Office of Superfund Remediaton and Technology IrmovaUon (OSRTI)
United Slates Environmental Protection Agency (USER*i)
Washington, DC 2CM60
OSWER 9240,1-53
EPA-540-R-11-016
September 2011
USEPA Contract Laboratory Program (CLP)
National
Functional
Guidelines
for Chlorinated Dibenzo-p-Oioxins (CDDs)
and Chlorinated Dibenzofurans (CDFs)
Data Review
Final
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NOTICE
The policies and procedures set forth here are intended as guidance to the United States Environmental
Protection Agency (hereafter referred to as EPA) and other governmental employees. They do not
constitute rule making by EPA, and may not be relied upon to create a substantive or procedural right
enforceable by any other person. The Government may take action that is at variance with the policies and
procedures in this manual.
This document may be obtained from the EPA's Contract Laboratory Program (CLP) Web site at:
http://www.epa.gov/superfund/programs/clp/guidance.htm
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Chlorinated Dioxin and Furan Data Review
TABLE OF CONTENTS
ACRONYMS iii
INTRODUCTION 1
DATA QUALIFIER DEFINITIONS 2
PRELIMINARY REVIEW 3
DATA REVIEW NARRATIVE 4
I. Holding Times, Storage, and Preservation 5
II. Performance Evaluation Samples (PES) 7
III. System Performance Checks 9
IV. High Resolution Gas Chromatograph/High Resolution Mass Spectrometer (HRGC/HRMS)
Initial Calibration 17
V. High Resolution Gas Chromatograph/High Resolution Mass Spectrometer (HRGC/HRMS)
Calibration Verification 21
VI. Method Blank Analysis 24
VII. Laboratory Control Sample (LCS) Analysis 27
VIII. Sample Dilution 29
IX. Identification Criteria 31
X. Compound Quantitation 34
XI. Second Column Confirmation and Isomer Specificity 38
XII. Toxicity Equivalent Quantity Determination 40
XIII. Estimated Detection Limit (EDL) and Estimated Maximum Possible Concentration (EMPC) 41
XIV. Labeled Compound Recoveries 43
XV. Regional Quality Assurance/Quality Control (QA/QC) 45
XVI. Overall Assessment of Data 46
APPENDIX A: DATA TABLES A-l
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Chlorinated Dioxin and Furan Data Review
LIST OF TABLES
Table 1. Qualifier Definitions 2
Table 2. Holding Times, Storage, and Preservation Evaluation Actions 6
Table 3. PE Sample Data Evaluation Actions 8
Table 4. System Performance Checks 16
Table 5. Initial Calibration 20
Table 6. Calibration Verification Evaluation Actions 23
Table 7. Method Blank Evaluation Actions 26
Table 8. Laboratory Control Sample (LCS) Recovery Actions 28
Table 9. Labeled Compound Recovery Actions 44
Table A.I. Descriptors, Exact Mass-to-Charge (m/z) Ratios, m/z Types, and Elemental Compositions of
the Chlorinated-p-Dioxins/Chlorinated Dibenzofurans (CDDs/CDFs) A-2
Table A.2. Gas Chromatography (GC) Retention Time (RT) Window Defining Mixture (WDM) and
Isomer Specificity Check (ISC) Standard A-4
Table A.3. Relative Retention Times (RRT) and Quantitation Reference of the Native and Labeled
CDDs/CDFs A-5
Table A.4. Theoretical Ion Abundance Ratios and Quality Control (QC) Limits A-6
Table A.5. Concentration of CDDs/CDFs in Calibration and Calibration Verification Solutions A-7
Table A.6. Acceptance Criteria for Laboratory Control Sample (LCS) A-8
Table A.7. Labeled Compound Recovery in Samples When All CDDs/CDFs are Tested A-9
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Chlorinated Dioxin and Furan Data Review
%D
%R
%RSD
%Valley
ASB
CDD
CDF
CDWG
CLP
CPS
CRQL
CS
CWA
DCDPE
DQO
EDL
EMPC
EPA
GC
HRGC
HpCDD
HpCDF
HpCDPE
HRMS
HxCDD
HxCDF
HxCDPE
ISC
LCS
MQO
NCDPE
NFG
Ng
ng/kg
ng/L
NRAS
OCDD
OCDF
OCDPE
OSRTI
OSWER
ACRONYMS
Percent Difference
Percent Recovery
Percent Relative Standard Deviation
Percent Valley
Analytical Services Branch of OSWER/OSRTI
Chlorinated Dibenzo-p-Dioxin
Chlorinated Dibenzofuran
Chlorinated Dioxins Workgroup
Contract Laboratory Program
Column Performance Solution
Contract Required Quantitation Limit
Calibration Standard
Clean Water Act
Decachlorodiphenyl ether
Data Quality Objective
Estimated Detection Limit
Estimated Maximum Possible Concentration
United States Environmental Protection Agency
Gas Chromatography/Gas Chromatograph
High Resolution Gas Chromatograph
Heptachlorinated Dibenzo-p-Dioxin
Heptachlorinated Dibenzofuran
Heptachlorodiphenyl Ether
High Resolution Mass Spectrometer
Hexachlorinated Dibenzo-p-Dioxin
Hexachlorinated Dibenzofuran
Hexachlorodiphenyl Ether
Isomer Specificity Check
Laboratory Control Sample
Measurement Quality Objective
Nonachlorodiphenyl Ether
National Functional Guideline
Nanograms (10~9 grams)
Nanograms per kilogram
Nanograms per liter
Non-Routine Analytical Services program
Octachlorinated Dibenzo-p-Dioxin
Octachlorinated Dibenzofuran
Octachlorodiphenyl Ether
Office of Superfund Remediation and Technology Innovation
Office of Solid Waste and Emergency Response
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Chlorinated Dioxin and Furan Data Review
PCDF
PCDPE
PE
PES
PeCDD
PeCDF
PFK
pg/L
PO
QA
QAPP
QATS
QC
RR
RR (Mean RR)
RRF
RRF (Mean RRF)
RRT
RSD
RT
S/N
SAP
SDG
SDWA
SICP
SIM
SOP
SOW
TCDD
TCDF
TCL
TEF
TEQ
TICP
TIFSD
TO
TOPO
TOCOR
TR/COC
WDM
Polychlorinated Dibenzofuran
Polychlorinated Diphenyl Ether
Performance Evaluation
Performance Evaluation Sample
Pentachlorinated Dibenzo-p-Dioxin
Pentachlorinated Dibenzofuran
Perfluorokerosene
Picograms per liter
EPA Project Officer (under the NRAS program, usually Regional personnel)
Quality Assurance
Quality Assurance Project Plan
Quality Assurance Technical Support (an EPA contract)
Quality Control
Relative Response
Mean Relative Response
Relative Response Factor
Mean Relative Response Factor
Relative Retention Time
Relative Standard Deviation
Retention Time
Signal-to-Noise
Sampling and Analysis Plan
Sample Delivery Group
Safe Drinking Water Act
Selected Ion Current Profile
Selected Ion Monitoring
Standard Operating Procedure
Statement of Work
Tetrachlorinated Dibenzo-p-Dioxin
Tetrachlorinated Dibenzofuran
Target Compound List
Toxicity Equivalency Factor
Toxic Equivalent Quantity
Total Ion Current Profile
Technology Innovation and Field Services Division
Task Order
Task Order Project Officer
Task Order Contract Officer Representative
Traffic Report/Chain of Custody
Window Defining Mixture
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Chlorinated Dioxin and Furan Data Review
INTRODUCTION
These National Functional Guidelines for Chlorinated Dioxin and Furan Data Review (hereafter referred
to as the NFG) are designed to offer guidance on technical evaluation and review of data for chlorinated
dibenzo-p-dioxins (CDD) and chlorinated dibenzofurans (CDF) as generated under the USEPA Analytical
Services Branch Statement of Work for Analysis of Chlorinated Dibenzo-p-Dioxins (CDDs) and
Chlorinated Dibenzofurans (CDFs) Multi-Media, Multi-Concentration (DLM02.2) (hereafter referred to
as DLM02.X or DLM02.2). The DLM02.2 SOW is based on EPA Method 1613 (Revision B) and SW-
846 Method 8290A (Revision 1) which use High Resolution Gas Chromatography/High Resolution Mass
Spectrometry (HRGC/HRMS). In some applications, this document may be used as a Standard Operating
Procedure (SOP). In other more subjective areas, only general guidance is offered due to the complexities
and uniqueness of data relative to specific samples. For example, areas where the application of specific
SOPs is possible are primarily those in which definitive performance criteria are established. These
criteria are concerned with specifications that are not sample-dependent; they specify performance
requirements that should fully be under a laboratory's control. These specific areas include blanks,
calibration standards, Performance Evaluation Sample (PES) materials, and instrument performance
checks.
EPA Method 1613 (Revision B) can be obtained at the following link:
http://www.epa.gOv/waterscience/methods/l 613 .pdf
EPA SW-846 Method 8290A (Revision 1) can be obtained at the following link:
http://www.epa.gov/epaoswer/hazwaste/test/pdfs/8290a.pdf
As stated above, the NFG are intended to assist in the technical review of analytical data generated
through the DLM02.2 SOW. Determining contract compliance is not an intended objective of these
guidelines. The data review process provides information on the quality of analytical data, based on
specific Quality Control (QC) criteria. To provide more specific usability statements, the reviewer must
have a complete understanding of the intended use of the data. For this reason, it is recommended that
whenever possible, the reviewer should obtain usability requirements from the data user prior to
reviewing the data. When this is not possible, the data user is encouraged to communicate any questions
to the reviewer.
At times, there may be a need to use data which do not meet all contract requirements and technical
criteria. Use of these data does not constitute either a new requirement standard or full acceptance of the
data. The only exception to this condition is in the area of the requirements for individual sample analysis;
if the nature of the sample itself inhibits the attainment of specifications, appropriate allowances must be
made. Any decision to utilize data for which performance criteria have not been met is strictly to facilitate
the progress of projects requiring the availability of the data. A contract laboratory submitting data that
are out of specification may be required to reanalyze samples or resubmit data, even if the previously
submitted data have been utilized due to program needs.
Because of the toxicity of the analytes, these guidelines 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.
Please note that in these guidelines, the isotopically-labeled PCDDs/PCDFs that are added to each sample
prior to extraction, and ultimately are used for analyte quantitation, are called, "labeled standards," and
the labeled PCDDs/PCDFs that are added just prior to injection are called, "internal standards."
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Chlorinated Dioxin and Furan Data Review
DATA QUALIFIER DEFINITIONS
The following definitions provide brief explanations of the data qualifiers assigned to results in the data
review process. If the data reviewer chooses to use additional qualifiers, a complete explanation of those
qualifiers must accompany the data review.
Table 1. Qualifier Definitions
Data
Qualifier
Qualifier Definitions
U
The analyte was analyzed for but not detected. The value preceding the "U" may represent
the adjusted Contract Required Quantitation Limit (see DLM02.X, Exhibit D, Section 1.2
and Table 2), or the sample specific estimated detection limit (EDL, see Method 8290A,
Section 11.9.5).
The analyte was positively identified and the associated numerical value is the approximate
concentration of the analyte in the sample (due either to an issue with the quality of the
data generated because certain QC criteria were not met, or the concentration of the analyte
was below the adjusted CRQL).
UJ
The analyte was not detected (see definition of "U" flag, above). The reported value should
be considered approximate.
R
The sample results are unusable due to the quality of the data generated because certain
criteria were not met. The analyte may or may not be present in the sample.
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PRELIMINARY REVIEW
To use this document effectively, the reviewer must have an understanding of the analytical method and a
general familiarity with the sample delivery group (SDG) or sample Case at hand. The exact number of
samples, their assigned numbers, their matrix, and the number of laboratories involved in their analysis
are essential information. Background information on the site is also helpful, but often this information
may be difficult to locate. If available, the field notes should be reviewed. The site manager is the best
source for answers to questions, or for further direction.
Please note that individual Task Orders (TOs) may modify the DLM02.X SOW requirements, which will
affect the generated data. For example, holding times, extraction procedures, compound analyses and
calibration requirements, etc., may be affected by an individual TO, depending on project requirements.
Thus, the TO requirements must be taken into consideration, along with the requirements in the statement
of work (SOW) document, when reviewing the data.
The SDGs or Cases often have unique samples which require special attention by the reviewer. These
samples may include field blanks, field duplicates, and Performance Evaluation Samples (PES) which
need to be identified. The sampling records must provide:
1. The Region where the samples were taken
2. A complete list of samples with information on:
a. Laboratories involved
b. Shipping dates
c. Preservatives
d. Sample matrix
e. Field blanks*
f Field duplicates*
g. Field spikes*
h. Quality Control (QC) audit samples*
* If applicable.
The TR/COC documentation includes sample descriptions, date(s) andtime(s) of sampling, sample
location, and sample matrix. The laboratory's SDG Narrative is another source of general information.
Notable problems with matrices, insufficient sample volume for analysis or reanalysis, samples received
in broken containers, and unusual events should be listed in the SDG Narrative. As required in DLM02.X,
Exhibit B, Section 2.5.1.2, any equations used to process sample data should be provided to enable a
recalculation of the data. This should include examples of each type of calculation used to generate the
actual results.
The SDG Narrative for the sample data package must include a Laboratory Certification Statement
(exactly as stated in the DLM02.X SOW), signed by the Laboratory Manager or their designee. This
statement authorizes the validation and release of sample data results. In addition, the laboratory must
also provide comments in the SDG Narrative describing in detail any problems encountered in processing
the samples associated with the data package.
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Chlorinated Dioxin and Furan Data Review
DATA REVIEW NARRATIVE
It is strongly encouraged that a Data Review Narrative should accompany the laboratory data forwarded
to the intended data recipient (client) or user to promote communications. A copy of the Data Review
Narrative should also be submitted to the TOCOR or SMO. The TOCOR with assigned oversight
responsibility for the laboratory producing the data must be kept informed of all contract compliance
issues noted during the review process.
The Data Review Narrative should include comments that clearly identify the problems associated with a
Case or SDG and state any resulting limitations that should be placed on the data. Documentation must
include the sample number, analytical method or modification, extent of the problem, and assigned
qualifiers.
Additional information that should be included in the Data Review Narrative includes, but should not be
limited to, calculation checks, documentation of any approved laboratory deviations from the contract
SOW, and an explanation of any laboratory-assigned data qualifiers that may be found in the data.
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Chlorinated Dioxin and Furan Data Review
I. Holding Times, Storage, and Preservation
A. Review Items:
FORM 1DFA, 1DFB, 1DFC, or 1DFD (FORM I-HR CDD-1, CDD-2, CDD-3, or CDD-4), EPA
Sample TR/COC documentation, raw data, and sample extraction sheets. Reference DLM02.X,
Exhibit B, Section 3.4.1 - Section 3.4.4 and Exhibit D, various sections.
B. Objective:
To ascertain the validity of sample results based on the contractual holding time, storage, and
preservation of the sample from time of collection to time of sample extraction and analysis.
C. Criteria:
i. Aqueous and soil samples must be stored at 4°C (±2°C) in the dark from the time of collection
until extraction. If residual chlorine is present in aqueous samples, 80 mg of sodium thiosulfate
per liter of sample is added. If the aqueous sample pH is >9, it must be adjusted to pH 7-9 with
sulfuric acid.
2. Aqueous and soil samples must be extracted and analyzed within 35 days of the last sample
receipt date in the SDG per contract requirements. However, technical holding time requirements
allow that water and soil samples may be stored at 4°C (± 2°C), and tissue samples and sample
extracts can be stored at <-10°C in the dark for up to one year (DLM02.X, Exhibit D, Section
8.3).
3. Fish and tissue samples must be received at the laboratory at a temperature of <4°C and must be
stored at the laboratory at <-10°C until prepared. Once thawed, tissue samples must be extracted
within 24 hours.
NOTE: Aqueous samples, subject to compliance with the SDWA and/or CWA (40CFR Part
136.3), may have unique holding time requirements. Check the current 40 CFR Part 136.3
reference. Other analytical protocols may specify different storage conditions.
4. Holding times for oily matrices have not been established. The aqueous holding times are
recommended in this situation. Holding times for fish and tissue samples have not been
established; however, they should be extracted within one year of collection as recommended in
EPA Method 1613 (Revision B). As always, the professional judgment of the reviewer remains
the final authority in issues such as these.
D. Evaluation:
1. Technical holding times for sample extraction are established by comparing the sampling dates
on the TR/COC documentation with the dates of extraction on the sample extraction sheets and
on FORM I-HR CDD-1, CDD-2, CDD-3, or CDD-4. To determine whether the samples were
analyzed within the holding time after extraction, compare the dates of extraction on the sample
extraction sheets with the dates of analysis on FORM I-HR CDD-1.
2. Verify that the TR/COC documentation indicates that the samples were received intact and iced at
4°C (±2°C). Special consideration should be given for samples delivered directly from the field to
the laboratory. Note in the Data Review Narrative 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.
3. The impact on data quality of holding time exceedances depends on all the factors discussed
above. Regional standard operating procedures (SOPs) may have secondary criteria for data
qualification when the primary criteria have been exceeded. The reviewer should rely on
professional judgment, but should completely document the logic behind data qualification
decisions.
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Chlorinated Dioxin and Furan Data Review
E. Action:
1. If holding times are exceeded, qualify all detects as estimated "J" and qualify non-detects as
estimated "UJ" or unusable "R" (see Evaluation, Section D, above). Document that holding times
were exceeded (see Table 2).
2. If shipment and storage conditions are exceeded, either on the first analysis or upon reanalysis,
use professional judgment to determine if the detects or non-detects are affected and qualify with
estimated "J" or "UJ", respectively.
3. If sodium thiosulfate preservative has not been added to aqueous samples with a chlorine
residual, qualify all detects as estimated "J" and non-detects as rejected "R". If a residual chlorine
test has been performed and found to be negative, do not qualify the data due to lack of sodium
thiosulfate preservative.
4. There is limited information concerning holding times for oily samples; use professional
judgment. It is recommended to apply aqueous holding time criteria to oily samples.
5. Use professional judgment to evaluate holding times for fish and tissue samples.
6. For all sample extracts correctly stored and analyzed outside the 35-day contractual holding time,
but within the 1-year technical holding time, no qualification of the data is necessary.
7. For all sample extracts not correctly stored and analyzed outside the 3 5-day contractual holding
time but within the 1-year technical holding time, qualify detects estimated "J" and non-detects
estimated "UJ".
8. Qualify detects in sample extracts analyzed outside the 1-year technical holding time as estimated
"J". Qualify non-detects estimated "UJ" or unusable "R", depending on professional judgment.
9. When holding times are exceeded, note in the Data Review Narrative the effect that the exceeded
holding times will have on the data and also note as an action item for the TOCOR or SMO.
Table 2. Holding Times, Storage, and Preservation Evaluation Actions
Evaluation
Technical
Holding Time
Storage
Temperature
Preservation
Sample Extract
Holding Time*
Sample Extract
Holding Time**
Sample
Type
Aqueous
Soil
Fish, Tissue
Aqueous
Soil
Fish, Tissue
Aqueous
All types
All types
Criteria Exceedance
>1 year
>1 year
>1 year
>4°C shipment and storage
>4°C shipment and storage
>4°C shipment and
>-10°C storage
C12 present but Thiosulfate not
added
pH not adjusted when required
>35 days <1 year
>35 days <1 year
>1 year
Action
Detected
Associated
Compounds
J
J
Non-Detected
Associated
Compounds
UJorR
UJorR
Use professional judgment
J
J
J
J
J
UJ
UJ
UJ
R
UJ
No qualification
J
J
UJ
UJorR
* If correctly stored
* * If not correctly stored
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Chlorinated Dioxin and Furan Data Review
II. Performance Evaluation Samples (PES)
A. Review Items:
FORM 1DFA (FORM I-HR CDD-1), Performance Evaluation Sample (PES) scoring information
from the QATS laboratory, PES instructions (shipped with samples should be included in the
deliverable).
B. Objective:
Data for PESs are generated to provide information on the overall accuracy and bias of the analytical
method and on laboratory performance. Results for PESs are evaluated for false negatives, false
positives, and accuracy of target compound quantitation.
C. Criteria:
1. The Region may provide the laboratory with PESs to be analyzed with each sample delivery
group (SDG). These may include blind spikes and/or blind blanks. The laboratory must analyze a
PES when provided by the Region.
2. The Region may score the PES based on data provided by QATS.
D. Evaluation:
1. If PESs are included in the SDG, verify that the results are within the action limits [99% (3a)
confidence interval] and warning limits [95% (2a) confidence interval]. If a blind blank is
included, verify that no target analytes are present. The results of the blind blank analysis should
be comparable to the associated method blank (see Section VI of this document, Method Blank
Analysis).
2. If a significant number (i.e., half or more) of the analytes in the PES fall outside of the 95% or
99% warning or action criteria, or if a number of false positive results are reported, the reviewer
must evaluate the overall impact on data quality.
E. Action:
If a result is not within acceptance criteria for any congener, evaluate the other Quality Control (QC)
samples in the SDG [laboratory control sample (LCS), calibration, labeled standard recovery, internal
standard recovery, and cleanup standard recovery]. In such situations, the PES may not be
representative of the field samples. Performance evaluation samples are only one indicator of
technical performance of the laboratory. In general, for PES analytes not within the 95% confidence
intervals or warning performance windows but within the 99% confidence interval, qualify associated
sample detects as estimated "J" and non-detects as estimated "UJ". For data outside the 95% or 99%
confidence intervals and scored as "warning-high" or "action-high", qualify associated sample detects
as estimated "J". Non-detect results should not be qualified in this instance. If the results are scored as
"action-low", qualify the associated sample detects as estimated "J" and non-detects as unusable "R"
(see Table 3). Contact the TOCOR and/or SMO if reanalysis of samples is required.
For Example: If HxCDD is quantitated beyond the high end of the action limit and all samples
are non-detects for this compound, the usability of the data would not be affected. On the other
hand, in the situation described in Section D.2 above, it may be necessary to qualify all sample
data, and not only those analytes present in the PES.
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Chlorinated Dioxin and Furan Data Review
Table 3. PE Sample Data Evaluation Actions
Criteria
Results are not within the 95% confidence interval (>2a) but inside
the 99% interval (<3a), and are biased low (Warning - Low)
Results are not within the 95% confidence interval (>2a) but inside
the 99% interval (<3a), 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
Detected
Associated
Compounds
J
J
J
J
Non-Detected
Associated
Compounds
UJ
No
qualification
No
qualification
R
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Chlorinated Dioxin and Furan Data Review
III. System Performance Checks
Prior to analyzing the calibration solutions, blanks, samples, and QC samples, the analyst must establish
the HRGC and HRMS operating conditions necessary to obtain optimum performance. There are three
fundamental HRGC/HRMS system performance checks, including Mass Calibration and Resolution, the
Mass Spectrometer Selected Ion Monitoring (SIM) scan descriptor switching times, and Gas
Chromatographic (GC) resolution. There is a fourth performance check that should be considered in
evaluating data quality, instrument stability. These four checks are discussed below.
1. Mass Calibration and Mass Spectrometer Resolution
A. Review Items:
Hardcopy of the Mass Spectrometer resolution demonstration. Reference DLM02.X, Exhibit D,
Sections 9.2 and 9.2.1.4.
B. Objective:
Perform mass calibration and set Mass Spectrometer resolution to >10,000 using perflurokerosene
(PFK) as a calibrant. This is a fundamental requirement for any laboratory using DLM02.X and other
HRMS methods. If mass calibration and resolution tuning are not correctly performed, interferences
may degrade CDD/CDF identification and quantitation.
C. Criteria:
Laboratories are required to provide evidence of Mass Spectrometer resolving power > 10,000 at the
beginning and end of each 12-hour analytical sequence. Documentation of Mass Spectrometer
resolving power must include a hardcopy peak profile of a high-mass reference signal from PFK (e.g.,
m/z 380.9760) obtained during peak matching with another high-mass ion (e.g., m/z 304.9824). The
selection of the low- and high-mass ions must be such that they provide the largest voltage jump in
the mass descriptor being checked. The format of the peak profile representation must allow manual
determination (i.e., by the data reviewer) of Mass Spectrometer resolution [the horizontal axis should
be a calibrated mass scale, with amu or ppm per division. The result of the peak width measurement
must appear on the hardcopy. The deviation between the exact mass measured m/z (m/zmon) and the
target m/z (m/zth) must be <5 ppm (i.e., the value found for m/z 380.9760 must be accurate to ±
0.0019)].
Res.ppm = —— > 10,000
ml zth-ml Zn,
D. Evaluation:
Verify that the Mass Spectrometer has been tuned to a resolving power of > 10,000. A demonstration
of Mass Spectrometer resolving power is provided in EPA SW-846 Method 8290A (Revision 1),
Figure 5. Additional information about interpretation of the chart may be found in 8290A, Figure 2.
E. Action:
Mass Spectrometer resolution is critical to the success of this method of CDD/CDF analysis. In the
event that Mass Spectrometer resolution is < 10,000, the risk of false positive results may exist. If a
demonstration of the required mass resolution is not provided, the reviewer must carefully evaluate
other factors to determine whether or not there is sufficient evidence of adequate resolution to
preclude interference from other ions with similar mass-to-charge ratios (m/z). This may include, but
should not be 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, baseline noise in calibrations,
blanks and in the lock mass trace, and calibration performance. The appropriate course of action,
based on these factors and the professional judgment of the reviewer, may range from no qualification
to rejection of all positive results.
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Chlorinated Dioxin and Furan Data Review
2. Window Defining Mixture (WDM)
A. Review Items:
FORM 5DFA (FORM V-HR CDD-1). Reference DLM02.X, Exhibit B, Section 3.4.8 and Section 4
and Exhibit D, Section 9.2.3.
B. Objective:
Prior to the calibration of the FiRGC/HRMS system, establish the appropriate switching times for the
SIM descriptors (see Table A. 1) and verify the chromatographic resolution. The switching times are
determined by the analysis of the WDM which contains the first and last eluting isomers in each
homologous series (see Table A.2). It is not necessary to analyze the WDM if only 2,3,7,8-TCDD and
2,3,7,8-TCDF are requested. Chromatographic resolution is verified by analyzing one of three Isomer
Specificity Check (ISC) solutions, depending on the GC column used for analysis. The WDM and
ISC can be combined in a single Column Performance Solution (CPS) analysis at the discretion of the
analyst.
The 12-hour time period begins with the injection of the WDM or CPS.
C. Criteria:
1. To evaluate the Mass Spectrometer 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, once at the beginning and end of each 12-hour period during which
standards or samples are analyzed and whenever adjustments or instrument maintenance activities
are performed that may affect Retention Times (RTs). This commercially available, 16-
component mixture contains the first and last eluting isomers in each homologous series.
Mixtures are available for various columns. The mixture for the DB-5 (or equivalent) column
may not be appropriate for the DB-225 or other columns. The standard must contain the
compounds listed in Table A.2, at a minimum.
2. The ions in each of the five recommended descriptors are arranged for minimal overlap between
the descriptors. The ions for the TCDD and TCDF isomers are in the first descriptor, the ions for
the PeCDD and PeCDF isomers are in the second descriptor, the ions for the HxCDD and
HxCDF isomers are in the third descriptor, the ions for the HpCDD and HpCDF isomers are in
the fourth descriptor, and the ions for the OCDD and OCDF isomers are in the fifth descriptor. In
some cases, TCDD/DF and PeCDD/DF are combined in a single descriptor.
3. The descriptor switching times are set such that the isomers that elute from the GC during a given
RT window will also be those isomers for which the ions are monitored. If homologue overlaps
between descriptors occur, the laboratory may use professional judgment in setting the switching
times. The switching times are not to be set such that a change in descriptors occurs at or near the
expected RT of any 2,3,7,8-substituted isomers.
4. The WDM must be analyzed at the following frequency:
• Before initial calibration on each instrument and GC column used for analysis;
• Each time a new initial calibration is performed, regardless of reason;
• Each time adjustments or instrument maintenance activities are performed that may affect
RTs; and
• At the beginning and ending of each 12-hour sample analysis period prior to the calibration
verification.
5. If the laboratory uses a GC column that has a different elution order than the columns specified,
the laboratory must ensure 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.
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Chlorinated Dioxin and Furan Data Review
6. Analysis on a single GC column (as opposed to situations requiring second column confirmation)
is acceptable if the required separation of all of the 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 XI).
D. Evaluation:
1. Verify that the WDM is analyzed at the required frequency.
2. Examine the WDM chromatograms to determine whether the switching times have been
optimized properly, 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 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 A.3.
E. Action:
1. If the WDM was not analyzed at the required frequency 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, results may be usable without qualification. Qualify total
homologue results as estimated "J" or "UJ" since one or more CDDs/CDFs may not have been
detected (these are generally all qualified as J/UJ due to the nature of the quantitation method, see
X.E.2).
2. If the chromatography for the calibration standards indicates a significant problem with descriptor
switching times such that 2,3,7,8-substituted target analytes may have been missed, qualify all
associated data as unusable "R". Notify the TOCOR and/or SMO to decide if sample reanalysis is
necessary.
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Chlorinated Dioxin and Furan Data Review
3. Chromatographic Resolution
A. Review Items:
FORM 5DFB (FORM V-HR CDD-2), and the corresponding Selected Ion Current Profile (SICP) of
each isomer and each of the analyses reported on FORM 5DFB. Reference DLM02.X, Exhibit B,
Section 3.4.9 and Section 4, and Exhibit D, Section 9.2.4.
B. Objective:
Evaluate the ability of the GC column to resolve the closely eluting dioxin and furan isomers. An
evaluation [isomer specificity check (ISC)] must be made for each column used in the analysis of
samples.
C. Criteria:
The resolution criteria must be evaluated using measurements made on the SICPs for the appropriate
ions for each isomer. Measurements are not to be performed on Total Ion Current Profiles (TICPs).
1. For analyses on a DB-5 (or equivalent) GC column, the chromatographic resolution is evaluated
by the analysis of the commercially available, 4-component DB-5 ISC standard prior to both the
initial and calibration verification procedures for each instrument and GC column used for
analysis. The laboratory may combine the ISC and WDM in a single Column Performance
Solution (CPS) analysis.
a. 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% using the following equation:
%Valley = -xlOO
y
Where,
x = The measurement from the baseline to the deepest part of the valley between
2,3,7,8-TCDD and 1,2,3,8-TCDD
y = The peak height of 2,3,7,8-TCDD
b. For the DB-5 (or equivalent) column, the 12-hour sample analysis period begins by 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 calibration verification solutions. Evaluate the chromatographic resolution using QC
criteria listed above.
2. The chromatographic resolution for analyses on the confirmational (DB-225 or equivalent) GC
column is evaluated using a commercially available, 3-component DB-225 ISC standard
containing the tetrachlorinated dibenzofuran (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 of <25% using the following equation:
%Valley = -xlOO
y
Where,
x = The measurement from the baseline to the deepest part of the valley between
2,3,7,8-TCDF and 2,3,4,7-TCDF
y = The peak height of 2,3,7,8-TCDF
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Chlorinated Dioxin and Furan Data Review
Further analysis may not proceed until the GC resolution criteria have been met.
3. If the laboratory uses a GC column other than the columns specified here, 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 shall be resolved with a valley of <25%.
4. Analysis on a single GC column (as opposed to situations requiring second column confirmation)
is acceptable if the required separation of all of the 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.
D. Evaluation:
Verify that the ISC or CPS has been analyzed at the appropriate frequency, and examine the SICPs to
verify that the =S= 25% valley criteria have been m elExamples of GC resolution can be found in EPA
Method 1613, (Revision B), Figures 6 and 7, and SW-846 Method 8290A (Revision 1), Figure 4.
Technical acceptance criteria must be met before any standards, samples, QC samples, and required
blanks are analyzed. However, if the ISC or CPS is not present, but a successful calibration check
standard has been analyzed, and chromatographic performance in the samples does not indicate
interference with and 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
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:
If the GC resolution on the DB-5 (or equivalent) column does not meet the specifications for TCDD,
professional judgment should be used to evaluate the severity of the non-compliant chromatographic
resolution and qualify results as necessary. These failed resolution criteria can be indicative of the
potential for poor resolution between other closely eluting homologues, as well as between CDD/CDFs
and interfering compounds. Qualify all detects as estimated "J" (see Table 4) and notify SMO to schedule
sample reanalysis. Please note that resolution criteria should not affect HpCDD, OCDD, or OCDF since
there is only one isomer in each group, and these results should not be qualified. Non-detect results
should not be affected by resolution non-compliance.
September 2011 13
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Chlorinated Dioxin and Furan Data Review
4. Instrument Stability
A. Review Items:
Raw data for the midpoint (CSS) standard and WDM at the beginning of the 12-hour sample analysis
period and lock-mass trace (should be present in each injection).
B. Objective:
Demonstrate that the HRGC/HRMS system has retained adequate stability.
1. The WDM or CPS is analyzed at the beginning and end of each 12-hour period or analytical
sequence during which samples and standards are analyzed. The use of the WDM as a measure of
instrument stability includes the evaluation of the presence of the WDM isomers in each
descriptor over time.
2. The CSS standard is analyzed at the beginning and end of each 12-hour period or analytical
sequence, after the WDM. The end analysis may also serve as the beginning analysis of the
subsequent 12-hour period. The use of the CSS standard as a measure of instrument stability
includes the evaluation of GC retention times, relative ion abundance criteria, sensitivity, and
calibration criteria.
3. A channel monitoring one of the ions of the PFK that is continuously bled into the system should
be present in each set of SICPs. The use of the lock-mass trace as a measure of instrument
stability includes evaluating the shape of the response peaks in the peak matching experiment,
and the ability, over time, of the system to show adequate peak shape.
C. Criteria:
The CSS solution must meet the following QC criteria:
1. Absolute RT criteria: The absolute RT of the first internal standard must exceed 25.0 minutes on
the DB-5 column (or equivalent column), and 15.0 minutes on the DB-225 column (or equivalent
column).
2. Relative Retention Time (RRT) criteria: The RRTs of the native and labeled CDDs/CDFs shall be
within the limits described in Section V and Table A.3.
3. Ion abundance ratio criteria: All native and labeled CDDs/CDFs in the CSS standard must be
within their respective ion abundance ratios (see Table A.4).
4. Instrument sensitivity criteria: The peaks representing both native and labeled analytes in the CSS
standard must have signal-to-noise (S/N) ratios >10:1.
5. Response criteria: The Percent Difference (%D) of the Relative Response (RR) must be within
±25% of the mean RR of the initial calibration. The %D of the mean Relative Response Factor
(RRF) must be within ±35% of the initial calibration. Use the following equation to calculate the
%D:
Response™ - Response;,*
Response^
Where,
Responsever = Response (RR or RRF) observed during calibration verification
Responsemt = Mean response (RR or RRF ) established during initial calibration
according to DLM02.X, Exhibit D
September 2011 14
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Chlorinated Dioxin and Furan Data Review
D. Evaluation:
i. Verify that the CSS standard meets the criteria for both RT and RRT, ion abundance ratio, S/N
ratio, and response (%D associated with RR and RRF). If the RT changes by more than ± 15
seconds when compared to previous calibration standards, the reviewer should carefully examine
subsequent samples to determine if the change is an isolated occurrence or if the RTs of the
internal standards are consistent throughout the 12-hour period. If the CSS internal standard RTs
have changed by more than ±15 seconds but subsequent sample internal standards are consistent
and in compliance with the initial calibration, the cause may have been a delayed injection.
Similarly, if ion abundance ratios are outside the ± 15% window, examine other peaks in the
standard, and sample analyses to determine whether there is a consistent pattern. This may be
caused by a co-eluting interferent with a response on one channel, or there may be an issue with
mass spectrometer tuning.
2. An example of the measurement of S/N can be found in EPA SW-846 Method 8290A (Revision
1) and can be obtained at: http://www.epa.gov/sw_846/pdfs/8290a.pdf Also, as a qualitative
check, examine the lock-mass trace for each descriptor. In a calibration standard, it should be
quiet, with no excursions over 10% of scale. Excessive spikes or drift may indicate sample
carryover or a poorly performing system.
E. Action:
1. The RTs and RRTs of the CSS internal standards are indicative of the stability of the
chromatographic system. Notify SMO to schedule sample reanalysis under a compliant
calibration. If this is not possible, use caution in interpreting the data (see Table 4). If the
evidence indicates system RTs have changed, descriptor switching times may no longer be valid.
However, for the recommended DB-5 and DB-225 (or equivalent) columns, this should have no
impact on the 2,3,7,8 target analytes, only on the combined homologue totals. The direction of
bias in homologue totals in this situation is unknown (and these are generally all qualified as J/UJ
anyway due to the nature of the quantitation method, see X.E.2).
2. The relative ion abundance, sensitivity (S/N, RRF), and stability (%D) determined from the CSS
calibration check are all indicators of instrument stability. Qualify detects as estimated "J" if any
of these criteria fail. Failure of the S/N criteria (S/N ratio <10:1 in the CSS calibration verification
standard) is especially indicative of degraded instrument performance. Qualify all positive results
in associated samples as estimated "J" and reject non-detects ("R") because of the possibility of
false negatives. When relative ion abundances are non-compliant in the calibration check
standard, and a trend is evident, the laboratory should be contacted to repeat the analytical
sequence. If no trend is observed, the impact should be on quantitation of detects and non-detects.
All results should be "J" qualified. If only the %D criterion is not met, follow the data
qualification action described in Section V and Table 6 ("J" all).
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Chlorinated Dioxin and Furan Data Review
Table 4. System Performance Checks
Criteria
Mass Spectrometer resolution ofD D 0,000 is not
demonstrated
WDM fails, or
WDM adjustments are not made, or
WDM is not reported, and
Calibration standard performance is acceptable
WDM fails, and
WDM adjustments are not made, and
Calibration standards indicate a problem in detecting 2,3,7,8-
substituted congeners because of gross errors in the scan
descriptor times
ISC fails (GC Resolution (% Valley) of >25%), or
ISC adjustments are not made
ISC fails, or
ISC adjustments are not made, and
Calibration standards or samples indicate a problem in
resolving 2,3,7,8-substituted congeners
RT changes >15 seconds or RRT changes not within the
values in Table A. 3
Relative ion abundance criteria is not within windows in CS3
(12-hour) standard
S/N ratio < 10: 1 in CS3 standard
%D greater than criteria in CS3 standard
Action1
Detected
Associated
Compounds
Ror
professional
judgment
J-Homologue
Totals Only
R
J all tetra - hexa-
congeners
R
Non-Detected
Associated
Compounds
No qualification
UJ-Homologue
Totals Only
R
Not qualified
R
Use professional judgment for
qualification of target analytes; qualify
homologue totals as estimated (J, UJ).
J
J
J
UJ
R
UJ
1. In any case where data would by rejected by these rules, the reviewer should contact the TOPO to discuss requesting the laboratory to
reanalyze or to re-extract and reanalyze.
September 2011
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Chlorinated Dioxin and Furan Data Review
IV. High Resolution Gas Chromatograph/High Resolution Mass Spectrometer
(HRGC/HRMS) Initial Calibration
A. Review Items:
FORM 6DFA (FORM VI-HR CDD-1), FORM 6DFB (FORM VI-HR CDD-2), and raw data for all
standards. Reference DLM02.X, Exhibit B, Section 3.4.11, Section 3.4.12, and Section 4, and Exhibit
D, Section 9.3.
B. Objective:
Establish compliance requirements for satisfactory instrument calibration to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data for the CDDs/CDFs.
The objective of the initial calibration is to establish a linear range, Mean Relative Responses (RR s)
of the unlabeled native analytes and the Mean Relative Response Factors (RRF) for the labeled
internal standards and cleanup standard. The initial calibration is to be used for routine quantitation of
samples using the RR s and RRF established from the five Calibration Standards (CS1, CS2, CS3,
CS4, and CSS). Subsequent calibration verifications occurring every 12 hours thereafter are not to be
used for quantitation of samples, nor is the initial midpoint (CS3) solution to be used for this purpose.
C. Criteria:
The initial calibration criteria are strict because of their use in quantitation of sample data and the
infrequency of initial calibration. Thus, the initial calibration affects the quality of the data based on it
for an extended period of time.
Once the perfluorokerosene (PFK), window defining mixture (WDM), isomer specificity check
(ISC), and column performance solution (CPS) solutions have all been analyzed, and after the
descriptor switching times have all been verified, the five calibration standards described in Table A.5
must be analyzed prior to any sample analysis.
The following criteria must be met for the initial calibration to be acceptable: GC resolution; ion
abundance ratio; retention time (RT); relative retention time (RRT); instrument sensitivity [signal-to-
noise (S/N)]; linearity of analyte response associated with relative response (RR) and relative
response factor (RRF); analyte concentration (ng/mL); and calibration frequency.
1. GC resolution criteria: Use DB-5, DB-225, or equivalent columns (see Section III.3).
2. Ion abundance criteria: The relative ion abundance criteria for CDDs/CDFs listed in Table A.4,
must be met for all CDD/CDF peaks, including the isotope-labeled peaks, in all solutions. The
lower and upper limits of the ion abundance ratios represent a ±15% window around the
theoretical abundance ratio for each pair of selected ions (see Table A.I, for m/z types and Table
A.4 for m/z ratios). The 37Cl4-2,3,7,8- TCDD cleanup standard contains no 35C1, therefore the ion
abundance ratio criteria do not apply to this compound.
3. Retention Time criteria: For all calibration solutions, the RTs of the isomers 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 exceed 25 minutes on the DB-5 (or equivalent)
column and 15 minutes on the DB-225 (or equivalent) column to ensure adequate resolution
between targets and to separate known interfering substances.
4. Mass Spectrometer sensitivity criteria: For all calibration solutions, including the CS1 solution,
the S/N ratio must be >10.
Linearity criteria: The RRF s and Percent Relative Standard Deviation (%RSD) of the five RRFs
(CS1-CS5) for each compound applicable to RRF (internal standard) treatment is calculated. The
percent relative standard deviation (%RSD) of the five RRFs (CS1-CS5) must not exceed 35%
for these compounds. Likewise, the RR and %RSD of the five RRs (CS1-CS5) for each
compound applicable to RR (isotope dilution) treatment is calculated. The %RSD of the five RRs
(CS1-CS5) must not exceed 20% for these compounds.
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Chlorinated Dioxin and Furan Data Review
6. Concentration criteria: All initial calibration standards must be analyzed at the correct
concentration levels (see Table A.5).
7. Frequency criteria: Each HRGC/HRMS system must be initially calibrated to meet the terms of
the contract whenever:
• The laboratory takes corrective action which may change or affect the initial calibration
criteria.
• The calibration verification (CSS calibration verification) acceptance criteria cannot be met
even after corrective action (see Sections III.4 and V).
D. Evaluation:
1. Verify that the PFK resolution check was performed, and WDM, ISC, and CPS solutions were
analyzed before the calibration standards.
2. Verify that all analytes in all calibration solutions are present at the correct concentrations (see
Table A.5).
3. Verify that the requirements for frequency of initial calibration were observed.
4. Verify that the five RRF %RSDs are <35%.
5. Verify that the five RR %RSDs are <20%.
6. Verify that the ion abundance ratios in each calibration standard are within ±15% of the limits
listed in Table A.4.
7. Verify that the GC resolution criteria are met [Percent Valley (% Valley) <25%].
8. Verify that the instrument sensitivity criteria are met (S/N > 10) in all Selected Ion Current
Profiles (SICPs).
9. Verify that the RT criteria for each target analyte and internal standard have been met. If this
cannot be verified in the documentation, examine the SICPs for each descriptor. All analytes must
be present in the proper descriptor, and RRT and minimum RT criteria must be met. Verify that
RTs are consistent between the calibration standards, and between the calibration and any
subsequent samples.
E. Action:
1. Concentrations and Frequency
All initial calibration standards, except CS1, must be analyzed at the concentrations described in
the DLM02.X Statement of Work (SOW). Calibration standard CS1 may be analyzed at either the
specified 0.5 ng/mL concentration, or at a lower level such as 0.1 ng/mL. As long as the criteria
specified in the method (and in Item D above) are met, this is a measure that adds value and is
generally allowed. Initial calibrations must be performed when the contract is awarded, whenever
significant instrument maintenance is performed (e.g., ion source cleaning, GC column
replacement, etc.), or if calibration verification criteria are not met. If no initial calibration has
been performed, the data should not be considered definitive (reject or flag as screening-level
only). If the prescribed calibration levels have not been used, it may be necessary to modify the
linear range for reporting (with approval of the data user). If an otherwise compliant initial
calibration has been performed, but not at the prescribed frequency, the data may be usable with
qualification as estimated.
2. Ion Abundance Ratios
Failed ion abundance ratio criteria for any analyte is a cause for concern, and may indicate that
the Mass Spectrometer is not tuned correctly, that the ion source is dirty, or that other electronic
problems exist. If there is a systemic problem resulting in failed ion ratios in the calibration,
qualify sample results analyzed immediately after that initial calibration using the RRF or RR
values for quantitation as unusable "R" for that analyte, because both the RRF and RR values
depend on the areas used in the ion abundance ratio.
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Chlorinated Dioxin and Furan Data Review
Using professional judgment, a more in-depth review may be performed to minimize the
qualification of data. To illustrate this approach, consider the following hypothetical example:
• If the ion abundance ratio is not within the limits for an analyte in the CS1 solution (see Table
A.4), qualify the low-end results for that analyte (below the CS2 concentration from Table
A.5) as unusable "R", or qualify as a non-detect 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 ion abundance ratio is not within the limits for an analyte in the
CSS - CSS solutions (see Table A.4), qualify all results for that analyte as unusable "R".
3. GC Resolution
Failed resolution criteria can have an impact on closely eluting pairs other than the TCDD
isomers subject to these criteria. Qualify all results as estimated "J". Request a reanalysis for all
samples following a failed resolution to ensure the qualitative and quantitative results. The factors
at play here affect calculated detection limits as well as positive results. Qualify all results as
estimated ("J/UJ").
4. Analyte Response
If the %RSD is not within ± 20% and ±35% for the RR and RRF, respectively, qualify detects
and non-detects as estimated "J". The reviewer may discard either the CS1 or CSS values for the
initial calibration and recalculate the %RSD. If discarding either of these points brings the %RSD
within the specified limits, qualify either the low- or high-end hits, 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 project data quality objectives (DQOs) are negatively impacted.
5. Sensitivity
Problems with the S/N ratio not being met usually occur in the CS1 standard. If this is the case,
professional judgment could be used to increase the reporting limit to the lowest calibration
standard which meets criteria (CS2 standard concentration), depending on data requirements.
Qualify any positive results below the CS2 standard as estimated. As stated in the paragraph
above on ion ratios, 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. Therefore, this approach should not be applied to standards higher than CS 1.
If the 10:1 S/N ratio requirements are not met due to a more systematic lack of sensitivity, qualify
any detects as estimated "J" and non-detects as unusable "R" for all associated samples.
6. Retention Time
If the RT criteria described above have not been met, contact the TOCOR or SMO to discuss
reanalysis of the initial calibration and all samples, or reject the data. In sample-specific,
potentially matrix-caused cases of RTs not meeting the absolute RT criteria, 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.
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Chlorinated Dioxin and Furan Data Review
Table 5. Initial Calibration
Criteria
Initial calibrations are not performed
Initial calibration not performed at proper frequency (but other
factors are acceptable)
Ion Abundance Ratio is not within ± 15% of theoretical
values, as described in Table A.4
GC Resolution (% Valley) of >25%
Linearity: RRF %RSDs is not within ± 35%; RR %RSDs is
not within ± 20%
Sensitivity <10: 1 S/N ratio for all SICPs
RTs: Not within appropriate windows and absolute RT of
internal standard 13C12-1,2,3,4-TCDD >25 minutes on DB-5
(or equivalent) column, or >15 minutes on DB-225 (or
equivalent) column
Action
Detected
Associated
Compounds
R
J
R or professional
judgment
J
J
J
R
Non-Detected
Associated
Compounds
R
UJ
R or professional
judgment
UJ
UJ
R or professional
judgment
R
September 2011
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Chlorinated Dioxin and Furan Data Review
V. High Resolution Gas Chromatograph/High Resolution Mass Spectrometer
(HRGC/HRMS) Calibration Verification
A. Review Items:
FORM 7DFA (FORM VII-HR CDD-1), FORM 7DFB (FORM VII-HR CDD-2), and raw data from
the midpoint (CSS) standard. Reference DLM02.X, Exhibit B, Section 3.4.13 and Section 4, and
Exhibit D, Section 9.4.
B. Objective:
Establish compliance requirements for satisfactory calibration to ensure that the instrument is capable
of producing acceptable qualitative and quantitative data. Calibration verification is used to validate
the relative responses (RRs) and relative response factors (RRFs) of the initial calibration on which
quantitations are based, and to check for satisfactory performance of the instrument on a day-to-day
basis.
C. Criteria:
The laboratory must not proceed with sample analysis until an acceptable calibration verification has
been performed and documented according to the following criteria: ion abundance ratios; retention
times (RTs); relative retention times (RRTs); instrument sensitivity [signal-to-noise (S/N)]; and
analyte response [Percent Difference (%D) associated with the RR and RRF].
1. Ion abundance criteria: The ion abundance ratio criteria listed in Table A.4 must be met for all
CDD/CDF peaks, including the labeled versions of native compounds and the internal standards.
2. Absolute RT criteria: The RT of the first-eluting internal standard (13C12-1,2,3,4-TCDD) on the
DB-5 (or equivalent) column and the DB-225 (or equivalent) column must meet the absolute RT
criteria. In addition, if the absolute RTs of the internal standards are not within ± 15 seconds of
the RTs obtained during the initial calibration, the descriptor switching times may not be
optimum for detecting all homologues.
3. RRT criteria: The RRTs of the native and labeled CDDs/CDFs must be within the defined limits
(see Table A.3).
4. Instrument sensitivity criteria: For the CS3 solution, the S/N ratio must be >10:1 for all
CDD/CDF peaks, including the labeled versions of native compounds and the internal standards.
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Chlorinated Dioxin and Furan Data Review
5. Analyte response criteria: The measured RRFs and RRs of each analyte and standard (labeled and
internal) must be within ±25% (RR) and ±35% (RRF) of the mean values established during
initial calibration:
[(RRF -RRE)xlOO]
% Difference =
RRF.
i
Where,
RRFC = RRF established during calibration verification
RRF; = RRF established during initial calibration
And:
[(RR -RR.)xlOO
% Difference = •
c i
RR.
i
Where,
= RR established during calibration verification
= RR established during initial calibration
D. Evaluation:
1. Verify that the calibration verification was run at the required frequency [following the window
defining mixture (WDM) or column performance solution (CPS( in each 12-hour period] and that
the calibration verification was compared to the correct initial calibration.
2. Verify from the raw data that the ion abundance ratios listed in Table A.4 were all met.
3. Verify from the raw data that the absolute RT criteria for the compound 13Ci2-l,2,3,4-TCDD were
met. Although the statement of work (SOW) no longer includes the requirement for the
laboratory to verify that absolute retention times are within ±15 seconds of the initial calibration,
an excursion outside this range may mean that some homologues will be missed.
4. Verify from the raw data that the RRT criteria for the native and labeled CDDs/CDFs were met.
5. Verify from the raw SICP data that the S/N ratio is > 10:1 for the unlabeled CDD/CDF ions,
labeled compounds, and internal standards.
6. Verify from the raw data that the measured RRs and RRFs of each analyte, labeled and otherwise,
in the CS3 solution are within ±25% (RRs) and within ±35% (RRFs) of the mean values
established during initial calibration.
E. Action:
If the calibration verification was not analyzed at the required frequency, contact the TOCOR and/or
SMO to initiate sample reanalysis.
1. Use professional judgment to qualify any analyte in samples associated with a calibration
verification not meeting the RT and/or RRT criteria (see Table 6).
2. The failure to meet the ion abundance criteria listed in Table A.4 is indicative of poor tuning,
gross contamination, or system instability. Qualify positive results as estimated "J" and non-
detects as rejected ("R") because of the possibility of false negatives. Notify SMO to schedule
sample reanalysis under a compliant calibration.
3. If the S/N ratio ^10:1 limit is not met in a calibration verification, qualify all detects as estimated
"J" and all non-detects as unusable "R".
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Chlorinated Dioxin and Furan Data Review
Since the initial calibration is used to generate the RR and RRF values used for quantitation, the
%D relative to the initial calibration's Mean RR (RR) or Mean RRF (RRF ) is a crucial criterion
for review. Qualify data associated with an analyte with a %D not within ±25% (RR) and not
within ±35% (RRF) as estimated "J". Recalibrate the HRGS/HRMS and reanalyze the affected
samples.
Table 6. Calibration Verification Evaluation Actions
Criteria
Ion abundance ratios not within ± 15% window
Absolute RT of internal standard 13C12-1,2,3,4-TCDD >25 minutes
onDB-5 (or equivalent) column, or >15 minutes onDB-225 (or
equivalent) column
Internal standards in the calibration verification not within 15
seconds of the RT in the initial calibration
RRTs in the calibration verification not within the limits defined in
Table A.3
Sensitivity: S/N < 10 for all compounds
%D for RRs not within ± 25%, %D for RRFs not within ± 35%
Action
Detected
Associated
Compounds
J
Non-Detected
Associated
Compounds
R
Use professional judgment
Use professional judgment for
qualification of target analytes; qualify
homologues as estimated (J, UJ).
Use professional judgment
J
J
R
UJ
September 2011
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Chlorinated Dioxin and Furan Data Review
VI. Method Blank Analysis
A. Review Items:
FORM 4DF (FORM IV-HR CDD) and raw data. Reference DLM02.X, Exhibit B, Section 3.4.7, and
Exhibit D, Section 12.1.
B. Objective:
Determine the existence and magnitude of contamination resulting from laboratory (or field)
activities. The criteria for evaluation of blanks apply to any method blank associated with samples. If
problems with a blank exist, all associated data must be carefully evaluated to determine whether or
not there is an inherent variability in the data, or if the problem is an isolated occurrence not affecting
other data. It is recommended to handle the Total Homologues contamination in the same way as the
evaluation for OCDD/OCDF.
It should be noted that other QC samples, i.e., field equipment rinsates, or laboratory solvent blanks,
should also be considered in making decisions regarding system contamination.
C. Criteria:
Acceptable laboratory method blanks must not contain any chemical interference or electronic noise
at or above the contract required quantitation limit (CRQL) at the m/z of the specified unlabeled
CDD/CDF ions (the concentration of OCDD/OCDF in the method blank must be less than three times
the CRQL). The levels of non-2,3,7,8 homologues should also not exceed the CRQLs for the target
congeners in the series.
1. There must be at least one laboratory method blank for each batch of samples extracted. The
laboratory is required to analyze the method blank on each analytical system used to analyze
samples. This includes both the DB-5 primary column (or equivalent) and the DB-225
confirmatory column (or equivalent) whenever any associated samples require 2,3,7,8-TCDF
confirmation (either a positive result or an estimated maximum possible concentration (EMPC)
value exceeds the CRQL).
2. A peak that meets identification criteria as a CDD/CDF in the method blank must not exceed the
CRQL for that analyte except in the case of OCDD/OCDF and Total Homologues, where the
maximum allowable amount is less than three times (<3x) the CRQL.
3. If a group of samples and the associated method blank are contaminated, rerun the associated
detects and any samples containing peaks that meet the qualitative identification criteria.
NOTE: Report results for all peaks with signal-to-noise (S/N) ratio >2.5, even if they are
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Chlorinated Dioxin and Furan Data Review
OCDD/OCDF in the method blank must be <3x the CRQL. The levels of non-2,3,7,8
homologues should also not exceed the CRQLs for the target congeners in the series. Even
though the statement of work (SOW) cites the CRQL as the limit for method blank
contamination, users who report data down to the estimated detection limit (EDL) or EMPC
should consider for data qualification any target analytes that are present, in addition to any
chemical or electronic interference. This may require examination of the raw data in addition to
reported results.
3. For those users who use the EDL or EMPC as a surrogate for calculating the toxic equivalent
quantity (TEQ) for non-detects, the issue of blank contamination is of particular significance.
Special caution is advised 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 Toxicity Equivalence Factors (TEF), (i.e., TCDD and PeCDD in the
2005 WHO mammalian TEFs).
E. Action:
1. If the highest associated method blank is contaminated with a CDD/CDF greater than or equal to
the CRQL, qualify all detects as estimated "J". Non-detects for those analytes should not be
affected.
2. Most data users want to use results reported down to the EDL or EMPC. Therefore, whereas the
SOW describes in terms of laboratory requirements, the following actions are presented in terms
of the EDL/EMPC. The EDLs for individual CDD/CDFs are not listed in the SOW, but are
determined for each sample (see Section XIII).
a. If method blanks are contaminated with CDD/CDFs above the EDL, then there is a potential
impact on all sample results. Using this approach, all associated positive results should be
qualified as estimated "J". Non-detects should not be affected.
b. In the case where minimal contamination may exist, but it is significantly exceeded by the
response in the samples, the reviewer may apply no qualification to the data. Alternatively,
the reviewer may apply expanded criteria to qualify associated sample results. For example,
sample results may be qualified as non-detects up to a value of 2 to 5 times the amount
present in the highest associated blank (lOx for OCDD/F & homologues) to discount possible
contamination, but not qualified above that. Use of either approach requires careful
professional judgment in the evaluation of the effects of contamination to avoid reporting
false negatives.
c. The validator should note that 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, compared, 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 calculate sample specific blank action results by
adjusting the blank concentration with sample specific factors.
3. There may be instances where little or no contamination was present in the associated blanks, but
qualification of the sample is deemed appropriate. Professional judgment should be used in these
situations. One example would be where the method blank did not satisfy one of the identification
criteria, either the 2.5 * S/N requirement, or the ion ratio requirement to report an analyte present,
but the actual sample contained the analyte with an acceptable ion ratio, and/or with slightly
greater than 2.5 * S/N and less than five times the possible blank concentration. An explanation
of the rationale used for this determination should be provided in the Data Review Narrative.
4. If an instrument blank was not analyzed following a sample analysis which contained an
analyte(s) at high concentrations, the sample analysis results must be evaluated for carryover.
Professional judgment should be used to determine if instrument cross-contamination has affected
any positive compound identification(s).
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Chlorinated Dioxin and Furan Data Review
Blanks or samples run after a Performance Evaluation Sample (PES), Laboratory Control Sample
(LCS), or Calibration Verification should be carefully examined to determine the occurrence of
instrument or syringe carry-over. Since the efficiency of sample transfer can vary dramatically
according to apparatus and operator techniques, professional judgment should be used in each
case to determine whether sample or blank results are attributable to carry-over.
When there is convincing evidence that contamination is isolated to a particular instrument,
matrix, or concentration level, professional judgment should be used to determine if qualification
should only be applied to certain associated samples (as opposed to all of the associated samples).
If gross contamination exists (i.e., saturated peaks), all samples in the sequence, including the
calibration checks, may be affected. All affected compounds in the associated samples may be
considered to be unusable ("R" qualifier) in this case. This is a contract issue, as the laboratory
should take corrective action prior to reporting the data, and should be regarded as an action item
to be reported to the TOCOR and/or SMO for resolution with the contract laboratory.
Table 7. Method Blank Evaluation Actions
Method Blank Result
«CRQLorEDL
>CRQLorEDL
Gross contamination
Sample Result
Not detected
>CRQL or EDL and » Blank Result
Not detected
>CRQL or EDL and < Blank Result
> CRQL or EDL and >[~31ank Result
Positive
Action
No qualification
No qualification
or use professional judgment to avoid
false pos. or neg. (see E.2.b above)
No qualification
U*
J
or use professional judgment
R
* The calculated sample result should be reported with a "U" flag in these cases.
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Chlorinated Dioxin and Furan Data Review
VII. Laboratory Control Sample (LCS) Analysis
A. Review Items:
FORM 3DFA (FORM III-HR CDD-1) and raw data. Reference DLM02.X, Exhibit B, Section 3.4.6,
and Exhibit D, Section 12.2.
B. Objective:
Provide data on the accuracy of the analytical method by preparing and analyzing a sample of spiked
reference matrix LCS for each matrix analyzed. If a matrix is not represented in a sample delivery
group (SDG), no spiked LCS is required for that matrix. EPA has identified a number of reference
matrices to be used for the spiked LCS, and the laboratory must use an aliquot of that matrix for its
own LCS work (see DLM02.X, Exhibit D, Section 7.6). When a reference matrix that simulates the
sample matrix under test is not readily available, EPA retains the option to supply the laboratory with
a reference matrix containing the expected interferences for a particular project.
C. Criteria:
1. For each SDG, the laboratory must prepare a spiked LCS for all of the matrix types that occur in
that SDG (see DLM02.X, Exhibit D).
2. The recovery of each spiked analyte must be in the range in Table A.6.
3. The LCS must meet the technical acceptance criteria for sample analysis (see DLM02.X, Exhibit
D, Section 11.3).
D. Evaluation:
Confirm that the spiking solution was added to the LCS, and that the CDD/CDF analytes were at their
correct concentrations. Verify that calculations, and transcriptions from raw data, were performed
correctly.
E. Action:
1. If LCS recovery results are greater than the upper acceptance limits, qualify all detected
associated sample data for those analytes which fail in the LCS as estimated "J" (see Table 8).
Notify the TOCOR and/or SMO concerning samples associated with a non-compliant LCS to
decide on re-extraction and reanalysis.
2. Recovery of the LCS below the lower primary recovery range, but above 10%, may be indicative
of a low bias in laboratory performance, and as such should only warrant a "J" or a "UJ" qualifier.
It also may, in conjunction with other performance factors, lead to the conclusion that laboratory
performance is unacceptable. In this case, qualification of non-detected results should be based on
professional judgment.
3. If LCS results are <10%, qualify positive results for those analytes as estimated ("J") and non-
detects as unusable ("R") in all of the associated samples. Notify SMO concerning samples
associated with a non-compliant LCS to decide on re-extraction and reanalysis.
4. If the laboratory failed to prepare and analyze the LCS at the required frequency, note this in the
Data Review Narrative and notify the TOCOR and/or SMO. If no LCS was done and
performance of other QC is poor (i.e., poor recovery in samples, compromised method blanks),
the reviewer may not be able to determine whether the fault lies with the laboratory or the matrix.
The only option may be to reject the data ("R").
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Chlorinated Dioxin and Furan Data Review
Table 8. Laboratory Control Sample (LCS) Recovery Actions
Criteria
%R > Upper Acceptance Limit
% R >10% but < Lower Acceptance Limit
%R<10%
LCS performed but not at required frequency
LCS not performed
Action
Detected
Associated
Compounds
J
J
J
J
J
Non-Detected
Associated
Compounds
No qualification
UJ
R
Use professional
judgment
Use professional
judgment
September 2011
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Chlorinated Dioxin and Furan Data Review
VIII. Sample Dilution
A. Review Items:
Raw data (quantitation reports and chromatograms, prep and/or injection logs). Reference DLM02.X,
Exhibit D, Section 10.6.6.
B. Objective:
A calibrated range is defined by the initial calibration. All sample results must be within the
calibrated range to be reported without qualification.
C. Criteria:
If the selected ion current profile (SICP) area at either quantitation m/z for any compound (except
OCDD and OCDF) exceeds the calibration range of the system, the laboratory must take steps to
bring those analytes within the calibration range. According to the DLM02.X SOW, the laboratory
must first perform a solvent dilution of the extract after adding additional labeled compounds,
followed by (if the maximum allowable dilution was unsuccessful) re-extraction of the sample with a
smaller or diluted sample aliquot. The sample extract may be diluted by a factor of up to 100 times
(lOOx) with n-nonane. The instrument internal standard in the extract is adjusted to 100 pg/(iL, and an
aliquot of this diluted extract is analyzed by the internal standard method. If more than a dilution of
lOOx is required, the laboratory must prepare a smaller aliquot of the original sample and take the
smaller aliquot through the processing and cleanup steps.
D. Evaluation:
1. Extract Dilution:
a. Verify that all reported sample values (except OCDD or OCDF) are within the calibration
range. Even though the laboratory is not required to take action if the response of OCDD
or OCDF exceeds the calibration range, extremely high levels of these analytes may carry
over between injections and affect overall chromatographic and detector performance.
Most laboratories will perform dilutions in the event that any analyte, including
OCDD/OCDF, exceeds the system linear range (i.e., produces a flat-topped peak).
b. Examine the preparation and/or run logs to verify a proper dilution scheme. 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
re-submission of the data.
c. Verify that the internal standard calculations used to determine analyte concentrations in
the diluted sample were performed correctly.
NOTE: Under this dilution scheme, the recovery correction aspect of the isotope
dilution technique is lost. However, the laboratory should not correct for the
recovery determined from the initial run. Initial labeled compound recovery is
a factor that should be considered qualitatively by the reviewer.
d. Verify that a dilution factor of <100x was used and correctly documented, or that prior
communication with the Regional customer was documented.
2. Dilution by Re-extraction and Reanalysis:
a. Verify that all reported sample values (except OCDD or OCDF) are within the calibration
range. If substantial differences are noted between the initial analysis and the
dilution/reanalysis of a sample, examine the preparation and/or run logs to verify a proper
dilution scheme. 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 re-submission of the data.
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Chlorinated Dioxin and Furan Data Review
b. Examine the prep and/or run logs to verify a proper approach to analyzing a smaller aliquot.
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 re-
submission of the data.
E. Action:
1. Qualify all of the sample detects as estimated " J" which are not within the calibration range,
taking into account the initial run and all successfully analyzed dilutions.
2. If unexplained differences are identified between undiluted and diluted results, the reviewer may
choose to request further analytical work, qualify the results, use the original results, or reject the
results. Be sure to attach adequate justification in the Data Review Narrative for your decision.
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Chlorinated Dioxin and Furan Data Review
IX. Identification Criteria
A. Review Items:
FORM 1DFA (FORM I-HR CDD-1), FORM 2DF (FORM II-HR CDD), and raw data. Reference
DLM02.X, Exhibit B, Section 3.4.1 - 3.4.5, and Exhibit D, Section 11.1.
B. Objective:
Unambiguously identify a gas chromatograph (GC) peak as a CDD or a CDF.
C. Criteria:
For a GC peak to be unambiguously identified as a CDD or CDF, it must meet all of the following
criteria:
1. Retention Times (RTs) and Relative Retention Times (RRTs)
Retention times 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 2,3,7,8-substituted isomers for which an isotopically
labeled counterpart or internal standard is present in the sample extract, the RRT at the
maximum peak height of the analyte must be within the RRT window in Table A.3. The RRT
is calculated as follows:
^^T, RT of analyte
KJxl —
RT of corresponding internal standard
b. To make a positive identification of the non-2,3,7,8-substituted isomers (tetra- through
hepta-) for which a labeled standard is not available, the RT must be within the RT window
established by the window defining mixture (WDM) for the corresponding homologous
series.
2. Peak Identification
Both of the specified ions listed in Table A.I, and on the FORMs Is for each CDD/CDF
homologue, must be present in the SICP. The ion current response for the two quantitation ions
for the analyte in question must maximize simultaneously within the same 2 seconds. This
requirement also applies to the labeled versions of the native and internal standards, as well as to
the non-2,3,7,8 CDD/CDF congeners. For the cleanup standard, only one ion is monitored.
3. Signal-to-Noise (S/N) Ratio
The integrated ion current for each native analyte ion listed in Table A.I, must be at least 2.5
times (2.5x) the background noise and must not have saturated the detector (applies to sample
extracts only). The labeled and internal standard ions, however, must be at least lOx the
background noise and must also not have saturated the detector (applies to sample extracts only).
In the case of the various calibration standard solutions, the S/N ratio must be >10:1 for all of the
CDD/CDF compounds, whether or not they are labeled. Each peak representing a non-2,3,7,8
CDD or CDF should also meet the minimum S/N requirement.
4. Ion Abundance Ratios
The ratio of the integrated areas of the two exact m/z's must be within the limit specified in Table
A.4, or within ±10% of the ratio in the most recent Midpoint Calibration Standard (CS3). The ion
ratio criterion applies to all 2,3,7,8-native and labeled CDDs/CDFs as well as to peaks
representing non-2,3,7,8-substituted CDDs/CDFs.
The ion abundance ratio criteria for native and labeled analytes and for internal standards must be
met using peak areas to calculate ratios, if possible. If interferences are present and ion abundance
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Chlorinated Dioxin and Furan Data Review
ratios 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. If the
peak is a CDD/CDF, the ion abundance ratios may be determined using peak heights instead of
areas. In this event, the laboratory must quantitate the peaks as "H" using peak heights rather than
areas for both the target analyte and the labeled compound or internal standard.
5. Polychlorinated Diphenyl Ether (PCDPE) Interferences
If PCDPE interferences are detected above the 2.5:1 S/N ratio limit, as indicated by the presence
of peaks at the exact m/z(s) monitored for these interferents (see Table A. 1), their presence may
interfere with quantitative determination of any of the furans. Additional extract cleanup with
clean glassware and reagents can eliminate these interferents.
6. Homologous Series Totals
Peaks are commonly found in each descriptor which pass all identification criteria for target
2,3,7,8-substituted CDD/CDF analytes except retention time. These peaks represent the many less
toxic non-2,3,7,8-substituted CDDs/CDFs. These compounds do not have associated toxic
equivalent quantities (TEQs), but the total quantity of CDDs or CDFs in each homologous series
is required by certain data users. All peaks identified as non-2,3,7,8 CDDs/CDFs must meet the
same qualitative criteria as the 2,3,7,8-substituted target analytes, except RT.
D. Evaluation:
1. Evaluate chromatograms for each selected ion current profile (SICP) to verify adequate system
performance, proper scaling, and adequate presentation to allow a visual comparison of lock-mass
trace and PCDPE interference channel to the associated target ion channels for the purpose of
verifying positive identifications.
2. Verify that the RRTs for the 2,3,7,8-substituted compounds are within the RRT windows listed in
Table A.3.
3. Verify that the RTs for the non-2,3,7,8-substituted compounds are within the RT windows
established by the WDM for the corresponding homologues (FORM 5DFA).
4. Verify from the SICPs that the ion current responses for the two quantitation ions for each analyte
maximize simultaneously (within the same 2 seconds).
5. Verify from the SICPs that for each analyte ion listed in Table A.I, the S/N ratio is > 2.5:1 and
that the detector has not been saturated. If an analyte is flagged with an asterisk (*), it means the
laboratory determined that the analyte failed one or more qualitative identification criteria and an
estimated maximum possible concentration (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, and if so, note the magnitude of that interference (see Items 3 and 5, below).
6. Verify from the Forms I that the ion abundance ratios are within the criteria listed in Table A.4, or
within ±10% of the ratio in the most recent Midpoint Calibration Standard (CS3).
7. Verify that no PCDPE interferences exist at the retention time of each target analyte.
8. If homologue totals are to be reported, check to see that both ions are present and maximize
within two seconds, and that they meet the S/N and ion ratio requirements. It is not common
practice to calculate EMPC values for non-2,3,7,8-substituted CDDs/CDFs that fail the ion ratio
test. If detector saturation occurs in a region of the SICP that is clearly due to either a non-2,3,7,8
CDD/CDF or to an interferent, it is normally not interpreted as a positive result and no further
action is required by the laboratory.
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Chlorinated Dioxin and Furan Data Review
E. Action:
1. If a peak falls outside of the Table A.3 and/or the WDM windows, examine the SICP to evaluate
whether there is a peak within the Table A.3 and/or WDM criteria. If there is no peak, consider
the analyte as a non-detect. Refer to Section XIII for determination of an EDL or EMPC.
2. If 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. Refer to Section XIII for determination of
an EDL or EMPC.
3. If PCDPE interferences are identified above the 2.5:1 S/N ratio limit, consider the magnitude of
the PCDPE vs. that of the target analytes. If the raw abundance of the PCDPE interference is
significant (i.e., greater than 10% of that for the associated target furans), qualify associated
CDFs as non-detects at an estimated quantity ("UJ"), or rejected ("R"), depending on professional
judgment. If the interference is minor (i.e., <10% of the associated target furans), qualify detects
and non-detects as estimated (J or UJ respectively).
4. If S/N criteria are not satisfied, consider the analyte to be not detected. Refer to Section XIII for
determination of an EDL or EMPC.
5. If ion abundance criteria are not satisfied, 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. This is an added benefit to unequivocally confirm
that the peak present is dioxin/furan. But ion abundance outside the criteria does not
unequivocally prove that dioxins/furans are not present. It only indicates that either an
interference is present for one of the ions, or that another compound may be present. The standard
qualifiers ("U" or "J") may not be appropriate in this case. The reviewer should rely on
professional judgment and organizational policy to decide how to qualify EMPCs. Refer to
Section XIII for determination of an EDL or EMPC.
6. In the event that non-2,3,7,8-substituted CDDs/CDFs are improperly identified, the reviewer may
need to re-evaluate the raw data or forward a request, through the Task Order Contract Officer
Representative (TOCOR), for a data re-submission from the laboratory.
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Chlorinated Dioxin and Furan Data Review
X. Compound Quantitation
A. Review Items:
FORM 1DFA (FORM I-HR CDD-1), FORM 2DF (FORM II-HR CDD), and raw data. Reference
DLM02.X, Exhibit D, Section 11.2.
B. Objective:
The objective is to verify that sample results for 2,3,7,8-substituted congeners, and that homologue
totals were reported correctly.
C. Criteria:
i. In an isotope dilution method, a known amount of labeled compounds is added to every sample
prior to extraction. This provides a correction for recovery of each corresponding native
compound because the native compound and its labeled compound exhibit similar effects upon
extraction, concentration, and Gas Chromatography (GC). Method 1613B uses labeled standards
for determining quantitative results for all target analytes except 1,2,3,7,8,9-HxCDD and OCDF.
The labeled 1,2,3,7,8,9-HxCDD is used as an internal standard (along with the labeled 1,2,3,4-
TCDD) to measure the recovery of the other labeled congeners. It is added to the extract just prior
to analysis. The labeled OCDF is not used because of a potential interference problem.
2. Native 1,2,3,7,8,9-HxCDD is quantitated using the average of the responses of the labeled
compound of the other two 2,3,7,8-substituted HxCDDs: 1,2,3,4,7,8-HxCDD and 1,2,3,6,7,8-
HxCDD. As a result, the concentration of native 1,2,3,7,8,9-HxCDD is corrected for the average
recovery of the other two HxCDDs. Also, because there is no labeled OCDF added prior to
extraction, in instances where OCDD and OCDF behave differently during sample extraction,
concentration, and cleanup procedures, this may decrease the accuracy of the OCDF results.
However, given the low toxicity of this compound relative to the other dioxins and furans, the
potential decrease in accuracy is not considered significant.
3. An estimate of quantitative results is determined for any peaks representing non-2,3,7,8-
substituted CDDs/CDFs using an average of the response factors from all of the labeled standard
2,3,7,8-isomers at the same level of chlorination. The homologue totals are then determined by
summing the results of target and non-target CDDs/CDFs for each level of chlorination.
4. The mean Relative Response (RR )values from the initial calibration data are used to determine
concentrations directly using the following equations:
All Matrices Other than Aqueous:
CL X (Axi + A.2) Vex
Solids (ng/kg) =
Wx(AL, + AL2)
Where,
CL = Concentration of the labeled standard added to the extract (includes any amount
added during dilution procedures, see Section VIII)
Axi,Ax2 = Areas of the signals for both quantitation ions of the CDD/CDF
ALi,AL2 = Areas of the labeled standard ions
Vex = Effective final volume of the extract
W = The Sample Weight
RR = The Mean Relative Response for the isomer of interest from the initial
calibration (see DLM02.X, Exhibit D)
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Aqueous:
Where,
A1S,A2S
All, A2i
Vex
Z1
RR
Aqueous(pg/L) =
C..x(Al. + A2.)V,
V.x(AL + A2ixRR
CT. =
Quantity (pg) of appropriate labeled standard added to the extract (includes any
amount added during dilution procedures, see Section VIII)
Areas of the signals for both quantitation ions of the CDD/CDF
Areas of the labeled standard ions
Effective final volume of the extract
Sample volume extracted in liters
The Mean Relative Response for the isomer of interest from the initial
calibration (see DLM02.X, Exhibit D)
The internal standard method is used to compute the concentrations of the 1,2,3,7,8,9-HxCDD,
OCDF, C-labeled analogs, and the 37Cl-labeled cleanup standard in the extract using the mean
Relative Response Factors (RRFs) determined from the initial calibration data (see DLM02.X,
Exhibit D, Section 11.2.2) and the following equation:
Cra(ng/mL) =
(A1S+A2S)CIS
(A1IS+A2IS)RRF
Where,
CEX = The concentration of the labeled compound in the extract
ds = The concentration of the internal standard
RRF is defined in DLM02.X, Exhibit D, Section 9.3.4.4. The other terms are as
defined in DLM02.X, Exhibit D, Section 9.3.4.2.
6. The amount of moisture in solid samples should not have an impact on the calculation of
quantitative results, since the SOW (Exhibit D, 10.1.3) requires the laboratory to prepare a
equivalent of 10 grams dry-weight of aqueous samples containing greater than one percent solids,
the fact that most laboratories report sample weight on a dry-weight basis, because of the
extremely low water solubility of CDD/CDF analytes, and due to the prescribed use of the
Soxhlet-Dean/Stark procedure. Values utilized as CRQLs should be equal to those given in
DLM02.X, Exhibit C, provided that sample volume or dry weight, extract final volume, and
injection volume are the same as those in DLM02.X, Exhibit D. However, if any one of these
factors is different, the CRQL used for data qualification should be adjusted, as shown below:
Aqueous Adjusted CRQL:
Adjusted CRQL = Contract CRQL x ^ x^ T'
/T7" \ /T 7 \
Where,
Vt
V0
vx
V,
= Volume of the concentrated extract (uL)
= Actual sample volume used (ml)
= Contract sample volume (1000 mL)
= Contract concentrated extract volume (uL)
September 2011
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Chlorinated Dioxin and Furan Data Review
Soil/Sediment Adjusted CRQL:
Adjusted CRQL = Contract CRQL x
Where,
Vt = Volume of the concentrated extract (uL)
Ws = Actual mass extracted (g)
Wx = Contract sample weight (10 g)
Vc = Contract concentrated extract volume (uL)
Extract Concentrations by Relative Response:
CEX (ng/ml) =
(A1N+A2N)CL
(A1L+A2L)RR
Where,
CEX = The concentration of the native compound in the extract
CL = The concentration of the internal standard
RRF is defined in DLM02.X, Exhibit D, Section 9.3.4.4. The other terms are as defined in
DLM02.X, Exhibit D, Section 9.3.4.2
There is only one m/z for the 37C1-labeled cleanup standard.
D. Evaluation:
i. Use raw data to verify the correct calculation of all sample results reported by the laboratory.
Before verifying calculations for solid samples, the reviewer should 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
confirmational column.
2. Compare retention times, internal standard recoveries, ion ratios, S/N determination, positive
results, dilution results, estimated detection limits (EDLs), estimated maximum possible
concentrations (EMPCs), and quantitation limits between the processed raw data reports and the
reported detects and non-detects in the sample results.
a. Check the reported CRQLs for accuracy and compliance with DLM02.X, Exhibit C. Check
reported results to verify that those less than the quantitation limit are qualified as estimated.
If, due to a difference in weights or volumes used, the CRQL should be adjusted, verify that
this has been done properly using the example equations above.
b. SOW requirements for the laboratory to complete the results reporting form (FORM I-HR
CDD-1) are given in DLM02.X, Exhibit B, Section 3.4.1.
3. Check qualifiers applied by the laboratory before finalizing data qualification. Data qualifiers
applied by the laboratory must conform to the instructions in DLM02.X, Exhibit D, Section
3.4.1.5.
4. The amount of moisture in a solid sample may have an impact on data representativeness (i.e., if
there is >70% moisture in a solid sample), depending on the nature of the equilibria between the
two phases, and analyte solubility characteristics. However, due to the extremely low solubility of
dioxins/furans in water, they should be expected to be contained in the solid phase. This fact
notwithstanding, the reviewer should be aware of any local standard operating procedures (SOPs)
and/or concerns of the data user and evaluate the data on this basis.
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Chlorinated Dioxin and Furan Data Review
E. Action:
i. If any discrepancies are found, the Region's designated representative may contact the laboratory
to obtain additional information that could provide a resolution. If a discrepancy remains
unresolved, the reviewer must use professional judgment to decide which value is the most
accurate. Under these circumstances, the reviewer may determine that qualification of data is
warranted. Note in the Data Review Narrative a description of the reasons for data qualification
and the qualification that is applied to the data.
2. Because of the quantitation technique used for non-2,3,7,8-substituted CDDs/CDFs (see Section
III under Criteria), it is common practice to qualify all homologue totals as estimated ("J"
qualifier) or "UJ" if all are non-detect.
3. Note, for Task Order Contract Officer Representative (TOCOR) action, numerous or significant
failures to accurately quantify the target compounds, homologue totals, or toxic equivalent
quantities (TEQs), or to properly evaluate and adjust quantitation limits.
4. Apply appropriate qualification to the data, including all QC criteria discussed in these
guidelines, in addition to those appropriate to any Regional data reporting policies. It is
recommended that a Data Review Narrative be developed to document the review process,
including the impact on data quality of any anomalies found.
5. It is highly recommended that the data review process applied to each analyte, sample, sample
delivery group (SDG), and/or project be characterized for the benefit of those who may
subsequently review or use the data. The terminology and labels for communicating the stages
and processes used for laboratory analytical data verification and validation have been developed
by an EPA workgroup and are published in Guidance for Labeling Externally Validated
Laboratory Analytical Data for Superfund Use, EPA-540-R-08-005, 13 January, 2009.
September 2011 37
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Chlorinated Dioxin and Furan Data Review
XI. Second Column Confirmation and Isomer Specificity
A. Review Items:
FORM 1DFC (FORM I-HR CDD-3) and raw data. Reference DLM02.X, Exhibit B, Section 3.4.3
and Exhibit D, Section 11.1.2.
B. Objective:
Isomer specificity for all 2,3,7,8-substituted CDDs/CDFs cannot be achieved on the 60-meter DB-5
column alone. Historically, problems have been associated with the separation of 2,3,7,8-TCDF from
closely eluting isomers, 1,2,3,9-TCDF and 2,3,4,7-TCDF. There is toxicological concern associated
with 2,3,7,8-TCDF; therefore, a second column confirmation is used and additional analyses may be
required for some samples. The confirmatory analysis is not required when the GC column that was
used meets isomer specificity requirements for both 2,3,7,8-TCDD and 2,3,7,8-TCDF. The column
must meet all criteria established in DLM02.X, Exhibit D, Section 9.
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 reported, or where 2,3,7,8-TCDF is reported as an estimated
maximum possible concentration (EMPC) at or above the Contract Required Quantitation Limit
(CRQL). The laboratory may utilize one of the following options to achieve better isomer
specificity than can be obtained on the DB-5 column (or equivalent) alone.
2. The sample extract may be reanalyzed on a DB-225 (or equivalent) GC column to achieve better
GC resolution and, therefore, better identification and quantitation of the individual 2,3,7,8-
substituted isomers.
3. The sample extract may be analyzed on a GC column capable of resolving all of the 2,3,7,8-
substituted CDDs/CDFs from other isomers, but not necessarily capable of resolving all of the
non-2,3,7,8-substituted isomers from one another.
4. Regardless of the GC column used, for a GC peak to be identified as a 2,3,7,8-substituted
CDD/CDF isomer, it must meet all of the criteria listed in DLM02.X, Exhibit D (ion abundance
ratio, S/N ratio, RT, etc.). If using any GC column other than those specified (DB-5, DB-225), the
laboratory shall clearly document in the SDG Narrative the elution order of all analytes of interest
on any such column (DLM02.X, Exhibit B, Section 2.5.1.1).
5. For any sample analyzed on a DB-5 (or equivalent) column in which 2,3,7,8-TCDF is reported as
an EMPC, regardless of TEF-adjusted concentration or matrix, analysis of the extract is required
on a second GC column which provides better specificity for these two isomers.
D. Evaluation:
1. Verify that second column confirmation is used whenever 2,3,7,8-TCDF is detected or is reported
as an EMPC in any sample at or above the CRQL. The confirmatory analysis is not required
when the GC column that was used meets isomer specificity requirements for both 2,3,7,8-TCDD
and 2,3,7,8-TCDF. The column must meet all criteria established in DLM02.X, Exhibit D,
Section 9. Verify that quantitation is performed on both columns and reported on the appropriate
page of FORM I. The two concentrations should not be combined or averaged, especially if the
second column confirmation analysis is performed on a different instrument. Verify that the final
sample result for 2,3,7,8-TCDF is reported from the confirmation column (the column having
greater specificity for 2,3,7,8-TCDF).
2. Verify that second column confirmation analysis meets all criteria previously discussed in this
document (initial calibration requirements, linearity specifications, etc.).
NOTE: Second column confirmation analysis is usually performed on a different instrument
than that used for primary analysis. The confirmatory analysis is not required when
the GC column that was used meets isomer specificity requirements for both 2,3,7,8-
September2011 38
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Chlorinated Dioxin and Furan Data Review
TCDD and 2,3,7,8-TCDF. The column must meet all criteria established in
DLM02.X, Exhibit D Section 9.
E. Action:
1. If second-column confirmation was required but was not performed, contact the TOCOR and/or
SMO to direct the laboratory to perform the analysis.
2. If second-column confirmational analysis was performed, but the result is a non-detect, report the
lowest value obtained (from either column), qualified as "U".
September 2011 39
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Chlorinated Dioxin and Furan Data Review
XII. Toxicitv Equivalent Quantity Determination
A. Review Items:
FORM 1DFB (FORM I-HR CDD-2) and raw data. Reference DLM02.X, Exhibit B, Section 3.4.2
and Exhibit D, Section 11.2.8.
B. Objective:
The exclusion of homologues such as mono-, di-, tri-, and the non-2,3,7,8-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 listed in Table
A.6. Hence, only the 2,3,7,8-substituted tetra- through octa- isomers are included in the Toxic
Equivalent Quantity (TEQ) or Toxicity Equivalence Factors (TEF)-adjusted concentration
calculations. The TEFs used in these calculations are derived and published by the World Health
Organization (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: 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.
C. Criteria:
1. The criteria for calculating TEQ will depend upon Regional policies. Two common approaches
are outlined below:
a. The first approach is to include only those 2,3,7,8-substituted congeners that were detected in
the sample (per DLM02.X, Exhibit B, Section 3.4.2.2) and that meet all of the qualitative
identification criteria. Under this approach, a zero is used for any estimated maximum
possible concentration (EMPC) or estimated detection limit (EDL) values in the TEF
calculations. The results of this calculation (usually for mammalian toxicity only) are
reported on FORM I-HR CDD-1 and FORM I-HR CDD-2, and if confirmations were
performed, also on FORM I-HR CDD-3.
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 included in the
calculation as surrogates for the non-detect results.
2. If directed by the Regional customer, the laboratory will use the TEFs for birds and fish to
determine TEQs for these other organisms as well. The results of this calculation are reported on
optional FORM I-HR CDD-4.
D. Evaluation:
1. Verify that the TEF calculations were correctly performed, in accordance with Regional policy.
2. In the determination of total TEQ for a sample, consider the impact of using estimated quantities
in the TEQ calculation. If any, or a portion, of the total TEQ number has been derived from
qualified results, the reviewer may decide to qualify the TEQ. For example if more than 10% of
the total represents "J"-qualified values, then the total may also be "J" qualified.
E. Action:
If calculations were not correctly performed by the laboratory, notify the TOCOR and/or SMO of the
deficiency.
September 2011 40
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Chlorinated Dioxin and Furan Data Review
XIII. Estimated Detection Limit (EDL) and Estimated
Maximum Possible Concentration (EMPC)
A. Review Items:
FORM 1DFA (FORM I-HR CDD-1) and raw data. Reference DLM02.X, Exhibit D, Section 1 1.2.5
and Section 11.2.6.
B. Objective:
For each analyte that is not detected, calculate an EDL. The sample-specific EDL is an estimate made
by the laboratory of the concentration of a given analyte that must be present to produce a signal with
a peak height of at least 2.5 times (2.5x) the background noise signal level. The estimate is specific to
a particular analysis of the sample and will be affected by sample size, dilution, etc. There is
toxicological significance of CDDs/CDFs; therefore, the EDL value is reported for non-detected
analytes rather than simply reporting the respective CRQL.
The EMPC value is applied to a sample when the S/N ratio is at least 2.5:1 for both quantitation ions,
but the ion abundance ratio criteria are not met.
C. Criteria:
1. EDL
The EDL is calculated for each 2,3,7,8-substituted isomer that is not identified, regardless of
whether or not any non-2,3, 7,8-substituted isomers in that homologous series are present. The
EDL is also calculated for those 2,3,7,8-substituted isomers where responses for both of the
quantitation ions are less than 2.5 times (<2.5x) the background level, and therefore do not meet
the identification criteria.
The formulas below are used to calculate an EDL for each absent 2,3,7,8-substituted CDD/CDF.
The background level (Hx) is determined by measuring the height of the noise at the expected
RTs of both of the quantitation ions of the particular 2,3,7,8-substituted isomer. The expected RT
is determined from the most recent analysis of the midpoint standard (CS3) performed on the
same HRGC/HRMS system that was used for the analysis of the samples that are associated with
the EDL calculations. In addition, if there is a matching labeled analog present, the RT of the
expected analyte should be within ± 2 sec. of that of the labeled analog.
All Matrices Other than Aqueous:
Solids EDL (ng/kg) =
W x (HL, + HL2) x RR
Where,
EDL = Estimated Detection Limit for 2,3,7,8-substituted CDDs/CDFs
QL = Quantity (pg) of appropriate labeled standard added prior to sample extraction
Hxi,Hx2 = Peak heights of the noise for both quantitation ions of the CDD/CDF
HLi,HL2 = Peak heights of the labeled standard ions
D = Dilution Factor
W = Weight extracted in grams
— _ The Mean Relative Response for the isomer of interest from the initial
RR ~ calibration (see DLM02.X, Exhibit D)
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Chlorinated Dioxin and Furan Data Review
Aqueous:
Aqueous EDL (pg/L) =
2.5 x QL x
Hx2) x D
V x
I + HL2) x RR
Where,
EDL = Estimated Detection Limit for 2,3,7,8-substituted CDDs/CDFs
QL = Quantity (pg) of appropriate labeled standard added prior to sample extraction
Hxi,Hx2 = Peak heights of the noise for both quantitation ions of the CDD/CDF
HLi,HL2 = Peak heights of the labeled standard ions
D = Dilution Factor
V = Volume extracted in liters
_ The Mean Relative Response for the isomer of interest from the initial
calibration (see DLM02.X, Exhibit D)
2. EMPC
An EMPC is calculated for 2,3,7,8-substituted isomers that are characterized by a response with
an S/N ratio of at least 2.5:1 for both of the quantitation ions, but that do not meet the ion
abundance ratio criteria outlined in Section IX.
The EMPC is calculated according to one of the following formulas:
All Matrices Other than Aqueous:
RR =
EMPC (ng/kg) =
CExXD
Ws
Where,
D = Dilution Factor
Ws = Sample dry weight in kg
CEX = The quantity of the native compound in the extract in nanograms (ng/ (iL * extract
volume in (iL)
Aqueous:
CEX X D
Where,
D
Vs
CEX
EMPC (pg/L) =
Dilution Factor
Sample volume in liters
The quantity of the native compound in the extract in picograms (pg/ (iL * extract
volume in
D. Evaluation:
1. Verify that EDLs and EMPCs are correctly calculated.
2. An EDL must be reported for each undetected analyte. The EDL must be
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Chlorinated Dioxin and Furan Data Review
XIV. Labeled Compound Recoveries
A. Review Items:
FORM 1DFA (FORM I-HR CDD-1) and raw data. Reference DLM02.X, Exhibit B, Section 3.4 and
Exhibit D, Section 11.2.7, and Exhibit D, Tables 2 and 7.
B. Objective:
The 15 labeled CDDs/CDFs serve as the isotopic dilution quantitative mechanism in this method. The
recovery of these compounds, along with the recovery of the cleanup standard, is a critical measure of
the effectiveness of the laboratory and method to extract the compounds of interest.
C. Criteria:
1. Recovery of the labeled cleanup standard should be monitored as an indicator of method
efficiency through the extract cleanup. If the original sample, prior to any dilutions, has more than
one labeled compound or cleanup standard with a Percent Recovery (%R) not within the limits
specified in Table A.7, re-extract and reanalyze that sample.
Values below 100% indicate loss of labeled and unlabeled compounds during the analytical
process. Values over 100% indicate errors in the quantitation of the labeled compounds, or
problems with the cleanup of the sample extracts. Within the limits, the use of isotope dilution or
internal standard quantitation (depending on the analyte) will produce acceptable results for the
target compounds. Outside the limits, the quantitation accuracy or precision of the results will be
affected.
2. Re-extract and reanalyze if the labeled compounds are not present with at least a 10:1 S/N ratio at
their respective m/z(s).
3. If any of the labeled compound ion abundance ratios specified in Table A.4 are not within the
contract-specified control limits, reanalyze the sample extract on an analytical system meeting
system performance, and initial and calibration verification criteria. If the problem corrects itself,
use the data from the second analysis and disregard the data from the first analysis. No additional
re-extraction and reanalysis are required. If the failed ion abundance ratios persist through the
second analysis, process the extract through additional cleanup steps, or re-extract and reprocess
the sample through sufficient cleanup steps to remove possible interferences.
4. If 13C12-2,3,7,8-TCDD is not resolved from 13C12-1,2,3,4-TCDD with a valley of <25% on the
DB-5 (or equivalent) column, or 13C12-2,3,7,8-TCDD is not resolved from 13C121,2,3,4-TCDD
with a valley of <25% on the DB-225 (or equivalent) column, adjust the HRGC/HRMS operating
conditions, recalibrate the instrument, and reanalyze the affected sample. This criterion applies to
sample analysis; no re-extraction and reanalysis are required if the second analysis resolves the
problem. If this criterion is not met for a calibration standard, reanalyze associated samples after
instrument recalibration. Re-extraction is not ordinarily required unless the resolution difficulties
reappear after recalibration.
D. Evaluation:
1. Verify that the labeled compound and the internal standard recoveries fall within the required
limits.
2. Verify that the S/N ratio of the labeled compound is ^ 10:1.
3. Verify that the labeled compound, internal standard, and clean-up standard recoveries fall within
the required limits, prior to any dilutions being performed.
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Chlorinated Dioxin and Furan Data Review
E. Action:
1.
2.
3.
If the recoveries of the labeled compounds are not within the limits in Table A.7, but other
identification criteria and the S/N requirement have not been met, the laboratory should have
performed a reanalysis. If no reanalysis is found, contact the TOCOR or SMO to initiate
reanalysis.
The 37Cl-labeled cleanup standard is used to monitor the efficiency of the cleanup; it is added to
the sample extracts after extraction and before any cleanup steps. Low recovery of the labeled
compounds and the cleanup standard suggests that losses may be due to the performance of the
cleanup steps. Thus, re-extraction and reanalysis of the sample may yield better results. If the
labeled compound recoveries are low (<40%), and the cleanup standard recovery is not, the
recovery problems may be associated with the extraction procedures or related to a particularly
difficult matrix. In this case, reanalysis may only serve to confirm a "matrix effect". If recovery
of only the cleanup standard is low, the presence of interference should be investigated.
Otherwise, the possibility of improper calibration of the cleanup standard or a spiking error
should be considered. Qualify all results associated with non-compliant clean-up standard
performance as estimated ("J" or "UJ").
In the event that labeled compound recoveries are <10%, the reviewer should note whether this is
accompanied by a loss of signal (i.e., S/N <10). If this is the case, the impact may make both
positive and non-detect results unusable ("R"-qualify all results). Otherwise, positive results
should be considered estimated ("J").
If any of the labeled compounds (exclusive of the recovery standard) fail the ion ratio criteria but
the associated calibration standard was acceptable, quantitative results may have been influenced
by interference. Qualify all associated results as estimates ("J" or "UJ"). If ion ratio criteria were
not met in the calibration standard, follow the actions prescribed in Table 6.
Professional judgment is advised before taking action based on recovery standard performance. If
a wide range is noted in cleanup standard recoveries between samples and laboratory quality
control (QC) that correspond to other QC indicators, this parameter may be used as a data quality
issue.
Table 9. Labeled Compound Recovery Actions
Criteria
%R >Upper Acceptance Limit
% R >10% but less than Lower Acceptance Limit
%R<10%
<10%andS/N>10:l
<10%andS/N<10:l
Ion abundance ratio criteria Calibration compliant
not met Calibration non-compliant
Clean-up Standard Recovery < Lower Acceptance Limit
Action
Detected
Associated
Compounds
J
J
Non-Detected
Associated
Compounds
UJ
UJ
(see below)
J
R
J
J
J
R
R
UJ
R
UJ
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Chlorinated Dioxin and Furan Data Review
XV. Regional Quality Assurance/Quality Control (OA/OC)
A. Review Items:
FORM 1DFA (FORM I-HR CDD-1), chromatograms, quantitation reports, Traffic Report/Chain of
Custody (TR/COC) documentation, and raw data for Regional Quality Control (QC) samples.
Performance evaluation sample (PES) scoring information from the Quality Assurance Technical
Support (QATS) laboratory is evaluated as per Section II, above. Reference DLM02.X, Exhibit B,
Section 3.4, and Exhibit D, Section 11.2.
B. Objective:
In addition to evaluating the results of performance evaluation spikes and/or blind blanks, assess the
impact on data quality of any other QA/QC samples initiated by the Region, including field
duplicates, equipment rinsates, or reagent blanks.
C. Criteria:
1. The frequency of Regional QA/QC samples should be defined in the quality assurance project
plan (QAPP).
2. Performance criteria for Regional QA/QC samples should also be defined in the Quality
Assurance Project Plan (QAPP).
D. Evaluation:
The reviewer must decide whether the results of Regional QA/QC samples impact all samples in the
project, or only those directly associated (i.e., in the same sample delivery group (SDG), collected the
same day, prepared together, or contained in the same analytical sequence). Results for PESs are
evaluated for false negatives, false positives, and accuracy of target compound quantitation (see
Section II). Equipment rinsate samples should not contain any CDD/CDF contamination. Moreover,
they should be comparable to the associated method blank(s). Field duplicates should be evaluated for
comparability (i.e., precision). The reviewer must decide whether poor precision is the fault of the
laboratory, or a result of sample nonhomogeneity in the field. Laboratory observations of sample
appearance may become important in these situations.
E. Action:
Any action must be in accordance with 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.
Like PES, Regional QA/QC samples are only indicators of technical performance of laboratory
and/or field operations. If a result is not within acceptance criteria for any congener, evaluate the
other Quality Control (QC) samples in the SDG [Laboratory Control Sample (LCS), calibration,
labeled standard recovery, internal standard recovery, and cleanup standard recovery]. Consider the
possibility that the Regional QA/QC samples may not be representative of the field samples. In
general, for Regional QA/QC performance not within QAPP specifications, qualify associated sample
detects as estimated "J" and non-detects as estimated "UJ"; however, QAPP-specific rules should be
controlling. The impact on overall data quality should be assessed after consultation with the data
user and/or field personnel. Contact the TOCOR if reanalysis of samples is required.
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Chlorinated Dioxin and Furan Data Review
XVI. Overall Assessment of Data
A. Review Items:
Entire data package, data review results, Quality Assurance Project Plan (QAPP), if available, and the
Sampling and Analysis Plan (SAP), if available.
B. Objective:
Assess the overall quality of the data.
C. Criteria:
The overall assessment of a data package is a collection of observations and findings as a result of the
review process, and discussion the impact of qualifications on the overall use of the data. In addition,
contract compliance issues should be brought to the attention of the TOCOR and/or SMO.
D. Evaluation:
1. Evaluate any technical problems which have not been previously addressed.
2. Remember that analytical problems are often additive in nature.
3. 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.
4. If appropriate information is available, the reviewer may assess the usability of the data to assist
the data user in avoiding inappropriate application of the data.
E. Action:
1. 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.
2. Also, usually under separate cover, document any contract-related deficiencies, including
completeness and usability of the Case Narrative for TOCOR and/or Contract Officer records and
possible action.
September 2011 46
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Appendix A
APPENDIX A: DATA TABLES
Extracted from:
USEPA Statement of Work (SOW) for Analysis of Chlorinated Dibenzo-p-Dioxins (CDDs) and
Chlorinated Dibenzofurans (CDFs), Multi-Media, Multi-Concentration, DLM02.2, Dated December 2009
September 2011 A-l
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Table A.I. Descriptors, Exact Mass
Elemental Compositions of the Chlorinated-p-
-to-Charge (m/z) Ratios, m/z Types, and
Dioxins/Chlorinated Dibenzofurans (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
435.8169
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+2
Elemental Composition
C7Fn
C12H435C140
Ciz H4 35C1337C1 0
13C12H435C14O
13C12H435C1337C1O
C12 H4 35C14 O2
da H4 35C13 37C1 02
C12H437C1402
C7F13
13C12H435C1402
13C12H435C1337C102
C12 H4 35C15 37C1 0
C12 H3 35C14 37C1 0
C12 H3 35C13 37C12 O
13C12H335C1437C10
13C12H335C1337C120
C9F13
C12 H3 35C14 37C1 02
C12 H3 35C13 37C12 02
13C12H335C1437C102
13C12H335C1337C12O2
C12 H3 35C16 37C1 0
C12 H2 35C15 37C1 0
Ciz H2 35C14 37C12 0
13C12H235C160
13C12H235C1537C1O
C12 H2 35C15 37C1 02
Ci2 H2 35C14 37C12 02
CgFis
13C12H235C1537C1O2
13C12H235C1437C12O2
C9F17
Ciz H2 35C16 37C12 0
C12 H 35C16 37C1 0
C12 H 35C15 37C12 O
13C12H35C17O
13C12H35C1637C1O
C12 H 35C16 37C1 02
C12 H 35C15 37C12 O2
C9F17
13C12H35C1637C1O2
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
HpCDD3
September 2011
A-2
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Descriptor
5
Exact m/z1
437.8140
479.7165
441.7428
442.9728
443.7399
457.7377
459.7348
469.7779
471.7750
513.6775
m/z Type
M+4
M+4
M+2
Lock
M+4
M+2
M+4
M+2
M+4
M+4
Elemental Composition
13C12H35C1537C1202
C12 H 35C17 37C12 O
C12 35C17 37C1 0
Ci0F17
Ci2 35C16 37C12 0
C12 35C17 37C1 02
C12 35C16 37C12 O2
13C12 35C17 37C1 02
13C12 35C16 37C12 02
C12 35C18 37C12 O
Substance2
HpCDD3
NCDPE
OCDF
PFK
OCDF
OCDD
OCDD
OCDD3
OCDD3
DCDPE
'Nuclidic masses used:
H = 1.007825 C = 12.00000 13C = 13.003355
0=15.994915 35C1 = 34.968853 37C1 = 36.965903
Homologous series Definition:
TCDD = Tetrachlorodibenzo-p-dioxin
TCDF = Tetrachlorodibenzofuran
PeCDD = Pentachlorodibenzo-p-dioxin
PeCDF = Pentachlorodibenzofuran
HxCDD = Hexachlorodibenzo-p-dioxin
HxCDF = Hexachlorodibenzofuran
HpCDD = Heptachlorodibenzo-p-dioxin
HpCDF = Heptachlorodibenzofuran
OCDD = Octachlorodibenzo-p-dioxin
OCDF = Octachlorodibenzofuran
HxCDPE = Hexachlorodiphenyl ether
HpCDPE = Heptachlorodiphenyl ether
OCDPE = Octachlorodiphenyl ether
NCDPE = Nonachlorodiphenyl ether
DCDPE = Decachlorodiphenyl ether
PFK = Perfluorokerosene
3Labeled compound.
4There is only one m/z for 37Cl4-2,3,7,8,-TCDD (cleanup standard).
F= 18.9984
September 2011
A-3
-------
Table A.2. Gas Chromatography (GC) Retention Time (RT) Window Defining Mixture (WDM)
and Isomer Specificity Check (ISC) Standard
CDD/CDF
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
September 2011
A-4
-------
Table A.3. Relative Retention Times (RRT) and Quantitation Reference
of the Native and Labeled CDDs/CDFs
CDD/CDF
Retention Time and
Quantitation Reference
Relative Retention Time
Compounds using 1SC12-1,2,3,4-TCDD as the injection 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
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
13C12-2,3,7,8-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 13C12-1,2,3, 7,8,9-HxCDD as the injection 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
lrThe retention time reference for 1,2,3,7,8,9-HxCDD is 13C12-l,2,3,6,7,8-HxCDD.
1,2,3,7,8,9-HxCDD is quantified using the averaged responses of 13Ci2-l,2,3,4,7,8-HxCDD and
13C12-l,2,3,6,7,8-HxCDD.
September 2011
A-5
-------
Table A.4. Theoretical Ion Abundance Ratios and Quality Control (QC) Limits
Number of
Chlorine Atoms
42
5
6
63
7
74
8
m/z's
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 Limit1
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
:QC limits represent ±15% windows around the theoretical ion abundance ratios.
2Does not apply to 37Cl4-2,3,7,8-TCDD (cleanup standard).
3Used for 13C12-HxCDF only.
4Used for 13C12-HpCDF only.
September 2011
A-6
-------
Table A.5. Concentration of CDDs/CDFs in Calibration and Calibration Verification Solutions
CDD/CDF
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
Cleanup Standard
37Cl4-2,3,7,8-TCDD
Internal Standards
13C12-1,2,3,4-TCDD
13C12-l,2,3,7,8,9-HxCDD
CS1
(ng/mL)
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
0.5
100
100
CS2
(ng/mL)
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
2
100
100
CS3
(ng/mL)
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
10
100
100
CS4
(ng/mL)
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
40
100
100
CSS
(ng/mL)
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
200
100
100
September 2011
A-7
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Table A.6. Acceptance Criteria for Laboratory Control Sample (LCS)
CDD/CDF
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 (% 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
September 2011
A-8
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Table A.7. Labeled Compound Recovery in Samples When All CDDs/CDFs are Tested
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
37Cl4-2,3,7,8-TCDD
Test Cone (ng/mL)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
10
Labeled Compound Recovery (%)
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
35-197
September 2011
A-9
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September 2011 A-10
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