OSWER 9240.1-37
EPA 540-R-02-003
August 2002
USEPA ANALYTICAL OPERATIONS/DATA QUALITY
CENTER (AOC)
NATIONAL FUNCTIONAL GUIDELINES
FOR
CHLORINATED DIOXIN/FURAN DATA REVIEW
Final
Office of Emergency and Remedial Response
U.S. Environmental Protection Agency
Washington, DC 20460
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NOTICE
The policies and procedures set forth here are intended as guidance to the United States Environmental
Protection Agency (hereafter referred to as USEPA) and other governmental employees. They do not
constitute rule making by USEPA, and may not be relied upon to create a substantive or procedural right
enforceable by any other person. The Government may take action that is at variance with the policies and
procedures in this manual.
This document can be obtained from the following USEPA Web site at:
http://www.epa.gov/superfund/programs/clp/guidance.htm
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TABLE OF CONTENTS
INTRODUCTION 1
DATA QUALIFIER DEFINITIONS 2
PRELIMINARY REVIEW 2
DATA REVIEW NARRATIVE 3
DIOXIN DATA REVIEW 4
I. Holding Times. Storage, and Preservation 5
II. Performance Evaluation Samples 8
III. Mass Calibration and Mass Spectrometer Resolution 10
IV. Window Defining Mix 11
V. Chromatographic Resolution 14
VI. Instrument Stability 17
VII. High Resolution Gas Chromatograph/High Resolution Mass Spectrometer Initial
Calibration 20
VIII. High Resolution Gas Chromatograph/High Resolution Mass Spectrometer Calibration
Verification 25
IX. Identification Criteria 28
X. Method Blank Analysis 31
XI. Laboratory Control Sample Analysis 33
XII. Toxicitv Equivalency Factor and Isomer Specificity 34
XIII. Dilution by Addition of Solvent 36
XIV. Dilution by Reextraction and Reanalysis 37
XV. Second Column Confirmation 38
XVI. Estimated Detection Limit and Estimated Maximum Possible Concentration 40
XVII. Labeled Compound Recoveries 43
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XVIII. Regional Quality Assurance and Quality Control
XIX. Overall Assessment of Data
45
46
LIST OF TABLES
Table 1. Holding Times, Storage, Preservation .
Table 2. Action Limits
Table 3. System Performance Checks
Table 4. Instrument Stability
Table 5. Initial Calibration
Table 6. Calibration Verification
Table 7. Identification Criteria
Table 8. Blank Actions for Laboratory Analyses
. 7
. 9
16
19
23
27
30
32
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ACRONYMS
CDD Chlorinated Dibenzo-p-Dioxin
CDF Chlorinated Dibenzofuran (also PCDF)
CDWG Chlorinated Dioxins Work Group
CLP Contract Laboratory Program
CPS Column Performance Solution
CRQL Contract Required Quantitation Limits
CS Calibration Standard
CWA Clean Water Act
DQO Data Quality Objective
EDL Estimated Detection Limit
EMPC Estimated Maximum Possible Concentration
HRGC High Resolution Gas Chromatograph
HRMS High Resolution Mass Spectrometer
ISC Isomer Specificity Check
LCS Laboratory Control Sample
PCDPE Polychlorinated diphenyl ether
PE Performance Evaluation
PES Performance Evaluation Sample
PFK Perfluorokerosene
QA Quality Assurance
QAPP Quality Assurance Project Plan
QATS Quality Assurance Technical Support
QC Quality Control
RR Relative Response
RRF Relative Response Factor
RSD Relative Standard Deviation
RT Retention Time
RRT Relative Retention Time
SAP Sampling and Analysis Plan
SDG Sample Delivery Group
SDWA Safe Drinking Water Act
SICP Selected Ion Current Profile
SIM Single Ion Monitoring
S/N Signal-to-noise Ratio
SOP Standard Operating Procedure
SOW Statement of Work
TCL Target Compound List
TEF Toxicity Equivalency Factor
TICP Total Ion Current Profile
TOPO Task Order Proj ect Officer
VTSR Validated Time of Sample Receipt
WDM Window Defining Mix
USEPA United States Environmental Protection Agency
in
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INTRODUCTION
This document is designed to offer guidance on USEPA Chlorinated Dibenzo-p-dioxin (CDD)
and Chlorinated Dibenzofuran (CDF) data evaluation and review. In some applications it 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 are 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 (PE) standard materials, and instrument
performance checks.
These guidelines include the requirements for the USEPA Statement of Work (SOW) for
Analysis of CDDs and CDFs, DLM01.4 dated January 2002. This SOW is based on USEPA Methods
1613B and 8290A which employ High Resolution Gas Chromatography and High Resolution Mass
Spectrometry (HRGC/HRMS).
This document is intended to assist in the technical review of analytical data generated through
this SOW. Determining contract compliance is not the intended objective of these guidelines. The data
review process provides information on analytical limitations of data based on specific Quality Control
(QC) criteria. In order 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 issues from the user prior to reviewing the data. When this is not
possible, the user should be 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. 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 which are out of specification may be required to rerun samples or resubmit data, even if
the previously submitted data have been utilized due to program needs. Data which do not meet specified
requirements are never fully acceptable. 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.
This document offers guidelines for the review of data generated by the DLM01.4 SOW.
Professional judgment should always be used to determine the ultimate usability of the data.
August 2002 1 Final
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DATA QUALIFIER DEFINITIONS
The following definitions provide brief explanations for the qualifiers assigned to results in the
data review process. If a Region chooses to use additional qualifiers, a complete explanation of those
qualifiers should accompany the data review.
U
The analyte was analyzed for, but was not detected above the Contract Required Quantitation
Limit (CRQL) for the sample.
The analyte was positively identified; the associated numerical value is the approximate
concentration of the analyte in the sample.
N
The analysis indicates the presence of an analyte for which there is presumptive evidence to
make a "tentative identification".
NJ
The analysis indicates the presence of an analyte that has been "tentatively identified" and the
associated numerical value represents its approximate concentration.
UJ
The analyte was not detected above the adjusted CRQL. However, the reported adjusted CRQL
is approximate and may be inaccurate or imprecise.
R
The sample results are unusable. The analyte may or may not be present in the sample.
PRELIMINARY REVIEW
This document is for the review of analytical data generated through the USEPA Chlorinated
Dibenzo-p-dioxins (CDDs) and Chlorinated Dibenzofurans (CDFs) Statement of Work (SOW) DLM01.4
and any future editorial revisions. In order to use this document effectively, the reviewer should have an
understanding of the analytical method and a general overview of the Sample Delivery Group (SDG) or
sample Case at hand. The exact number of samples, their assigned numbers, their matrix, and the number
of laboratories involved in their analysis are essential information. Background information on the site is
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 may modify the 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 task order depending on project requirements. Thus,
the task order requirements must be taken into consideration, along with the requirements in the National
Functional Guidelines (NFG), when reviewing the data.
The SDGs or Cases routinely have unique samples which require special attention by the reviewer.
These samples include field blanks, field duplicates, and Performance Evaluation (PE) samples which need
to be identified. The sampling records should provide:
1. The Region where the samples were taken; and
2. Complete list of samples with information on:
a. Sample matrix;
b. Field blanks*;
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c. Field duplicates*;
d. Field spikes*;
e. Quality Control (QC) audit samples*;
f. Shipping dates;
g. Preservatives; and
h. Laboratories involved.
* If applicable.
The Traffic Report/Chain of Custody (TR/COC) documentation includes sample descriptions and
date(s) and time(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 found in the
SDG Narrative.
The SDG Narrative for the Sample Data Package must include a Laboratory Certification Statement
(exactly as stated in the 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.
DATA REVIEW NARRATIVE
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 Task Order Project Officer (TOPO) assigned oversight responsibility for the
Laboratory producing the data.
The Data Review Narrative should include comments that clearly identify the problems associated
with a Case or Sample Delivery Group (SDG) and state the limitations of the data. Documentation should
include the Sample Number, analytical method or modification, extent of the problem, and assigned
qualifiers.
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Dioxin Data Review
DIOXIN DATA REVIEW
The data requirements to be checked are listed below:
I. Holding Times, Storage, and Preservation
II. Performance Evaluation Samples
III. Mass Calibration and Mass Spectrometer Resolution
IV. Window Defining Mix
V. Chromatographic Resolution
VI. Instrument Stability
VII. High Resolution Gas Chromatograph/High Resolution Mass Spectrometer Initial Calibration
VIII. High Resolution Gas Chromatograph/High Resolution Mass Spectrometer Continuing
Calibration
IX. Identification Criteria
X. Method Blank Analysis
XI. Laboratory Control Sample Analysis
XII. Toxicity Equivalency Factor and Isomer Specificity
XIII. Dilution by Addition of Solvent
XIV. Dilution by Reextraction and Reanalysis
XV. Second Column Confirmation
XVI. Estimated Detection Limit and Estimated Maximum Possible Concentration
XVII. Labeled Compound Recoveries
XVIII. Regional Quality Assurance and Quality Control
XIX. Overall Assessment of Data
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Dioxin Data Review
I. Holding Times, Storage, and Preservation
A. Review Items:
Form 1DFA (Form I-HR CDD-1), USEPA Sample Traffic Report/Chain of Custody (TR/COC)
documentation, raw data, and sample extraction sheets.
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:
1. Water 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 must be added. If the sample pH is >9, the sample pH must be adjusted to pH 7-9
with sulfuric acid.
2. 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.
3. Analysis of sample extracts must be completed within 30 days of extraction.
4. Sample extracts can be stored up to one year from the date of extraction in the event that
reanalysis is required.
5. Holding times for oily matrices have not been established. The aqueous holding times are
recommended in this case. Holding times for fish and tissue samples have not been established,
however, they should be extracted within one year of collection as recommended in USEPA
Method 1613B. As always, the professional judgment of the reviewer remains the final authority
in issues such as these.
NOTE: Water samples subject to compliance with the Clean Water Act (CWA) or Safe Drinking
Water Act (SDWA) (40CFR Part 136.3) may require extraction within 7 days from the
time of collection to the day of extraction.
D. Evaluation:
1. Contractual holding times for sample extraction are established by comparing the sampling dates
on the TR/COC documentation with the dates of extraction on Form I-HR CDD-1 and on the
sample extraction sheets. To determine if 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.
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Dioxin Data Review
2. Verify that the TR/COC documentation indicates that the samples were received intact and iced at
4°C (±2°C). If the samples were not iced, or there were any problems with the samples upon
receipt, then discrepancies in the sample condition could affect the data.
E. Action:
1. If holding times are exceeded, flag all positive results as estimated "J", and sample quantitation
limits as estimated "UJ", and document that holding times were exceeded. The reviewer may
determine that non-detect data are unusable "R".
2. If shipment and storage conditions are exceeded, either on the first analysis or upon reanalysis,
the reviewer may determine that positive results or the associated quantitation limits are estimates
and should be qualified with "J" or "UJ", respectively.
3. If sodium thiosulfate preservative has not been added to aqueous samples, qualify all positive
results "J" and detection limits "UJ". If a residual chlorine test has been performed and found to
be negative, then data should not be flagged due to lack of sodium thiosulphate preservative.
4. Due to limited information concerning holding times for oily samples, it is left to the discretion of
the data reviewer to apply water holding time criteria to oily samples. Professional judgment is
required to evaluate holding times for oily samples. Professional judgment is also required to
evaluate holding times for fish and tissue samples.
5. If extracts are analyzed outside the 30 day holding time, for all sample types, qualify positive
results "J" and detection limits "UJ".
6. Whenever possible, the reviewer should comment in the Data Review Narrative on the effect that
the exceeded holding times will have on the resulting data.
7. When holding times are exceeded, it should be noted as an action item for the Task Order Project
Officer (TOPO).
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Dioxin Data Review
Table 1. Holding Times, Storage, Preservation
Evaluation
Contractual
Holding Time
Storage
Preservation
Sample Extract
Holding Time
Sample
Type
Aqueous
Soil
Fish, Tissue
Aqueous
Soil
Fish, Tissue
Aqueous
All types
Criteria
>1 year
>1 year
>1 year
>6°C shipment
and storage
>6°C shipment
and storage
>4°C shipment
>~10°C
storage
Not added
>30 days
Action
Qualify positives as "J"
Quality detection limits as "UJ"
Qualify positives as "J"
Qualify detection limits as "UJ"
Use professional judgment
Qualify positives as "J"
Qualify detection limits as "UJ"
Qualify positives as "J"
Qualify detection limits as "UJ"
Qualify positives as "J"
Qualify detection limits as "UJ"
Qualify positives as "J"
Qualify detection limits as "UJ"
Qualify positives as "J"
Qualify detection limits as "UJ"
August 2002
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Dioxin Data Review
II. Performance Evaluation Samples
A. Review Items:
Form 1DFA (Form I-HR CDD-1), Performance Evaluation (PE) sample score information from the
Quality Assurance Technical Support Laboratory (QATS).
B. Objective:
To evaluate the Laboratory's ability to achieve acceptable results through the analysis of PE samples.
C. Criteria:
1. The Region may provide the Laboratory with a PE sample to be analyzed with each Sample
Delivery Group (SDG). The Laboratory must analyze PE samples when provided by the Region.
2. The Region may score the PE samples based on data provided by QATS.
D. Evaluation:
If PE samples are included in the SDG, verify that the PE sample results are within the 99% (3O)
confidence interval or action window of the experimentally determined true values provided by
QATS.
E. Action:
If a result is outside of the action limits (99% confidence interval) for any congener, the other Quality
Control (QC) samples in the SDG should be evaluated [Laboratory Control Sample (LCS),
calibration, labeled standard recovery, internal standard recovery, and clean-up standard recovery].
In such situations, the PE sample may not be representative of the field samples. PE samples are only
one indicator of technical performance of the Laboratory. In general, for PE sample analytes outside
the 95% confidence intervals or action performance windows but within the 99% confidence interval,
qualify associated sample data as estimated "J". For data outside the 99% confidence interval, qualify
the associated sample data as rejected "R". The Regional Task Order Project Officer (TOPO) should
be contacted to determine if reanalysis of samples is required. Under certain circumstances, it may be
necessary to utilize data that are not within the 99% confidence interval before reanalysis can take
place. As always, the reviewer must use their best professional judgment to determine the usability of
the data.
For Example: If HxCDD is quantitated beyond the high-end of the action limit, and all samples are
non-detects for this compound, then the usability of the data would not be affected.
NOTE: Qualify only those analytes that fail to meet criteria.
Final 8 August 2002
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Dioxin Data Review
Table 2. Action Limits
Criteria
Results are outside the 95% confidence interval
but inside the 99% interval (<3O)
Results are outside the 99% confidence interval
(>30)
Action
Qualify
Qualify
the associated sample
the associated sample
data as estimated "J"
data as rejected "R"
August 2002
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Dioxin Data Review
III. Mass Calibration and Mass Spectrometer Resolution
A. Review Items:
Hardcopy of mass spectrometer resolution demonstration.
B. Objective:
Mass calibration and mass spectrometer resolution > 10,000 must be performed by the Laboratory
with Perfluorokerosene (PFK) calibrant. This is a fundamental requirement for any Laboratory using
DLM01.4 and other High Resolution Mass Spectrometry (HRMS) methods (e.g., 1613B, 8290A). If
mass calibration and resolution tuning is not properly performed, interferences may degrade
Chlorinated Dibenzo-p-dioxin and Chlorinated Dibenzofuran (CDD/CDF) identification and
quantitation. Mass calibration and resolution is the first part of the three fundamental High
Resolution Gas Chromatography/HRMS (HRGC/HRMS) system performance checks. The second
fundamental performance check is the mass spectrometer Selected Ion Monitoring (SIM) scan
descriptor switching times. The third fundamental performance check is Gas Chromatograph (GC)
resolution.
C. Criteria:
Laboratories are required to provide evidence of mass spectrometer resolution > 10,000 at least once
at the beginning of each 12-hour analysis period. 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
any of the five mass descriptors. The minimum resolving power of 10,000 must be demonstrated at
the beginning and end of each 12-hour analytical sequence. The format of the peak profile
representation must allow manual determination of mass spectrometer resolution, i.e., the horizontal
axis must be a calibrated mass scale (amu or ppm per division). The result of the peak width
measurement should appear on the hardcopy. The deviation between the exact m/z and the
theoretical m/z monitored should be <5 ppm.
D. Evaluation:
Verify that the mass spectrometer has been tuned to a resolution of > 10,000. A demonstration of
mass spectrometer resolving power is provided within USEPA Method 8290A, Section 8.2.2.3, and in
Figure 5.
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 or is not demonstrated, all of the associated data
should be rejected "R".
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Dioxin Data Review
IV. Window Defining Mix
A. Review Items:
Form 5DFA (Form V-HR CDD-1).
B. Objective:
Prior to the calibration of the High Resolution Gas Chromatrograph/High Resolution Mass
Spectrometer (HRGC/HRMS) system, it is necessary to establish the appropriate switching times for
the Selected Ion Monitoring (SIM) descriptors (see Table 8 in DLM01.4, Exhibit D, Section 15.0),
and to verify the chromatographic resolution. The switching times are determined by the analysis of
the Window Defining Mix (WDM) which contains the first and last eluting isomers in each
homologue (see Table 5 in DLM01.4, Exhibit D, Section 15.0). Chromatographic resolution is
verified by analyzing one of two Isomer Specificity Check (ISC) solutions, depending on the Gas
Chromatograph (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. Mass spectrometer
Selected Ion Monitoring (SIM) scan descriptor switching times is the second of the three fundamental
HRGC/HRMS system performance checks.
The 12-hour time period begins with the injection of the WDM or CPS.
C. Criteria:
1. The WDM shall be analyzed after the Perfluorokerosene (PFK) tune and before any calibration
standards on each instrument and GC column used for analysis in order to evaluate the mass
spectrometer SIM scan descriptor switching times. This commercially available, 16-component
mix contains the first and last eluting isomers in each homologue. Mixes are available for various
columns. The mix for the DB-5 (or equivalent) column may not be appropriate for the DB-225 or
other columns.
2. The ions in each of the five recommended descriptors are arranged so that there is minimal to no
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, the tetra- and pentachlorinated dioxins and furans 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
Retention Time (RT) window will also be those isomers for which the ions are monitored.
Should homologue overlap between descriptors occur, the Laboratory may use discretion in
setting the switching times. However, 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.
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Dioxin Data Review
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
• During each 12-hour sample analysis period prior to the calibration verification.
5. If the Laboratory employs a GC column that has a different elution order than the columns
specified here, the Laboratory must ensure that the first and last eluting isomers in each
homologue 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 Chlorinated-p-Dioxin/Chlorinated Dibenzofuran (CDD/CDF) GC columns.
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 V, Chromatographic Resolution).
D. Evaluation:
1. Verify that the WDM is analyzed at the required frequency.
2. Examine the WDM chromatograms to determine when descriptor switching times are turned on
and off.
3. Note the RT of each first and last eluting isomer in each homologue for identification of
switching times.
4. Each positive dioxin and furan result (tetra through hepta) must have an RT within the limits
established by the WDM for the corresponding homologue. The 2,3,7,8-substituted dioxins and
furans must also meet the Relative Retention Time (RRT) limits in Table 2 of Exhibit D, Section
15.0.
E. Action:
1. If the WDM was not analyzed at the required frequency or proper adjustments in descriptor
switching times are not evident, but the calibration standards met specifications, then the
individual 2,3,7,8-substituted target analyte results may be usable without qualification. Total
homologue results, however, should be qualified "J" since one or more CDDs/CDFs may not
have been detected.
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Dioxin Data Review
2. If the chromatography for the calibration standards indicate a significant problem with descriptor
switching times, all of the associated data should be rejected "R". The Task Order Project Officer
(TOPO) for the Laboratory performing the analysis should be notified to decide if sample
reanalysis is necessary.
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Dioxin Data Review
V. Chromatographic Resolution
A. Review Items:
Form 5DFB (Form V-HR CDD-2), and the corresponding Selected Ion Current Profile (SICP) of each
isomer for each of the analyses reported on Form 5DFB.
B. Objective:
To evaluate the ability of the Gas Chromatograph (GC) column to resolve the closely eluting dioxin
and furan isomers. An evaluation must be made for each column used in the analysis of samples. GC
resolution is the third of the three fundamental High Resolution Gas Chromatograph/High Resolution
Mass Spectrometer (HRGC/HRMS) system performance checks listed in Table 3.
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 Isomer Specificity Check (ISC)
standard prior to both the initial and continuing calibration procedures for each instrument and
GC column used for analysis. The ISC and Window Defining Mix (WDM) can be combined in a
single Column Performance Solution (CPS) analysis at the discretion of the analyst.
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 = - x 100
y
Where,
y = The peak height of 2,3,7,8-TCDD.
x = Measurement from baseline to the deepest part of the valley
between 2,3,7,8-TCDD and 1,2,3,8-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 and
continuing calibration solutions. Evaluate the chromatographic resolution using the Quality
Control (QC) criteria stated above.
2. For analyses on a DB-225 (or equivalent) GC column, the chromatographic resolution is
evaluated before the analysis of any calibration standards by the analysis of the commercially
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Dioxin Data Review
available, 3-component DB-225 ISC that contains the TCDF isomers that elute most closely with
2,3,7,8-TCDF on the GC column (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 shall be resolved with
a valley of <25% using the following equation:
Valley = - x 100
y
Where,
y = The peak height of 2,3,7,8-TCDF.
x = Measurement from baseline to the deepest part of the
valley between 2,3,7,8-TCDF and 2,3,4,7-TCDF.
b. 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, as
stated above.
D. Evaluation:
Verify from the SICPs that the <25% valley criteria are met. Examples of GC resolution can be
found in USEPA Methods 1613B and 8290.
E. Action:
If the GC resolution does not meet the specifications, all positive sample results and Estimated
Detection Limits (EDLs) for 2,3,7,8-TCDD and/or 2,3,7,8-TCDF, whichever failed, should be
qualified as "J" and the Task Order Project Officer (TOPO) should be notified to decide on sample
reanalysis.
August 2002 15 Final
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Table 3. System Performance Checks
Criteria
Mass Calibration and Resolution
HRMS SIM Descriptor Switching Times
HRGC Resolution
Action
If mass spectrometer resolution of > 10,000 is not
demonstrated, reject "R" all of the associated
sample data.
If the WDM fails or adjustments are not made, or
if the WDM is not reported, estimate "J" all
affected total homologue results in the associated
samples. (If the WDM fails, adjustments are not
made and the calibration standards indicate a
problem in detecting 2,3,7,8-substituted
congeners because of gross errors in the scan
descriptor times, "R" all of the associated sample
data.)
If the CPS fails or is not reported, estimate "J" all
associated sample results for 2,3,7,8-TCDF and/or
2,3,7,8-TCDD, whichever failed.
Final
16
August 2002
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Dioxin Data Review
VI. Instrument Stability
A. Review Items:
Raw data for the midpoint (CSS) standard at the beginning of the 12-hour sample analysis period.
B. Objective:
To demonstrate that the High Resolution Gas Chromatograph/High Resolution Mass Spectrometer
(HRGC/HRMS) system has retained adequate stability, the CSS standard is analyzed at the beginning
of each 12-hour period during which samples and standards were analyzed. The CSS standard is also
analyzed at the end of each 12-hour period or analytical sequence. This analysis may also serve as
the analysis at the beginning of the subsequent 12-hour period. The use of the CSS standard as a
measure of instrument stability includes the evaluation of Gas Chromatograph (GC) Retention Times
(RTs), relative ion abundance criteria, sensitivity, and calibration criteria.
C. Criteria:
The CSS solution must meet the following QC criteria:
1. Absolute RT criteria. The absolute RT of the first internal standard 13C12- 1,2,3,4-TCDD shall be
within ±15 seconds of the absolute RTs of the identical compound obtained during initial
calibration. If the RT of the first internal standard changes by more than ±15 seconds, the
Laboratory should adjust the switching times of the descriptors and analyze the Window Defining
Mix (WDM) before proceeding with further analyses. Additionally, the absolute RT of the
aforementioned first internal standard must exceed 25.0 minutes on the DB-5 column, and 15.0
minutes on the DB-225 column.
2. Relative Retention Time (RRT) criteria. The RRTs of the native and labeled Chlorinated
Dibenzo-p-Dioxins/Chlorinated Dibenzofurans (CDDs/CDFs) shall be within the limits defined
in Section VII, HRGC/HRMS Initial Calibration (also see Table 2 in DLM01.4, Exhibit D,
Section 15.0).
3. Ion abundance ratio criteria. All CDDs/CDFs in the CSS standard (both native and labeled) must
be within their respective ion abundance ratios (see Table 9 in DLM01.4, Exhibit D, Section
15.0).
4. Instrument sensitivity criteria. The peaks representing both native and labeled analytes in the
CSS standard must have signal-to-noise (S/N) ratios > 10.0.
5. Response criteria. The Relative Response (RR) must be within ±25% of the RR of the initial
calibration. The Relative Response Factor (RRF) must be within ±35% of the initial calibration.
Use the following equation to calculate the Percent Difference (%D):
Response^, - Response,,.,,,
%D = ^ ^ x 100
Response^
August 2002 17 Final
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Dioxin Data Review
Where,
Responsever = Response established during calibration verification.
Response^ = Mean response established during initial calibration according to
DLM01.4 Exhibit D, Equations 4 and 5.
D. Evaluation:
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). An example of the measurement of S/N can be
found in USEPA Method 8290A.
E. Action:
1. The RTs and RRTs of the CSS internal standards will tell the reviewer much about the stability of
the instrument. 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 RT of the internal standard is consistent in the 12-
hour period. No qualification of sample data is necessary if the sample internal standard RTs are
consistent. The reviewer should exercise professional judgment in qualifying the sample data if
the CSS internal standard RT is > 15 seconds different from subsequent sample internal standards.
2. The ion abundance, sensitivity, and calibration criteria are all critical indicators of instrument
stability (see Table 4). Failure to satisfy the ion abundance criteria, S/N 10:1 criteria, or the %D
RR and RRF criteria each indicate significant problems with the instrument. The reviewer should
qualify all of the associated sample data as estimated "J" if any of these criteria fail. The S/N
criteria are especially indicative of severely degraded instrument performance. For all affected
analytes, Estimated Detection Limits (EDLs) in associated samples should be rejected "R" if the
S/N measurement in the CSS continuing calibration standard is <10:1.
Final 18 August 2002
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Dioxin Data Review
Table 4. Instrument Stability
Criteria
RT changes >15 seconds or RRT changes outside
the values in Table 2 of DLM01.4, Exhibit D,
Section 15.0
Relative ion abundance criteria is outside
windows in CSS (12-hour) standard
S/N ratio <10: 1 in CSS standard
Percent Difference (%D) greater than criteria in
CSS standard
Action
Use professional judgment
"J" associated sample results
"J" associated sample results
"R" associated EDLs
"J" associated sample results
August 2002
19
Final
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Dioxin Data Review
VII. High Resolution Gas Chromatograph/High Resolution
Mass Spectrometer 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.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data for the compounds on
the Target Compound List (TCL).
The objective of the initial calibration is to establish a linear range and mean Relative Responses
(RRs) and the mean Relative Response Factors (RRFs) for the instrumentation. The initial calibration
is to be used for routine quantitation of samples using the RRs and RRFs established from the five
Calibration Standards (CS1, CS2, CSS, CS4, and CSS). Subsequent continuing calibrations occurring
every 12 hours thereafter are not to be used for quantitation of samples, nor is the initial midpoint
(CSS) solution to be used for this purpose.
C. Criteria:
The initial calibration criteria are strict because the initial calibration is used for quantitation of
sample data and is not frequently performed. Thus, the initial calibration affects the quality of the
data based on it for an extended period of time.
Initial Calibration
Once the Perfluorokerosene (PFK), Window Defining Mix (WDM), Isomer Specificity Check (ISC),
and Column Performance Solution (CPS) solutions have all been analyzed, and once the descriptor
switching times have all been verified, then the five CSs described in Table 4 of Exhibit D, Section
15.0, shall be analyzed priorto any sample analysis.
The following criteria must be met for the initial calibration to be acceptable: Gas Chromatograph
(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 RR and
RRF; analyte concentration (ng/mL); and calibration frequency.
1. GC resolution criteria. For DB-5, DB-225, or equivalent columns, see the criteria in Section V,
Chromatographic Resolution.
2. Ion abundance criteria. The relative ion abundance criteria for Chlorinated Dibenzo-p-
Dioxins/Chlorinated Dibenzofurans (CDDs/CDFs) listed in Table 9 of DLM01.4, Exhibit D,
Section 15.0, 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 8 DLM01.4,
Final 20 August 2002
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Dioxin Data Review
Exhibit D, Section 15.0, for m/z types and exact m/z ratios). The 37Cl4-2,3,7,8-TCDD clean-up
standard contains no 35C1, therefore the ion abundance ratio criteria do not apply to this
compound.
3. Retention Time (RT) 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 13C12-1,2,3,4-TCDD must exceed 25 minutes on the DB-5 (or
equivalent) column and 15 minutes on the DB-225 (or equivalent) column.
4. Mass Spectrometer sensitivity criteria. For all calibration solutions, including the CS1 solution,
the S/N ratio must be > 10.0.
5. Linearity criteria. The RRFs and Percent Relative Standard Deviation (%RSD) of the five RRFs
(CS1-CS5) for each compound applicable to RRF (internal standard) treatment is calculated.
The %RSD of the five RRFs (CS1-CS5) must not exceed 35% for these compounds.
Likewise, the mean 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.
6. Concentration criteria. All initial Calibration Standards (CSs) must be analyzed at the
concentration levels shown in Table 4 of DLM01.4, Exhibit D, Section 15.0.
7. Frequency criteria. Each HRGC/HRMS system must be initially calibrated to meet the terms of
the contract whenever:
• The Contractor takes corrective action which may change or affect the initial calibration
criteria discussed directly above.
The calibration verification (CS3 continuing calibration) acceptance criteria cannot be met
even after corrective action. See Section VI, Instrument Stability, and Section VIII, High
Resolution Gas Chromatograph/High Resolution Mass Spectrometer Calibration Verification,
for CS3 criteria.
D. Evaluation:
1. Verify that the PFK, WDM, ISC, and CPS solutions were analyzed before the calibration
standards.
2. Verify that all analytes in all calibration solutions are present at the concentrations listed in Table
5.
3. Verify that the requirements for frequency of initial calibration were observed.
4. Verify that the %RSD of the five RRFs is < 35%.
5. Verify that the %RSD of the five RRs is <20%.
August 2002 21 Final
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Dioxin Data Review
6. Verify that the ion abundance ratios in each CS are within ±15% of the limits listed in Table 9 of
DLM01.4, Exhibit D, Section 15.0.
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 involving the WDM and the internal standards are met.
E. Action:
1. Concentrations and Frequency
All initial calibration standards must be analyzed at the concentrations described in the Statement
of Work (SOW). 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 continuing calibration criteria are not met.
2. Ion Abundance Ratios
If an analyte in a calibration standard failed the ion abundance ratio criteria, sample results
analyzed immediately after that initial calibration using the RRFs or RR values for quantitation
would be flagged "R" for that analyte, because both the RRF and RR values depend on the areas
used in the ion abundance ratio. Failed ion abundance ratio criteria for any analyte is a cause for
concern, and may indicate that the Mass Spectrometer is not tuned properly, the zero point is not
properly adjusted, or other problems.
At the reviewer's discretion, a more in-depth review to minimize the qualification of data may be
accomplished by considering the following hypothetical examples:
If the ion abundance ratio is outside the limits for an analyte in the CS 1 solution, then the
low-end results for that analyte (below the CS2 concentration from Table 5) are flagged "R".
• If the ion abundance ratio is outside the limits for an analyte in the CS5 solution, then the
high-end results for that analyte (above the CS4 concentration from Table 5) are flagged "R".
3. GC Resolution
If failed resolution criteria involved TCDD isomers, then only those isomers would be flagged as
"J". Reanalysis should be requested for all samples following a failed resolution to ensure the
quantity of isomers present. When GC resolution capability is lacking, the only alternative is to
assume that 2,3,7,8-TCDD is the only isomer present. This worst-case scenario may not be
warranted.
Final 22 August 2002
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Dioxin Data Review
4. Analyte Response
If the %RSD is >20% and >35% for the RR and RRF, respectively, the positive hits shall be
qualified as estimated "J". The reviewer may choose to look at the RR and RRF values for the
initial calibration, discard either the CS1 or CSS values, and recalculate the %RSD. If discarding
either of these points brings the %RSD within the specified limits, then the reviewer should
qualify either the low- or high-end hits, depending on which point was discarded. If either of
these scenarios affected a majority of the data, then reanalysis should be performed.
5. Sensitivity
If the S/N 10:1 sensitivity requirements are not met, qualify any Estimated Detection Limits
(EDLs) for those analytes as unusable "R" for all associated samples.
6. Retention Time
Failed RT criteria during the initial calibration require the rejection of all data "R" associated
with the failed analyte(s) and reanalysis of all affected samples. No action is taken for non-
detects. Systematic RT problems affecting the entire set of data require complete rejection of the
data package followed by reanalysis of all the samples.
Table 5. Initial Calibration
Criteria
Concentrations in Table 4 of DLM01.4, Exhibit
D, Section 15.0
Frequency as described above
Ion Abundance Ratios, ±15% of theoretical
values, as described in Table 9 of DLMO 1 .4,
Exhibit D, Section 15.0
GC Resolution (% Valley) of <25%
Linearity: RRF %RSDs <35%; RR %RSDs
<20%
Sensitivity: 10:1 S/N for all SICPs
Action
Reject "R" all associated sample results if initial
calibrations are not performed at the prescribed
concentration and frequency
Reject all associated sample data for compounds
with failed ion ratios in the initial calibration
Qualify all associated sample data as estimated
"J"
Qualify all associated sample data as estimated
"J" for those analytes failing the initial calibration
RSD criteria
If there are points from the low- or high- end of
the calibration curve, qualify either the low- or
the high-end detect as estimated "J"
Reject "R" all associated EDLs
August 2002
23
Final
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Dioxin Data Review
Table 5. Initial Calibration Cont.
Criteria
RTs: 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
Reject "R" all associated sample data
Final
24
August 2002
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Dioxin Data Review
VIII. High Resolution Gas Chromatograph/High Resolution
Mass Spectrometer 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.
B. Objective:
Compliance requirements for satisfactory calibration are established 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 check for satisfactory performance of the instrument on a day-
to-day basis.
C. Criteria:
Calibration verification criteria. The Laboratory shall 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
RRandRRF].
1. Ion abundance criteria. The ion abundance ratio criteria listed in Table 9 of DLM01.4, Exhibit D,
Section 15.0, shall be met for all Chlorinated Dibenzo-p-Dioxin/Chlorinated Dibenzofuran
(CDD/CDF) peaks, including the labeled versions of native compounds and the internal
standards.
2. Absolute Retention Time (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 found in Section VI, Instrument Stability. In addition, the absolute
RT of the internal standards must be within 15 seconds of the RTs obtained during the initial
calibration.
3. RRT criteria. The RRTs of the native and labeled CDDs/CDFs shall be within the limits defined
in Section VII, HRGC/HRMS Initial Calibration.
4. Instrument sensitivity criteria. For the CSS solution, the signal-to-noise (S/N) ratio shall be
> 10.0 for all CDD/CDF peaks, including the labeled versions of native compounds and the
internal standards.
5. Analyte response criteria. The measured RRFs and RRs of each analyte and standard (labeled
and internal) must be within ±35% (RRF) and within ±20% (RR) of the mean values established
during initial calibration:
August 2002 25 Final
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Dioxin Data Review
% Difference =
[(RRFC - RRF;) x 100]
RRFi
Where,
RRFj = RRF established during initial calibration
RRFC = RRF established during continuing calibration
And:
% Difference =
[(RRc - RR;) x 100]
RRR
Where,
RRj = RR established during initial calibration
RRC = RR established during continuing calibration
D. Evaluation:
1. Verify that the calibration verification was run at the required frequency [following the Window
Defining Mix (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 9 of DLM01.4, Exhibit D,
Section 15.0, were all met.
3. Verify from the raw data that the absolute RT criteria for the compound 13C12-1,2,3,4-TCDD were
met.
4. Verify from the raw data that the RRT criteria for the native and labeled CDDs/CDFs were met.
5. Verify from the raw Selected Ion Current Profile (SICP) data that the S/N ratio is > 10.0 for the
unlabeled CDD/CDF ions, and >10.0 for the 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 CSS solution are within ±25% (RRs) and within ±35% (RRFs) of the mean values
established during initial calibration.
Final
26
August 2002
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Dioxin Data Review
E. Action:
If the calibration verification was not analyzed at the required frequency, contact the Task Order
Project Officer (TOPO) to initiate sample reanalysis.
1. Any analyte in samples associated with a continuing calibration not meeting the RT and/or RRT
criteria should be qualified using professional judgment.
2. Any analyte in samples associated with a continuing calibration not meeting the ion abundance
criteria listed in Table 9 of DLM01.4, Exhibit D, Section 15.0, is to be estimated "J". The High
Resolution Gas Chromatograph/High Resolution Mass Spectrometer (HRGS/HRMS) must be
recalibrated and the affected samples must be reanalyzed.
3. If the > 10.0 S/N ratio limit is not met in a continuing calibration, all associated data should be
estimated "J" and all associated EDLs should be rejected "R".
4. 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 (RRS) or RRF (RRFs) is a crucial criterion for
review. Data associated with an analyte with a %D >20% (RR) and > 35% (RRF) should be
estimated "J". The HRGS/HRMS must be recalibrated and the affected samples should be
reanalyzed.
Table 6. Calibration Verification
Criteria
Ion abundance ratios inside 15% window
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
Internal standards must be within 15 seconds of
the RTs in the initial calibration
RRTs must be within the limits defined in Table 2
of DLM01.4, Exhibit D, Section 15.0
Sensitivity: S/N 10:1 for all compounds
%D for RRs must be within ±20%
%D for RRFs must be within ±35%
Action
Estimate "J" all associated sample results
Use professional judgment
Estimate "J" all of the associated sample results
Reject "R" associated EDLs
Estimate "J" all associated sample results
August 2002
27
Final
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Dioxin Data Review
IX. Identification Criteria
A. Review Items:
Form 1DFA (Form I-HR CDD-1), Form 2DF (Form II-HR CDD), and raw data.
B. Objective:
To unambiguously identify a Gas Chromatographic (GC) peak as a Chlorinated Dibenzo-p-Dioxin
(CDD) or a Chlorinated Dibenzofuran (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) are required for all chromatograms; scan numbers are optional. For
positive identifications, RTs for the two quantitation ions must maximize within 2 seconds. RTs
shall either be printed at the apex of each peak on the chromatogram, or each peak shall be
unambiguously labeled with an identifier that refers to the quantitation report. The
chromatogram, the quantitation report, or a combination of both shall contain the RT of each peak
and its area.
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 Relative
Retention Time (RRT) at the maximum peak height of the analyte must be within the RRT
window in Table 2 of DLM01.4, Exhibit D, Section 15.0. The RRT is calculated as follows:
_ RT of analyte _
RT of corresponding internal standard
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 Mix (WDM) for the corresponding homologue.
2. Peak Identification
Both of the specified ions listed in Table 8 of DLM01.4, Exhibit D, Section 15.0, and on Form I
for each CDD/CDF homologue, must be present in the Selected Ion Current Profile (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 standards and to the internal standards. For the clean-up standard, only one ion is
monitored.
Final 28 August 2002
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Dioxin Data Review
3. Signal-to-Noise (S/N) Ratio
The integrated ion current for each native analyte ion listed in Table 8 of DLMO1.4, Exhibit D,
Section 15.0, 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 10.Ox 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 > 10.0 for all of the CDD/CDF compounds, whether or not they are labeled.
4. Ion Abundance Ratios
The ion abundance ratio criteria listed in Table 9 of DLMO 1.4, Exhibit D, Section 15.0, for native
and labeled analytes and for internal standards must be met using peak areas to calculate ratios.
If interferences are present and ion abundance ratios are not met using peak areas, but all other
qualitative identification criteria are met (RT, S/N, presence of both ions), then the Laboratory
may use peak heights to evaluate the ion ratio.
If the Laboratory High Resolution Gas Chromatograph/High Resolution Mass Spectrometer
(HRGC/HRMS) Interpretation Specialist has judged the peak to be a CDD/CDF, then the ion
abundance ratios may be determined using peak heights instead of areas. Quantitate the peaks
using peak heights rather than areas for both the target analyte and the labeled compound or
internal standard. The Laboratory should have flagged this data "H".
5. Polychlorinated Diphenyl Ether (PCDPE) Interferences
If PCDPE interferences are detected above the 2.5 S/N ratio limit, as indicated by the presence of
peaks at the exact m/z(s) monitored for these interferents (see Table 8 of DLMO 1.4, Exhibit D,
Section 15.0), all CDF sample results with a coeluting PCDPE interference should be qualified as
estimated "J".
D. Evaluation:
1. Verify that the RRTs for the 2,3,7,8-substituted compounds are within the RRT windows listed in
Table 2 of DLMO 1.4, Exhibit D, Section 15.0.
2. 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).
3. Verify from the SICPs that the ion current responses for the two quantitation ions for each analyte
maximize simultaneously (within the same 2 seconds).
4. Verify from the SICPs that for each analyte ion listed in Table 8 of DLM01.4, Exhibit D, Section
15.0, the S/N ratio is > 2.5 and that the detector has not been saturated. If an analyte is flagged
with an asterisk (*), then verify the presence of the CDD/CDF using professional judgment.
5. Verify from the Forms I that the ion abundance ratios are within the criteria listed in Table 9 of
DLM01.4, Exhibit D, Section 15.0.
August 2002 29 Final
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Dioxin Data Review
6. Verify that no PCDPE interferences exist.
E. Action:
1. If a peak falls outside of the Table 3 and/or the WDM windows, then the results are rejected "R".
2. If ion current responses for the two quantitation ions for an analyte fail to maximize
simultaneously (within 2 seconds), the result should be rejected "R".
3. If ion abundance criteria are not satisfied, then the data should be rejected "R".
4. If S/N criteria are not satisfied, then the data should receive a "J" flag.
5. If PCDPE interferences exist above the 2.5 S/N ratio limit, qualify associated CDFs as estimated
"J".
Table 7. Identification Criteria
Criteria
Signals must maximize within 2 seconds
S/N ratio must be >2.5
Ion abundance ratios must be within the limits in
Table 9 of DLM01.4, Exhibit D, Section 15.0, or
within 10% of the ratio in the most recent CS3
standard
RRTs for 2,3,7,8-substituted CDD and CDF must
be within the limits in Table 2 of DLMO 1 .4,
Exhibit D, Section 15.0
The RT of non-substituted CDDs/CDFs must be
within the RTs established by the WDM
PCDPE ion S/N >2.5
Action
If signals do not maximize simultaneously (within
2 seconds) the result is rejected "R"
If the signals do not satisfy the S/N ratio, the
result is estimated "J"
If the ion abundance criteria are not satisfied, the
result is rejected "R"
Reject "R" sample results failing the RT criteria
Qualify associated CDF sample result as
estimated "J"
NOTE: Professional judgment should always be used in determining the proper identification of
analytes.
Final
30
August 2002
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Dioxin Data Review
X. Method Blank Analysis
A. Review Items:
Form 4DF (Form IV-HR CDD) and raw data.
B. Objective:
The purpose of Laboratory (or field) blank analysis is to determine the existence and magnitude of
contamination resulting from Laboratory (or field) activities. The criteria for evaluation of blanks
apply to any blank associated with samples (e.g., method blanks, instrument blanks, trip blanks, and
equipment blanks). 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.
C. Criteria:
Method Blank Criteria
1. 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 Chlorinated Dibenzo-p-Dioxin/Chlorinated Dibenzofuran (CDD/CDF) ions. There
must be at least one Laboratory method blank for each batch of samples extracted.
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, where the maximum allowable
amount is < three times (3x) the CRQL.
3. If the method blank extracted along with a group of samples is contaminated, then the associated
positive samples, and any samples containing peaks that do not meet all of the qualitative
identification criteria for a contaminated method blank, should have been rerun.
NOTE: Report results for all peaks with signal-to-noise (S/N) ratio >2.5, even if they are
CRQL for the native compounds. The concentration of OCDD/OCDF in the
method blank must be <3x the CRQL.
August 2002 31 Final
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Dioxin Data Review
E. Action:
1. If the method blank is contaminated with a CDD/CDF > the CRQLs listed in the Statement of
Work (SOW), or Sxthe CRQLs for OCDD/OCDF, qualify all associated positive sample results
and EDLs for those analytes as estimated "J".
2. In some cases, the reviewer might also consider rejecting positive sample results which are below
method blank contaminant concentrations. Also, a sample or sample set with results at levels
similar to the levels reported in the method blank might also be rejected.
Table 8. Blank Actions for Laboratory Analyses
Method Blank
Result
CRQL
=CRQL
Gross contamination
Sample Result
Not detected
CRQL
CRQL but CRQL and > Blank Result
CRQL
Positive
Action for Samples
No action
Report CRQL value with a "U"
Use professional judgment
Report CRQL value with a "U"
Report the blank concentration
for the sample with a "U" or
qualify the data as estimated (J)
Use professional judgment
Report CRQL with a "U"
Use professional judgment
Qualify results as unusable (R)
Final
32
August 2002
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Dioxin Data Review
XL Laboratory Control Sample Analysis
A. Review Items:
Form 3DFA (Form III-HR CDD-1) and raw data.
B. Objective:
To provide data on the accuracy of the analytical method, the Laboratory is required to prepare and
analyze a sample of spiked reference matrix [the Laboratory Control Sample (LCS)] for each matrix
analyzed. If a matrix is not represented in a Sample Delivery Group (SDG), then no spiked sample
(LCS) is required for that matrix. USEPA 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
DLM01.4, Exhibit D, Section 7.6). When a reference matrix that simulates the sample matrix under
test is not readily available, USEPA 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 sample (LCS) for all of the matrix types that
occur in that SDG (see DLM01.4, Exhibit D, Section 1.1).
2. The recovery of each spiked analyte must be in the range in Table 6 (see DLM01.4, Exhibit D,
Section 15.0).
3. The LCS must meet the technical acceptance criteria for sample analysis (see DLMO1.4, Exhibit
D, Section 11.3).
D. Evaluation:
Confirm that the spiking solution was added to the reference matrix sample (LCS), and that the
Chlorinated-p-Dioxin/Chlorinated Dibenzofuran (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 outside of the recovery limits, then the reviewer should qualify all
associated sample data for those analytes which fail in the LCS as estimated "J". If the
Laboratory failed to prepare and analyze the LCS at the required frequency, note this in the Data
Review Narrative and notify the Task Order Project Officer (TOPO).
2. If LCS results are <10%, those analytes and Estimated Detection Limits (EDLs) should be
rejected "R" in all of the associated samples. The TOPO should be contacted concerning samples
associated with a non-compliant LCS to decide on reextraction and reanalysis.
August 2002 33 Final
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Dioxin Data Review
XII. Toxicitv Equivalency Factor and Isomer Specificity
A. Review Items:
Form 1DFB (Form I-HR CDD-2) and raw data.
B. Objective:
Isomer specificity for all 2,3,7,8-substituted Chlorinated Dibenzo-p-Dioxins/Chlorinated
Dibenzofurans (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-TCDD from 1,2,3,7-71,2,3,8-TCDD and
1,2,3,9-TCDD, and separation of 2,3,7,8-TCDF from 1,2,3,9-TCDF and 2,3,4,7-TCDF. Because of
the toxicological concern associated with 2,3,7,8-TCDD and 2,3,7,8-TCDF, additional analyses may
be required for some samples, as described below.
The exclusion of homologues such as mono-, di-, tri-, and the non-2,3,7,8-substituted isomers in the
higher homologues, does not mean that they are not toxic. Their toxicity, as estimated at this time, is
much less than the toxicity of the native 2,3,7,8-substituted isomers listed in Table 6 (DLM01.4,
Exhibit D, Section 15.0). Hence, only the 2,3,7,8-substituted tetra through octa isomers are included
in the Toxicity Equivalency Factor (TEF) calculations. The procedure for calculating the 2,3,7,8-
TCDD TEFs for the Target Compound List (TCL) analytes is not claimed by the Chlorinated Dioxins
Work Group (CDWG) to be based on a thoroughly established scientific foundation. Rather, the
procedure represents a "Consensus Recommendation on Science Policy."
The 2,3,7,8-TCDD TEF-adjusted concentration of a sample is used by the Laboratory as an aid in
determining when second column confirmation or reextractions and reanalyses are required.
C. Criteria:
1. When calculating the 2,3,7,8-TCDD TEF-adjusted concentration of a sample, the Laboratory
shall include only those 2,3,7,8-substituted isomers that were detected in the sample and that met
all of the qualitative identification criteria. The Laboratory does not include Estimated Maximum
Possible Concentration (EMPC) or Estimated Detection Limit (EDL) values in the TEF
calculations.
2. For each 2,3,7,8-substituted isomer positively identified in the sample, the TEF from 1DFB
(Form I-HR CDD-2) is multiplied by the concentration from 1DFA (Form I-HR CDD-1) to give
the TEF-adjusted concentration. The sum of the TEF-adjusted concentrations serves as an aid in
determining when second column confirmation or reextractions and reanalyses are required. The
OCDD data should be included in the TEF calculations only if the OCDD concentration in the
sample is greater than the OCDD concentration in the blank.
D. Evaluation:
Verify that the TEF calculations were properly performed.
Final 34 August 2002
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NOTE: A Region may require that the reviewer recalculate the TEFs using EMPCs and EDLs. The
Laboratory, however, is not required to perform such calculations.
E. Action:
The reviewer has all of the data needed to calculate TEFs. If calculations were not properly
performed by the Laboratory, then notify the Task Order Project Officer (TOPO) of the deficiency.
August 2002 35 Final
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Dioxin Data Review
XIII. Dilution by Addition of Solvent
A. Review Items:
Raw data (quantitation reports and chromatograms).
B. Objective:
A calibrated range is defined by the initial calibration. All sample results must be within the
calibrated range judged to be acceptable.
C. Criteria:
If the Selected Ion Current Profile (SICP) area at either quantitation m/z for any compound exceeds
the calibration range of the system, a solvent dilution of the extract can be performed. The sample
extract is diluted by a factor of up to 20 with n-nonane, the instrument internal standard in the extract
is adjusted to 100 pg/uL, and an aliquot of this diluted extract is analyzed by the internal standard
method. If more than a dilution of 20 times (20x) is required, contact the Task Order Project Officer
(TOPO).
D. Evaluation:
1. Verify that all reported sample values are within the calibration range.
2. Verify that the internal standard calculations used to determine analyte concentrations in the
diluted sample were performed correctly.
3. Verify that a dilution factor of <20 was employed and properly documented.
4. Verify that the Laboratory contacted the TOPO prior to diluting the sample by a factor of >20.
E. Action:
1. Compare the original and diluted analyses of the sample. If substantial differences are noted, use
professional judgment to qualify results.
2. If a sample value is outside of the calibration range, and appropriate dilution was not performed,
qualify all of the sample data which are out of range as estimated "J".
Final 36 August 2002
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Dioxin Data Review
XIV. Dilution by Reextraction and Reanalysis
A. Review Items:
Raw data (quantitation reports and chromatograms).
B. Objective:
A calibrated range is defined by the initial calibration. All sample results must be within the
calibrated range to be acceptable.
C. Criteria:
If the Selected Ion Current Profile (SICP) area at either quantitation m/z for any compound exceeds
the calibration range of the system, a smaller sample aliquot is re-extracted and reanalyzed.
D. Evaluation:
1. Verify that all reported sample values are within the calibration range.
2. Verify that the internal standard and/or isotope dilution calculations used to determine analyte
concentrations in the diluted sample were performed correctly.
3. Verify that a smaller sample size was employed and properly documented.
4. Verify that the Percent Solids (% Solids) procedure in DLM01.4, Exhibit D, Section 10.1.4.1,
was carried out for soil/sediment samples, even if no dilutions were subsequently required.
E. Action:
If a sample value is outside of the calibration range, and reextraction was not performed, all of the
sample data that is out-of-range should be estimated "J".
August 2002 37 Final
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Dioxin Data Review
XV. Second Column Confirmation
A. Review Items:
Form 1DFC (Form I-HR CDD-3) and raw data.
B. Objective:
Isomer specificity for all 2,3,7,8-substituted Chlorinate-p-Dioxins/Chlorinated Dibenzofurans
(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 1,2,3,9-TCDF and 2,3,4,7-TCDF. Because
of the toxicological concern associated with 2,3,7,8-TCDF, a second column confirmation is
employed.
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 either of the two options listed below to achieve better
isomer specificity than can be obtained on the DB-5 column alone.
a. The sample extract may be reanalyzed on a DB-225 (or equivalent) Gas Chromatograph (GC)
column in order to achieve better GC resolution and, therefore, better identification and
quantitation of the individual 2,3,7,8-substituted isomers.
b. 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.
2. 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 DLM01.4, Exhibit D, Section 11, such
as ion abundance ratio, signal-to-noise (S/N) ratio, Retention Time (RT), etc. In addition, when
using any GC column other than those specified here (DB-5, DB-225), the Laboratory shall
clearly document, in the Sample Delivery Group (SDG) Narrative, the elution order of all of the
analytes of interest on any such column.
3. 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 Toxicity Equivalency Factor (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 employed whenever 2,3,7,8-TCDF is detected in any
sample at any level (S/N ratio for the peak must be >2.5).
Final 38 August 2002
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Dioxin Data Review
2. 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.
3. Verify that second column confirmation analysis meets all criteria previously discussed in this
document (i.e., initial calibration requirements, linearity specifications, etc.).
NOTE: Second column confirmation analysis is usually performed on a different instrument than
that used for primary analysis.
E. Action:
If second column confirmation is required but was not performed, the reviewer should reject "R" the
2,3,7,8-TCDF results.
August 2002 39 Final
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Dioxin Data Review
XVI. Estimated Detection Limit and Estimated Maximum Possible Concentration
A. Review Items:
Form 1DFA (Form I-HR CDD-1) and raw data.
B. Objective:
For each analyte that is not detected, an Estimated Detection Limit (EDL) is calculated. The sample-
specific EDL is an estimate made by the Laboratory of the concentration of a given analyte that
would have to 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. Because of the toxicological significance of Chlorinated-p-
Dioxins/Chlorinated Dibenzofurans (CDDs/CDFs), the EDL value is reported for non-detected
analytes rather than simply reporting the respective Contract Required Quantitation Limit (CRQL).
The Estimated Maximum Possible Concentration (EMPC) value is applied to a sample when the
signal-to-noise (S/N) ratio is at least 2.5 for both quantitation ions, but the ion abundance ratio criteria
are not met.
C. Criteria:
1. Estimated Detection Limit
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 homologue are present. The EDL is
also calculated for those 2,3,7,8-substituted isomers where responses for both of the quantitation
ions are <2.5 times (2.5x) the background level, and therefore do not meet the identification
criteria.
The formulae 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
Retention Times (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 High Resolution Gas Chromatograph/High Resolution Mass
Spectrometer (HRGC/HRMS) system that was used for the analysis of the samples that are
associated with the EDL calculations.
All Matrices Other than Water:
2.5 x Q x (H.+H.) x D
Soil EDL (ng/Kg) = — ^ ^
W x (HIS1+HIS2) x RR
Final 40 August 2002
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Dioxin Data Review
Water:
2.5 x Q x (H.+H,) x D
Aqueous EDL (pg/L) = ——
V x (HIS1+HIS2) x RR
Where,
EDL = Estimated Detection Limit for 2,3,7,8-substituted CDDs/CDFs
QIS = Quantity (pg) of appropriate internal standard added prior to sample
extraction
Hxi,Hx2 = Peak heights of the noise for both quantitation ions of the CDD/CDF
HIS1,HIS2 = Peak heights of the internal standard ions
D = Dilution Factor
V = Volume extracted in liters
W = Weight extracted in grams
RR = The mean Relative Response for the isomer of interest from the initial
calibration (See DLM01.4, Exhibit D, Section 9.3.4.3)
2. Estimated Maximum Possible Concentration
An EMPC is calculated for 2,3,7,8-substituted isomers that are characterized by a response with a
S/N ratio of at least 2.5 for both of the quantitation ions, but that do not meet the ion abundance
ratio criteria outlined in Section IX, Identification Criteria.
The EMPC is calculated according to one of the following formulae:
All Matrices Other than Water:
™ D)
EMPC (ng/Kg) =
ws
Where,
D = Dilution Factor
Ws = Sample weight (dry weight) in Kg
CEX = The concentration of the native compound in the extract
August 2002 41 Final
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Dioxin Data Review
Water:
EMPC (pg/L) =
(CEX x D)
Where,
D = Dilution Factor
Vs = Sample volume in liters
CEX = The concentration of the native compound in the extract
D. Evaluation:
1. Verify that EDLs and EMPCs are properly calculated.
2. An EDL must be reported for each undetected analyte. Except when increased due to dilution of
the extract, an EDL must be
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Dioxin Data Review
XVII. Labeled Compound Recoveries
A. Review Items:
Form 1DFA (Form I-HR CDD-1) and raw data.
B. Objective:
The 15 labeled Chlorinated-p-Dioxins/Chlorinated Dibenzofurans (CDDs/CDFs) serve as the isotopic
dilution quantitative mechanism in this method. The recovery of these compounds, along with the
recovery of the clean-up standard, is a critical measure of the effectiveness of the Laboratory and
method to extract the compounds of interest.
C. Criteria:
1. If the original sample, prior to any dilutions, has any labeled compound or internal standard with
a Percent Recovery (% Recovery) outside the limits specified in Table 9 (DLMO1.4, Exhibit D,
Section 15.0), then reextraction and reanalysis of that sample is required.
Values below 100% indicate loss of labeled and unlabeled compounds during the entire analytical
process. Values over 100% indicate errors in the quantitation of the labeled compounds, or
problems with the addition of the internal standards to 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. If the labeled compounds are not present with at least a 10:1 signal-to-noise (S/N) ratio at their
respective m/z(s), then reextraction and reanalysis are required.
3. If any of the labeled compound ion abundance ratios specified in Table 9 (DLMO 1.4, Exhibit D,
Section 15.0) are outside of the contract-specified control limits, then the sample extract must be
reanalyzed on the same Gas Chromatograph (GC) column and Mass Spectrometer used for the
original analysis. If the problem corrected itself, then the Laboratory should have used the data
from the second analysis and disregarded the data from the first analysis. No additional
reextraction and reanalysis are required. If, however, the failed ion abundance ratios persist
through the second analysis, then reextraction and reanalysis are required.
4. If the absolute Retention Time (RT) of 13C12-1,2,3,4-TCDD shifts by more than ±15 seconds from
the RTs of that standard in the initial calibration, then the sample extract must be reanalyzed after
the Laboratory has investigated the cause of the RT shift and taken corrective action. No
reextraction is required for such an analysis.
5. 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 13C12-1,2,3,4-TCDD
with a valley of <25% on the DB-225 (or equivalent) column, then the Laboratory shall adjust the
High Resolution Gas Chromatograph/High Resolution Mass Spectrometer (HRGC/HRMS)
operating conditions, recalibrate the instrument, and reanalyze the affected sample. This criterion
August 2002 43 Final
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Dioxin Data Review
applies to sample analysis, and no reextraction and reanalysis are required if the second analysis
resolves the problem. If this criterion is not met for a calibration standard, however, then all
associated samples must be reanalyzed after instrument recalibration. Reextraction should not
ordinarily be required in this case, but is required if 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.
3. Verify that the ion abundance ratios of the labeled compounds are within the required limits.
E. Action:
1. If the recovery of the labeled compounds are outside of the limits in Table 9 (DLM01.4, Exhibit
D, Section 15.0), the reviewer should qualify all associated sample results as estimated "J". If no
reanalysis is found, then contact the Task Order Project Officer (TOPO) to initiate reanalysis.
2. The chlorine-37-labeled clean-up standard is added to the sample extracts after extraction and
before any clean-up steps. It is used to monitor the efficiency of the clean-up steps. Low
recoveries of the labeled compounds and the clean-up standard suggest that losses may be due to
the performance of the clean-up steps. Thus, reextraction and reanalysis of the sample may yield
better results. If the labeled compound recoveries are low (<40%), but the clean-up standard
recovery is not, then the recovery problems may be associated with the extraction procedures or
related to a particularly difficult matrix. Therefore, reanalysis may only serve to confirm a
"matrix effect".
Final 44 August 2002
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Dioxin Data Review
XVIII. Regional Quality Assurance and Quality Control
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.
B. Objective:
To evaluate the results of any Regional Quality Assurance (QA) and QC samples initiated by the
Region, including field duplicates, Regional Performance Evaluation (PE) samples, blind spikes, and
blind blanks. (It is highly recommended that Regions adopt the use of these QA/QC samples.)
C. Criteria:
Criteria are determined by each Region.
1. The PE sample frequency may vary. A PE sample may be included as frequently as once per
Sample Delivery Group (SDG).
2. The analytes present in the PE sample must be correctly identified and quantitated.
D. Evaluation:
Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
review. Each Region will handle the evaluation of PE samples on an individual basis. Results for PE
samples should be compared to the acceptance criteria for the specific PE samples, if available.
E. Action:
Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
results. Unacceptable results for PE samples should be noted for Task Order Project Officer (TOPO)
action.
August 2002 45 Final
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Dioxin Data Review
XIX. 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 brief narrative in which the data reviewer expresses
their comments, concerns, and opinions about the quality and usability of the data.
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 Data
Quality Objectives (DQOs)], 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. Use professional judgment to determine if there is any need to qualify data which were not
already qualified based on the Quality Control (QC) criteria previously discussed.
2. Write a brief narrative to give the data user an indication of the analytical limitations of the data.
Any inconsistencies between data and the Sample Delivery Group (SDG) Narrative should be
noted for Task Order Project Officer (TOPO) action. If sufficient information on the intended use
and required quality of the data is available, then the reviewer should include their assessment of
the usability of the data within the given context.
Final 46 August 2002
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