic Congeners sample results > CRQLs or
> Blank Results.
5. In the case where minimal contamination may exist, the reviewer may decide not to assign
qualification to sample results at considerably high concentrations. Alternatively, expanded
criteria may be applied when significant contamination occurs. For example, sample results that
are at 2x to 5x the results of the highest contaminated associated blank may be reported and
qualified as non-detect (U). However, sample results greater than these amounts may be reported
without qualification. Using either approach requires careful professional judgment when
evaluating the effects of contamination to avoid reporting false negatives.
6. There may be instances where little or no contamination was present in the associated blanks, but
qualification of the sample is deemed necessary. For example, an analyte in the method blank
was not reported as detected because it did not satisfy one of the identification criteria (either the
S/N ratio or the IAR), but in the associated sample it met the IAR requirement, and/or had a
slightly higher S/N ratio than specified, and was detected at < 5x the blank concentration. Use
professional judgment to qualify sample results in these situations and provide an explanation of
the rationale used for data qualifications in the Data Review Narrative.
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7. Blanks or samples analyzed after a PE sample, Laboratory Control Sample (LCS), LCS Duplicate
(LCSD), or CCV should be carefully examined to determine the occurrence of instrument or
syringe carry-over. Use professional judgment to determine whether sample or blank results are
attributable to carry-over.
8. When there is convincing evidence that contamination is isolated to a particular instrument,
matrix, or concentration level, use professional judgment to determine if qualification should only
be applied to certain associated samples (as opposed to all of the associated samples).
9. If gross contamination exists (i.e., saturated peaks), qualify detects and non-detects as unusable
(R). The laboratory should have taken corrective action prior to reporting the data. Therefore,
report the situation to the EPA Regional CLP COR for resolution.
Table 21. Blank Actions for CBC Analysis
Blank Type
Method, Instrument,
Field, Equipment
Blank Result
< l/2x CRQL
> l/2x CRQL
> MDL or EDL but
< l/2x CRQL
Gross contamination
Sample Result
Non-detect
CRQL or > Blank
Result
Non-detect
CRQL and < Blank
Result
> CRQL and > Blank
Result
Non-detect
> MDL or EDL but
CRQL or > Blank
Result
Non-detect and detect
Action
No qualification
Report at CRQL and
qualify as non-detect (U)
Use professional judgment
No qualification
Report at CRQL and
qualify as non-detect (U)
Report at Blank Result and
qualify as non-detect (U)
Use professional judgment
No qualification
Report at CRQL and
qualify as non-detect (U)
Use professional judgment
R
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VI. Labeled Compounds
A. Review Items
Form 2-HR and raw data. (SOW HRSM01.2 - Exhibit B, Section 3.4.6 and Exhibit D - CBC,
Section 11.2.2)
B. Objective
The objective is to measure the extraction efficiency of the analytical method by the recovery of the
labeled compounds. These compounds are added to all samples prior to sample preparation and are
used to quantify the target analytes.
C. Criteria
1. A labeled compound spiking solution, that includes labeled WHO Toxic/LOC Congener target
analytes and the cleanup standard, shall be added to each sample, blank, and LCS/LCSD at the
concentrations specified in the SOW.
2. The Percent Recovery (%R) of each labeled compound is calculated according to the SOW
equation.
3. Each labeled compound must meet the IAR requirement specified in Table 28 (in the CBC Tables
section in this document). If the IAR for any labeled compound is outside the limits, the sample
extract shall be reanalyzed. If the problem corrects itself, the second analysis shall be considered
compliant. If the IAR fails in the second analysis, the extract shall be processed through
additional cleanup steps, or the sample re-extracted and reprocessed through sufficient cleanup
steps to remove the possible interferences.
4. If any labeled compound S/N ratio is < 10 at its m/z(s), the samples must be re-extracted and
reanalyzed.
5. If any labeled compound %R is < 100%, there may have been loss of the labeled compound and
target analyte during the analytical process. If any labeled compound %R is > 100%, there may
have been errors in the quantitation of the labeled compound or problems with the cleanup of the
sample extracts.
6. If the original sample, prior to any dilutions, has more than one labeled compound or cleanup
standard with a %Rthat is not within the limits specified in Table 30 (in the CBC Tables section
in this document), it shall be re-extracted and reanalyzed due to an efficiency issue with the
extract cleanup procedure.
D. Evaluation
1. Verify that a Form 2-HR is included for each sample, blank, and LCS/LCSD. Verify that the
required labeled compounds, internal standards, and cleanup standard are present in each sample,
blank, and LCS/LCSD, and that the %Rs for each labeled compound and cleanup standard are
calculated correctly.
2. Verify that the IAR of each labeled compound is within the limits in Table 28 (in the CBC Tables
section in this document).
3. Verify that the S/N ratio of each labeled compound is > 10.
4. Verify that the labeled compounds and cleanup standard %R values fall within the required limits
prior to any dilutions.
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E. Action
1. If the required labeled compounds, internal standards, and cleanup standard are not present in
each sample, blank, and LCS/LCSD, or the %R for each labeled compound and cleanup standard
are not calculated correctly, use professional judgment to evaluate the effect on the data.
2. If a labeled compound (exclusive of the cleanup standard) fails the IAR criteria in a sample but
the lARs for that labeled compound in all of the associated calibration standards are acceptable,
qualify detects as estimated (J) and non-detects as estimated (UJ). If the IAR for that labeled
compound also fails in any of the associated calibration standards, qualify detects and estimated
(J) and non-detects as unusable (R).
3. If the %R for any labeled compound is < 10% and the S/N ratio > 10, qualify detects as estimated
low (J-) and non-detects as unusable (R).
4. If the %R for any labeled compound is < 10% and the S/N ratio < 10, qualify detects and non-
detects as unusable (R).
5. If the %R for any labeled compound is > 10% but < lower acceptance limit, qualify detects as
estimated low (J-) and non-detects as estimated (UJ).
6. If the %R for any labeled compound is > lower acceptance limit and < upper acceptance limit,
detects and non-detects should not be qualified.
7. If the %R for any labeled compound is > upper acceptance limit, qualify detects as estimated high
(J+) and non-detects as estimated (UJ).
8. If the %R of the cleanup standard is < lower acceptance limit, qualify detects as estimated (J) and
non-detects as estimated (UJ). If a wide range of cleanup standard %R is noted between samples,
use professional judgment to qualify sample results.
9. If the %Rs for the labeled compounds were not within the QC limits, and other identification
criteria and S/N ratio requirements were not met, the laboratory should have performed a
reanalysis. If the sample was not reanalyzed, contact the EPA Regional CLP COR to arrange for
reanalysis.
Table 22. Labeled Compound Recovery Actions for CBC Analysis
Criteria
IAR criteria not met in sample but met in all associated
calibration standards
IAR fails in sample and fails in any one of associated
calibration standards
%R < 10% and S/N ratio > 10
%R < 10% and S/N ratio < 10
%R > 10% but < Lower Acceptance Limit
Lower Acceptance Limit < %R < Upper Acceptance Limit
%R > Upper Acceptance Limit
%R of Cleanup Standard < Lower Acceptance Limit
Action
Detect
J
J
J-
R
J-
No qualification
J+
J
Non-detect
UJ
R
R
R
UJ
No qualification
UJ
UJ
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VII. Laboratory Control Sample/Laboratory Control Sample Duplicate
A. Review Items
Form 3A-HR, Form 3B-HR, preparation logs, instrument logs, and raw data. (SOW HRSM01.2 -
Exhibit B, Section 3.4.7 and Exhibit D - CBC, Section 12.2)
B. Objective
The objective is to evaluate the accuracy of the analytical method and laboratory performance.
C. Criteria
1. The laboratory shall prepare spiked LCS/LCSD samples for each matrix type that occurs in an
SDG by the same procedures used for the associated samples.
2. The LCS/LCSD shall meet the technical acceptance criteria for sample analysis.
3. The %R and Relative Percent Difference (RPD) of each spiked analyte shall be calculated
according to the SOW equations.
4. The %R of each spiked analyte must be within the QC limits in Table 30 (in the CBC Tables
section in this document).
5. The RPD of each spiked analyte must be within the QC limits specified in the SOW.
D. Evaluation
1. Verify that Form 3A-HR and Form 3B-HR are included for the LCD/LCSD. Verify that the LCS
and LCSD were prepared and analyzed at the required frequency.
2. Verify that the spiking solution was added to the LCS/LCSD, and that the target analytes were at
the correct concentrations.
3. Verify that calculations and transcriptions from raw data were performed correctly.
4. Verify that the %R of each spiked analyte is within the QC limits.
5. Verify that the RPD of each spiked analyte is within the QC limits.
E. Action
1. If the LCS and LCSD analyses were not performed, or not performed at the required frequency,
be sure to note this in the Data Review Narrative. Qualify detects as estimated (J) and use
professional judgment to qualify non-detects.
2. If the %R of any LCS/LCSD spiked analyte is < 10%, qualify detects as estimated low (J-) and
non-detects as unusable (R). Contact the EPA Regional CLP COR regarding samples associated
with a non-compliant LCS/LCSD to determine whether re-extraction and reanalysis are
necessary.
3. If the %R of any LCS/LCSD spiked analyte is > 10% but < lower acceptance limit, qualify
detects as estimated low (J-) and non-detects as estimated (UJ).
4. If the %R of any LCS/LCSD spiked analyte is > lower acceptance limit and < upper acceptance
limit, detects and non-detects should not be qualified.
5. If the %R of any LCS/LCSD spiked analyte is > upper acceptance limit, qualify detects as
estimated high (J+). Non-detects should not be qualified. Contact the EPA Regional CLP COR
regarding samples associated with a non-compliant LCS/LCSD to determine whether for
re-extraction and reanalysis are necessary.
6. If the RPD of any LCS/LCSD spiked analyte is > 30%, use professional judgment to qualify
detects and non-detects. This limit is only advisory.
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7. %R and/or RPD failure, in conjunction with other performance factors, may indicate that the
laboratory performance is unacceptable. In this case, use professional judgment to qualify detects
and non-detects.
Table 23. LCS/LCSD Recovery and RPD Actions for CBC Analysis
Criteria
LCS/LCSD not performed
LCS/LCSD not performed at required frequency
%R<10%
%R > 10% but < Lower Acceptance Limit
Lower Acceptance Limit < %R < Upper Acceptance Limit
%R > Upper Acceptance Limit
RPD > 30%
Action
Detect
J
J
J-
J-
No qualification
J+
Use professional
judgment
Non-detect
Use professional
judgment
Use professional
judgment
R
UJ
No qualification
No qualification
Use professional
judgment
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VIII. Target Analyte Identification
A. Review Items
Form 1A-HR, Form 2-HR, and raw data. (SOW HRSM01.2, Exhibit D - CBC, Section 11.1)
B. Objective
The objective is to provide unambiguous identification of the target analyte.
C. Criteria
For a GC peak to be identified as a CBC target analyte, it must meet all of the following criteria:
1. Retention Times (RTs) and Relative Retention Times (RRTs)
RTs are required for all chromatograms; scan numbers are optional. For positive identifications,
RTs for the two quantitation ions must maximize within 2 seconds. RTs must either be printed at
the apex of each peak on the chromatogram, or each peak must be unambiguously labeled with an
identifier that refers to the quantitation report. The chromatogram, the quantitation report, or a
combination of both must contain the RT of each peak and its area.
a. To make a positive identification of the target analyte, the RRT at the maximum peak height
of the analyte must be within the RRT window in Table 27 (in the CBC Tables section in this
document). The RRT must be calculated using the SOW equation.
b. To make a positive identification of the target analyte for which a labeled standard is not
available, the RT must be within the RT window established by the WDM for the
corresponding homologous series.
2. Peak Identification
For each target analyte, both specified quantitation ions listed in Table 25 (in the CBC Tables
section in this document), and the RT reported on Form 1A-HR, must be present in the raw data.
The ion current responses for the two quantitation ions must maximize simultaneously within the
same 2 seconds. This requirement also applies to non-WHO Toxic/LOC Congener target
analytes, the labeled compounds, and the internal standards. For the cleanup standard, only one
ion is monitored.
3. Ion Abundance Ratios (lARs)
The IAR for the target analytes, labeled compounds, and internal standards must be within the
limits specified in Table 28 (in the CBC Tables section in this document), or within ±15% of the
ratio in the most recent CCV calibration standard. The ratios shall be calculated using peak areas.
If interferences are present and lARs are not met using peak areas, but all other qualitative
identification criteria are met (RT, S/N, presence of both ions), the laboratory may use peak
heights to evaluate the ion ratio. The lARs for any target analytes and the associated labeled
compounds and/or internal standards may be determined using peak heights instead of areas.
4. Signal-to-Noise (S/N) Ratio
The integrated ion current for each target analyte ion listed in Table 25 (in the CBC Tables
section in this document) must be at least 3x the background noise and must not have saturated
the detector (applies to sample extracts only). The labeled compound and internal standard ions,
however, must be at least lOx the background noise and must also not have saturated the detector.
5. Non-WHO Toxic Congeners
Peaks are commonly found in each descriptor which pass all identification criteria for all target
analytes. The non-WHO Toxic target analytes do not have associated TEQs, but the total
quantity of CBCs in each homologous series is required by certain data users. All peaks
identified as non-toxic must meet the same qualitative criteria as the WHO Toxic Congeners.
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D. Evaluation
1. Evaluate chromatograms for each SICP to verify adequate system performance, proper scaling,
and adequate presentation. This evaluation allows a visual comparison of lock-mass trace and
any interference channel to the associated target ion channels for verifying positive
identifications.
2. Verify that the RRTs for the target analytes and labeled compounds are within the RRT windows
listed in Table 27 (in the CBC Tables section in this document).
3. Verify that the RTs for the target analytes are within the RT windows established by the WDM
for the corresponding homologues.
4. Verify that the lARs on Form 1A-HR and Form 2-HR are within the criteria listed in Table 28 (in
the CBC Tables section in this document), or within ±15% of the ratio in the most recent CCV
calibration standard.
5. Verify that the SICPs of the two quantitation ions for each target analyte maximize
simultaneously (within the same 2 seconds).
6. Verify that the S/N ratio is > 3 for each analyte and that the detector has not been saturated. If an
analyte is flagged with an asterisk (*), it means that the laboratory determined that the analyte
failed one or more qualitative identification criteria and an EMPC has been reported. Examine
the SICPs to determine whether there is some interference that could potentially cause the ion
ratio to fail.
7. Verify that no interferences exist on chromatograms at the expected retention time of each target
analyte.
NOTE: If interference is suspected by non-toxic mono- and di-ortho CBCs with toxics PCB-77,
-126, or -169, or if non-PCB interference from complex matrices is suspected with
PCB-81, -123, -126, or -169, check to see whether the optional clean-up procedure by
carbon column was performed. If necessary, contact the EPA Regional CLP COR to ask
the laboratory to go back and perform this step.
8. For non-WHO Toxic Congener identification, verify that both ions are present and maximize
within 2 seconds, and that they meet the S/N and IAR requirements. If detector saturation occurs
in a region of the SICP that is clearly due to an interferent, it is normally not interpreted as a
positive result and no further action is required by the laboratory. EMPC, EDL, or MDL should
not to be included in homologue calculation.
E. Action
1. If the RRT for any of the target analytes or labeled compounds falls outside the limits listed in
Table 27 (in the CBC Tables section in this document) and the RT falls outside the WDM
windows, examine the SICP to evaluate whether there is a peak that meets the RRT and RT
criteria. If there is no peak, consider the analyte as a non-detect with the reported EDL and
qualify as non-detect (U) for the WHO Toxic Congeners. For non-WHO Toxic Congeners, it is
considered to be non-detect at the CRQL.
2. If the IAR criteria are not met, examine the other information provided to be sure the other
criteria have been met. Check the calculation of EMPC results and/or ask the laboratory to
recalculate and re-report these results. The isotope dilution method provides the ability to
calculate ion ratios for the two ions monitored. If the IAR is outside the criteria, it does not
unequivocally prove that CBCs are not present; it indicates that either interference is present for
one of the ions, or that another compound may be present. Use professional judgment to decide
how to qualify EMPCs.
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3. If the ion current responses for the two quantitation ions for an analyte fail to maximize
simultaneously (within 2 seconds), examine the SICP to evaluate whether there are peaks or
shoulders that do meet the 2-second criterion. If there are no peaks or shoulders that meet the
2-second criterion, consider the analyte as a non-detect. In a case where a peak is present but did
not meet all identification criteria, the analyte should be considered as detected and the result
should be reported as EMPC as applicable.
4. If the S/N criteria are not met, consider the analyte as a non-detect with the reported EDL and
qualify as non-detect (U) for WHO Toxic Congeners. In cases where EDL < the adjusted MDL,
the adjusted MDL is reported and qualified as non-detect (U).
5. In the event that any CBCs are improperly identified, it may be necessary to re-evaluate the raw
data, or forward a request through the EPA Regional CLP COR for possible data resubmission
from the laboratory.
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IX. Target Analyte Quantitation
A. Review Items
Form 1A-HR, Form 1D-HR, Form 2-HR, and raw data. (SOW HRSM01.2 - Exhibit B, Sections
3.4.2, 3.4.3, and 3.4.5; and Exhibit D - CBC, Section 11.2)
B. Objective
The objective is to verify that the reported target analyte and Homologue Totals results are accurately
calculated.
C. Criteria
1. For an isotope dilution method, known amounts of labeled compounds and LOG compounds are
added to the samples to provide recovery corrections for the target analytes, and the
concentrations of the labeled compounds are used for the quantitation of the associated target
analytes.
2. All other target analytes that do not have associated labeled compounds are determined by the
internal standard method using the following five labeled congeners: PCB-9L, PCB-52L,
PCB-101L, PCB-138L, and PCB-194L.
3. The RR values from the initial calibration are used to determine the WHO Toxic/LOC Congener
target analyte concentrations using the equation for the specific matrix in the SOW.
4. The amount of moisture in solid samples should not have an impact on the calculation of
quantitative results since the laboratory is required to prepare an equivalent of 10 grams dry-
weight of solid or aqueous samples containing > 1% solids. The CRQLs of the samples should
be equal to those listed in SOW HRSM01.2 Exhibit C, Table 3 - Chlorinated Biphenyl
Congeners Target Analyte List and Contract Required Quantitation Limits, and Table 5 - World
Health Organization Toxic Congeners Target Analyte List and Contract Required Quantitation
Limits, provided that sample volume or dry weight, extract final volume, and injection volume
are the same as in Exhibit D - CBC of the SOW. However, if any one of these factors is
different, the CRQL used for data qualification should be adjusted, using the equations for the
specific matrix in the SOW.
D. Evaluation
1. Use the raw data to verify the correct calculation of all sample results reported by the laboratory.
Before verifying calculations for solid samples, check whether the reported weight is a dry weight
or a total weight (including any moisture). Only the dry weight should be used in these
calculations. Each type of calculation should be verified, including those from the confirmation
column, if utilized.
2. Compare RTs, internal standard recoveries, ion ratios, S/N determination, positive results,
dilution results, EDLs and/or MDLs, EMPCs, and CRQLs in the processed raw data reports and
applicable forms (i.e., Form 1A-HR and Form 2-HR) with the reported detects and non-detects in
the sample results.
3. Check the reported CRQLs for accuracy and compliance with SOW HRSMO1.2 Exhibit C, Table
3 - Chlorinated Biphenyl Congeners Target Analyte List and Contract Required Quantitation
Limits, and Table 5 - World Health Organization Toxic Congeners Target Analyte List and
Contract Required Quantitation Limits. Verify that the CRQLs are adjusted based on sample
volume or weight.
4. Verify whether the reported results are < adjusted CRQLs. Check that the laboratory has
followed the requirements in SOW HRSMO 1.2 Exhibit B - Reporting and Deliverables
Requirements for reporting results on Form 1A-HR and Form 1D-HR.
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5. The amount of moisture in a solid sample may have an impact on data representativeness. Due to
the extremely low solubility of CBCs in water, they should be contained in the solid phase.
However, be aware of any EPA Regional Standard Operating Procedures (SOPs) and/or concerns
of the data user and evaluate the data accordingly.
E. Action
1. If any discrepancies are found, contact the EPA Regional CLP COR, who may contact the
laboratory to obtain additional information that could resolve any issues. If a discrepancy
remains unresolved, use professional judgment to decide which value is the most accurate and to
determine whether qualification of the data is required. Record the qualification applied to the
data and the reasons for the qualification in the Data Review Narrative.
2. Qualify WHO Toxic Congener results that are > the EDLs or adjusted MDLs and < the adjusted
CRQLs as estimated (J).
3. Qualify non-WHO Toxic Congener results that are < the adjusted CRQLs as estimated (J).
4. Qualify Homologue Totals detects as estimated (J) and non-detects as estimated (UJ).
5. If numerous or significant failures occurred with the quantitations of the target analytes,
Homologue Totals, CRQLs, or TEQs, notify the EPA Regional CLP COR for appropriate action.
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X. Second Column Confirmation
A. Review Items
Form 1A-HR and raw data. (SOW HRSM01.2, Exhibit B, Sections 2.4.5.1 and 3.4.2; and Exhibit
D - CBC, Section 11.1.1.5)
B. Objective
The objective is to confirm the presence of WHO Toxic Congener target analytes PCB-156 and
PCB-157 in a sample, when these two analytes are not resolved on the column used for the initial
analysis.
C. Criteria
1. Second column confirmation is an optional analysis when the sample extract is reanalyzed on a
DB-1 (or equivalent) column to achieve resolution for target analytes PCB-156 and PCB-157.
2. Regardless of the GC column used, sample reanalysis must meet all of the criteria specified in
Exhibit D - CBC (IAR, S/N ratio, RT, etc.) of the SOW. If any GC columns other than those
specified in the SOW (SPB-Octyl, DB-1) are used, the laboratory shall clearly document the
elution order of all analytes of interest on any such column in the SDG Narrative.
D. Evaluation
1. Verify that the confirmation analysis meets the sample analysis criteria listed in Exhibit D - CBC
of the SOW.
2. Verify that quantitation is performed on the confirmation column and that the results are reported
on a separate Form 1A-HR.
3. Verify that the two concentrations for PCB-156 and PCB-157 are not combined or averaged for
TEF calculations.
E. Action
1. If second column analysis was requested but not performed, contact the EPA Regional CLP COR
for an explanation or to direct the laboratory to resubmit the data.
2. If a second column confirmation analysis was performed and the result is confirmed to be a
detect, report the result from the confirmation analysis. If the result from the confirmation
analysis is a non-detect, report the result at the EDL or adjusted MDL and qualify as non-detect
(U).
3. If resolution of the confirmation analysis is unattainable, use professional judgment to qualify the
detected PCB-156/157.
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XI. Estimated Detection Limit and Estimated Maximum Possible Concentration
A. Review Items
Form 1A-HR and raw data. (SOW HRSM01.2 - Exhibit D - CBC, Sections 11.2.5 and 11.2.6)
B. Objective
The objective is to verify that the sample-specific EDLs and EMPCs are accurately calculated and
reported.
C. Criteria
1. The EDL is an estimated concentration of a given analyte that must be present to produce a signal
with a peak height of at least 3x the background noise signal.
a. The EDL is calculated for each WHO Toxic Congener that is not positively identified. If the
EDL is less than the adjusted MDL, then the adjusted MDL value shall be reported on Form
1A-HR with a "UM" qualifier.
b. The EDL must be calculated using the equation for the specific matrix in the SOW. The
background level (Hx) is determined by measuring the height of the noise at the expected RTs
of both quantitation ions of the particular target analyte. The expected RT is determined from
the most recent analysis of the CCV calibration standard performed on the same
HRGC/HRMS system that was used for the analysis of the samples. In addition, if there is an
associated labeled compound present, the RT of the expected analyte should be within ±2
seconds of that of the labeled compound.
2. The EMPC is the estimated maximum possible concentration for analytes that do not meet all
technical acceptance criteria.
a. An EMPC is calculated for WHO Toxic Congeners that are characterized by a response that
meets the RT requirement, with an S/N ratio of at least 3 for both quantitation ions, but does
not meet the IAR criteria.
b. The EMPC must be calculated using the equation for the specific matrix in the SOW.
D. Evaluation
1. Verify that an EDL or adjusted MDL is reported for each undetected WHO Toxic Congener. The
EDL must be < CRQL, except when increased due to dilution of the extract.
2. Verify that the analytes that were reported as EMPCs meet all of the identification criteria, except
for lARs.
3. Verify that the EDLs and EMPCs are calculated correctly.
E. Action
1. If the non-detects were not reported at the EDL or adjusted MDL, notify the EPA Regional CLP
COR of the deficiency.
2. Qualify WHO Toxic Congeners results reported with EMPCs as estimated (J) or as non-detect
(U), in accordance with EPA Regional SOPs.
3. If calculations were not correctly performed by the laboratory, notify the EPA Regional CLP
COR of the deficiency.
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XII. Toxic Equivalent Determination
A. Review Items
Form 1A-HR, Form 1C-HR, and raw data. (SOW HRSM01.2 - Exhibit B, Section 3.4.3 and Exhibit
D - CBC, Section 11.2.8)
B. Objective
The objective is to verify that the Total TEQs for the WHO Toxic Congener target analytes are
accurately calculated and reported.
C. Criteria
1. The criteria for calculating the TEF-adjusted concentrations and the Total TEQs will depend upon
EPA Regional policies. Two common approaches are outlined below:
a. The first approach is to include only detected WHO Toxic Congeners that meet all of the
qualitative identification criteria and use a zero for any EMPC or EDL value in the
calculations. If additional column analysis or confirmations were performed, additional
Forms 1A-HR should be provided and the final results used in the calculations.
b. In the second approach, in addition to the results of any positively identified WHO Toxic
Congeners, the reported values of any EMPCs or EDLs are also used in the calculations.
2. The laboratory shall perform the calculations (as specified in the SOW) and report the TEFs for
all three species (Mammal, Fish, and Bird). The results of the TEF and Total TEQ calculations
must be reported on Form 1C-HR.
NOTE: The TEFs used in these calculations are derived and published by WHO. Updates of
TEFs are published by WHO approximately every five years for mammalian toxicity.
The timetable has been longer for other types of organisms (i.e., birds and fish).
D. Evaluation
1. Verify that the TEF and Total TEQ calculations were performed correctly.
2. In the determination of the Total TEQ for a sample, consider the impact of using estimated
quantities in the Total TEQ calculation.
E. Action
1. If the calculations were not correctly performed by the laboratory, notify the EPA Regional CLP
COR of the deficiency.
2. If any, or a portion, of the Total TEQ number has been derived from qualified results, use
professional judgment to decide whether or not to qualify the Total TEQ accordingly. For
example, if more than 10% of the total represents "J"-qualified values, then the total may also be
"J" qualified. Be sure to document these decisions in the Data Review Narrative.
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XIII. Regional Quality Assurance and Quality Control
A. Review Items
Form 1A-HR, Form 1B-HR, chromatograms, quantitation reports, TR/COC Record documentation,
and raw data. (SOW HRSM01.2 - Exhibit B, Sections 2.4 and 3.4)
B. Objective
The objective is to use results from the analysis of EPA Regional Quality Assurance/Quality Control
(QA/QC) samples, including PE samples, field duplicates, blind spikes, and blind blanks to assess the
impact on data quality and determine the validity of the analytical results.
C. Criteria
1. The frequency of EPA Regional QA/QC samples should be defined in the QAPP.
2. Performance criteria for EPA Regional QA/QC samples should also be defined in the QAPP.
3. The EPA Region may provide the laboratory with PE samples to be analyzed with each SDG.
These samples may include blind spikes and/or blind blanks. The laboratory must analyze a PE
sample when provided by the EPA Region.
4. The EPA Region may score the PE samples based on data provided by QATS.
D. Evaluation
1. Determine whether the results of EPA Regional QA/QC samples impact all samples in the project
or only those directly associated (i.e., in the same SDG, collected on the same day, prepared
together, or contained in the same analytical sequence).
2. If PE samples are included in the SDG, verify that the results are within the warning limits [95%
(2a) confidence interval] and action limits [99% (3a) confidence interval].
3. If a significant number (i.e., half or more) of the analytes in the PE samples fall outside of the
95% or 99% warning or action criteria, or if a number of false positive results are reported,
evaluate the overall impact on data.
4. If a blind blank is included in the SDG, verify that no target analytes are present in that sample.
The results of the blind blank analysis should be comparable to those in the associated method
blank (see Section V - Blanks in this document).
5. Equipment rinsate samples should not contain any target analyte contamination. Moreover, they
should be comparable to the associated method blank(s).
6. Evaluate field duplicates for comparability (i.e., precision).
7. Determine whether poor precision is the fault of the laboratory, or a result of sample non-
homogeneity in the field. Laboratory observations of sample appearance may become important
in these situations.
E. Action
Any action must be in accordance with EPA Regional specifications and criteria for acceptable
QA/QC sample results. Note in the Data Review Narrative any observations and the impact on data
quality of any QA/QC issues.
If a result is not within the acceptance criteria for any CBC, evaluate the other QC samples in the
SDG (e.g., LCS/LCSD, calibration, labeled standard recovery, internal standard recovery, and
cleanup standard recovery). In such situations, the PE sample may not be representative of the field
samples. PE samples are only one indicator of technical performance of the laboratory.
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1. In general, if the PE sample analytes results are not within the 95% confidence interval or
warning performance window, but are within the 99% confidence interval, qualify detects as
estimated (J) and non-detects as estimated (UJ).
2. For data outside the 95% or 99% confidence interval and scored as "warning-high" or "action-
high", qualify detects as estimated (J). Non-detects should not be qualified.
3. If the results are scored as "action-low", qualify detects as estimated (J) and non-detects as
unusable (R). Contact the EPA Regional CLP COR if reanalysis of samples is required. For
example, if PCB-77 was quantitated beyond the high end of the action limit and was not detected
in any of the samples, the usability of the data would not be affected. On the other hand, in the
situation described in Section D.3 above, it may be necessary to qualify all sample data, and not
only those analytes present in the PE samples.
4. In general, for EPA Regional QA/QC performance not within QAPP specification, qualify detects
as estimated (J) and non-detects as estimated (UJ). The impact on overall data quality should be
assessed after consultation with the data user and/or field personnel. Contact the EPA Regional
CLP COR if reanalysis of samples is required.
Table 24. PE Sample Data Actions for CBC Analysis
Criteria
Results are not within the 95% confidence interval (> 2a)
but inside the 99% interval (< 3 a), and are biased low
(Warning - Low)
Results are not within the 95% confidence interval (> 2a)
but inside the 99% interval (< 3 a), and are biased high
(Warning - High)
Results are outside the 99% confidence interval (> 3a) and
biased high (Action - High)
Results are outside the 99% confidence interval (> 3a) and
biased low (Action - Low)
Action
Detect
J
J
J
J
Non-detect
UJ
No qualification
No qualification
R
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XIV. Overall Assessment of Data
A. Review Items
Entire data package, data review results, and (if available) the QAPP and Sampling and Analysis Plan
(SAP).
B. Objective
The objective is to provide an overall assessment of data quality and usability.
C. Criteria
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems. Contract compliance issues should be directed to the EPA
Regional CLP COR.
2. It is appropriate to make professional judgments and express concerns, as well as to comment on
the validity of the overall data for a Case, especially when there are several QC criteria that are
outside of the specification parameters.
3. Reported analyte concentrations must be quantitated according to the appropriate equations, as
listed in the method.
4. If the concentration for any WHO Toxic Congener target analyte exceeds the calibration range,
the laboratory must perform sample dilution to bring the analyte concentration within the
calibration range. The laboratory shall either dilute the sample extract (when the labeled
compounds in the extract meets the criteria) or re-extract the sample with a smaller or diluted
aliquot. The sample extract may be diluted with a solvent such as n-nonane as long as the 10:1
S/N criterion continues to be met for the labeled compounds. Otherwise, a smaller aliquot of the
original sample should be used for re-extraction and reanalysis.
5. If qualifiers other than those used in this document are needed to describe or qualify the data,
thoroughly document/explain the additional qualifiers used.
D. Evaluation
1. Evaluate any technical problems which have not been previously addressed.
2. Review all available information including, but not limited to: the QAPP [specifically, the
Measurement Quality Objectives (MQOs)], the SAP, and any communications from the data user
that concern the intended use and desired quality of the data.
3. If appropriate information is available, assess the usability of the data to assist the data user.
4. Evaluate sample dilutions to determine the validity of sample results.
I. Extract Dilution:
a. Verify that all WHO Toxic Congener target analyte concentrations in the diluted sample
are within the calibration range. To determine the calibration range for coeluted WHO
Toxic Congener target analytes, multiply the calibration range of the target analyte by the
number of co-eluted peaks.
b. Examine the preparation and/or analysis logs to verify that a proper dilution scheme was
followed. Also examine the SICPs to determine whether any peaks saturated the
detector.
c. Verify that the internal standard calculations used to determine analyte concentrations in
the diluted sample extract were performed correctly. If the laboratory calculated or
reported the results incorrectly, it may be necessary to request a resubmission of the data.
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NOTE: The laboratory should not correct the results of the diluted sample extract for the
labeled compounds recoveries determined from the initial analysis. However,
initial labeled compound recovery is a factor that should be considered
qualitatively during this evaluation.
d. Verify that a dilution factor of < 10 was used and correctly documented, or that prior
communication with the EPA Regional customer was documented.
II. Dilution by re-extraction and reanalysis:
a. Verify that all WHO Toxic Congener target analyte concentrations in the diluted sample
are within the calibration range. If substantial differences are noted between the initial
analysis and the diluted re-extraction/reanalysis, examine the preparation and/or run logs
to verify that a proper dilution scheme was followed. Also examine the SICPs to
determine whether any peaks saturated the detector. If the laboratory calculated or
reported the results incorrectly, it may be necessary to request a resubmission of the data.
Check the calculation of results from a diluted sample and a re-extracted sample (if
present) to verify correct determination of results.
E. Action
1. Use professional judgment to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
2. Use professional judgment to qualify sample results that are > adjusted MDLs or EDLs and non-
detects if the adjusted MDL or EDL exceeds adjusted CRQL.
3. If a sample was not diluted properly when sample results for WHO Toxic Congener target
analytes exceeded the upper limit of the calibration range, qualify sample results that are
> adjusted MDLs or EDLs as estimated (J).
4. If unexplained differences are identified between the initial and the diluted sample results, use
professional judgment to qualify sample results.
5. Include a summary of these observations in the Data Review Narrative to give the data user an
indication of any limitations on the use of the data. If sufficient information on the intended use
and required quality of the data is available, include an assessment of the data usability within the
given context. This may be used as part of the formal Data Quality Assessment (DQA).
6. If any discrepancies are found, the laboratory may be contacted by the EPA Regional CLP COR
to obtain additional information for resolution. If a discrepancy remains unresolved, use
professional judgment to determine if qualification of the data is warranted.
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CBC Tables
The following tables are referenced in the preceding documentation for the CBC data review. The table
information is also available in SOW HRSMO1.2, but the table titles may not be the same as they are in
this document.
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Table 25. Descriptors, Exact m/z Ratios, m/z Types, and m/z Formulas of the CBCs
Function and
Chlorine Level
Fn-1; Cl-1
Fn-2; Cl-2, 3
Fn-3; Cl-3, 4, 5
Exact m/z1
188.0393
190.0363
200.0795
202.0766
218.9856
222.0003
223.99742
225.9944
234.0406
236.0376
242.9856
255.9613
257.9584
268.0016
269.9986
255.9613
257.9584
259.9554
268.0016
269.9986
280.9825
289.9224
291.9194
293.9165
301.9626
303.9597
323.8834
325.8804
327.8775
337.9207
339.9178
m/z Type
M
M+2
M
M+2
lock
M
M+2
M+4
M
M+2
lock
M
M+2
M
M+2
M
M+2
M+4
M
M+2
lock
M
M+2
M+4
M
M+2
M
M+2
M+4
M+2
M+4
m/z Formula
12C12 H9 35C1
12C12 H9 37C1
13C12 H9 35C1
13C12 H9 37C1
C4F9
Ci2 H8 C12
12C12 H8 35C1 37C1
12C12 H8 35C12
13C12 H8 35C12
13C12 H8 35C1 37C1
C6F9
12C12 H7 35C13
12C12 H7 35C12 37C1
13C12 H7 35C13
13C12 H7 35C12 37C1
12C12 H7 35C13
12C12 H7 35C12 37C1
12C12 H7 35C1 37C12
13C12 H7 35C13
13C12 H7 35C12 37C1
C6Fn
Ci2 H6 C\4
12C12 H6 35C13 37C1
12C12 H6 35C12 37C12
Ci2 H6 C\4
13C12 H6 35C13 37C1
12C12 H5 35C15
12C12 H5 35C14 37C1
12C12 H5 35C13 37C12
13C12 H5 35C14 37C1
13C12 H5 35C13 37C12
Substance
Cl-1 CB
Cl-1 CB
13C12 Cl-1 CB
13C12 Cl-1 CB
PFK
Cl-2 PCB
Cl-2 PCB
Cl-2 PCB
13C12 Cl-2 PCB
13C12 Cl-2 PCB
PFK
Cl-3 PCB
Cl-3 PCB
13C12 Cl-3 PCB
13C12 Cl-3 PCB
Cl-3 PCB
Cl-3 PCB
Cl-3 PCB
13C12 Cl-3 PCB
13C12 Cl-3 PCB
PFK
Cl-4 PCB
Cl-4 PCB
Cl-4 PCB
13C12 Cl-4 PCB
13C12 Cl-4 PCB
Cl-5 PCB
Cl-5 PCB
Cl-5 PCB
13C12 Cl-5 PCB
13C12 Cl-5 PCB
April 2016
88
-------
High Resolution Data Review
CBC
Table 25. Descriptors, Exact m/z Ratios, m/z Types, and m/z Formulas of the CBCs (Con't)
Function and
Chlorine Level
Fn-4; Cl-4, 5, 6
Fn-5; Cl-5, 6, 7
Exact m/z
289.9224
291.9194
293.9165
301.9626
303.9597
323.8834
325.8804
327.8775
330.9792
337.9207
339.9178
359.8415
361.8385
363.8356
371.8817
373.8788
323.8834
325.8804
327.8775
337.9207
339.9178
354.9792
359.8415
361.8385
363.8356
371.8817
373.8788
393.8025
395.7995
397.7966
405.8428
407.8398
454.9728
m/z Type
M
M+2
M+4
M+2
M+4
M
M+2
M+4
lock
M+2
M+4
M+2
M+4
M+6
M+2
M+4
M
M
M+4
M+2
M+4
lock
M+2
M+4
M+6
M+2
M+4
M+2
M+4
M+6
M+2
M+4
QC
m/z Formula
Ci2 H6 C14
12C12 H6 35C13 37C1
12C12 H6 35C12 37C12
13C12 H6 35C13 37C1
13C12 H6 35C12 37C12
12C12 H5 35C15
12C12 H5 35C14 37C1
12C12 H5 35C13 37C12
C7F15
13C12 H5 35C14 37C1
13C12 H5 35C13 37C12
12C12 H4 35C15 37C1
Ci2 Fl4 C14 C12
12C12 H4 35C13 37C12
13C12 H4 35C15 37C1
13C12 H4 35C14 37C12
12C12 H5 35C15
12C12 H5 35C14 37C1
12C12 H5 35C13 37C12
13C12 H5 35C14 37C1
13C12 H5 35C13 37C12
C9F13
12C12 H4 35C15 37C1
Ci2 Fl4 C14 C12
12C12 H4 35C13 37C13
13C12 H4 35C15 37C1
13C12 H4 35C14 37C12
12C12 H3 35C16 37C1
12C12 H3 35C15 37C12
12C12 H3 35C14 37C13
13C12 H3 35C16 37C1
13C12 H3 35C15 37C12
Cn FIV
Substance
Cl-4 PCB
Cl-4 PCB
Cl-4 PCB
13C12 Cl-4 PCB
13C12 Cl-4 PCB
Cl-5 PCB
Cl-5 PCB
Cl-5 PCB
PFK
13C12 Cl-5 PCB
13C12 Cl-5 PCB
Cl-6 PCB
Cl-6 PCB
Cl-6 PCB
13C12 Cl-6 PCB
13C12 Cl-6 PCB
Cl-5 PCB
Cl-5 PCB
Cl-5 PCB
13C12 Cl-5 PCB
13C12 Cl-5 PCB
PFK
Cl-6 PCB
Cl-6 PCB
Cl-6 PCB
13C12 Cl-6 PCB
13C12 Cl-6 PCB
Cl-7 PCB
Cl-7 PCB
Cl-7 PCB
13C12 Cl-7 PCB
13C12 Cl-7 PCB
PFK
April 2016
89
-------
High Resolution Data Review
CBC
Table 25. Descriptors, Exact m/z Ratios, m/z Types, and m/z Formulas of the CBCs (Con't)
Function and
Chlorine Level
Fn-6; Cl-7, 8, 9, 10
Exact m/z
393.8025
395.7995
397.7966
405.8428
407.8398
427.7635
429.7606
431.7576
439.8038
441.8008
442.9728
454.9728
461.7246
463.7216
465.7187
473.7648
475.7619
495.6856
497.6826
499.6797
507.7258
509.7229
511.7199
m/z Type
M+2
M+4
M+6
M+2
M+4
M+2
M+4
M+6
M+2
M+4
QC
lock
M+2
M+4
M+6
M+2
M+4
M+2
M+4
M+6
M+2
M+4
M+6
m/z Formula
12C12 H3 35C16 37C1
12C12 H3 35C15 37C12
12C12 H3 35C14 37C13
13C12 H3 35C16 37C1
13C12 H3 35C15 37C12
12C12 H2 35C17 37C1
12C12 H2 35C16 37C12
12C12 H2 35C15 37C13
13C12 H2 35C17 37C1
13C12 H2 35C16 37C12
Cio F13
Cn F13
12C12 H! 35C18 37C1
12C12 H! 35C17 37C12
12C12 H! 35C16 37C13
13C12 H! 35C18 37C1
13C12 H! 35C17 37C12
12C12 H4 35C19 37C1
12C1235C1837C12
12C12 35C17 37C13
13c1235ci937ci
13C12 35C18 37C12
13C12 35C17 37C13
Substance
Cl-7 PCB
Cl-7 PCB
Cl-7 PCB
13C12 Cl-7 PCB
13C12 Cl-7 PCB
Cl-8 PCB
Cl-8 PCB
Cl-8 PCB
13C12 Cl-8 PCB
13C12 Cl-8 PCB
PFK
PFK
Cl-9 PCB
Cl-9 PCB
Cl-9 PCB
13C12 Cl-9 PCB
13C12 Cl-9 PCB
Cl-10 PCB
Cl-10 PCB
Cl-10 PCB
13C12 Cl-10 PCB
13C12 Cl-10 PCB
13C12 Cl-10 PCB
Isotopic masses used for accurate mass calculation:
'H 1.0078
12C 12.0000
13C 13.0034
35C1 34.9689
37C1 36.9659
19F 18.9984
; An interference with PFK m/z 223.9872 may preclude meeting 10:1 S/N for the DiCB at the CS-1
calibration level (Exhibit D - Chlorinated Biphenyl Congeners Analysis, Section 9.4.3 and Table 6
Concentrations of Chlorinated Biphenyl Congeners in Calibration and Verification Solutions in the
SOW). If this interference occurs, 10:1 S/N must be met at the CS-2 level.
April 2016
90
-------
High Resolution Data Review
CBC
Table 26. Gas Chromatography RT WDM for CBC Analysis
CBC
Monochlorobiphenyl
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
First Eluted
PCB-1
PCB-4
PCB-19
PCB-54
PCB-1 04
PCB-155
PCB-188
PCB-202
PCB-208
Last Eluted
PCB-3
PCB-15
PCB-37
PCB-77
PCB-126
PCB-1 69
PCB-189
PCB-205
PCB-206
April 2016
91
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High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs
Congener No.
Retention Time
Relative Retention
Time Limits
Quantitation Reference
Compounds using 9L (13Ci2-2,5-DiCB) as internal standard
CB Congener
Monochlorobiphenyls
1
2
3
1L
3L
3L
0.9988-1.0036
0.9847-0.9908
0.9990-1.0031
1L
1L/3L
3L
Dichlorobiphenyls
4
10
9
7
6
5
8
14
11
13
12
13/12
15
4L
4L
4L
4L
4L
4L
4L
15L
15L
15L
15L
15L
15L
0.9990-1.0030
1.0110-1.0170
1.1331-1.1391
1.1451-1.1512
1.1642-1.1702
1.1862-1.1922
1.1942-1.2002
0.9246-0.9288
0.9673-0.9715
0.9822-0.9865
0.9843-0.9886
0.9829-0.9872
0.9993-1.0021
4L
4L/15L
4L/15L
4L/15L
4L/15L
4L/15L
4L/15L
4L/15L
4L/15L
4L/15L
4L/15L
4L/15L
15L
Trichlorobiphenyls
19
30
18
30/18
17
27
24
16
32
34
23
29
26
26/29
25
31
28
19L
19L
19L
19L
19L
19L
19L
19L
19L
19L
19L
19L
19L
19L
37L
37L
37L
0.9992-1.0025
1.0936-1.0985
1.1002-1.1051
1.0969-1.1018
1.1215-1.1264
1.1355-1.1404
1.1420-1.1470
1.1511-1.1560
1.2266-1.2315
1.2430-1.2479
1.2504-1.2553
1.2660-1.2742
1.2668-1.2750
1.2668-1.2750
0.8348-0.8380
0.8460-0.8492
0.8551-0.8604
19L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
April 2016
92
-------
High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs (Con't)
Congener No.
20
28/20
21
33
21/33
22
36
39
38
35
37
Retention Time
37L
37L
37L
37L
37L
37L
37L
37L
37L
37L
37L
Relative Retention
Time Limits
0.8578-0.8631
0.8567-0.8620
0.8626-0.8679
0.8642-0.8695
0.8631-0.8684
0.8802-0.8834
0.9316-0.9348
0.9449-0.9481
0.9663-0.9695
0.9834-0.9866
0.9995-1.0011
Quantitation Reference
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
19L/37L
37L
Labeled Compounds
1L
3L
4L
15L
19L
37L
9L
9L
9L
9L
9L
52L
0.7125-0.7390
0.8510-0.8774
0.8677-0.8942
1.2302-1.2478
1.0608-1.0873
1.0754-1.0928
9L
9L
9L
9L
9L
52L
Compounds using 52L (13Ci2-2,2',5,5'-TeCB) as internal standard
CB Congener
Tetrachlorobiphenyls
54
50
53
50/53
45
51
45/51
46
52
73
43
69
49
69/49
48
65
47
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
0.9993-1.0021
1.0923-1.0993
1.0937-1.1007
1.0930-1.1000
1.1259-1.1329
1.1280-1.1350
1.1273-1.1343
1.1434-1.1476
1.2042-1.2084
1.2091-1.2133
1.2133-1.2175
1.2189-1.2259
1.2245-1.2315
1.2217-1.2287
1.2378-1.2420
1.2476-1.2545
1.2483-1.2552
54L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
April 2016
93
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High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs (Con't)
Congener No.
44
44/47/65
62
75
59
59/62/75
42
41
71
40
41/40/71
64
72
68
57
58
67
63
61
70
76
74
61/70/74/76
66
55
56
60
80
79
78
81
77
Retention
Time
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
54L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
81L
77L
Relative Retention
Time Limits
1.2503-1.2573
1.2483-1.2552
1.2594-1.2664
1.2608-1.2678
1.2636-1.2706
1.2615-1.2685
1.2748-1.2790
1.2916-1.2986
1.2958-1.3028
1.2979-1.3049
1.2958-1.3028
1.3070-1.3112
0.8323-0.8349
0.8406-0.8432
0.8527-0.8553
0.8610-0.8636
0.8645-0.8671
0.8719-0.8745
0.8775-0.8827
0.8805-0.8858
0.8814-0.8866
0.8827-0.8871
0.8814-0.8866
0.8914-0.8940
0.8970-0.8997
0.9123-0.9149
0.9179-0.9205
0.9248-0.9275
0.9700-0.9726
0.9857-0.9883
0.9996-1.0013
0.9996-1.0013
Quantitation Reference
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
54L/81L/77L
81L
77L
Labeled Compounds
54L
81L
77L
52L
52L
52L
0.8232-0.8348
1.3287-1.3403
1.3513-1.3629
52L
52L
52L
April 2016
94
-------
High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs (Con't)
Congener No.
Retention Time
Relative Retention
Time Limits
Quantitation Reference
Compounds using 101L (13Ci2-2,2',4,5,5'-PeCB) as internal standard
CB Congener
Pentachlorobiphenyls
104
96
103
94
95
100
93
102
98
95/100/93/102/98
88
91
88/91
84
89
121
92
113
90
101
113/90/101
83
99
83/99
112
119
108
86
97
125
87
108/119/86/97/125/87
117
116
85
104L
104L
104L
104L
104L
104L
104L
104L
104L
104L
104L
104L
104L
104L
104L
104L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
0.9994-1.0017
1.0146-1.0202
1.0795-1.0829
1.0896-1.0929
1.1058-1.1114
1.1092-1.1148
1.1137-1.1193
1.1176-1.1232
1.1204-1.1260
1.1131-1.1187
1.1321-1.1389
1.1366-1.1422
1.1344-1.1411
1.1484-1.1517
1.1652-1.1685
1.1725-1.1758
0.8627-0.8651
0.8761-0.8801
0.8769-0.8809
0.8773-0.8813
0.8769-0.8809
0.8911-0.8960
0.8923-0.8964
0.8915-0.8964
0.8972-0.8996
0.9037-0.9102
0.9037-0.9102
0.9057-0.9122
0.9057-0.9122
0.9074-0.9139
0.9102-0.9143
0.9065-0.9130
0.9228-0.9277
0.9248-0.9297
0.9265-0.9305
104L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
April 2016
95
-------
High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs (Con't)
Congener No.
117/116/85
110
115
110/115
82
111
120
107
124
107/124
109
123
106
118
122
114
105
127
126
Retention
Time
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
123L
118L
118L
114L
105L
105L
126L
Relative Retention
Time Limits
0.9240-0.9289
0.9309-0.9350
0.9317-0.9358
0.9313-0.9354
0.9415-0.9439
0.9464-0.9488
0.9581-0.9606
0.9890-0.9931
0.9894-0.9935
0.9890-0.9931
0.9959-0.9984
0.9996-1.0012
1.0024-1.0049
0.9996-1.0012
1.0101-1.0125
0.9999-1.0012
0.9992-1.0012
1.0320-1.0343
0.9996-1.0011
Quantitation Reference
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
104L/123L/1 14L/1 18L/105L
123L
104L/123L/1 14L/1 18L/105L
118L
104L/123L/1 14L/1 18L/105L
114L
105L
104L/123L/1 14L/1 18L/105L
126L
Labeled Compounds
104L
123L
118L
114L
105L
126L
101L
101L
101L
101L
101L
101L
0.8211-0.8303
1.1331-1.1424
1.1424-1.1516
1.1590-1.1683
1.1808-1.1900
1.2700-1.2792
101L
101L
101L
101L
101L
101L
Compounds using 138L (13Ci2-2,2',3,4,4',5'-HxCB) as internal standard
CB Congener
Hexachlorobiphenyls
155
152
150
136
145
148
151
135
154
155L
155L
155L
155L
155L
155L
155L
155L
155L
0.9995-1.0014
1.0093-1.0121
1.0131-1.0159
1.0266-1.0294
1.0340-1.0368
1.0742-1.0770
1.0938-1.0984
1.0970-1.1017
1.0989-1.1035
155L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
April 2016
96
-------
High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs (Con't)
Congener No.
151/135/154
144
147
149
147/149
134
143
134/143
139
140
139/140
131
142
132
133
165
146
161
153
168
153/168
141
130
137
164
138
163
129
160
138/163/129/160
158
166
128
128/166
159
162
167
156
Retention Time
155L
155L
155L
155L
155L
155L
155L
155L
155L
155L
155L
155L
155L
155L
155L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
167L
156L/157L
Relative Retention
Time Limits
1.0961-1.1007
1.1119-1.1147
1.1213-1.1259
1.1227-1.1273
1.1217-1.1264
1.1297-1.1343
1.1311-1.1357
1.1306-1.1353
1.1390-1.1437
1.1395-1.1441
1.1390-1.1437
1.1474-1.1502
1.1521-1.1549
1.1618-1.1665
1.1726-1.1754
0.8853-0.8874
0.8906-0.8926
0.8937-0.8958
0.9035-0.9069
0.9048-0.9083
0.9041-0.9076
0.9101-0.9122
0.9195-0.9216
0.9240-0.9261
0.9268-0.9289
0.9324-0.9373
0.9324-0.9373
0.9341-0.9390
0.9369-0.9404
0.9341-0.9390
0.9418-0.9439
0.9599-0.9634
0.9634-0.9669
0.9617-0.9651
0.9815-0.9836
0.9881-0.9902
0.9997-1.0010
0.9983-1.0003
Quantitation Reference
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
155L/156L/157L/167L/169L
167L
156L/157L
April 2016
97
-------
High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs (Con't)
Congener No.
157
156/157
169
Retention
Time
156L/157L
156L/157L
169L
Relative Retention
Time Limits
0.9990-1.0024
0.9990-1.0010
0.9997-1.0010
Quantitation Reference
156L/157L
156L/157L
169L
Labeled Compounds
155L
167L
156L
157L
169L
156L/157L
138L
138L
138L
138L
138L
138L
0.7960-0.8034
1.0664-1.0739
1.0974-1.0996
1.0959-1.1033
1.1738-1.1761
1.0981-1.1003
138L
138L
138L
138L
138L
138L
Compounds using 194L (13C12-2,2',3,3',4,4',5,5'-OcCB) as internal standard
CB Congener
Heptachlorobiphenyls
188
179
184
176
186
178
175
187
182
183
185
183/185
174
177
181
171
173
171/173
172
192
193
180
180/193
191
170
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
188L
189L
189L
189L
189L
189L
189L
189L
0.9996-1.0012
1.0100-1.0123
1.0203-1.0227
1.0323-1.0346
1.0442-1.0466
1.0765-1.0789
1.0924-1.0948
1.0988-1.1012
1.1035-1.1059
1.1147-1.1171
1.1191-1.1215
1.1167-1.1191
1.1227-1.1251
1.1338-1.1362
1.1426-1.1450
1.1489-1.1529
1.1501-1.1525
1.1489-1.1529
0.9026-0.9044
0.9083-0.9102
0.9144-0.9162
0.9147-0.9165
0.9144-0.9162
0.9220-0.9238
0.9410-0.9428
188L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
188L/189L
April 2016
98
-------
High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs (Con't)
Congener No.
190
189
Retention Time
189L
189L
Relative Retention
Time Limits
0.9507-0.9525
0.9997-1.0009
Quantitation Reference
188L/189L
189L
Octachlorobiphenyls
202
201
204
197
200
197/200
198
199
198/199
196
203
195
194
205
202L
202L
202L
202L
202L
202L
202L
202L
202L
205L
205L
205L
205L
205L
0.9996-1.0011
1.0193-1.0228
1.0340-1.0361
1.0396-1.0417
1.0442-1.0463
1.0417-1.0438
1.1031-1.1066
1.1045-1.1066
1.1035-1.1070
0.9198-0.9216
0.9236-0.9253
0.9493-0.9510
0.9908-0.9925
0.9997-1.0009
202L
202L/205L
202L/205L
202L/205L
202L/205L
202L/205L
202L/205L
202L/205L
202L/205L
202L/205L
202L/205L
202L/205L
202L/205L
205L
Nonachlorobiphenyls
208
207
206
208L
208L
206L
0.9997-1.0009
1.0174-1.0193
0.9997-1.0008
208L
208L/206L
206L
Decachlorobiphenyl
209
209L
0.9997-1.0008
209L
Labeled Compounds
188L
180L
170L
189L
202L
205L
208L
206L
209L
194L
194L
194L
194L
194L
194L
194L
194L
194L
0.7275-0.7333
0.8775-0.8834
0.9026-0.9084
0.9587-0.9645
0.8264-0.8322
1.0044-1.0131
0.9488-0.9546
1.0358-1.0445
1.0643-1.0730
194L
194L
194L
194L
194L
194L
194L
194L
194L
Cleanup Standards
28L
111L
178L
52L
101L
138L
0.9209-0.9324
1.0730-1.0823
1.0052-1.0127
52L
101L
138L
April 2016
99
-------
High Resolution Data Review
CBC
Table 27. RRTs and Quantitation References of the Target and Labeled CBCs (Con't)
Congener No.
Retention Time
Relative Retention
Time Limits
Quantitation Reference
Internal standards
9L
52L
101L
138L
194L
138L
138L
138L
138L
138L
0.4183-0.4276
0.6388-0.6481
0.8021-0.8115
0.9996-1.0011
1.2777-1.2870
138L
138L
138L
138L
138L
Table 28. Theoretical lARs and QC Limits for CBC Analysis
Number of
Chlorine Atoms
1
2
3
4
5
6
7
8
9
10
m/z Forming Ratio
m/(m+2)
m/(m+2)
m/(m+2)
m/(m+2)
(m+2)/(m+4)
(m+2)/(m+4)
(m+2)/(m+4)
(m+2)/(m+4)
(m+2)/(m+4)
(m+4)/(m+6)
Theoretical Ratio
3.13
1.56
1.04
0.77
1.55
1.24
1.05
0.89
0.77
1.16
QC Limits
Lower
2.66
1.33
0.88
0.65
1.32
1.05
0.89
0.76
0.65
0.99
Upper
3.60
1.79
1.20
0.89
1.78
1.43
1.21
1.02
0.89
1.33
April 2016
100
-------
High Resolution Data Review
CBC
Table 29. Concentration of CBCs in Initial Calibration and CCV Solutions
CBC
2-MoCB
4-MoCB
2,2'-DiCB
4,4'-DiCB
2,2',6-TrCB
3,4,4'-TrCB
2,2',6,6'-TeCB
3,3',4,4'-TeCB
3,4,4',5-TeCB
2,2',4,6,6'-PeCB
2,3,3',4,4'-PeCB
2,3,4,4',5-PeCB
2,3',4,4',5-PeCB
2',3,4,4',5-PeCB
3,3',4,4',5-PeCB
2,2',4,4',6,6'-HxCB
2,3,3',4,4',5-HxCB
2,3,3',4,4',5'-HxCB
2,3',4,4',5,5'-HxCB
3,3',4,4',5,5'-HxCB
2,2',3,4',5,6,6'-HpCB
2,3,3',4,4',5,5'-HpCB
2,2',3,3',5,5',6,6'-OcCB
2,3,3',4,4',5,5',6-OcCB
2,2',3,3',4,4',5,5',6-NoCB
2,2',3,3',4,5,5',6,6'-NoCB
DeCB
Analyte Name
PCB-1
PCB-3
PCB-4
PCB-15
PCB-19
PCB-37
PCB-54
PCB-77
PCB-81
PCB-1 04
PCB-1 05
PCB-1 14
PCB-1 18
PCB-123
PCB-1 26
PCB-155
PCB-156
PCB-157
PCB-167
PCB-169
PCB-188
PCB-189
PCB-202
PCB-205
PCB-206
PCB-208
PCB-209
Solution Concentration (ng/mL)
CS1
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
CS2
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
CS3
(CCV)
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
CS4
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
CSS
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
Labeled Toxics/LOC/Window Defining Mix
13C12-2-MoCB
13C12-4-MoCB
13C12-2,2'-DiCB
13C12-4,4'-DiCB
13C12-2,2',6-TrCB
13C12-3,4,4'-TrCB
13C12-2,2',6,6'-TeCB
13C12-3,3',4,4'-TeCB
13C12-3,4,4',5-TeCB
PCB-1L
PCB-3L
PCB-4L
PCB-15L
PCB-1 9L
PCB-37L
PCB-54L
PCB-77L
PCB-81L
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
April 2016
101
-------
High Resolution Data Review
CBC
Table 29. Concentration of CBCs in Initial Calibration and CCV Solutions (Con't)
CBC
13C12-2,2',4,6,6'-PeCB
13C12-2,3,3',4,4'-PeCB
13C12-2,3,4,4',5-PeCB
13C12-2,3',4,4',5-PeCB
13C12-2',3,4,4',5-PeCB
13C12-3,3',4,4',5-PeCB
13C12-2,2',4,4',6,6'-HxCB
13C12-2,3,3',4,4',5-HxCB
13C12-2,3,3',4,4',5'-HxCB
13C12-2,3',4,4',5,5'-HxCB
13C12-3,3',4,4',5,5'-HxCB
13C12-2,2',3,4',5,6,6'-HpCB
13C12-2,3,3',4,4',5,5'-HpCB
13C12-2,2',3,3',5,5',6,6'-OcCB
13C12-2,3,3',4,4',5,5',6-OcCB
13C12-2,2',3,3',4,4',5,5',6-NoCB
13C12-2,2',3,3',4,5,5',6,6'-NoCB
13C12-DeCB
Analyte Name
PCB-104L
PCB-105L
PCB-114L
PCB-118L
PCB-123L
PCB-126L
PCB-155L
PCB-156L
PCB-157L
PCB-167L
PCB-169L
PCB-188L
PCB-189L
PCB-202L
PCB-205L
PCB-206L
PCB-208L
PCB-209L
Solution Concentration (ng/mL)
CS1
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
CS2
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
CS3
(CCV)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
CS4
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
CSS
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Cleanup Standard
13C12-2,4,4'-TrCB
13C12-2,3,3',5,5'-PeCB
13C12-2,2',3,3',5,5',6-HpCB
PCB-28L
PCB-111L
PCB-178L
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Internal Standard
13C12-2,5-DiCB
13C12-2,2',5,5'-TeCB
13C12-2,2',4',5,5'-PeCB
13C12-2,2',3',4,4',5'-HxCB
13C12-2,2',3,3',4,4',5,5'-OcCB
Combined 209-Congener
Standard
MoCB thru TrCB
TeCB thru HpCB
OcCB thru DeCB
PCB-9L
PCB-52L
PCB-101L
PCB-138L
PCB-194L
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Solution Concentration (ng/mL)
25
50
75
April 2016
102
-------
High Resolution Data Review
CBC
Table 30. QC Limits for CBC in CCV, LCS/LCSD, and Labeled Compounds in Samples
CBC
2-MoCB
4-MoCB
2,2'-DiCB
4,4'-DiCB
2,2',6-TrCB
3,4,4'-TrCB
2,2',6,6'-TeCB
3,3',4,4'-TeCB
3,4,4',5-TeCB
2,2',4,6,6'-PeCB
2,3,3',4,4'-PeCB
2,3,4,4',5-PeCB
2,3',4,4',5-PeCB
2',3,4,4',5-PeCB
3,3',4,4',5-PeCB
2,2',4,4',6,6'-HxCB
2,3,3',4,4',5-HxCB
2,3,3',4,4',5'-HxCB
2,3',4,4',5,5'-HxCB
3,3',4,4',5,5'-HxCB
2,2',3,4',5,6,6'-HpCB
2,3,3',4,4',5,5'-HpCB
2,2',3,3',5,5',6,6'-OcCB
2 3 3' 4 4' 5 5' 6-OcCB
2,2',3,3',4,4',5,5',6-NoCB
2,2',3,3',4,5,5',6,6'-NoCB
DeCB
Labeled Compound
13C12-2-MoCB
13C12-4-MoCB
13C12-2,2'-DiCB
13C12-4,4'-DiCB
13C12-2,2',6-TrCB
13C12-3,4,4'-TrCB
13C12-2,2',6,6'-TeCB
13C12-3,3',4,4'-TeCB
Analyte
Name
PCB-1
PCB-3
PCB-4
PCB-1 5
PCB-1 9
PCB-3 7
PCB-54
PCB-77
PCB-81
PCB-1 04
PCB-1 05
PCB-1 14
PCB-1 18
PCB-1 23
PCB-1 26
PCB-155
PCB-156
PCB-157
PCB-1 67
PCB-1 69
PCB-188
PCB-189
PCB-202
PCB-205
PCB-206
PCB-208
PCB-209
PCB-1L
PCB-3L
PCB-4L
PCB-15L
PCB-1 9L
PCB-37L
PCB-54L
PCB-77L
Test
Cone
(ng/mL)
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
100
100
100
100
100
100
100
100
CCV
%Recovery
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
LCS/LCSD
%Recovery
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
60-135
15-145
15-145
15-145
15-145
15-145
15-145
15-145
40-145
Labeled
Compound
%Recovery
in Sample
N/A
5-145
5-145
5-145
5-145
5-145
5-145
5-145
10-145
April 2016
103
-------
High Resolution Data Review
CBC
Table 30. QC Limits for CBC in CCV, LCS/LCSD, and Labeled Compounds in Samples (Con't)
CBC
13C12-3,4,4',5-TeCB
13C12-2,2',4,6,6'-PeCB
13C12-2,3,3',4,4'-PeCB
13C12-2,3,4,4',5-PeCB
13C12-2,3',4,4',5-PeCB
13C12-2',3,4,4',5-PeCB
13C12-3,3',4,4',5-PeCB
13C12-2,2',4,4',6,6'-HxCB
13C12-2,3,3',4,4',5-HxCB
13C12-2,3,3',4,4',5'-HxCB
13C12-2,3',4,4',5,5'-HxCB
13C12-3,3',4,4',5,5'-HxCB
13C12-2,2',3,4',5,6,6'-HpCB
13C12-2,3,3',4,4',5,5'-HpCB
13C12-2,2',3,3',5,5',6,6'-OcCB
13C12-2,3,3',4,4',5,5',6-OcCB
13C12-2,2',3,3',4,4',5,5',6-NoCB
13C12-2,2',3,3',4,5,5',6,6'-NoCB
13C12-2,2',3,3',4,4',5,5',6,6'-DeCB
Cleanup Standards
13C12-2,4,4'-TrCB
13C12-2,3,3',5,5'-PeCB
13C12-2,2',3,3',5,5',6-HpCB
Analyte
Name
PCB-81L
PCB-104L
PCB-105L
PCB-114L
PCB-118L
PCB-123L
PCB-126L
PCB-155L
PCB-156L
PCB-157L
PCB-167L
PCB-169L
PCB-188L
PCB-189L
PCB-202L
PCB-205L
PCB-206L
PCB-208L
PCB-209L
PCB-28L
PCB-111L
PCB-178L
Test
Cone
(ng/mL)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
CCV
%Recovery
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
50-145
65-135
75-125
75-125
LCS/LCSD
%Recovery
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
40-145
15-145
40-145
40-145
Labeled
Compound
%Recovery
in Sample
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
10-145
5-145
10-145
10-145
April 2016
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High Resolution Data Review
CBC
Table 31. CBC Toxic Equivalency Factors (TEFs)
Analyte Name
PCB-77
PCB-81
PCB-105
PCB-114
PCB-118
PCB-123
PCB-126
PCB-156
PCB-157
PCB-167
PCB-169
PCB-189
Source
TEF
Mammal
0.0001
0.0003
0.00003
0.00003
0.00003
0.00003
0.1
0.00003
0.00003
0.00003
0.03
0.00003
WHO* 2005
Fish
0.0001
0.0005
0.000005
0.000005
0.000005
0.000005
0.005
0.000005
0.000005
0.000005
0.00005
0.000005
Bird
0.05
0.1
0.0001
0.0001
0.00001
0.00001
0.1
0.0001
0.0001
0.00001
0.001
0.00001
WHO* 1998
*World Health Organization
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High Resolution Data Review CBC
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High Resolution Data Review Appendix A
APPENDIX A: GLOSSARY
Aliquot - A measured portion of a field sample, standard, or solution taken for sample preparation and/or
analysis.
Analysis Date/Time - The date and military time (24-hour clock) of the injection of the sample, standard,
or blank into the High Resolution Gas Chromatograph/High Resolution Mass Spectrometer
(HRGC/HRMS).
Analyte - A chlorinated biphenyl congener (CBC), chlorinated dibenzo-^-dioxin (CDD), or chlorinated
dibenzofuran (CDF) tested for by the methods in the Statement of Work (SOW). The analytes are listed
in Exhibit C - Chlorinated-p-Dioxins and Chlorinated Dibenzofurans and Chlorinated Biphenyl
Congeners Target Analyte List and Contract Required Quantitation Limits of the SOW.
Analytical Sample - Any solution or media introduced into an instrument on which an analysis is
performed; excluding instrument calibration, Continuing Calibration Verification (CCV), and tunes. Note
the following are all defined as analytical samples: undiluted and diluted samples (EPA and non-EPA),
Laboratory Control Samples (LCSs), LCS Duplicates (LCSDs), Performance Evaluation (PE) samples,
and Preparation Blanks.
Analytical Sequence - The order of actual instrumental analysis of the samples, from the time of
instrument calibration through the analysis of the final sample. All sample analyses during the analytical
sequence are subject to the Quality Control (QC) protocol set forth in Exhibit D - Analytical Methods and
Exhibit F - Programmatic Quality Assurance/Quality Control Elements of the Statement of Work (SOW),
unless otherwise specified in the individual methods.
Analytical Services Branch (ASB) - The division of the United States Environmental Protection
Agency's (EPA's) Office of Superfund Remediation and Technology Innovation (OSRTI) responsible for
the overall management of the Contract Laboratory Program (CLP).
Blank - An analytical sample that has negligible or unmeasurable amounts of a substance of interest.
The blank is designed to assess specific sources of contamination. Types of blanks may include
calibration blanks, instrument blanks, method blanks, and field blanks. See the individual definitions for
types of blanks.
Calibration Standards - A series of known standard solutions used by the analyst for calibration of the
instrument (i.e., preparation of the calibration 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).
Chlorinated Biphenyl Congener (CBC) - One of the 209 individual chlorinated biphenyl congeners
determined using this Method. The 209 CBCs are listed in Exhibit C - Chlorinated-p-Dioxins and
Chlorinated Dibenzofurans and Chlorinated Biphenyl Congeners Target Analyte List and Contract
Required Quantitation Limits of the Statement of Work (SOW).
Cleanup Standard - A standard containing either 37Cl4-2,3,7,8-TCDD or PCB-28L, PCB-111L, and
PCB-178L that is added to all extracts prior to cleanup. The purpose of this standard is to measure the
efficiency of the cleanup process.
Column Performance Solution (CPS) - When the Window Defining Mixture (WDM) and the Isomer
Specificity Check solutions are combined, the solution is identified as the CPS.
Congener - Individual compound belonging to a group or class of compounds with a similar general
structure.
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High Resolution Data Review Appendix A
Contamination - A component of a sample or an extract that is not representative of the environmental
source of the sample. Contamination may stem from other samples, sampling equipment, while in transit,
from laboratory reagents, laboratory environment, or analytical instruments.
Continuing Calibration Verification (CCV) - The mid-point calibration standard (CSS) that is used to
verify that the instrument response factors developed during the initial calibration are still valid.
Contract Compliance Screening (CCS) - A screening of electronic and hardcopy data deliverables for
completeness and compliance with the contract. This screening is done under EPA direction by the
Sample Management Office (SMO) Contractor.
Contract Laboratory Program (CLP) - Supports the EPA's Superfund effort by providing a range of
state-of-the-art chemical analytical services of known and documented quality. This program is directed
by the Analytical Services Branch (ASB) of the Office of Superfund Remediation and Technology
Innovation (OSRTI) of the EPA.
Contract Required Quantitation Limit (CRQL) - Minimum level of quantitation acceptable under the
contract Statement of Work (SOW), and supported by the analysis of standards.
Control Limits - A range within which specified measurement results must fall to be compliant. Control
limits may be mandatory, requiring corrective action if exceeded, or advisory, requiring that
noncompliant data be flagged.
Date - The date format for all reporting forms is MM/DD/YYYY - Where MM = 01 for January, 02 for
February, ... 12 for December; DD = 01 to 31; YYYY = 2015, 2016, etc.
Day - Unless otherwise specified, day shall mean calendar day.
Descriptor - A set of specific target analyte mass fragments monitored during a set timeframe.
Dry Weight - The weight of a sample based on percent solids. The weight after drying in an oven.
EPA Regional Contract Laboratory Program Contracting Officer's Representative (Regional CLP
COR) - The EPA official who monitors assigned CLP laboratories (either inside or outside of the
Regional CLP COR's respective Region), responds to and identifies problems in laboratory operations,
and participates in on-site laboratory audits.
Estimated Detection Limit (EDL) - The concentration of an analyte required to produce a signal with
peak height of at least 3 times the background signal level. The EDL is calculated for each 2,3,7,8-
substituted and World Health Organization (WHO) Toxic congener for which the response of the primary
and secondary ions is less than 3 times the background level.
Estimated Maximum Possible Concentration (EMPC) - The EMPC is calculated for analytes for
which the quantitation and/or confirmation ion(s) has signal to noise in excess of 3, but does not meet the
ion ratio identification criteria.
Field Blank - A blank used to provide information about contaminants that may be introduced during
sample collection or transport. This includes trip blanks, rinsates, equipment blanks, etc.
Field Quality Control (QC) - Any QC samples submitted from the field to the laboratory. Examples
include, but are not limited to, field blanks, field duplicates, and field spikes.
Field Sample - A portion of material received from the field to be analyzed that is contained in single or
multiple containers and identified by a unique EPA Sample Number.
Form - A hardcopy and/or electronic information/data entry sheet with locked preformatted structure that
guides and/or controls user entry/input.
Gel Permeation Chromatography (GPC) - A size-exclusion chromatographic technique that is used as
a cleanup procedure for removing large organic molecules, particularly naturally occurring macro-
molecules such as lipids, polymers, viruses, etc.
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High Resolution Data Review Appendix A
Holding Time - The elapsed time expressed in days from the date of receipt of the sample by the
Contractor until the date of its analytical procedures (e.g., extraction or analysis).
Homologue - A group of compounds that have the same molecular weight, but not necessarily the same
structural arrangement.
Initial Calibration - Analysis of analytical standards for a series of different concentrations; used to
define the quantitative response, linearity, and dynamic range of the instrument to target analytes.
Instrument Blank - A blank designed to determine the level of contamination either associated with the
analytical instruments, or resulting from carryover.
Internal Standard - For chlorinated biphenyl congeners (CBCs), a chemical compound (usually isotope-
labeled) that is used as a reference for quantitation of target chemical compounds in a sample. In the
context of the high resolution Gas Chromatography/Mass Spectrometry (GC/MS) methods, internal
standards are added to every blank, Quality Control (QC) sample, and sample extract aliquot just prior to
analysis to facilitate internal standard quantitation of the labeled isotope dilution standards.
Internal Standard Quantitation - A means of determining the concentration of a target analyte using a
standard that is added to the sample just prior to analysis. In the context of the high resolution Gas
Chromatography/Mass Spectrometry (GC/MS) methods, internal standard quantitation is applied to
determine the amount recovered, after sample preparation and clean-up, of the labeled compounds added
to the samples prior to initial preparation, that are used for isotope dilution quantitation.
Isomer - Chemical compounds that have the same molecular formula, but differ in structural
arrangement and properties. For example, 1,2,3,4-TCDD and 2,3,7,8-TCDD are structural isomers.
Isotope Dilution Quantitation - A means of determining the concentration of a target analyte using a
standard that is added to the sample prior to any sample preparation steps. It utilizes isotopically labeled
compounds that are chemically as similar as possible to each target analyte (i.e., a labeled analog) to
mimic the response of the analyte to sample preparation steps, thereby accounting for any related losses.
Labeled Compounds - Carbon-13 isotopically-labeled compounds that are added to every sample and
are present at the same concentration in every blank, Quality Control (QC) sample, and calibration
solution in the high resolution Gas Chromatography/Mass Spectrometry (GC/MS) methods for the
purpose of measuring recovery or for quantitation.
Laboratory - Synonymous with Contractor, as used herein.
Laboratory Control Sample (LCS) - A sample of blank matrix spiked with known quantities of
analytes. The LCS is analyzed exactly like a sample. Its purpose is to assure that the results produced by
the laboratory remain within the limits specified in this Method for precision and recovery.
Laboratory Control Sample Duplicate (LCSD) - A second LCS prepared and analyzed to measure
laboratory precision.
Mass Resolution - The ability of a mass spectrometer to distinguish the difference between two charged
particles with different mass-to-charge ratios. Two singly charged particles with masses of 300 and 301
atomic mass units (u) have a difference of 1 u and require a mass resolution of 1. Mass resolution is also
stated in terms of parts per million (ppm). Two singly charged particles with masses of 300.2959 and
300.3259 u have a resolution of 0.03 u, which could also be stated as 100 ppm. They would require a
mass resolution of 100 ppm or 0.03/300 (1/10,000) their nominal mass to enable the instrument to
distinguish them. Thus, we say that a resolution of 10,000 is needed.
Matrix - The predominant material of which the sample to be analyzed is composed. For the purpose of
this document, the sample matrices are: aqueous/water, soil/sediment, ash, tissue (non-human), oil, and
biosolids.
Matrix Effect - In general, the effect of a particular matrix on the constituents under study. This is
particularly pronounced for clay particles which may adsorb chemicals and catalyze reactions. Matrix
effects may prevent extraction of target analytes.
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High Resolution Data Review Appendix A
m/z Ratio - The ratio of mass to charge of a charged particle; used in mass spectrometry to focus specific
charged fragments of target analytes on the detector. This specificity is obtained by varying the electronic
field and magnetic field strengths.
Method Blank - A clean reference matrix sample (i.e., reagent water, silica sand, or corn oil) spiked with
labeled compounds and labeled internal standards that is carried throughout the entire analytical
procedure. The method blank is used to define the level of contamination associated with the processing
and analysis of samples.
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 7 replicates of the sample, the mean value must be 3.14s above the blank, where "s" is the
standard deviation of the 7 replicates.
Percent Solids (%Solids) - The proportion of solid in a soil/sediment sample determined by drying an
aliquot of the sample.
Perfluorokerosene (PFK) - A mixture of compounds used to calibrate the exact m/z scale in the Fiigh
Resolution Mass Spectrometer (HRMS).
Performance Evaluation (PE) Sample - A sample of known composition provided by an EPA Region
for Contractor analysis during routine analysis of field samples. Used by the EPA to evaluate Contractor
performance.
Preparation Log - An official record of sample preparation (extraction, cleanup).
Quality Assurance Technical Support (QATS) Laboratory - A Contractor-operated facility operated
under the QATS contract, awarded and administered by the EPA.
Raw Data - The originally recorded and unprocessed measurements from any measuring device such as
analytical instruments, balances, pipettes, thermometers, etc. Reported data are processed raw
measurement values that may have been reformatted from the original measurement to meet specific
reporting requirements such as significant figures and decimal precision.
Relative Percent Difference (RPD) - The relative percent difference is based on the mean of the two
values, and is reported as an absolute value (i.e., always expressed as a positive number or zero).
Relative Response (RR) - A measure of the detector response of the native analyte compared to its
labeled compound analog. RRs are determined using the area responses of both the primary and
secondary exact m/z for each compound in each calibration standard.
Relative Response Factor (RRF) - The ratio of the response of a given compound to its corresponding
internal standard. Response factors are determined using the area responses of both the primary and
secondary exact m/z for each compound in each calibration standard.
Relative Retention Time (RRT) - A ratio of the retention time of a compound to that of a standard (such
as an internal standard).
Relative Standard Deviation (RSD) - The standard deviation times 100 divided by the mean. Also
termed "coefficient of variation".
Resolution - Also termed Separation or Percent Resolution, the separation between peaks on a
chromatogram, calculated by dividing the depth of the valley between the peaks by the peak height of the
smaller peak being resolved, multiplied by 100.
Retention Time (RT) - The time a target analyte is retained on a Gas Chromatograph (GC) column
before elution. The identification of a target analyte is dependent on a target analyte's retention time
falling within the specified retention time window established for that analyte. The RT is dependent on
the nature of the column's stationary phase, column diameter, temperature, flow rate, and other
parameters.
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High Resolution Data Review Appendix A
Sample - A portion of material to be analyzed that is contained in single or multiple containers and
identified by a unique sample number.
Sample Delivery Group (SDG) - A unit within a sample Case that is used to identify a group of samples
for delivery. An SDG is defined by the following, whichever is most frequent:
• Each 20 field samples [excluding Performance Evaluation (PE) samples] within a Case, or
• Each 7 calendar day period during which field samples in a Case are received (said period
beginning with the receipt of the first sample in the SDG).
• All samples scheduled with the same level of deliverables.
• In addition, all samples assigned to an SDG must have been scheduled under the same contractual
turnaround time.
Samples may be assigned to SDGs by matrix (e.g., all soil/sediment samples in one SDG, all
aqueous/water samples in another) at the discretion of the laboratory. Laboratories shall take all
precautions to meet the 20 sample per SDG criteria.
Sample Management Office (SMO) - A Contractor-operated facility operated under the SMO contract,
awarded and administered by the EPA.
Sample Number (EPA Sample Number) - A unique identification number designated by EPA for each
sample. The EPA Sample Number appears on the sample Traffic Report/Chain of Custody (TR/COC)
Record which documents information on that sample.
SDG Narrative - Portion of the data package which includes laboratory, contract, Case, and Sample
Number identification, and descriptive documentation of any problems encountered in processing the
samples, along with corrective action taken and problem resolution. Complete Sample Delivery Group
(SDG) Narrative specifications are included in Exhibit B - Reporting and Deliverables Requirements of
the Statement of Work (SOW).
Selected Ion Current Profile (SICP) - The line described by the signal at an exact m/z.
Select Ion Monitoring (SIM) - A mode of Mass Spectrometry (MS) operation in which specific m/e
ratios are monitored, as opposed to scanning the entire mass range.
Signal-to-Noise Ratio (S/N) - The height of the signal as measured from the mean (average) of the noise
to the peak maximum divided by the width of the noise.
Soil - Synonymous with soil/sediment, sediment, and sludge as used herein.
Statement of Work (SOW) - A document which specifies how laboratories analyze samples under a
particular contract.
Target Analyte List (TAL) - A list of analytes designated by the Statement of Work (SOW) for
analysis.
Technical Holding Time - The maximum length of time that a sample may be held from the collection
date until extraction and/or analysis.
Time - hh:mm:ss - When required to record time on any deliverable item, time shall be expressed in
Military Time [i.e., a 24-hour clock (0000-2359)].
Toxic Equivalency Factor (TEF) - An estimate of the toxicity of a specific congener relative to 2,3,7,8-
tetrachlorodibenzo-/?-dioxin.
Toxic Equivalent (TEQ) - The product of the concentration of each individual World Health
Organization (WHO) toxic chlorinated biphenyl congener (CBC) or each individual 2,3,7,8-substituted
dibenzo-p-dioxin and dibenzofuran multiplied by their respective Toxic Equivalency Factors (TEFs).
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High Resolution Data Review Appendix A
Traffic Report/Chain of Custody Record (TR/COC) - An EPA sample identification form completed
by the sampler, which accompanies the sample during shipment to the laboratory and is used to document
sample identity, sample chain of custody, sample condition, and sample receipt by the laboratory.
Window Defining Mixture (WDM) - Prior to analyzing the calibration solutions, blanks, samples, and
Quality Control (QC) samples, the WDM is analyzed to evaluate descriptor switching times.
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High Resolution Data Review
Appendix B
APPENDIX B: HIGH RESOLUTION DATA REVIEW SUMMARY
CASE NO.
LABORATORY
MA NO.
REVIEWER NAME
SDGNo.
EPA REGIONAL CLP COR ACTION
SITE
NO. OF SAMPLES/MATRIX
SOW NO.
COMPLETION DATE
REGION
FYI
Review Criteria
Preservation and Holding Times
System Performance Checks
Initial Calibration
Continuing Calibration Verification
Blanks
Labeled Compound
Laboratory Control Sample/Laboratory
Control Sample Duplicate
Target Analyte Identification
Compound Quantitation
Method
CDD/CDF
CBC
April 2016
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High Resolution Data Review
Appendix B
Review Criteria
Second Column Confirmation
Estimated Detection Limit and Estimated
Maximum Possible Concentration
Toxic Equivalent Determination
Regional QA/QC
Overall Assessment of Data
Method
CDD/CDF
CBC
April 2016
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