United States
Environmental Protection
Agency
EPA-910-R-14-003
May 2014
www.epa.gov
R10 Data Validation and
Review (
Polychlorinated Dibenzo-p-
Dioxin and Polychlorinated
Dibenzofuran Data (PCDD/
PCDF) Using Method 1613B,
and SW846 Method 8290A
U.S. Environmental Protection Agency
Office of Environmental Assessment
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
United States Environmental Protection Agency May 2014
Seattle WA 98101 Page 1 of 88
Data Validation and Review Guidelines for
Polychlorinated Dibenzo-p-Dioxin and Polychlorinated Dibenzofuran Data (PCDD/PCDF)
Using Method 1613B, and SW846 Method 8290A
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
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NOTICE
The policies and procedures set forth here are intended as guidance to the United States Environmental
Protection Agency Region 10 (hereafter referred to as RIO) 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.
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United States Environmental Protection Agency
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Acknowledgement
Special thanks to the following for the peer review of this document: Donald M Brown, EPA
RIO QA Chemist, Karin Feddersen, QA Officer, Washington State Department of Ecology
Laboratory, Brian Boling, Organic Laboratory Manager, Oregon DEQ Laboratory and Peter
Kepler, HRGC/HRMS Chemist, Analytical Resources, Inc.
For Questions contact:
Gina Grepo-Grove, RIO QA Manager
US EPA Office of Environmental Assessment
1200 6th Ave Suite 900 MS-OEA/095
Seattle WA 98101
(206) 553-1632
grepo-grove.gina@ epa.gov
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TABLE OF CONTENTS
1. General Information 5
2. Scope/Application 5
3. Analytical Methods 6
4. Overall Implementation of Data Review 6
5. Elements of Data Review 8
6. Data Validation Procedure 8
6.1. Data Validation Deliverables 9
6.2. Laboratory Documentation and Deliverables 9
6.3. Holding Time Evaluation 11
6.4. Sample Integrity, Handling and Processing 12
6.5. Sample Preparation and Sample Clean-Up 14
6.6. System Performance Checks 17
6.7. Mass Calibration and Tuning 17
6.8. SEVI Scan Descriptor Switching Times 18
6.9. Chromatographic Resolution 21
6.10. Instrument Stability 22
6.11. Initial Calibration 22
6.12. Initial Precision & Recovery Check (TPR) 26
6.13. On-Going Precision and Recovery Check (OPR) 27
6.14. Continuing Calibration or Verification (VER) 27
6.15. Blanks Analyses 30
6.16. Performance TEST Sample/Standard Reference Material (PTs/SRMs) 32
6.17. Laboratory Control Samples (LCS) 34
6.18. Internal Standard (Labeled Compound) Recoveries 35
6.19. Compound Identification 37
6.20. Compound Quantitation 39
6.21. Toxicity Equivalency Quotients (teqs) 40
6.22. Laboratory Contact 40
6.23. Overall Assessment of the Data 40
7. List of Validation Qualifiers 41
Appendix A - PCDD/PCDF Validation Worksheets 42
Appendix B- Puget Sound Sediment Reference Material: Requesting, Analyzing, Validating
and Reporting Data Procedure 65
Appendix C - Rules, Calculations and Equations 78
Definitions 85
References 88
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1. GENERAL INFORMATION
This document defines the minimum requirements, responsibilities and methodology for
polychlorinated dibenzodioxin/polychlorinated dibenzofuran (PCDDs/PCDFs) data verification
and validation processes.
The objective of this document is to assist the RIO Quality Staff and other external data
reviewers in the review and validation of PCDDs and PCDFs analytical data generated by
commercial laboratories.
2. SCOPE/APPLICATION
The information contained in this document is provided by Region 10 as guidance to be used by
the data reviewers/validators and the regulated community in making judgments necessary to
determine if the generated results meet the data quality objectives of the program for the
intended application or use.
The National Functional Guidelines (NFG) for dioxin and furan data review was not used
entirely in this document because the NFG's criteria are based on the OSWER's Contract
Laboratory Program (CLP) contract Statement of Work (SOW) for the Superfund program.
Other EPA environmental programs do not have access to the CLP and instead, use the analytical
services provided by commercial laboratories that utilize the CWA Method 1613b, or SW846
Method 8290A. This document is intended for use by the data reviewers evaluating
PCDD/PCDF analytical data generated by commercial laboratories using the EPA analytical
methods cited above and not the CLP SOW.
This document is designed to offer guidance and consistency for data reviewers and describe the
scope and contents of data validation and validation conducted on PCDD/PCDF laboratory
analytical data packages in support of the various environmental programs within EPA. The
validation procedures discussed in this SOP is based on OSWER Directive 9200.1, Guidance for
Labeling Externally Validated Laboratory Analytical Data for Superfund Use, EPA-540-R-08-
005, January 2009 and the technical specifications and quality control (QC) requirements of the
Clean Water Act EPA Method 1613B, Tetra Through Oeta-Chlorinated Dioxins and Furans by
Isotope Dilution High Resolution Gas Chromatography/High resolution Mass Spectrometry
(HRGC/HRMS), EPA 921-B-94-005, 1994, re-issued March, 2012, and the EPA's SW846
Method 8290A, Polychlorinated Dibenzo-p-Dioxins (PCDDs) and Polychlorinated
Dibenzofurans (PCDFs by High Resolution Gas Chromatography/High resolution Mass
Spectrometry (HRGC/HRMS), February 2007.
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The use of this SOP is restricted to use by, or under supervision of personnel appropriately
experienced in residue analysis of organic compounds and skilled in GC/MS or HRGC/HRMS
operations and techniques.
3. ANALYTICAL METHODS
The analytical method to be used for the analysis of PCDDs/PCDFs depends mostly on program
requirements.
To meet the Clean Water Act (CWA) and Safe Drinking Water Act (SOWA), Method 1613b is
highly recommended. In addition, Method 1613b clean-up procedures for extracts in this method
are required, resulting in lower reporting limits and less chromatographic interferences. Strict
adherence to the QC requirements of this method is necessary. This method is highly
recommended for risk assessment.
SW846 Method 8290A is recommended for RCRA and hazardous wastes samples for the
analysis of dioxins and furans. This is also an HRGC/HRMS method, the difference with Method
1613b is that the analyst has the option to choose the clean-up techniques to use for the extract,
and the reporting limits are usually higher than Method 1613b.
SW846 Method 8280B -the same sample preparation techniques and analytical procedures
(selected ion monitoring) are followed as the Method 8290A, the only difference, is that a low
resolution mass spectrometer is used, resulting in higher reporting limits than the Method 8290A
and chromatographic interferences are usually encountered during analysis. This method is
recommended for PCDD/PCDF site characterization and clean-up but not for the low level
PCDD/PCDF determination needed for risk assessments.
4. OVERALL IMPLEMENTATION OF DATA REVIEW
Data verification includes two activities: inventory of the data package to ensure compliance
with the statement of work in terms of the required deliverables, and various checks of the data
to determine if a problem has occurred resulting in data that may need qualification. Analytical
data validation for PCDD/PCDF methods includes a technical review of sample custody, sample
handling and preparation, holding times, instrument calibration, instrument performance, quality
control samples, identification of target compounds, quantitation and reporting limits and the
effects of Quality Control (QC) performance and/or deficiencies on the quality of the associated
data.
There are five stages of data validation: Stage 1, Stage 2A, Stage 2B, Stage 3 and Stage 4. The
cost of data validation depends on the intellectual rigor involved in the evaluation of the
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information provided by the laboratory which is dictated by the different stages of data validation
prescribed in the EPA-540-R-08-005. January 2009 document. Data Note that Stage 1 to Stage
2B only involves the assessment of summary data reports. Cross check with raw data or
instrument electronic output is not performed. Stages 3 & 4 involve checks for transcription
errors and cross-checks of the reported results with the instrument raw data output for
consistency.
Stage 1 validation is a verification and validation based only on completeness and compliance of
sample receipt condition checks. This stage only involves the evaluation of information
provided on the summary of analytical results (Forms 1) and the chain of custody
documentation. The validation report will include assessment results for holding time, sample
integrity and reporting limits.
Stage 2A validation is a verification and validation based on completeness and compliance
checks of sample receipt conditions and only sample-related QC results. Stage 2A validation
includes the evaluation of information provided in the summary of analytical results (Forms 1),
the chain of custody records, and results from the analysis of the following QC samples: method
blank results, laboratory control samples (required by the CLP program), on-going precision &
recovery check (OPR required by Method 1613b) and matrix spike and matrix spike duplicate
(not required by RIO). The validation report will cover assessment of holding time, sample
integrity, analytical and system performance through OPR results and bias and limitation of
reported results obtained from the QC sample analyses. Stage 2A validation corresponds to
WDOE's QA2 data review.
Stage 2B validation is a verification and validation based on completeness and compliance
checks of sample receipt conditions and both sample-related and instrument-related QC results.
The validation report will cover assessment of holding time, sample integrity, analytical and
system performance through OPR results and data bias obtained from the analysis of QC sample
plus the limitation of the data use obtained from the evaluation of calibration results.
Stage 3 validation incorporates Stage 2B requirements and also includes recalculation checks of
the QC results. 100% calculation checks can only be conducted if the data went through a full
electronic data review (as in the CLP program). For manual data validation, calculation checks of
the reported detected sample results and a minimum of 20% check of the QC samples and
standards are acceptable for Stage 3. The validation report will cover assessments listed in Stage
2B plus the calculation and transcription error checks.
Stage 4 validation incorporates Stage 3 requirements and also includes the review of the actual
instrument outputs. Due to the complexity of the analysis, Region 10 highly recommends the
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stage 4 data validation for PCDD/PCDF. This SOP will guide the user through a Stage 4
verification and validation.
5. ELEMENTS OF DATA REVIEW
To determine the quality, usability and limitations on data use of a PCDD/PCDF data package
the following QA Elements shall be evaluated by the data reviewer:
1. Holding Time and Preservation
2. Sample Integrity -Handling and Processing in the Field and in the laboratory
3. Sample Preparation
4. Sample Clean-up
5. System Performance
6. Initial Precision and Recovery Check (IPR) or Initial Demonstration of Capability
7. Initial Calibration
8. Continuing Calibration Verification
9. On-going Precision & Recovery Check
10. Blanks
11. Quality Assurance Performance Evaluation Sample or Standard reference
Material (PE sample or SRM)
12. Laboratory Control Sample
13. Instrument Recovery & Internal Standards Recovery
14. Compound Identification
15. Quantitation and Reporting Limits
16. Laboratory Contact (if needed)
17. Overall Assessment
List of validation qualifiers is at the end of this SOP. Appendix A has the PCDD/PCDF
validation worksheets. Appendix B is the RIO Sediment Reference Standard (SRM) Guidance
for Dioxin/Furan and Aroclors and Appendix C has equations used for calculations.
6. DATA VALIDATION PROCEDURE
Review the project specific DQOs, reporting limit requirements, targets goals and QC
requirements. If the data is for EPA use, the information listed above may be found in the site's
QA Project Plan (QAPP). The hierarchy of the criteria used during data validation are: (1)
criteria listed in the QAPP (2) criteria listed in the analytical method and (3) laboratory
established acceptance/control limits.
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6.1. DATA VALIDATION DELIVERABLES
Product submitted by the data reviewer/validator to RIO or other clients:
1. Data Validation Report
2. Validated Data Spreadsheet
3. List of Qualifiers
4. Other documents supporting the data validation report (optional)
6.2. LABORATORY DOCUMENTATION AND DELIVERABLES
Each data reviewer has their own style and procedure when validating analytical data but based
on the author's professional experience, the following procedure is recommended:
Data Package Completion Check
Data deliverables, both hard copy and electronic, vary from lab to lab depending on the
analytical methods used and the program/project requirements that are stipulated in their contract
for analytical services. Generally, the laboratory send a hard copy data, an electronic data
deliverables, usually referred to as EDDs with the summary of analytical results per analysis and
if needed, raw data.
The data review should organize the hard copy data and separate them per section, this will
facilitate an organized process for cross-checking information. For a stage 4 data validation, the
following must be included in the EDDs and the hard copy raw data submitted by the lab:
1. Case Narrative
2. Sample Traffic Reports/Chain of custody records
3. Sample Data
Tabulated Sample Results Summary with labeled internal standards
recoveries, mass/ions used for quantitation and the mass-ion ratios
Toxicity Equivalence Summary using the most recent WHO toxicity
equivalence factor (TEFs) in the calculation. Note: Some projects require the
calculations of min, mid and max TEQs. Check the summary form for
compliance
Second Column Confirmation for 2, 3, 7, 8 - TCDF. If a complete separation
of 2, 3, 7, 8-TCDF from other isomers is achieved, a second column
confirmatory run is not necessary.
Selected ion current profile (SICP) for each sample, including dilutions and
re-analyses. SICPs must be presented so the two quantitation ions, any
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relevant labeled compounds, and diphenyl ether interferents are on one page.
The internal standards can be presented on another page. The SICPs for the
lock mass ions (PFK) may be presented on another page. The SICP must show
the full time window scanned for each ion. Enlarge any SICP peak for any 2,
3, 7, 8-substituted congener present below the signal-to-noise (S/N) ratio of 10
or below the Required Reporting or Quantitation Limit. Each SICP must
contain the following header information: sample number, date and time of
analysis, absolute retention time (and scan number if available), the name of
identified compounds, HRGC/HRMS instrument ID, Lab file ID and Analyst
ID.
Complete data system report for each sample run in addition to the SICP-
usually referred to as the "raw data sheets. If manual integration was made or
the data system report has been edited, the analyst must sign and date the
changes made and the chromatogram displaying the unaltered and manual
integration shall be included in the package.
Second column confirmation run is required for all samples wherein 2, 3, 7, 8-
TCDF was identified at concentrations above the reporting limits or as EMPC.
4. Total Homologue Concentration Summary for each sample, blank and QC samples.
5. Calibration Data
Initial Calibration
Initial calibration summary for each instrument
Complete initial calibration data system report in chronological order per
instrument used and includes: PFK mass resolution checks and complete data
system reports for each standard analyzed
Continuing Calibration Verification
Continuing calibration summary in chronological order for each instrument
used
Complete continuing calibration data system report in chronological order per
instrument used and includes: FIRMS PFK mass resolution checks and
complete data system reports for each standard analyzed; RT of isomers per
homologue (window defining mix); HRGC column resolution check; internal
standard recovery summaries, mass ion ratios, and signal-to noise ratio check
for each standard analyzed. These verification checks are good for a 12 hour
analytical sequence. A12-hour Analytical Sequence Summary must also be
submitted by the lab.
6. Raw Quality Control Data
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Since the analytical method is an isotope dilution technique using labeled internal
standard for quantitation, the analysis of matrix spike and matrix spike duplicate
is not required. The following are the usual QC data submitted by the lab for
dioxin/furan analyses:
Method Blank Summary
On-Going Precision and Recovery (OPR) Laboratory Control Sample
Summary
PE Sample or Standard Reference Material
All QC samples analyzed for the project shall submit a tabulated summary of
results, SICPs and a complete data system report including labeled area
summaries
7. Miscellaneous Data
This is the section where a data reviewer may find the extraction and
extract clean-up bench sheets, instrument logs, standard traceability
certificates, standard preparation logs, project communication logs and
other information that may not be submitted in the final EDD but are still
relevant to the project. This is where the data reviewer will find hand-
written notations, problems encountered during sample receipt, sample
prep and analysis and the different corrective actions taken by the lab to
resolve or correct the problem. Sample clean-up and screening data may
also be found here (like the GPC clean-up chromatograms, clean-up
column preparations and verification checks, etc.).
8. Project EDD - usually submitted in a "comma-separated values" (.csv) or Excel (.xls
or .xlsx) file format. This file contains all of the reported results. When reviewing
data always refer and cross check the information obtained from the raw data with the
EDD submitted by the lab.
6.3. HOLDING TIME EVALUATION
Evaluation
Evaluate the following documents from the data package. Get the dates and from the information
gathered, prepare a holding time summary (see Worksheet 1):
Chain of custody documentation- sample collection date
Sample receipt date and sample control documentation from the laboratory
Sample extraction and clean-up worksheet - write the dates
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United States Environmental Protection Agency
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Instrument log summaries- get the sample names and date & time of injection
Cross check information with the summary of reported analytical results (Form 1)
Criteria
Table 1 Holding Time Criteria - 40 CFR 136:
Method 1613b
Matrix
Aqueous
Solids & Mixed
Phase
Tissue
Tissue Solids, &
Mixed Phase
Container
Glass
Glass
Glass
Glass
Sample
Condition Upon
receipt
Cool<6°C
Cool<6°C
Cool<6°C
Cool<6°C
(somewhat frozen)
Lab Preservation /Storage conditions
Field & Lab; Cool < 6 °C
0.008% Na2S2O3;pH<9
Field: Cool <6°C
Field: Cool < 6 °C
Lab:<-10°C
Lab:^-18°C(PSEP)
Holding Time
Extraction &
Analytical
1 year
7 days
24 hours
1 year
Table 2 - Holding Time Criteria SW846 Method 8290A
Matrix
All samples, aqueous
& solids
Fish & adipose tissues
Container
Glass
Glass
Preservation
Lab: Cool < 6 ° C, store in
the dark
Lab:<-10°C
store in the dark
Extraction
Holding Time
30 days from sample
collection
30 days from sample
collection
Analytical Holding
Time
45 days of extraction
45 days of extraction
Samples stored at the Lab at Cool < 6 ° C, in the dark are good for six months. The extraction
holding times of samples stored frozen @-10Cor-18C may be extended up to one year and
analytical holding time to additional one year (1613b). Note: Tissue samples must be extracted
within 24 hours of thawing.
Actions:
PCDDs and PCDFs are heavy and very stable in a variety of matrices. Under freezing conditions,
the holding time both extraction and analysis of extracts may be extended up to one year
(analysis). For samples not meeting the holding time criteria, results are flagged as estimated,
"J/UJ".
6.4. SAMPLE INTEGRITY, HANDLING AND PROCESSING
The chain-of-custody (COC) form documents that the integrity of the all field samples was
maintained from its origin of sample collection through sample handling, shipment, processing
and the laboratory analysis processes. The COC is used to ensure legal defensibility that proper
custody has been maintained from the time a sample is generated through its final disposition.
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Verification of sample documentation includes ensuring the sample is in possession of an
authorized person as noted on the COC, the sample was secured to prevent tampering (i.e. sealed
with COC during shipment), and/or the sample was placed in a designated secure area while
under custody of authorized personnel.
Tissue samples: Prior to processing tissue samples, the laboratory must determine the exact
tissue to be analyzed. Common requests for analysis of fish tissue include whole fish-skin on,
whole fish-skin removed, edible fish fillets (filleted in the field or by the laboratory), specific
organs, and other portions. Once the appropriate tissue has been determined, the sample must be
homogenized.
Homogenization: Samples are homogenized while still frozen, where practical. Sometimes, a site
specific homogenization SOP is developed by the lab and approved by EPA for use. Refer to that
SOP if it exist when evaluating tissue sample processing. If the laboratory must dissect the whole
fish to obtain the appropriate tissue for analysis, the unused tissues may be rapidly refrozen and
stored in a clean glass jar for subsequent use. When whole fish analysis is necessary, the entire
fish is homogenized. Homogenize the sample in a tissue homogenizer or equivalent equipment.
Cut tissue too large to feed into the grinder into smaller pieces. To assure homogeneity, grind
three times. Transfer the homogenized tissue to a clean jar with a fluoropolymer-lined lid. Seal
the jar and store the tissue at the method specific temperature (<-10°C for Method 1613b/ -18C
for PSEP). Return any tissue that was not homogenized to its original container and store at
method specific temperature (<-10°C for Method 1613b/ -18C for PSEP).
Evaluation: Verify and cross-check the signatures required in the chain of custody records, and
air bills. Note the conditions of the samples upon receipt at the lab, consistency of sample
documentation with the sample container labels, cooler and sample temperature (especially for
tissue samples). Check the sample control logs when the samples were received at the lab and
when the samples were taken in and out of the sample storage cooler or freezer for processing. In
summary, ensure that the integrity of the sample and extracts were maintained throughout the
analytical process. Check the miscellaneous section for corrective action non-conformance
memos and communication logs. These logs documents problems or potential problems
encountered during sample shipment and sample receipt at the lab.
Each sample received by the lab shall be labeled with a Sample Number and will be
accompanied by a Sample Chain of Custody Record bearing the Sample Number and descriptive
information regarding the sample. The field contractor shall complete the chain of custody record
and enter the sample name, sample location, date and time of sample collection, type of sampling
used (grab, composite, etc) and the name or initials of the field samplers. Both the field sampler
and the laboratory designated sample custodian must sign the Chain of Custody record.
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The condition of the samples upon receipt at the lab is also entered by the lab in the chain of
custody documentation and their Laboratory Information Management System (LIMS). Look
for discrepancies and inconsistencies between sample documentation and the laboratory
documentation. Tissue samples must be extracted within 24 hours of defrosting, therefore, the
tissue and shellfish samples must be frozen or partially frozen upon receipt at the lab to ensure
the maintenance of the integrity of the sample.
Tissue homogenization is documented in a separate bench sheet. The size of the fish (shellfish),
the weight and other characteristics prior to homogenization are documented in the bench sheets.
For ecological risk assessments, whole fish are used. For human health assessments, fish fillets
are used. Some projects have varied instructions on the parts of the specimen to be used for
analyses like: scaled vs unsealed; depurated vs not depurated; liver, blubber, right side fish fillets
compared with left side, etc. All of these instructions are included in the QAPP. Homogenized
tissue recoveries are also documented in the bench sheets.
Actions:
If the information provided by the lab is different from the chain of custody records and data
generated and/or other documentation problems are found, contact the lab for clarification. Note:
the PO/PM must be cc'd on all communication between the data reviewer, the field contractors
and the lab. If other discrepancies were identified, leading to the conclusion that the integrity of
the sample and data generated is compromised, work with the PM/PO, and the Agency's QA
Manager. Use professional judgment when flagging the data due to compromised sample
integrity.
6.5. SAMPLE PREPARATION AND SAMPLE CLEAN-UP
Evaluation: Note the following:
1. Extraction procedure used for each matrix: aqueous, solid, semi-solid or multi-phased,
fish/tissue.
Water samples:
o Use Method 330.4 or 330.5 to measure residual chlorine in the sample; pH
must be 7-9.
o Extraction for Method 1613b: Separately funnel liquid-liquid extraction-
Method 35 IOC; Solid phase extraction (SPE) - Method 3535A;
Continuous liquid-liquid extraction- Method 3520C; Soxhlet extraction
(SDS)-Method 3540C.
Semi-solid/Solid/Soil/Sediment samples:
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o Ultrasonic extraction - Method 3550C; pressurized fluid extraction -
Method 3 545 A; microwave extraction - Method 3546; Soxhlet extraction
(SDS) - Method 3540C for samples containing particles, filters and/or
disks.
Tissue samples
o Soxhlet extraction - Method 3540C; HC1 digestion (section 12.4.2 - method
1613b).
From the extraction bench sheets (miscellaneous data), extract the dates when extraction
started and ended. Note the analyst' initials. Note the amount of internal standards and clean-
up recovery standards added to the sample. Look for hand-written notations from the analyst;
sometimes they could provide explanations on unexpected variations from the expected
results.
2. Extract Clean-up Procedure: Measure clean-up efficiency by monitoring the clean-up
standard recoveries - 37CU-2, 3, 7, 8-TCDD.
Interferences co-extracted from samples will vary considerably from source to source,
depending on the diversity of the site being sampled. Interfering compounds may be present
at concentrations several orders of magnitude higher than the CDDs/CDFs. The most
frequently encountered interferences are chlorinated biphenyls, methoxy biphenyls,
hydroxydiphenyl ethers, benzylphenyl ethers, polynuclear aromatics, and pesticides.
Because very low levels of CDDs/CDFs are measured by this method, the elimination of
interferences is essential. Cleanup may not be necessary for relatively clean samples (e.g.,
treated effluents, groundwater, drinking water). If particular circumstances require the use of
a cleanup procedure, the analyst may use any or all of the procedures below or any other
appropriate procedure. Before using a cleanup procedure, the analyst must demonstrate that
the requirements of the Initial Precision and Recovery (IPR) can be met using the cleanup
procedure. If only 2, 3, 7, 8-TCDD and 2, 3, 7, 8-TCDF are to be determined, the cleanup
procedures may be optimized for isolation of these two compounds.
3. Note that each matrix has their own specific clean-up procedures recommended by the
Methods.
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Method 1613b Soil/sediment Extract Clean-up techniques:
Gel permeation chromatography (Section 13.2) removes high molecular weight
interferences that cause GC column performance to degrade. It should be used for all
soil and sediment extracts and may be used for water extracts that are expected to
contain high molecular weight organic compounds (e.g., polymeric materials, humic
acids).
Verify GPC calibration every 20 samples. In the verification, check the PCP
recovery. It must be >85%. If the calibration was not verified or did not meet the
criteria, the associated samples must be re-extracted and cleaned-up using the
calibrated GPC system. Check the documentation and chromatogram, as these will
give early indication of missed internal standards or other errors that happened during
sample extraction.
Basic silica gel clean-up is used to remove non-polar and polar interferences. For
extracts of samples known to contain large quantities of other organic compounds
(such as paper mill effluents), it may be advisable to increase the capacity of the silica
gel column. This may be accomplished by increasing the strengths of the acid and
basic silica gels. The acid silica gel (Section 7.5.1.2) may be increased in strength to
as much as 44% w/w (7.9 g sulfuric acid added to 10 g silica gel). The basic silica gel
(Section 7.5.1.3) may be increased in strength to as much as 33% w/w (50 mL IN
NaOH added to 100 g silica gel), or the potassium silicate (Section 7.5.1.4) may be
used.
The use of stronger acid silica gel (44% w/w) may lead to charring of organic
compounds in some extracts. The charred material may retain some of the analytes
and lead to lower recoveries of CDDs/CDFs. Increasing the strengths of the acid and
basic silica gel may also require different volumes of hexane than those specified
above to elute the analytes off the column. Therefore, the performance of the method
after such modifications must be verified by the IPR procedure
Activated Acid or Basic Alumina and Activated Florisil Clean-up are used to remove
chlorodiphenyl ethers. Any of these cleanup techniques may be used for sample
extract clean-up, provided that the laboratory can meet the performance specifications
for the recovery of labeled compounds in the IPR. The same type of alumina must be
used for all samples, including those used to demonstrate initial precision and
recovery and ongoing precision and recovery.
Carbon column clean-up (Carbopak CŪ & Celite 545Ū mix) is used to remove non-
polar interferences. For PCB congeners, the laboratories charge extra for carbon
column clean-up because it is an additional clean-up procedure used to determine the
concentrations of the toxic congeners in the WHO list and the interferences caused by
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the other PCB congeners and other organic materials are removed. Therefore, if total
PCB congener is desired, carbon column clean-up is not recommended.
HPLC is used to provide specificity for the 2, 3, 7, 8-substituted and other CDD and
CDF isomers. HPLC needs a column calibration verification every 20 extracts
analyzed. In the calibration verification, CDDs/CDFs recoveries must be between 75-
125% compared to the instrument calibration. If calibration was not verified or did
not meet the criteria, the associated samples must be re-extracted and cleaned-up
using the re-calibrated HPLC system.
Method 1613b Tissue Extract clean-ups:
Anthropogenic isolation column packed with silica gel, potassium silicate, granular
anhydrous sodium sulfate, acid silica gel and granular anhydrous sodium sulfate
(from bottom to top).
Acidified silica gel batch adsorption procedure- alternate clean-up procedure for
anthropogenic isolation column
Sulfuric acid and base back-extraction are used for removal of lipids from tissue
samples used with HC1 digested tissue extracts.
6.6. SYSTEM PERFORMANCE CHECKS
There are four fundamental HRGC/HRMS system performance checks, i.e., mass calibration and
resolution, selected ion monitoring (SIM) scan descriptor switching times, GC resolution and
instrument stability. Use information provided in Table 3 when assessing HRMS system
performance check.
6.7. MASS CALIBRATION AND TUNING
Frequency of check: at the beginning and end of each 12-hour QC period.
Criteria >10,000 resolving power of the selected ion current profile (SICP) of each target
analyte at the two exact mass/ions (m/zs) specified in Table 3 below.
Evaluation
The analysis time for CDDs/CDFs may exceed the long-term mass stability of the mass
spectrometer. Because the instrument is operated in the high-resolution mode, mass drifts of a
few ppm (e.g., 5 ppm in mass) can have serious adverse effects on instrument performance.
Therefore, a mass-drift correction is mandatory and a lock-mass m/z from PFK is used for drift
correction. Using a PFK molecular leak, the instrument must be tuned to meet the minimum
required resolving power of 10,000 (10% valley) at m/z 304.9824 (PFK) or any other reference
signal close to m/z 304 (from TCDF). Tuning chromatograms will be submitted by the lab
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conducted at the beginning and at the end of each analytical sequence for each mass descriptor.
The resolution must be greater than or equal to 10,000, and the deviation between the exact m/z
and the theoretical m/z (Table 3) for each exact m/z monitored must be less than 5 ppm.
Action
In the event that Mass Spectrometer resolution is <10,000, there may be evidence of system
noise and false positive results may exist. It is very unusual for labs to continue the analysis with
mass tuning resolution <10,000. However, if only one or two out of five descriptors show
resolution < 10,000, the reviewer must evaluate all the PFK resolution checks per instrument
submitted by the lab and look for trends. Using professional judgment, the reviewer may
consider qualifying only associated results as estimated, "J/UJ". If system noise is apparent and
interfering with the analysis, check the initial calibration and continuing calibration. Check the
signal to noise ratios, retention times, absolute retention times, mass-ion ratios, and GC
resolutions. If necessary, adjust or elevate the reporting limits to compensate for significant
baseline noise. If the signal to noise ratios, retention times, absolute retention times, mass-ion
ratios, and GC resolutions in the initial calibration and continuing calibration verifications are
acceptable, the data associated with a resolution <10,000 may only need to be flagged qualified
estimated, "J/UJ". Other QC results may be evaluated prior to rejecting the data based on mass
tuning resolution.
6.8. SIM SCAN DESCRIPTOR SWITCHING TIMES
In Method 1613b, the SIM scan descriptor switching times are monitored through the analysis of
the GC retention time window defining mix solution (WDM) and isomer specificity test
standard. The analysis of this standard is used to define the beginning and ending retention times
for the dioxin and furan isomers and to demonstrate isomer specificity of the GC columns
employed for determination of 2,3,7,8-TCDD and 2,3,7,8-TCDF. It is not necessary to monitor
the window-defining compounds if only 2, 3, 7, 8-TCDD and 2, 3, 7, 8-TCDF are to be
determined. In this case, an isomer-specificity test standard containing the most closely eluted
isomers may be used.
In Method 8290A, to check the first and last eluting dioxin and furan isomers for each
homologous series from tetra- through heptachlorinated congeners, the GC performance check
solutions (CPS) and high -resolution concentration calibration solution (HRCC-3) are used.
These two solutions are also commercially available as a combined standard. Use Table 3 as a
guide for the mass descriptors.
Frequency of the analysis of WDM or CPS
Before initial calibration on each instrument and GC column used for analysis;
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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 each 12-hour sample analysis period prior to the calibration
verification.
Evaluation
1. 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.
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. Note the RT of each first and last eluting isomer in each homologous series 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 homologous series. The 2, 3, 7, 8-
substituted dioxins and furans must also meet the Relative Retention Time (RRT) limits
listed in the summary Table 5 below or Table 2 Method 1613b.
Action
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.
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Table 3- Descriptors, Exact Mass-to-Charge (m/z), m/z Types and Common names of PCDDs/PCDFs
Descriptor
1
2
3
4
5
Exact m/z
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
435.8269
437.8140
479.7165
441.7428
442.9728
443.7399
457.7377
459.7348
469.7779
471.7750
513.6775
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
M + 2
Lock
M
M + 2
M
M + 2
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
QC
M + 2
M + 4
M+4
M + 2
Lock
M + 4
M + 2
M + 4
M + 2
M + 4
M+4
Common Name
PFK
TCDF
TCDF
13Ci2-2,3,7,8-TCDF
13Ci2-2,3,7,8-TCDF
TCDD
TCDD
37Cl4-2,3,7,8-TCDD
PFK
13Ci2-2,3,7,8-TCDD
13Ci2-2,3,7,8-TCDD
HxCDPE
PeCDF
PeCDF
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
PFK
PeCDD
PeCDD
13Ci2-l,2,37,8-PeCDD
13Ci2-l,2,37,8-PeCDD
HpCDPE
HxCDF
HxCDF
13C 12 -HxCDF
13Ci2 -HxCDF
HxCDD
HxCDD
PFK
13Ci2 -HxCDD
13Ci2- HxCDD
PFK
OCDPE
HpCDF
HpCDF
13Ci2- HpCDF
13Ci2- HpCDF
HpCDD
HpCDD
PFK
13Ci2- HpCDD
13Ci2- HpCDD
NCDPE
OCDF
PFK
OCDF
OCDD
OCDD
13Ci2-OCDD
13Ci2- OCDD
DCDPE
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6.9. CHROMATOGRAPHIC RESOLUTION
The resolution criteria must be evaluated using measurements made on the SICPs for the
appropriate ions for each isomer. Technical acceptance criteria must be met before any
standards, samples, QC samples, and required blanks are analyzed.
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 = valley between 2. 3. 7. 8-TCDD and 1.2.3.8 - TCDD (100)
Peak height of 2, 3, 7, 8-TCDD
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 = valley between 2. 3. 7. 8-TCDF and 2.3.4.7 - TCDF (100)
Peak height of 2, 3, 7, 8-TCDF
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%.
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.
Action
If the GC resolution on the DB-5 (or equivalent) column does not meet the specifications for
chromatographic resolution (% valley<25%), professional judgment should be used to evaluate
the severity of the non-compliant chromatographic resolution and qualify results as necessary.
The 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", non-detects are not qualified.
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6.10. INSTRUMENT STABILITY
Criteria: Either CSS solution (Method 1613b) or the HRCC-2 (Method 8290A) is used to
monitor instrument stability. The CS3/HRCC-3 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 listed in Table 5 below or Table 2 of Method 1613b.
3. Ion abundance ratio criteria: All native and labeled CDDs/CDFs in the CS3 standard must be
within their respective ion abundance ratios listed in Table 4 below.
4. Instrument sensitivity criteria: The peaks representing both native and labeled analytes in the
CS3 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
ą25% of the mean RR of the initial calibration. The %D of the mean Relative Response Factor
(RRF) must be within ą35% of the initial calibration. Use the following equation to calculate the
%D = Response (RRF or RR) from CCV -Mean Response (RR or RRF) ICAL (100)
Mean Response ICAL
Action:
The relative ion abundance, sensitivity (S/N, RRF), and percent difference (%D) determined
from the CS3 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 CS3
calibration verification standard) is especially indicative of degraded instrument performance.
Qualify all positive results in associated samples as estimated "J". Reporting limits may need
adjustment if the S/N ratio not met; non-detects ("UJ").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. % D not met the criteria, qualify all results estimated,
"J/UJ".
6.11. INITIAL CALIBRATION
The objective of the initial calibration is to establish a linear range, Mean Relative Responses
(RRs) of the unlabeled native analytes and the Mean Relative Response Factors (RRFs) for the
labeled internal standards and cleanup standard. The initial calibration is to be used for routine
quantitation of. Subsequent calibration verifications occurring every 12 hours thereafter are not
to be used for quantitation of samples, nor is the initial midpoint (CS3) solution is to be used for
this purpose.
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Criteria:
After the analyses of resolution check, and after meeting the criteria for system performance, the
initial calibration (minimum of 5 standards) 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.
Evaluation:
1. Verify that the PFK resolution check was performed, and system performance checks
passed.
2. Verify that all analytes in all calibration solutions are present at the correct
concentrations (see QAPP requirements).
3. Verify that the requirements for frequency of initial calibration were observed.
4. Verify that the ion abundance ratios in each calibration standard are within ą15% of the
limits listed in the methods.
5. Verify that the five RRF %RSDs (internal standards) are <35%.
6. Verify that the five RR %RSDs (native compounds) are <20%.
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) from CS1 standard.
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.
Action:
1. Criteria #1 - system performance check. If it not met, all of the succeeding analyses are
unusable. Initial calibration must not be analyzed at all.
2. Criteria #2 & 3- concentrations and frequency of analysis, CS1 must be at the reporting
level specific for the project, check the QAPP requirements. Frequency of analysis: check
the most recent date of initial calibration analysis for the same instrument. 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
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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.
3. Criteria # 4- 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, using professional judgment, a
more in-depth review may be performed to minimize the qualification of data. The +15%
expanded criteria is already included in Table 4, if the ion abundance ratios are still
outside the acceptance windows, the initial calibration is not acceptable and all
subsequent analyzes are unusable. Sometimes, the laboratory generates mass/ion ratios
for some of the target compounds, check the case narrative (usually for heptas and octas).
4. Criteria # 5 & 6 -Analyte response - internal standard and native compounds. If the
%RSD is not within ą 20% and ą 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. Criteria #7 - 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/UJ").
6. Criteria #8 - 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. If the S/N ratio is not met in CS2-CS5, qualify the associated
compound unusable, "R".
7. Criteria #9 - Retention Time. If 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, conduct a more detailed evaluation. If
a sample-specific 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
and associated data may need to be flagged estimated, "J/UJ", or unusable "R", using
reviewer's professional judgment.
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Table 4 - Theoretical Ion Abundance Ratios and Quality Control Limits
Number of Chlorine
Atoms
4 - Tetra CDD & CDF2
5 -Penta CDDs & CDFs
6- Hexa CDDs
13Ci2-HxCDFs only
7 - Hepta CDD
13Ci2-HpCDF only
8 - OCDD & OCDF
Theoretical Ratio
0.77
1.55
1.24
0.51
1.05
0.44
0.89
QC Limit1
Lower Limit
0.65
1.32
1.05
0.43
0.88
0.37
0.76
Upper Limit
0.89
1.78
1.43
0.59
1.20
0.51
1.02
^C limit represents + 15% windows around the theoretical ion abundance ratios.
2Does not apply to 37C14- 2, 3, 7, 8-TCDD (clean-up standard)
Table 5 - Relative Retention Times (RRT) and Quantitation Reference of the Native and
Labeled CDDs/CDFs
PCDD/PCDFs
Retention Time and Quantitation
Reference
Relative Retention Time
Compounds Using 13Ci2-l,2,3,4-TCDD as the injection internal standard
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,37,8-PeCDF
2,3,4,7,8-PeCDF
1,2,37,8-PeCDD
13Ci2 -2,3,7,8-TCDF
13Ci2- 2,3,7,8-TCDD
37Cl4-2,3,7,8-TCDD
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
13Ci2-l,2,37,8-PeCDD
13Ci2 -2,3,7,8-TCDF
13Ci2- 2,3,7,8-TCDD
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
13Ci2-l,2,37,8-PeCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-l,2,3,4-TCDD
0.999- .003
0.999- .002
0.999- .002
0.999- .002
0.999- .002
0.923- .103
0.976- .043
0.989- .052
1.000- .425
1.011- .526
1.000- .567
Compounds using 13Cn -1,2,3, 7,8,9-HxCDD as the injection internal standard
,2,3,4,7,8-HxCDF
,2,3,6,7,8-HxCDF
,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
,2,3,4,7,8-HxCDD
,2,3,6,7,8-HxCDD
,2,37,8,9-HxCDD1
,2,3,4,6,7,8-HpCDF
,2,3,4,7.8.9-HpCDF
,2,3,4,6,7,8-HpCDD
OCDF
OCDD
13Ci2-,2,3,4,7,8-HxCDF
13Ci2-l,2,3,6,7,8-HxCDF
13Ci2-l,2,3,7,8,9-HxCDF
13Ci2-2,3,4,6,7,8-HxCDF
13Ci2-,2,3,4,7,8-HxCDF
13Ci2-l,2,3,6,7,8-HxCDF
13Ci2-l,2,3,7,8,9-HxCDF
13Ci2-2,3,4,6,7,8-HxCDF
13Ci2-l,2,3,4,7,8-HxCDD
13Ci2-l,2,3,6,7,8-HxCDD
13Ci2-l,2,3,4,6,7,8-HpCDF
13Ci2-l,2,3,4,7.8.9-HpCDF
13Ci2-l,2,3,4,6,7,8-HpCDD
13Ci2-OCDD
13Ci2-OCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
0.999- .001
0.997- .005
0.999- .001
0.999- .001
0.999- .001
0.998- .004
1.000- .019
0.999- .001
0.999- .001
0.999- .001
0.999- .008
0.999- .001
0.944-0.970
0.949-0.975
0.977-1.047
0.959-1.021
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13Ci2-l,2,3,4,7,8-HxCDD
13Ci2-l,2,3,6,7,8-HxCDD
13Ci2-l,2,3,4,6,7,8-HpCDF
13Ci2-l,2,3,4,7.8.9-HpCDF
13Ci2-l,2,3,4,6,7,8-HpCDD
13Ci2-OCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
13Ci2 -1,2,3,7,8,9-HxCDD
0.977-1.000
0.981-1.003
1.043-1.085
1.057-1.151
1.086-1.110
1.032-1.311
The retention time reference for 1,2,3,7, 8, 9-HxCDD is 13Ci2-l, 2, 3, 6, 7, 8-HxCDD. 1,2,3,7, 8, 9-HxCDD is
quantitated using the averaged responses of 13Ci2-l,2,3,4,7,8-HxCDD and 13Ci2-l,2,3,6,7,8-HxCDD.
6.12. INITIAL PRECISION & RECOVERY CHECK (IPR)
The IPR check is required by Method 1613b and analyzed to establish the ability to generate
acceptable precision and recovery following the analytical method or Standard Operating
Procedure (SOP) established by the laboratory for the analysis. To the lab community, this is
also commonly referred to as the Initial Demonstration of Capability (IDOC).
For IPR, the following reference matrices are spiked with the labeled compound spiking solution
and the precision and recovery standard in sets of 4 and go through the same analytical processes
(extraction clean-up and analysis) as real samples:
Reagent water for aqueous samples
Playground sand, Ottawa sand or similar material can be used for high solids
reference matrix (soil/sediment). The reference material must be prepared by
extraction with methylene chloride and/or baking at 450 C for a minimum of 4
hours.
Glass-fiber filter, Gelman Type A, or equivalent as paper reference matrix. The
reference matrix paper must be cut to simulate the surface area of the paper
sample being analyzed.
Corn or other vegetable oil can be used as reference matrix for tissues. The oil
may be prepared by extraction with methylene chloride.
Using the results from the set of four analyses, the average concentration of the extracts (x) and
the standard deviation (s) of the concentrations for each compound are calculated by isotope
dilution for CDDs/CDFs with a labeled analog, and by internal standard for 1,2,3,7,8,9-HxCDD,
OCDF, and the labeled compounds. Compare the results with the acceptance criteria listed in
Table 6. If "x" and "s" meet the acceptance criteria for all compounds, system performance is
acceptable and analysis of blanks and samples may begin. If the criteria were not met, the IPR
will be repeated until it passed. Sample analyses may not proceed unless the IPR meets the
acceptance criteria.
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Action:
Not all laboratories submit the IPR results with the package. If that is the case, the validator must
contact the lab and request the IPR. The IPR and/or IDOC are required not only by the Method
1613b but also by the accreditation organizations. Sample analysis without an acceptable IPR is
unusable.
6.13. ON-GOING PRECISION AND RECOVERY CHECK (OPR)
The analysis of this QC sample prior to all blank and sample analyses is a requirement of
Method 1613b. A reagent blank water is spiked with a precision and recovery (PAR) solution
containing all the target CDDs and CDFs and corresponding internal standards, clean-up and
recovery standards. Native and labeled CDD/CDF recoveries are calculated and compared with
technical acceptance criteria listed in Table 6. Method 8290A does not require the analysis of
OPR. In Method 1613b, OPR and laboratory control sample (LCS) are considered the same and
used interchangeably.
Criteria, Evaluation & Action
For each CDD/CDF and labeled compound, compare the concentrations obtained for the OPR
analysis to the acceptance criteria listed in Table 6, below. If all compounds meet the acceptance
criteria, system performance is acceptable and analysis of blanks and samples may proceed. If,
however, any individual concentration falls outside of the range given, the extraction and clean-
up processes are not being performed properly for that compound. In this event, correct the
problem, re-prepare, extract, and clean up the sample batch and repeat the ongoing precision and
recovery test. Use professional judgment when qualifying data based on OPR. In Method 1613b,
OPR and laboratory control sample (LCS) are considered the same and used interchangeably.
6.14. CONTINUING CALIBRATION OR VERIFICATION (VER)
In Method 1613b, the calibration check is referred to as Verification standard (VER) whereas in
Method 8290A, this check is called Continuing Calibration Standard check. A Continuing
calibration or verification check standard CV check is used to validate the relative responses
(RRs) and the 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.
Frequency of Analysis: A midrange (CS3/HRCC-3) standard must be successfully analyzed at
the beginning and end of each 12 hour analysis period. At the start of a 12 hour sequence, the
check is analyzed after the WDM and resolution standard(s) and before OPR check/LCS, blanks
and samples are analyzed.
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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 recoveries (%R) or Difference (%D) associated with the
RR for the native compounds and RRFs for the labeled compounds].
Evaluation:
Continuing calibration ensures that the instrument(s) is capable of consistently producing
acceptable qualitative and quantitative data. A continuing calibration check must be performed
every 12-hour time period in which samples were analyzed. Different analytical methods have
different acceptance criteria listed for continuing calibration verification.
Method SW-8290A: The measured RRs for the unlabeled standards obtained during the routine
CCV runs must be within ą20 percent of the mean RR values established during the initial
calibration (RIO expanded criteria + 25%). The measured RFs for the labeled standards obtained
during the routine CCV runs must be within ą30% of the mean RF values established during the
initial calibration (RIO expanded criteria + 35%).
Method 1613B: The concentration of each of the unlabeled and labeled standards must be within
the limits listed in Table 6 below. Use the values listed in the CCV column. Inspect the
continuing calibration summary data and verify agreement with the raw data (quantitation sheets
and chromatograms).
Verify that the %D (Method 8290A) or the concentration (Method 1613B) for each compound is
within the specified range, or that the complete calibration curve was used for quantitation. If
criteria for the continuing calibration were not met, qualify detected results as estimated "J" and
non-detect results undetected/estimated "UJ".
1. Verify the frequency of analysis of CCVs in 12 hour analytical sequence. The CCV must
be analyzed after the analysis of acceptable system performance checks and results
compared to the correct initial calibration. Method 1613b requires that each 12 hour
analytical sequence is bracketed by an opening and ending CCV analyses.
2. Verify from the CCV raw data that the ion abundance ratios 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. Verify that absolute retention times are within ą15 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.
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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 for each target analyte and
corresponding labeled internal standards in the CSS solution are within the method
requirements specified above.
Actions:
1. Use professional judgment to qualify any analyte in samples associated with a calibration
verification not meeting the RT and/or RRT criteria.
2. All of the target compounds must meet the ion abundance ratios in a CCV. Failure to
meet the ion abundance criteria in a standard 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.
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".
4. Method 1613b - use the acceptance criteria listed in the Table 6.
5. Method 8290A- 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 ą25% (RR) and not within ą35% (RRF) as estimated "J". Recalibrate
the HRGS/HRMS and reanalyze the affected samples.
6. Situation: Front CCV passed but ending CCV failed some of the acceptance criteria. Data
does not need qualification if (1) samples analyzed before the CCVs met the technical
acceptance criteria and (2) no samples were analyzed after the failed CCV.
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Table 6- IPR, OPR and CCV Acceptance Criteria for Method 1613b
CDD/CDF
2,3,7,8-TCDD
1,2,37,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,37,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,37,8-PeCDF
2,3,4,7,8-PeCDF
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-HpCDF
1,2,3,4,7.8.9-HpCDF
OCDF
13Ci2- 2,3,7,8-TCDD
13Ci2-l,2,37,8-PeCDD
13Ci2-l,2,3,4,7,8-HxCDD
13Ci2-l,2,3,6,7,8-HxCDD
13Ci2-l,2,3,4,6,7,8-HPCDD
13Ci2-OCDD
13Ci2 -2,3,7,8-TCDF
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
13Ci2-,2,3,4,7,8-HxCDF
13Ci2-l,2,3,6,7,8-HxCDF
13Ci2-l,2,3,7,8,9-HxCDF
13Ci2-2,3,4,6,7,8-HxCDF
13Ci2-l,2,3,4,6,7,8-HpCDF
13Ci2-l,2,3,4,7.8.9-HpCDF
37CU- 2,3,7,8-TCDD
Cone.
(Ng/ml)
10
50
50
50
50
50
100
10
50
50
50
50
50
50
50
50
100
100
100
100
100
100
200
100
100
100
100
100
100
100
100
100
10
IF
s
(Ng/ml)
2.8
7.5
9.4
7.7
11.1
7.7
19.0
2.0
7.5
8.6
8.7
6.7
6.4
7.4
6.3
8.1
27.0
37
39
41
38
35
95
35
34
38
43
35
40
37
41
40
3.6
R
X
(Ng/ml)
8.3-12.9
38-66
9.4
7.7
11.1
38-65
89-127
8.7-13.7
43-62
36-75
41-59
46-60
42-61
37-74
45-65
43-63
74-126
28-134
27-184
29-147
34-122
34-129
21-138
31-113
27-156
16-279
27-152
30-122
24-157
29-136
32-110
28-141
39-154
OPR
% recovery
67-158
70-142
70-164
76-134
64-162
70-140
78-144
75-158
80 - 134
68-160
72 -134
84 - 130
78- 130
70-156
82-122
78-138
63-170
20-175
21-227
21-193
25-163
26-166
13-199
22-152
21-192
13-328
19-202
21-159
17-205
22-176
21-158
20-186
21-191
CCV
% recovery
78-129
78-130
78-128
78-128
82 - 122
86-116
79-126
84-120
82- 120
82-122
90-114
88-112
90-114
88-112
90-110
86-116
63-159
82-121
62-160
85-117
85-118
72-138
48-207
71-140
76-130
77-130
76-131
70-143
74-135
73-137
78-129
77-129
79-127
All specifications are from final extracts assuming a 20 uL final volume; s= standard deviation of the concentration;
x is the mean concentration calculated from 4 runs.
6.15. BLANKS ANALYSES
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
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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.
Criteria and Evaluation
1. Verify that each sample extract has an associated method blank that meets the acceptance
criteria specified in the method used. The methods require that a blank reference matrix
of an equivalent initial weight or volume be prepared by the same procedures, including
extract cleanup, and analyzed on each instrument used to analyze the samples. Care
should be exercised when evaluating the method blank(s) that were prepared with a given
sample extract. In addition, the reviewer may consider blanks analyzed in the same
analytical sequence and any performance evaluation sample (PES) blind blanks submitted
with the samples. Evaluation of field and equipment blanks should be done according to
Regional policy and the criteria established in the project Quality Assurance Project Plan
(QAPP). The reviewer should use the highest result from the same column to make
decisions about data qualification.
2. Verify that, with the exception of OCDD and OCDF (and Total Homologues), the
method blank(s) are free from contamination for the native compounds. The
concentration of OCDD/OCDF in the method blank must be
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& PCDFs detected in the sample at concentrations <5x MB are qualified non-
detects, "U". Sample results >5x MB are not qualified.
To avoid the needed considerations for matrix, weight, volumes or dilution
factors, when comparing blank and sample PCDD/PCDF, compare the area of
the target compound in the blank multiplied by 5 with the area of the
compound detected in the sample. Use the raw data to get those information.
2. 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.
3. 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).
4. 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.
5. 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).
6.16. PERFORMANCE TEST SAMPLE/STANDARD REFERENCE MATERIAL
(PTS/SRMS)
Data for PTs are generated to provide information on the overall accuracy and bias of the
analytical method and on laboratory performance. Results for PTs are evaluated for false
negatives, false positives, and accuracy of target compound quantitation. The Region may
provide the laboratory with PTs/SRM to be analyzed with each sample delivery group (SDG).
These may include blind spikes and/or blind blanks. The laboratory must analyze a PTs/SRM
when provided by the Region. For the Dredge Material Management Program (DMMP), the
analysis of a sediment reference material is required for dioxins and furans. The RIO
dioxin/furan Sediment Reference Material (SRM) may be requested from the DMMP Project
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Managers and sent by a Quality Staff from the RIO QA team. The Guidance for SRM
distribution and reporting for the DMMP is in Appendix B of this SOP.
If the PE sample was provided by RIO through the QA Technical Services in Las Vegas, NV.
Contact the project QA Officer for the true values.
Criteria
QC limits for the RIO dioxin/furan sediment reference material.
Acceptance Limits
Source
ą 50 Percent
Analyte
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
CAS No.
1746-01-6
40321-76-4
39227-28-6
67653-85-7
19408-74-3
35822-46-9
3268-87-9
51207-31-9
57117-41-6
57117-31-4
70648-26-9
57117-44-9
60851-34-5
72918-21-9
67562-39-4
55673-89-7
39001-02-0
Avg. Cone.
(ng/kg)
1.05
1.08
1.59
3.88
3.04
90.6
811
1.11
1.23
1.07
3.02
1.09
1.83
0.511
18.7
1.63
58.4
Action Low
-50%
0.525
0.542
0.797
1.94
1.52
45.3
406
0.557
0.613
0.533
1.51
0.545
0.917
0.255
9.36
0.815
29.2
Action High
+50%
1.57
1.63
2.39
5.82
4.55
136
1217
1.67
1.84
1.60
4.53
1.64
2.75
0.77
28.1
2.44
87.6
Evaluation
1. If PTs are included in the SDG, verify that the results are within the action limits [99%
(3o) confidence interval] and warning limits [95% (2o) 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.
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2. If a significant number (i.e., half or more) of the analytes in the PTs 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.
3. Acceptance criteria had been established for the RIO dioxin/furan SRM based on the
round robin participation from 8 laboratories. The concentration ranges of the RIO
dioxin/furan SRM are listed in Appendix B of this SOP.
Action:
If a result is not within acceptance criteria for any congener, evaluate the other Quality Control
(QC) samples in the SDG like laboratory control sample (LCS), calibration, labeled standard
recovery, internal standard recovery, and cleanup standard recovery. Performance evaluation
samples and standard reference materials are only one indicator of technical performance of the
laboratory. In general, for PES/SRM 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" (potential for false negatives).
6.17. LABORATORY CONTROL SAMPLES (LCS)
Some projects require the analysis of LCS. The CLP Dioxin analysis program requires the
analysis of LCS. OPR is a performance standard sample required by Method 1613b analyzed
before all samples and QC runs and recoveries compared with the initial precision and recovery
results (just like an initial calibration verification) whereas the LCS is a stand-alone QC sample
evaluated using the laboratory established recovery control limits or the project specific
acceptance limits specified in the QAPP.
An LCS is analyzed to provide accuracy of the analytical method. An LCS must be analyzed at a
frequency of at least one per 20 field samples of similar matrix. LCS% Recovery should fall
within specified limits defined by the QAPP or the laboratory's SOP.
If LCS recovery results are greater than the upper acceptance limits, qualify all detects for those
analytes which fail in the LCS as estimated "J". If the LCS recovery is below the primary
recovery range, but above 10%, it may indicate that there is a low bias in laboratory performance
and the associated data should be qualified as estimated "J" or "UJ". If the LCS results are
<10%, qualify positive results for those analytes as estimated "J" and non-detects as unusable
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"R" in all associated samples. If the laboratory failed to prepare and analyze the LCS at the
required frequency, use other QC results to determine the quality of the associated data and note
this in the Data Review Narrative.
6.18. INTERNAL STANDARD (LABELED COMPOUND) RECOVERIES
The recovery of the labeled internal standard analysis is an indicator of the performance of
laboratory extraction and analysis. This solution is added to all samples, blanks, and laboratory
QC samples prior to extraction. Internal standard performance results are critical to the overall
accuracy and precision of the analysis since target compound results for each dioxin and furan
isomer are quantitated based on the response of the corresponding labeled isomer.
There are three types of isotope- labeled compounds used for PCDD/PCDF analysis, i.e., the 15
labeled internal standards that are added to the samples and QC samples prior to extraction that
monitor extraction efficiency; the internal standard, 37Cl-2, 3, 7, 8 - TCDD, added prior to
extract clean-up, hence, monitors extract clean-up efficiency and the 2 injection or recovery
standards, 13Ci2-l, 2, 3, 4-TCDD and 13Ci2-l, 2, 3, 7, 8, 9-HxCDD, added prior to injection of
the extract into the instrument. The labeled clean-up standard is added to the extract prior to
clean-up. The recoveries of all these labeled standards are monitored to determine the overall
process and system efficiency
Criteria:
For Method SW-8290A: All internal standards should be within the range of 40-135 percent
recovery (%R). For Method 1613B: All concentrations of the labeled compounds should be
within the ranges given in Table 7 below. When results of the internal standards indicate
atypical method performance for samples, the samples should have been diluted or re-analyzed
to bring method performance within acceptable limits. Some laboratories established laboratory
specific acceptance criteria for internal standards used in PCDD/PCDF analysis using their
accumulated recoveries from a control chart. This is acceptable as the methods are performance
based. When this happens, the laboratories list their deviations in the data package's Case
Narrative.
Action
The labeled analogs of the native target compounds are used for sample result quantitation and
the associated results are automatically adjusted based on the amount of labeled internal standard
(IS) recovered. Therefore, if the labeled internal standard recovery is higher compared to the
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CCV, the associated sample result will possibly be low biased and likewise, if the internal
standard is lower than the CCV, the associated sample results may be high biased.
Therefore, if the labeled IS did not meet the low end acceptance limit, the compound associated
with this IS may be biased high and the associated detected result will need to be flagged
estimated, "J"; the associated non-detect is not qualified. If the IS recovery is extremely low
<10%, the associated detected result may be artificially high and needs to be qualified, estimated,
"J"; the bias in the non-detects EDL/RL are unknown and qualified unusable, "R". If a labeled
internal standard has a recovery greater than the upper control limit, the associated detected
native compound is qualified estimated, "J", indicating low bias in the associated results; non-
detects are also qualified estimated, "UJ". If the labeled IS recovery is extremely high^200%,
the associated detected native compound is qualified estimated, "J" and the non-detects are
qualified unusable "R", at the RL/EDL.
Sometimes there are instances when the laboratory uses the laboratory established acceptance
limits for labeled internal standards recovery. In instances like this, internal standards not
meeting the laboratory established acceptance limits are also qualified as stated above.
Clean-up recovery standards that are not within the acceptance limits but >10% indicates low
bias in the associated results are flagged estimated, "J/UJ". Extremely low recovery (<10%) or
no recovery indicate potential for false negatives; detected compounds are flagged estimated,
"J", and non-detected results are qualified unusable, "R". Note: The cleanup standard is not
required by method SW-8290A.
Injection standards, 13Clrl, 2, 3, 4- TCDD and 13Clrl, 2, 3, 7, 8, 9-HxCDD are added to samples
after extraction and prior to analysis. These recovery standards are used to calculate the labeled
internal standard analogs added before extraction. Recoveries for these two IS are not required to
be monitored.
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Table 7 - QC Limits for Labeled Compound Recoveries In Samples (Method 1613B)
Compounds
13Ci2-2,3,7,8-TCDD
13Ci2-2,3,7,8-TCDF
13Ci2-l,2,37,8-PeCDD
13Ci2-l,2,37,8-PeCDF
13Ci2-2,3,4,7,8-PeCDF
13Ci2-l,2,3,4,7,8-HxCDD
13Ci2-l,2,3,6,7,8-HxCDD
13Ci2 1-,2,3,4,7,8-HxCDF
13Ci2-l,2,3,6,7,8-HxCDF
13Ci2-l,2,3,7,8,9-HxCDF
13Ci2-2,3,4,6,7,8-HxCDF
13Ci2-l,2,3,4,6,7,8-HpCDD
13Ci2-l,2,3,4,6,7,8-HpCDF
13Ci2-l,2,3,4,7.8.9-HpCDF
13Ci2-OCDD
37CU-2,3,7,8-TCDD
Test Concentration
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
10
Labeled Compound Recovery QC Limits
Ng/ml
25-164
24-169
24-181
24-185
21-178
32-141
28-130
26-152
26-123
29-147
28-136
23-140
28-143
26-138
34-313
3.5-19.7
% recovery
25-164
24-169
24-181
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
6.19.
Criteria
COMPOUND IDENTIFICATION
Signal -to-noise ratio >2.5 (S/N>2.5)
Retention time within 2 seconds of the labeled analog or if there's no labeled
analog, within the retention time window established during the WDM analysis.
Ion-abundance ratio met- The ratio of the integrated areas of the two exact m/z's
must be within the limit specified in Table 4 or within ą10% 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.
Peak identification- the ion current response for the two quantitation ions for the
analyte and the labeled analog in question must maximize simultaneously within
the same 2 seconds
Absence of polychlorinated diphenyl ether co-elution or interference.
Evaluation
1. Check the sample result SICP chromatograms. SICPs must be presented so that the two
quantitation ions, any relevant labeled compounds, and chlorinated diphenyl ether
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(CDPE) interferents are all on one page. For example: for 2, 3, 7, 8-TCDF, the following
SICP chromatograms must be presented in one page: masses: 304 (m), 306 (m+ 2), 318
(labeled 2378-TCDF) and 375 (hexaclorodiphenyl ether). Note that diphenyl ethers are
only monitored in PCDFs and not PCDDs.
2. Signal-to-noise (S/N) ratio. Sometimes, the lab provides the S/N calculation in the Case
Narrative. However, data reviewers will need to check the noise against the sample result
response. For PCDD/PCDF analysis, most of the laboratories set their instrument
baseline noise threshold to 2.5 and therefore, any peak detected within the established
retention time window, and area >2.5 the noise level is reported by the data system as a
detected compound.
3. Using the SICP print-out (electronic or hard copy), check the retention times of the native
(parent &daughter masses), relevant labeled compounds and the CDPE channel. For a
compound to be reported as detected, the peaks/retention times for the masses of both
native and labeled compounds must be aligned and elute within 2 seconds of each other.
There should be no CDPE peak eluting at the same retention time as the masses of the
target compound and the mass- ion abundance ratio (m/z ratio) must be met. If all the
qualitative identification criteria are met except for the mass-ion abundance, the result is
reported as estimated maximum potential concentration (EMPC) by the laboratory. The
reviewer should rely on professional judgment and organizational policy to decide how to
qualify EMPCs. If the compound meets the expanded m/z ratio criteria, then the result
may be reported and flagged estimated, "J. If the m/z ratio did not meet the expanded
criteria, the result is reported non-detect, "U", at the level of detection.
4. If there are diphenyl ethers co-eluting interfering with the compound peak, even with
additional clean-up, the compound is flagged by the lab (usually "X" or "E") and also
reported as EMPC. During validation, the reviewer must check the contribution of the
CDPE peak to the masses being monitored. If the interference is significant (>25%) of
the compound peak, the sample result is flagged non-detect, "UJ" elevated at the level of
detection of the compound. If the interference of the CDPE is minimal (<25%), the
compound is reported and flagged estimated, "J", due to interferences.
5. Total PCDDs/PCDFs. The total concentration of peaks commonly found in each
descriptor and has S/N >2.5 are reported by the lab for total homologues. 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-
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substitued target analytes, except RT. Peaks not meeting the m/z ratio due to CDPE
interferences are reported as EMPC. These peaks must be flagged non-detects by the data
reviewer and concentrations deducted from the totals reported.
6. The PCDD/PCDF result flagged by the reviewer as non-detect must not be included in
the TEQ calculation.
6.20. COMPOUND QUANTITATION
Criteria
The estimated detection limits (EDLs) and/or reporting limits reported by the laboratory must
meet the data quality goals of the project. EDLs must be less than the Reporting Limits.
Evaluation:
The site specific or project specific data quality goals can be found in the QAPP. Compare the
reported results with the DQO goals. Concentrate on the EDLs and RLs of the non-detects and
determine if they are lower than the project screening or action level. If the EDLs or RLs did not
meet the screening or action levels specified in the QAPP, the DQOs are not met and there
maybe potential for data gaps.
Verify that EDLs are properly calculated. See Appendix C for formula. Recalculate 10% of
EDLs form raw data and compare with the reported results.
EDL must be reported for each undetected analyte, except when in it is increased due to dilution
of the extract.
An EMPC is calculated for 2, 3, 7, 8-substituted isomers that have S/N ration >2.5 for both ions,
but do not meet all the identification criteria. Verify that EMPCs are properly calculated. See
Appendix C for formula. Recalculate 10% of EMPCs from raw data and compare with the
reported results.
Action:
If EDLs are not properly calculated or reported, notify the Project Manager (PM) and Work
Assignment Manager (WAM) and contact the laboratory for clarification.
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If EDL>RL after adjusting for dilution, notify the Project Manager (PM) and Work Assignment
Manager (WAM) for action and note this non-compliance in the validation report.
If there is a discrepancy of >10% between reviewer's calculation and the value reported, request
laboratory clarification through the PM/WAM. If the discrepancy remains unresolved, use
professional judgment to decide which is more reliable values and if qualification of data is
warranted.
If EMPC reported is EDL, qualify data as non-detects reported at the level the analyte
was detected. If the EMPC is >RL, check the chromatogram for interferences. If interferences
can be minimized or removed by further extract clean-up, request additional clean-up from the
laboratory through the PM/WAM. If the peak cannot be isolated form the interferences, flag the
result estimated with a possible high bias.
6.21. TOXICITY EQUIVALENCY QUOTIENTS (TEQS)
TEQs are used by data users for risk assessments. For consistency, the laboratories providing
analytical services for PCDD/PCDF are requested by RIO to submit the PCDD/PCDF TEQs
using 3 scenarios: (1) ND=0; (2) ND=l/2 and (3) ND=1. These 3 calculations will reflect the
potential total toxicity min-max values in the sample. If the TEQs are derived from PCDD/PCDF
values that are flagged estimated, the total TEQ is also flagged estimated, "J". Use the most 2005
or most recent WHO Human and Mammalian Toxic Equivalency Factors (TEF) for Dioxin and
Dioxin-like Compounds in the TEQ calculations.
6.22. LABORATORY CONTACT
If the laboratory was contacted by the reviewer to obtain more information needed to complete
the review, the contact date, point of contact and summary of issues discussed and the name of
person who contacted the lab shall be included in this section of the Validation Report.
6.23. OVERALL ASSESSMENT OF THE DATA
In this section, the data validator shall report the following: (1) if the completion target goal has
been accomplished or not; (2) the percentage of the data points qualified unusable, if any and the
reasons for the qualification; (3) the percentage of the data points qualified estimated; (4) the
most common problem(s)/issues observed with the data is also discussed in this section and (5)
overall effect of the QC issues on the quality of the associated data.
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7. LIST OF VALIDATION QUALIFIERS
Data Qualifiers
U
UJ
R
JN
The substance or analyte was analyzed for, but no quantifiable concentration
was found at or above the sample quantitation or reporting limit (numerical
value).
The analyte was positively identified in the sample. The associated
numerical result is an estimate due to failure in meeting QC acceptance
limits.
The analyte was analyzed for, but was not detected at or above the estimated
quantitation or reporting limits due to one or more QA/QC requirements that
were not met.
The data are unusable for all purposes due to gross deficiencies in QA/QC
results.
The analysis indicates the presence of an analyte for which there is
presumptive evidence to make a "tentative identification". The associated
numerical result is an estimate. Data qualified "JN" are for screening
purposes only and will need confirmatory analysis to further increase
usability.
Bias Qualifiers Used for Hazard Ranking System (HRS) pre-scoring for NPL Listing (Note:
These bias qualifiers must be applied to qualified results supporting a Preliminary Assessment,
Site Investigation or Expanded Site Investigation projects only. Verify project needs with the
specific/project QAPP section 4.0 Data Validation and Usability).
Bias Qualifiers
L
H
K
Q
Low Bias
High Bias
Unknown Bias
Value reported below the method or contract required
reporting/ limits (CRQLs or RLs)
quantitation
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APPENDIX A - PCDD/PCDF VALIDATION WORKSHEETS
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PCDD/PCDF DATA VALIDATION WORK SHEET 1 -HOLDING TIME, SAMPLE INTEGRIT, PREPARATION &
EXTRACT CLEAN-UP EVALUATION
CRITERIA/ACTION
MATRIX
AQUEOUS/WATER
SOLIDS/MIXED SOLIDS
TISSUE
SOLID/TISSUE/SEMI-SOLID
PRESERVATIVE
6°C-Na2S2O3(Cl2)
6°C
6°C
-10 TO -18 °C
EXTRACTION HT
ANALYTICAL HT
1 YEAR (40 CFR 136- METHOD 1613B)
7 DAYS (40 CFR 136- METHOD 1613B)
EXTRACTION WITHIN 24 HOURS
(40 CFR 136- METHOD 1613B)
I YEAR (METHOD 1613B & PSEP)
QUALIFIERS
DETECTS
J
J
J
J
NON-DETECTS
UJ
UJ
UJ
UJ
LIST OF SAMPLES
EPA
Sample
Number
Location/
Description
Lab
Sample
Number
DATES
Sample
Collection
Lab Sample
Receipt
Homogenization
(Tissue)
Extraction
Clean-up 1
Clean-up2
Analysis 1
Analysis 2
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CHAIN OF CUSTODY
Signatures:
Field Sampler
Shipper
Delivery (Lab)
Cooler Temperature Check
Sample Condition
Transcription errors in
documentation
Sample receipt docs Lab
Sample Storage docs
SAMPLE PREP & CLEAN-UP
Tissue Homogenization docs
Extraction Method
Analyst signature
Initial Mass
Final Extract Volume
Clean-up Techniques
Analyst Signature
Yes
Yes
No
No
Comments
Comments
Qualified Samples:
Print Name & Signature Data Reviewer/Validator
Date
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EPA-910-R-14-003
May 2014
Page 45 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 2 - SYSTEM PERFORMANCE CHECK
CRITERIA/ACTION
Name of Instrument:
Date & Time of Analysis: Operator:
PFK Check at required frequency?
HR/MS MASS RESOLUTION
HR/MS Resolution failed;
No re-analysis
Low/high mass per homologue?
Frequency of Analysis of WDM
Descriptor switching times for 6 descriptors
Retention Times established by WDM
S/N for quantitation
S/N for standard
Simultaneous peak responses at M & M+2
masses?
Retention times (RTs) of each other M + M+2
GC Resolution
Ion Abundance met for all target compounds
System Stability - Absolute RT & RRT met
(CS3/HRCC3)
Criteria
Front & end
>10,000
Each descriptor
Front- sequence
Minimum overlap
between descriptor
First to last isomer per
homolog
>2.5 noise
>10 noise
Simultaneous peak
responses
within 2 seconds
%valley <25%
Table 4
Table 5
Yes
Required
Required
Required
No
If < criteria
write the number
Validation Qualifiers
Detects
Non-detects
If PFK analyzed only at the front - and other criteria met-
no qualification necessary
Missing descriptor
Overlap/co-elution
Use professional
judgment
If<2.5
If<10
RT criteria no met
Co-elution
Reported as EMPC
with calculation
m/z adjustment
Without
Use professional
judgment
No flag
R
J
J
No flag
R
UJ
UJ
Call the lab to resubmit the WDF
SICP
UJ
J
UJ
UJ
Unconfirmed detect; U
Unconfirmed detect; U
J
J
UJ
UJ
UJ
UJ
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List of Samples Affected by failed System Performance check and specify reason:
Print Name & Signature Data Reviewer/Validator Date
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Page 47 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 3- IPR/IDOC
Method 1613B: Calibration Standard Runs: Initial and On-Going Precision & Recovery Checks (IPR and OPR); Initial
Calibration and Continuing Calibration Verification
Method 8290A: Initial Demonstration of Capability (IDOC) and/or Method Detection Limit (MDL) Determination; Initial
Calibration and Continuing Calibration Verification
Instrument:
Date and Time of Analyses:
Operator:
Criteria/Action: IPR/IDOC
Method 1613B
Evaluation
Criteria
Refer to Table 6 criteria for IPR, OPR and CCV
Check standard deviations, & mean concentrations of
PCDDs/PCDFs analyzed for IPR and OPR. Compare values
with Table 6
Failed IPR/IDOC - All associated standard, sample & QC
runs are unusable - Laboratory did not meet EPA's FEM
Policy for competency; data will not be defensible in court.
Data may only be used for screening purposes.
Validation Qualifiers in
Associated Samples
Detects
Estimated, "J"
For screening
purposes only
Non-Detects
Use
professional
judgement
Print Name & Signature Data Reviewer/Validator
Date
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EPA-910-R-14-003
May 2014
Page 48 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 4- INITIAL CALIBRATION
Initial Calibration (Per Instrument)
Instrument:
Date and Time of Analysis
Operator:
System Performance Check
Concentrations
Frequency of Analysis
Ion Abundance Ratios
Native compound %RSD
Labeled internal standard RSD
GC Resolution
Sensitivity
Retention Time
Relative Retention Time
Criteria Not Met
See Worksheet 1
QAPP/SOP/Method
QAPP/SOP/Method
No Initial Calibration
Table 4 (Validation SOP)
Or Case Narrative
+ 25 %RSD RR
+ 35%RSD RRF
% valley<25%
S/N>10:lforCSl
S/N>10:1 CS2-CS5
Absolute RT of 13Ci2-
1,2,3,4-TCDD>25
minutes in DBS; >15
minutes in DB225
Table 5
Action- Associated Samples
Adjust RL/EDL
Screening level data
Screening level data
Use professional judgment Lab report as
EMPC- m/z corrected; > RL
Lab report as EMPC- m/z < RL
Remove CS1 or CSS and recalculate RSD
If CS1 is making RSD fail (out)
If CSS is out- flag concentrations>CS4
Check closely eluting compounds
Adjust EDLs/RLs
Problem with Instrument sensitivity
Use professional judgment. Sample matrix
may have caused RTs to shift. Check
SICP for interferences. If compound
meets other identification criteria, no flag
is necessary. If concentrations are affected
by interferences, flag results estimated.
Use professional judgment. Sample matrix
may have caused RTs to shift. Check
SICP for interferences. If compound
Validation Qualifiers
Detects
J
J
J
J
U
J
J
J
J
J
J
Non-detects
UJ
R
R
UJ/R
UJ
UJ
UJ
No flag
UJ
R
UJ
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RT and Quantitation Reference
Table 5; must be within 2
seconds of each pair ions
meets other identification criteria, no flag
is necessary. If concentrations are affected
by interferences, flag results estimated.
Sample matrix may have caused RTs to
shift. Check SICP for interferences. If
there are interferences, the RTs of the pair
ions and labeled analogs will also shift.
May cause false positives. Use
professional judgment.
Associated Samples:
Print Name & Signature Data Reviewer/Validator
Date
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May 2014
Page 50 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 5- CONTINUING CALIBRATION VERIFICATION
Continuing Calibration Verification Check (Per Instrument)
Instrument:
Date and Time of Analysis Operator:
System Performance Check
IPR/IDOC
Initial calibration
Concentrations
Frequency of Analysis
Native compound %D
Labeled internal standard
Native compound
Labeled internal standard
Ion Abundance Ratios
GC Resolution
Sensitivity
Criteria Not Met
See Worksheet 1
See Worksheet 3
See Worksheet 4
QAPP/SOP/Method (CS3/HRC3)
QAPP/SOP/Method (every 12
hours; front & back end - method
1613B sequence)
CCV from initial calibration
+ 25RR
+ 35RRF
Table 6 of the validation SOP
Table 4 (Validation SOP)
Or Case Narrative
% valley<25%
S/N>10:lforCSl
S/N>10:1 CS2-CS5
Action- Associated Samples
Adjust RL/EDL
No CCV -Initial calibration used;
estimated results
Only front end CCV - OK- 1C AL
RR/RRF used in calculation;
Failed Back end CCV - OK as
long as no samples analyzed after
the failed CCV
OK; sate in validation report
Method 8290A criteria
Method 1613B criteria
Lab report as EMPC- m/z
corrected; > RL
Lab report as EMPC- m/z < RL
Check closely eluting compounds
Adjust EDLs/RLs
Problem with Instrument
Validation Qualifiers
Detects
J
None
J
J
J
Non-detects
R
None
UJ
UJ
UJ
See internal std section
J
U
J
J
UJ/R
UJ
UJ
R
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sensitivity
Retention Time
Absolute RT of 13Ci2-l,2,3,4-
TCDD >25 minutes in DBS; >15
minutes in DB225
Use professional judgment.
Sample matrix may have caused
RTs to shift. Check SICP for
interferences. If compound meets
other identification criteria, no flag
is necessary. If concentrations are
affected by interferences, flag
results estimated.
Relative Retention Time
Table 5
Use professional judgment.
Sample matrix may have caused
RTs to shift. Check SICP for
interferences. If compound meets
other identification criteria, no flag
is necessary. If concentrations are
affected by interferences, flag
results estimated.
RT and Quantitation
Reference
Table 5; must be within 2 seconds
of each pair ions
Sample matrix may have caused
RTs to shift. Check SICP for
interferences. If there are
interferences, the RTs of the pair
ions and labeled analogs will also
shift. May cause false positives.
Use professional judgment.
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Samples Associated with the CCV:
Print Name & Signature Data Reviewer/Validator Date
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Seattle WA 98101
EPA-910-R-14-003
May 2014
Page 53 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 6- ON-GOING PRECISION AND RECOVERY (OPR)
OPR Check (Per Bath of Samples Extracted & Analyzed)
Instrument:
Date of Extraction:
Date and Time of Analysis
Operator:
System Performance Check
IPR/IDOC
Initial calibration
Continuing Calibration
Frequency of Analysis-OPR
Recoveries
Criteria
See Worksheet 1
See Worksheet 3
See Worksheet 4
See Worksheet 5
One per sample batch or one
per 20 samples
Table 6 of Validation SOP
Action- Associated Samples
Method 1613B only/ sometime
LCS analyzed instead of OPR
Use professional judgment for
qualifying associated data by
considering CCV results and
other QC runs (LCS)
Validation Qualifiers
Samples Associated with the OPR:
Print Name & Signature Data Reviewer/Validator
Date
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EPA-910-R-14-003
May 2014
Page 54 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 7 - BLANKS ANALYSIS
Instrument:
Date of Extraction:
Date and Time of Analysis
Operator:
System Performance Check
IPR/IDOC
Initial calibration
Continuing Calibration
OPR
Frequency of Analysis- MB
Contamination
Criteria
See Worksheet 1
See Worksheet 3
See Worksheet 4
See Worksheet 5
See Worksheet 6
One blank reference matrix per
sample batch/ one per 20
samples
5xMB
>5x RL OCDD/OCDF
Check cause of EMPCs in MB and
in associated samples (could be m/z
or CDPE)
IfCDPE
If m/z failed, check for correction
Validation Qualifiers
Detects
U
U
No flag
No flag
U
Corrected J
Uncorrected- U
Non-detects
U
U
U
U
U
UJ
UJ
List of Associated Samples:
Print Name & Signature Data Reviewer/Validator
Date
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EPA-910-R-14-003
May 2014
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PCDD/PCDF DATA VALIDATION WORKSHEET 8 - PE SAMPLE/REFERENCE MATERIAL ANALYSIS
Instrument:
Date of Extraction:
Date and Time of Analysis
Operator:
System Performance Check
IPR/IDOC
Initial calibration
Continuing Calibration
OPR
Blanks
Frequency of Analysis
Criteria
See Worksheet 1
See Worksheet 3
See Worksheet 4
See Worksheet 5
See Worksheet 6
See Worksheet 7
Regional/Program-Specific
Action- Associated Samples
See Appendix A- SRM
Guidance - Acceptance limits
only Advisory for data users
use only; do not flag associated
sample results
Validation Qualifiers
See Appendix A- SRM
Guidance - Acceptance limits
only Advisory for data users
use only; do not flag associated
sample results
List of Associated Samples:
Print Name & Signature Data Reviewer/Validator
Date
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May 2014
Page 56 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 9 - LABORATORY CONTROL SAMPLE (LCS) ANALYSIS
Instrument:
Date of Extraction:
Date and Time of Analysis
Operator:
System Performance Check
IPR/IDOC
Initial calibration
Continuing Calibration
OPR
Method Blanks
PE/SRM Analysis
Frequency of Analysis -LCS
Criteria
See Worksheet 1
See Worksheet 3
See Worksheet 4
See Worksheet 5
See Worksheet 6
See Worksheet 7
See Worksheet 8
One LCS per sample batch/ one
per 20 samples
Action- Associated Samples
QAPP or Lab specific control
limits
Within QC limits
10%
<10%
>Upper limit
Validation Qualifiers
Detects
Non-Detects
No flag
J
J
J
UJ
R
None
List of Associated Samples:
Print Name & Signature Data Reviewer/Validator
Date
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May 2014
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PCDD/PCDF DATA VALIDATION WORKSHEET 10A - LABELED STANDARD RECOVERIES
Instrument:
Operator:
CCV Date and Time of Analysis
15 Labeled Standard Analog
Clean-up standard
Criteria Method 1613B
Table 7 of validation SOP
Table 7 of validation SOP
Action- Associated
Samples
Upper Limit
>200% or 400% for
i3Ci2-OCDD
Upper Limit
<10%
Validation Qualifiers
Detects *
J (biased high)
J (artificially high)
J (biased low)
J (extremely biased low)
J (biased low)
J (biased high )
J Extremely low biased
Non-Detects
None
UJ
UJ
R (potential
false negative)
UJ
None
R (potential
false negative)
*See Narrative - Validation SOP
List Affected Samples
Print Name & Signature Data Reviewer/Validator
Date
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PCDD/PCDF DATA VALIDATION WORKSHEET 10B - LABELED STANDARD RECOVERIES
Instrument:
Operator:
CCV Date and Time of Analysis
15 All Labeled Internal
Standards Including Clean-up
standard
Criteria Method 8290A
40 - 135%
Action- Associated
Samples
Upper Limit
>200%
Validation Qualifiers
Detects
J (biased high)
J (artificially high)
J (biased low)
J (extremely biased low)
Non-Detects
None
UJ
UJ
R (potential false
negative)
List Affected Samples
Print Name & Signature Data Reviewer/Validator
Date
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EPA-910-R-14-003
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Page 59 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 11 - COMPOUND IDENTIFICATION
Sample Number:
Instrument:
Date of Extraction:
Date and Time of Analysis
Operator:
Compound Identification
(Individual CDD/CDF)
Total Homologues
Criteria
Signal to Noise Ratio
(S/N>2.5)
Mass-ion Abundance Ratio
Retention time
Peak ID - simultaneous peaks-
partner m/z
CDPE co-elution
Peaks must meet all criteria for
CDD/CDF identification
including m/z abundance ratio
Action- Associated Samples
Yes
No
Yes
No
Yes
No
Yes
No
Check SICP per descriptor &
compare with the non-2, 3, 7,
8-peak summary list. If
S/N>2.5 but m/z not met.
Check CDPE channel. Make
sure the peak does not co-elute
with a CDPE.
Re-calculate the total
homologue concentration
removing the peaks that were
flagged "U".
Validation Qualifiers
Detected
No
Detected
EMPCs
See worksheet
5 on EMPCs
Detected
-
J/U
Detect
Flag U. Then
No
Confirmed
ND
No
U
-
Non-detect
UJ
U
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
United States Environmental Protection Agency May 2014
Seattle WA 98101 Page 60 of 88
See Narrative for more details
Summary of detected results per sample:
Summary of non-2, 3, 7, 8- peaks not meeting compound identification and were flagged "U" in the Totals.
Print Name & Signature Data Reviewer/Validator Date
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EPA-910-R-14-003
May 2014
Page 61 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 12 - COMPOUND QUANTITATION
Sample Number:
Instrument:
Date of Extraction:
Date and Time of Analysis
Operator:
Check the calculation of detected results; 10% EDLS; 10%; 10% EMPCs of RLs using the equations provided in Appendix C.
List CDD/CDFs not meeting the project specific RL/EDL requirements/goals (refer to QAPP)
EDLs
Not properly calculated
Contact lab for resubmission
Qualificatioi
EMPCs
Incorrect calculation
EMPC>EDL RL
Contact lab for resubmission
Check Chromatogram for
interferences
UJ- elevated at level of
detection
1. Check Chromatogram for
interferences
Request the lab for additional
extract clean-up to remove
interferences through PM/WAM
Still not corrected, flag data J
Estimated value- "J"
Print Name & Signature Data Reviewer/Validator
Date
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
United States Environmental Protection Agency May 2014
Seattle WA 98101 Page 62 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 13 -TEQ Calculation
Sample Number:
Instrument:
Date of Extraction:
Date and Time of Analysis Operator:
Calculate TEQs using the 2005 or most recent WHO Human and Mammalian Toxic Equivalency Factors (TEF) for Dioxin and
Dioxin-like Compounds. Calculate using 3 scenarios (1) ND=0; (2) ND=l/2 and (3) ND=1. If the project goals require the use of
EDLs, use the EDLs in the calculations. If there are EMPCs reported, the EMPC values are used for the TEQ calculation for the
particular CDD/CDF. Totals are not used in the CDD/CDF TEQ calculations. If the concentrations used in the calculation are flagged
estimated (even 1 PCDD/PCDF), the TEQ is also flagged estimated. The TEQ unit is the same as the unit reported by the lab for the
CDD/CDF (ng/L or ng/Kg).
If TEQs are already calculated by the lab using ND-0; ND-1/2 and ND=1, check the calculations. Also, if any of the 2, 3, 7, 8-
CDD/CDF was flagged "U" during data validation, recalculate the TEQ and remove the flagged CDD/CDF in the TEQ calculation.
See Summary table below.
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May 2014
Page 63 of 88
Sample Number:
Instrument:
Date of Extraction:
Date and Time of Analysis
Chlorinated dibenzo-p-dioxins
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
Chlorinated Dibenzofurans
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8- PeCDF
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-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Totals
Reported
Results
2005 WHO TEF
1
1
0.1
0.1
0.1
0.01
0.0003
0.1
0.03
0.3
0.1
0.1
0.1
0.1
0.01
0.01
0.0003
ND=0
Qualifier
ND=l/2
Qualifier
ND= 1
Qualifier
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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
May 2014
Page 64 of 88
PCDD/PCDF DATA VALIDATION WORKSHEET 14 - OVERALL ASSESSMENT
Total Number of Data Points:
Holding Time/Preservation
Sample Integrity
Sample Prep
Sample Clean-up
System Performance
IPR/IDOC
Initial Calibration
Continuing Calibration
OPR
Blanks
PE Sample/ SRM
Laboratory Control Sample
Labeled Standard Recovery
Compound Identification
Compound Quantitation
TEQ
Total percentage
Percent Completion
Number of Data
Points - Estimated
Number of Data
Points Rej ected
Print Name & Signature Data Reviewer/Validator
Date
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
United States Environmental Protection Agency May 2014
Seattle WA 98101 Page 65 of 88
APPENDIX B- PUGET SOUND SEDIMENT REFERENCE MATERIAL: REQUESTING,
ANALYZING, VALIDATING AND REPORTING DATA PROCEDURE
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
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The Puget Sound Sediment Reference Material (SRM) has been developed to help assess/evaluate measurement accuracy and
monitor laboratory performance when analyzing for chlorinated dioxin, furans, and biphenyl compounds in sediment samples
collected from the Puget Sound area. The SRM is currently available free of charge, though recipients must pay shipping costs.
This document provides instructions for obtaining, analyzing, and reporting on the SRM. The guidance and procedures are
intended to ensure that SRM users:
Report methods used for analysis
Report QA/QC procedures used to verify and validate results, and
Report results that can be included in periodic recalculations of acceptance limits
The Puget Sound SRM has been established for chlorinated dibenzo-p-dioxins / chlorinated dibenzofurans (CDD/CDF) and/or
chlorinated biphenyl (CB) congener analysis using high resolution gas chromatography / high resolution mass spectrometry
(HRGC/HRMS) methods. This SRM is also suitable for Aroclor analysis using gas chromatography/electron capture detection
(GC/ECD) methods.
REQUEST PROCEDURE
The Seattle District Corps of Engineers, Washington Department of Ecology, and US EPA Region 10 have assigned staff to distribute
the Puget Sound SRM in support of agency missions, including regulatory programs. The request procedure is as follows:
Obtain the electronic Puget Sound SRM Request Form from the appropriate agency involved with the project (see agency
contact list below), or from the DMMO website.
Return completed form to agency contact.
Agency contact reviews and certifies/signs the bottom of the form as an "authorized agency requester", and then forwards
the signed form to the EPA Region 10 SRM Manager (Donald Brown) for processing.
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
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Request is processed, typically within a week.
Examples of how the request process works:
1. CWA 404 permit applicants would request from and submit the completed form to the Corps of Engineers DMMO contact.
2. A CERCLA PRP would submit the request form via EPA.
3. The State of Washington's ambient monitoring program would submit the form via Ecology.
The authorized agency contacts are available to help with any questions about the Request Form. Submission of incomplete forms
may delay the request processing.
AUTHORIZED AGENCY CONTACTS:
Seattle District Corps of Engineers - Dredged Material Management Office (DMMO):
David Fox (206) 764-6083, david.f.fox@usace.army.mil
Lauran Warner (206) 764-6550, lauran.c.warner@usace.army.mil
Kelsey van der Elst (206) 764-6945, kelsey.vanderelst@usace.army.mil
Washington Department of Ecology:
Laura Inouye (306) 407-6165, Iino461 @ecy.wa.gov
Tom Gries (360) 407-6327, tgri461@ecv.wa.gov
US Environmental Protection Agency Region 10:
Justine Barton (206) 553-6051, barton.iustine@epa.gov
Erika Hoffman (360) 753-9540, hoffman.erika@epa.gov
Donald Brown (206) 553-0717, brown.donaldm@epa.gov
SHIPPING
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
United States Environmental Protection Agency May 2014
Seattle WA 98101 Page 68 of 88
The Puget Sound SRM is stored at EPA's national Quality Assurance Technical Services (QATS) contractor located in Las Vegas,
Nevada. Lab contacts listed on the Request Form should be prepared to confirm shipping details (including UPS or FedEx account
number) if contacted by the EPA QATS contractor. The QATS contractor will generally ship the SRM within 24 hours of
receiving the completed Request Form from the EPA Region 10 SRM Manager. The SRM will arrive with specific instructions on
handling and storage requirements, data reporting requirements, as well as chain of custody paperwork.
When the SRM has been shipped, the EPA QATS contractor will provide a notification email to the EPA Region 10 SRM
Manager, the authorized agency contact (as indicated on the Request Form), and the destination laboratory. The email will include
the project name as indicated on the Request Form.
SRM Storage Requirements
Each amber glass bottle contains approximately 30 grams of the Puget Sound SRM.
The SRM contains compounds that are light sensitive and should be protected from light during storage. Store the SRM at 4°C ą
2°C until SRM preparation and analysis.
SRM Analysis Requirements
The SRM is to be analyzed as described in the appropriate methods employed for the analysis of CDD/CDF and/or CB congener
analytes using HRGC/HRMS instrumentation and/or Aroclors using GC/ECD instrumentation.
The following analytical methods may be used in the analysis of the SRM:
SW-846 Method 8082A (or current revision), "Polychlorinated Biphenyls (PCBs) by Gas Chromatography"
SW-846 Method 8290A (or current revision), " Polychlorinated Dibenzo-^-Dioxins (PCDDs) and Polychlorinated
Dibenzofurans (PCDFs) by High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry (HRGC/HRMS)"
Method 1613B (or current revision), "Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope Dilution
HRGC/HRMS"
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
United States Environmental Protection Agency May 2014
Seattle WA 98101 Page 69 of 88
Method 1668C (or current revision), "Chlorinated Biphenyl Congeners in Water, Soil, Sediment, Biosolids, and Tissue by
HRGC/HRMS"
Data Verification/Validation
SRM users may be held to different data validation requirements, depending on their program and project circumstances. Data
must be validated to EPA Stage 2B but it is strongly recommended that Stage 3 or better validation be conducted. For example, the
interagency Dredged Material Management Program (DMMP) strongly recommends third-party Stage 4 validation for all TCDD/F
data. Any validation narrative must indicate the validation stage used. Data validation stages are described in EPA-540-R-08-005
(see References).
Data Reporting
Individual laboratories typically provide all project data and validation reports to their clients. The client/project proponent is
responsible for ensuring that all information relative to the SRM, including associated QA data, is sent to the original agency
requester. For DMMP projects, submittal of the complete validated data package to the DMMO contact fulfills this requirement.
For SRM data meeting established QA requirements, the agency contact will submit the validated electronic data deliverable/data
summary sheets (or the equivalent) and validation reports relevant to the SRM to the EPA Region 10 SRM Manager. Changes
made by the data validator (e.g. modification of data qualifiers) must be clearly indicated on the data sheets. SRM data not
meeting established QA requirements will not be forwarded to EPA's QATS contractor; however, the QATS contractor will be
notified of the QA failure for their records.
The following are the minimum required deliverables for Puget Sound SRM data submissions. Also included below are optional
deliverables that may or may not be needed depending on the available deliverables.
REQUIRED DELIVERABLES
1. Data Validation Report - report that documents the analytical quality of the data. In regards to the Puget Sound SRM, this
report serves two functions. First, it confirms that data validation was completed, as the guidance requires data validation to at
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
United States Environmental Protection Agency May 2014
Seattle WA 98101 Page 70 of 88
least EPA Stage IIB. Second, the report documents the reasons for any failure to meet method, procedural, or contractual
requirements, as well as provides an evaluation of the impact of such failure on the overall data set.
2. Electronic Data Deliverable (EDD) - an electronic, tabular format for sharing, manipulating, and using data. EDDs should
be submitted in a comma- or tab-delimited file or as a Microsoft Excel spreadsheet. If in doubt about what to request from the
lab, ask for an EDD in EIM format.
3. SRM Sample Data Summary Report - similar to a Form 1 from the Contract Laboratory Program, this report should provide
a summary of the analytical parameters, analytical results, reporting limits, and laboratory/validation qualifiers. At a
minimum, the sample data summary report should include the following:
Identification and quantitation of target analytes including dilution and reanalysis
CAS numbers
Laboratory name
Project number
Project name
Sample ID number (SRM bottle bar code)
Agency sample number (if applicable)
Laboratory sample number
Date SRM received by the lab
Date and time of analysis
For Aroclor data, laboratory reporting limits and method detection limits
For Chlorinated Biphenyl Congener and Dioxin/Furan data, reporting limits and estimated detection limits
Laboratory qualifiers and definitions
Validation qualifiers
OPTIONAL DELIVERABLES
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Region 10 Office of Environmental Assessment EPA-910-R-14-003
United States Environmental Protection Agency May 2014
Seattle WA 98101 Page 71 of 88
1. Laboratory Case Narrative - laboratory report that describes the analytical process used by the lab to analyze the samples
and any problems encountered in processing the samples, along with corrective action taken and problem resolution. The
case narrative should only be submitted with the SRM data if there were significant problems during sample analysis that
affected the SRM or if there are other observations relevant to the SRM.
2. Raw Data - laboratory worksheets, records, notes, or instrument printouts that are the result of original observations and
activities. The chromatograms and integration reports associated with the SRM should be submitted with the SRM Sample
Data Summary Report, if possible.
3. Data Package - the entire laboratory package including all narratives, sample summary reports, QC reports, calibrations, and
raw data. The full data package should only be submitted if there were significant QC failures that affect the SRM result or if
the data did not go through the data validation process.
Storage and use of previously opened SRM is not recommended. However, it is requested that any additional data results derived
from use of the SRM be submitted to the EPA Region 10 SRM Manager.
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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
May 2014
Page 72 of 88
Performance / Acceptance Limits
The acceptance limits presented below are guidance values based on the original laboratory
round-robin associated with the development of the SRM. The implications associated with
not meeting these acceptance limits will be determined by data reviewers on a case-by-case
basis, based on the goals of their program/project. For now, the DMMP will review results on
a case-by-case basis and will consider the values advisory.
PCS Aroclors: A twelve-lab round-robin testing of the SRM (including commercial and
CLP labs) was used to calculate an acceptance limit for Aroclor 1260. The average Aroclor
1260 concentration found during the round robin was 108 ug/kg. The acceptance limit is set
at the 95% confidence interval.
Aroclor 1260:
Warning low: 41 ug/kg
Warning high: 180 ug/kg
CDD/CDF: A ten-lab round-robin testing of the SRM (including commercial and CLP labs)
was used to calculate an acceptance limit of ą50% action low and action high for each
congener as follows:
Acceptance
Limits Source
ą 50 Percent
Analyte
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6, 7, 8-HxCDD
1,2,3,7,8,9-HxCDD
1, 2,3,4,6, 7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6, 7, 8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4, 7, 8,9-HpCDF
OCDF
CAS No.
1746-01-6
40321-76-4
39227-28-6
67653-85-7
19408-74-3
35822-46-9
3268-87-9
51207-31-9
57117-41-6
57117-31-4
70648-26-9
57117-44-9
60851-34-5
72918-21-9
67562-39-4
55673-89-7
39001-02-0
Avg. Cone.
(ng/kg)
1.05
1.08
1.59
3.88
3.04
90.6
811
1.11
1.23
1.07
3.02
1.09
1.83
0.511
18.7
1.63
58.4
Action Low
-50%
0.525
0.542
0.797
1.94
1.52
45.3
406
0.557
0.613
0.533
1.51
0.545
0.917
0.255
9.36
0.815
29.2
Action High
+50%
1.57
1.63
2.39
5.82
4.55
136
1217
1.67
1.84
1.60
4.53
1.64
2.75
0.77
28.1
2.44
87.6
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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
May 2014
Page 73 of 88
CB Congeners: A ten-lab round-robin testing of the SRM (including commercial and CLP
labs) was used to calculate an acceptance limit of ą50% action low and action high for each
congener as follows:
Individually eluting congeners table
Congener #
1
3
4
6
7
8
9
11
15
16
17
19
22
25
27
31
32
35
37
42
46
48
52
56
60
63
64
66
67
68
72
77
82
84
92
94
96
103
Target Analyte
2-Chlorobiphenyl
4-Chlorobiphenyl
2,2'-Dichlorobiphenyl
2,3'-Dichlorobiphenyl
2,4-Dichlorobiphenyl
2,4'-Dichlorobiphenyl
2,5-Dichlorobiphenyl
3,3'-Dichlorobiphenyl
4,4'-Dichlorobiphenyl
2,2',3-Trichlorobiphenyl
2,2',4-Trichlorobiphenyl
2,2',6-Trichlorobiphenyl
2,3,4'-Trichlorobiphenyl
2,3',4-Trichlorobiphenyl
2,3',6-Trichlorobiphenyl
2,4',5-Trichlorobiphenyl
2,4',6-Trichlorobiphenyl
3,3',4-Trichlorobiphenyl
3,4,4'-Trichlorobiphenyl
2,2',3,4'-Tetrachlorobiphenyl
2,2',3,6'-Tetrachlorobiphenyl
2,2',4,5-Tetrachlorobiphenyl
2,2',5,5'-Tetrachlorobiphenyl
2,3,3',4'-Tetrachlorobiphenyl
2,3,4,4'-Tetrachlorobiphenyl
2,3,4',5-Tetrachlorobiphenyl
2,3,4',6-Tetrachlorobiphenyl
2,3',4,4'-Tetrachlorobiphenyl
2,3',4,5-Tetrachlorobiphenyl
2,3',4,5'-Tetrachlorobiphenyl
2,3',5,5'-Tetrachlorobiphenyl
3,3',4,4'-Tetrachlorobiphenyl
2,2',3,3',4-Pentachlorobiphenyl
2,2',3,3',6-Pentachlorobiphenyl
2,2',3,5,5'-Pentachlorobiphenyl
2,2',3,5,6'-Pentachlorobiphenyl
2,2',3,6,6'-Pentachlorobiphenyl
2,2',4,5',6-Pentachlorobiphenyl
Cl Level*
1
1
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
Avg
SD
Acceptance Low
(-50%)
Acceptance High
(+150%)
ng/kg dry weight
23
25
114
169
17
366
20
74
308
212
363
68
385
245
81
1132
237
26
355
413
75
246
3743
651
253
59
659
1654
56
22
37
135
486
1327
1180
20
29
57
2.6
8.4
16.5
30.4
3.3
65.5
4.0
10.5
36.5
21.3
31.7
9.7
47.8
34.8
6.5
113.8
30.9
4.3
44.7
55.9
11.8
44.4
447.6
139.8
124.4
11.4
81.3
301.0
10.2
4.9
7.5
19.3
33.3
31.5
72.1
1.6
2.0
3.5
12
13
57
85
8
183
10
37
154
106
182
34
192
122
40
566
118
13
178
206
37
123
1871
326
126
30
329
827
28
11
19
68
243
664
590
10
14
28
35
38
171
254
25
548
29
110
462
318
545
102
577
367
121
1697
355
39
533
619
112
369
5614
977
379
89
988
2481
84
34
56
203
729
1991
1770
30
43
85
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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
May 2014
Page 74 of 88
Individually eluting congeners table, continued
Congener
#
114
118
120
122
123
130
131
132
133
136
137
141
144
146
158
159
164
167
170
172
174
175
176
177
178
179
187
189
190
191
194
195
196
201
202
203
205
206
207
208
209
Target Analyte
2,3,4,4',5-Pentachlorobiphenyl
2,3',4,4',5-Pentachlorobiphenyl
2,3',4,5,5'-Pentachlorobiphenyl
2,3,3',4',5'-Pentachlorobiphenyl
2,3',4,4',5'-Pentachlorobiphenyl
2,2',3,3',4,5'-Hexachlorobiphenyl
2,2',3,3',4,6-Hexachlorobiphenyl
2,2',3,3',4,6'-Hexachlorobiphenyl
2,2',3,3',5,5'-Hexachlorobiphenyl
2,2',3,3',6,6'-Hexachlorobiphenyl
2,2',3,4,4',5-Hexachlorobiphenyl
2,2',3,4,5,5'-Hexachlorobiphenyl
2,2',3,4,5',6-Hexachlorobiphenyl
2,2',3,4',5,5'-Hexachlorobiphenyl
2,3,3',4,4',6-Hexachlorobiphenyl
2,3,3',4,5,5'-Hexachlorobiphenyl
2,3,3',4',5',6-Hexachlorobiphenyl
2,3',4,4',5,5'-Hexachlorobiphenyl
2,2',3,3',4,4',5-Heptachlorobiphenyl
2,2',3,3',4,5,5'-Heptachlorobiphenyl
2,2',3,3',4,5,6'-Heptachlorobiphenyl
2,2',3,3',4,5',6-Heptachlorobiphenyl
2,2',3,3',4,6,6'-Heptachlorobiphenyl
2,2',3,3',4,5',6'-Heptachlorobiphenyl
2,2',3,3',5,5',6-Heptachlorobiphenyl
2,2',3,3',5,6,6'-Heptachlorobiphenyl
2,2',3,4',5,5',6-Heptachlorobiphenyl
2,3,3',4,4',5,5'-Heptachlorobiphenyl
2,3,3',4,4',5,6-Heptachlorobiphenyl
2,3,3',4,4',5',6-Heptachlorobiphenyl
2,2',3,3',4,4',5,5'-Octachlorobiphenyl
2,2',3,3',4,4',5,6-Octachlorobiphenyl
2,2',3,3',4,4',5,6'-Octachlorobiphenyl
2,2',3,3',4,5',6,6'-Octachlorobiphenyl
2,2',3,3',5,5',6,6'-Octachlorobiphenyl
2,2',3,4,4',5,5',6-Octachlorobiphenyl
2,3,3',4,4',5,5',6-Octachlorobiphenyl
2,2',3,3',4,4',5,5',6-
Nonachlorobiphenyl
2,2', 3,3',4,4', 5,6,6'-
Nonachlorobiphenyl
2,2',3,3',4,5,5',6,6'-
Nonachlorobiphenyl
Decachlorobiphenyl
Cl Level*
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
9
9
9
10
Avg
SD
Congener #
Target Analyte
ng/kg dry weight
68
4021
19
44
54
591
116
4569
179
2141
223
3657
862
2029
1257
239
1068
367
5251
903
6604
249
806
3630
1237
2719
7316
185
1077
217
2624
1169
1579
373
487
1829
143
575
91
124
97
8.2
764.9
2.3
10.0
6.1
50.9
14.0
582.7
15.8
280.2
29.6
395.7
57.7
303.2
132.4
81.5
118.1
14.4
715.7
206.0
1100.6
29.0
95.6
471.6
194.2
293.5
1289.5
11.1
200.7
40.6
391.8
163.2
183.8
65.6
51.9
354.3
9.2
39.2
18.6
7.5
4.4
34
2011
9
22
27
296
58
2284
90
1071
112
1829
431
1014
628
119
534
184
2626
452
3302
125
403
1815
619
1359
3658
93
539
108
1312
585
789
187
243
914
71
288
46
62
48
102
6032
28
66
81
887
174
6853
269
3212
335
5486
1293
3043
1885
358
1602
551
7877
1355
9906
374
1209
5445
1856
4078
10974
278
1616
325
3936
1754
2368
560
730
2743
214
863
137
186
145
number of chlorine substituents
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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
May 2014
Page 75 of 88
Co-eluting congeners table
Congener
#
12
13
18
30
20
28
21
23
26
29
40
41
71
44
47
65
45
51
49
69
50
53
59
62
75
61
70
74
76
83
99
85
116
117
86
87
97
108
119
125
88
91
Co-eluting Pairs
3,4-Dichlorobiphenyl
3,4'-Dichlorobiphenyl
2,2',5-Trichlorobiphenyl
2,4,6-Trichlorobiphenyl
2,3,3'-Trichlorobiphenyl
2,4,4'-Trichlorobiphenyl
2,3,4-Trichlorobiphenyl
2,3,5-Trichlorobiphenyl
2,3',5-Trichlorobiphenyl
2,4,5-Trichlorobiphenyl
2,2',3,3'-Tetrachlorobiphenyl
2,2',3,4-Tetrachlorobiphenyl
2,3',4',6-Tetrachlorobiphenyl
2,2',3,5'-Tetrachlorobiphenyl
2,2',4,4'-Tetrachlorobiphenyl
2,3,5,6-Tetrachlorobiphenyl
2,2',3,6-Tetrachlorobiphenyl
2,2',4,6'-Tetrachlorobiphenyl
2,2',4,5'-Tetrachlorobiphenyl
2,3',4,6-Tetrachlorobiphenyl
2,2',4,6-Tetrachlorobiphenyl
2,2',5,6'-Tetrachlorobiphenyl
2,3,3', 6-Tetrachlorobiphenyl
2,3,4,6-Tetrachlorobiphenyl
2, 4,4', 6-Tetrachlorobiphenyl
2,3,4,5-Tetrachlorobiphenyl
2,3',4',5-Tetrachlorobiphenyl
2,4,4',5-Tetrachlorobiphenyl
2,3',4',5'-Tetrachlorobiphenyl
2,2',3,3',5-Pentachlorobiphenyl
2,2',4,4',5-Pentachlorobiphenyl
2,2',3,4,4'-Pentachlorobiphenyl
2,3,4,5,6-Pentachlorobiphenyl
2,3,4', 5,6-Pentachlorobiphenyl
2,2',3,4,5-Pentachlorobiphenyl
2,2',3,4,5'-Pentachlorobiphenyl
2,2',3,4',5'-Pentachlorobiphenyl
2,3,3', 4,5'-Pentachlorobiphenyl
2,3',4,4',6-Pentachlorobiphenyl
2,3',4',5',6-Pentachlorobiphenyl
2,2',3,4,6-Pentachlorobiphenyl
2,2',3,4',6-Pentachlorobiphenyl
Cl
Level*
2
2
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
Avg
70
615
1436
545
506
717
2026
224
1550
242
142
3251
2548
737
3337
674
SD
r
9.3
78.3
149.8
49.8
47.9
125.8
194.2
37.0
185.4
35.5
22.5
513.3
373.6
29.5
142.6
49.9
Acceptance
Low (-50%)
g/kg dry weight
35
307
718
273
253
359
1013
112
775
121
71
1626
1274
368
1668
337
Acceptance
High
(+150%)
105
922
2154
818
759
1076
3039
336
2325
363
213
4877
3821
1105
5005
1011
Co-eluting Sets
12/13
18/30
20/28
21/23
26/29
40/41/71
44/47/65
45/51
49/69
50/53
59/62/75
61/70/74/76
83/99
85/116/117
86/87/97/108/119/125
88/91
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Region 10 Office of Environmental Assessment
United States Environmental Protection Agency
Seattle WA 98101
EPA-910-R-14-003
May 2014
Page 76 of 88
Co-eluting congeners table, continued
Congener
#
90
101
113
93
95
98
100
102
107
124
110
115
128
166
129
138
160
163
134
143
135
151
154
139
140
147
149
153
168
156
157
171
173
180
193
183
185
197
200
198
199
Co-eluting Pairs
2,2',3,4',5-Pentachlorobiphenyl
2,2',4,5,5'-Pentachlorobiphenyl
2,3,3',5',6-Pentachlorobiphenyl
2,2',3,5,6-Pentachlorobiphenyl
2,2',3,5',6-Pentachlorobiphenyl
2,2',3,4',6'-Pentachlorobiphenyl
2,2',4,4',6-Pentachlorobiphenyl
2,2',4,5,6'-Pentachlorobiphenyl
2,3,3',4',5-Pentachlorobiphenyl
2,3',4',5,5'-Pentachlorobiphenyl
2,3,3',4',6-Pentachlorobiphenyl
2,3,4,4', 6-Pentachlorobiphenyl
2,2',3,3',4,4'-Hexachlorobiphenyl
2,3,4,4', 5,6-Hexachlorobiphenyl
2,2',3,3',4,5-Hexachlorobiphenyl
2,2',3,4,4',5'-Hexachlorobiphenyl
2,3,3', 4,5,6-Hexachlorobiphenyl
2,3,3', 4, 5,6-Hexachlorobiphenyl
2,2', 3,3', 5,6-Hexachlorobiphenyl
2,2',3,4,5,6'-Hexachlorobiphenyl
2,2',3,3',5,6'-Hexachlorobiphenyl
2,2',3,5,5',6-Hexachlorobiphenyl
2,2',4,4',5,6'-Hexachlorobiphenyl
2,2',3,4,4',6-Hexachlorobiphenyl
2,2',3,4,4',6'-Hexachlorobiphenyl
2,2', 3,4, 5,6-Hexachlorobiphenyl
2,2',3,4',5',6-Hexachlorobiphenyl
2,2',4,4',5,5'-Hexachlorobiphenyl
2,3',4,4',5',6-Hexachlorobiphenyl
2,3,3',4,4',5-Hexachlorobiphenyl
2,3,3',4,4',5'-Hexachlorobiphenyl
2,2',3,3',4,4',6-Heptachlorobiphenyl
2,2',3,3',4,5,6-Heptachlorobiphenyl
2,2',3,4,4',5,5'-Heptachlorobiphenyl
2,3,3',4',5,5',6-Heptachlorobiphenyl
2,2',3,4,4',5',6-Heptachlorobiphenyl
2,2', 3,4,5,5', 6-Heptachlorobiphenyl
2,2',3,3',4,4',6,6'-Octachlorobiphenyl
2,2',3,3',4,5,6,6'-Octachlorobiphenyl
2,2', 3,3', 4,5,5', 6-Octachlorobiphenyl
2,2',3,3',4,5,5',6'-Octachlorobiphenyl
Cl
Level*
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
8
8
8
8
Avg
SD
Acceptance
Low (-50%)
Acceptance
High
(+150%)
ng/kg dry weight
6957
5608
249
6488
1354
14189
657
6326
115
14314
13913
891
1794
12396
4184
496
3260
787.6
516.7
105.2
384.7
167.1
1183.2
45.0
374.1
18.7
1582.6
1343.2
52.1
202.8
1530.7
665.7
106.0
626.4
3478
2804
124
3244
677
7094
329
3163
58
7157
6956
446
897
6198
2092
248
1630
10435
8412
373
9733
2031
21283
986
9488
173
21471
20869
1337
2691
18594
6277
744
4890
Co-eluting Sets
90/101/113
93/95/98/100/102
107/124
110/115
128/166
129/138/160/163
134/143
135/151/154
139/140
147/149
153/168
156/157
171/173
180/193
183/185
197/200
198/199
* number of chlorine substituents
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Page 77 of 88
Recalculation of Acceptance Limits
The national EPA QATS contractor will store the SRM, conduct stability testing, and
maintain the SRM database used to recalculate acceptance limits. Timing for any acceptance
limit recalculations will depend on the quantity of high quality data received. It is anticipated
that the next recalculation will occur after 30 new data points have been received.
References
Revised Supplemental Information on Polychlorinated Dioxins and Furans (PCDD/F) for
Use in Preparing a Quality Assurance Project Plan (QAPP), dated November 8, 2010.
Guidance for Labeling Externally Validated Laboratory Analytical Data for Superfund Use,
dated January 13, 2009 (EPA-540-R-08-005).
Attachments
SRM Request Form (this form may be requested and returned in an electronic-fillable form
from/to agency contacts listed above). This form is also available on the Seattle District
DMMO website.
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APPENDIX C - RULES, CALCULATIONS AND EQUATIONS
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Appendix C - Rules, Calculations and Equations
1. In a series of calculations, carry the extra digits through to the final result, then round off.
2. If the digit to be removed is less than 5, the preceding digit stays the same. If the digit to be
removed is equal to or greater than 5, the preceding digit is increased by 1.
Equation 1: Chromatographic Peak Separation
%Valley = - x 100
y
x = Measurement from the baseline to the deepest part of the valley between 2, 3, 7, 8-TCDD
and 1, 2, 3, 8-TCDD
y = Peak height of 2, 3, 7, 8-TCDD
Equation 2: Percent Difference of the Relative Response
Responsever Responseint
%D = - - - - - - x 100
Responseint
Responsever = Response (RR or RRF) observed during calibration verification
Responseint = Mean response (RR or RRF) established during initial calibration according to
DLM02.2
Equation 3: Relative Percent Difference
\R1-R2\
RPD x 100
^(Rl,R2)
Rl = Result 1
R2 = Result 2
Equation 4: Internal Standard Percent Recovery
c -y- c
%R = - iĢ -Ģ!Ģ - x 100
Qis x Ars x RFn
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Ais = Sum of the integrated ion abundances of the quantitation ions (Table 6 of method) for the
labeled internal standard
Ars = Sum of the integrated ion abundances of the quantitation ions (Table 6 of method) for the
labeled recovery standard
Qis = Quantity, in pg, of the internal standard added to the sample before extraction
Qrs = Quantity, in pg, of the recovery standard added to the cleaned-up sample residue before
HRGC/HRMS analysis
RFm = Calculated mean relative response factor for the labeled internal standard relative to the
appropriate recovery standard.
Equation 5: Relative Response for Isotope Dilution Calibration (Method 1613B)
(Aln+A2n)C1
RR =
(All+A2l)C2
Aln = Area of the primary m/z for the PCDD/PCDF
A2n = Area of the secondary m/z for the PCDD/PCDF
All = Area of the primary m/z for the labeled compound
A2i = Area of the secondary m/z for the labeled compound
Ci = Concentration of the labeled compound in the calibration standard
C2 = Concentration of the native compound in the calibration standard
Equation 6: Concentration of unlabeled PCDD/PCDF congeners (SW 846)
A v D-
_ ns -\ yls
x ~ Ais X W X REn
Cx = concentration of unlabeled PCDD/PCDF congeners (or group of co-eluting isomers
within an homologous series) in pg/g
Ax = sum of the integrated ion abundances of the quantitation ions (Table 6 of method) for
unlabeled PCDDs/PCDFs
Ais = sum of the integrated ion abundances of the quantitation ions (Table 6 of method) for the
labeled internal standards
Qis = quantity, in pg, of the internal standard added to the sample before extraction
W = weight, in g, of the sample (solid or organic liquid), or volume in mL of an aqueous
sample
RFm = calculated mean relative response factor for the analyte
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Equation 7: Concentration of PCDD/PCDF in extract (Method 1613B)
Cex (All+A2l}RR
Cex = Concentration of the PCDD/PCDF in the extract (ng/nL)
Aln = Area of the primary m/z for the PCDD/PCDF
A2n = Area of the secondary m/z for the PCDD/PCDF
All = Area of the primary m/z for the labeled compound
A2i = Area of the secondary m/z for the labeled compound
Ci = Concentration of the labeled compound in the calibration standard
RR = Relative response
Equation 8: Compound Quantitation: All Matrices Other Than Aqueous
Solids ng/kg =
CL = Concentration of the labeled standard added to the extract (includes any
amount added during dilution procedures)
Axi = Areas of the signals for both quantitation ions of the CDD/CDF
AX2 = Areas of the signals for both quantitation ions of the CDD/CDF
An = Areas of labeled standard ions
AL2 = Areas of labeled standard ions
Vex = Effective volume of the extract
W = Sample weight
RR = Mean Relative Response for the isomer of interest from the initial calibration
Equation 9: Compound Quantitation: Aqueous
CLx(Als+A2s)Vex
Aqueous (pg/L} =
Vs x (Al-i + A2J x RR
CL = Quantity (pg) of appropriate labeled standard added to the extract (includes
any amount added during dilution procedures)
Als = Areas of the signals for both quantitation ions of the CDD/CDF
A2S = Areas of the signals for both quantitation ions of the CDD/CDF
Vex = Effective final volume of the extract
Vi = Sample volume extracted in liters
RR = Mean Relative Response for the isomer of interest from the initial calibration
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Equation 10: Compound Quantitation: Concentration of the Labeled Compound
(Al5+A2s)CI5
Cex (ng/ml} =
(A1IS + A2ls)RRF
CEX = Concentration of the labeled compound in the extract
Cis = Concentration of the internal standard
RRF = Mean Relative Response Factor determined from the initial calibration
data.
Equation 11: Compound Quantitation: Aqueous Adjusted CRQL
Adjusted CRQL = Contract CRQL x
VT = Volume of the concentrated extract (jiL)
Vo = Actual sample volume used (mL)
Vx = Contract sample volume (1000 mL)
Vc = Contract concentrated extract volume (jiL)
Equation 12: Compound Quantitation: Soil/Sediment Adjusted CRQL
Adjusted CRQL = Contract CRQL x
VT = Volume of the concentrated extract (jiL)
Ws = Actual mass extracted (g)
Wx = Contract sample weight (lOg)
Vc = Contract concentrated extract volume (jiL)
Equation 13: Compound Quantitation: Extract Concentrations by Relative Response
CEX = Concentration of the native compound in the extract
CL = Concentration of the internal standard
A!N = Area of the primary m/z for the PCDD/PCDF
A2N = Area of the secondary m/z for the PCDD/PCDF
A!L= Area of the primary m/z for the labeled compound
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A2L = Areas of the secondary m/z for the labeled compound
RR = Relative response
Equation 14: Estimated Detection Limit (EDL)
ALL MATRICES OTHER THAN AQUEOUS:
c r* m, f n ^ 2.5 x QL x (Hxl + HX2) x D
Solids EDL (nq kq] = =
^ ai a) w x (HL1 + HL2) x flfl
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 =Peak heights of the noise for both quantitation ions of the CDD/CDF
HX2 =Peak heights of the noise for both quantitation ions of the CDD/CDF
HLI =Peak heights of the labeled standard ions
HL2 = Peak heights of the labeled standard ions
D =Dilution factor
W =Weight extracted in grams
RR =Mean Relative Response for the isomer of interest from the initial calibration
Aqueous:
2.5 x QL x (Hxl + HX2) x D
Aqueous EDL (pg/L) =
V X (HL1 + HL2) X RR
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 =Peak heights of the noise for both quantitation ions of the CDD/CDF
HX2 =Peak heights of the noise for both quantitation ions of the CDD/CDF
HLI =Peak heights of the labeled standard ions
HL2 = Peak heights of the labeled standard ions
D =Dilution factor
V =Volume extracted in liters
RR =Mean Relative Response for the isomer of interest from the initial calibration
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Equation 15: Estimated Maximum Possible Concentration (EMPC)
All Matrices Other than Aqueous:
EMPC (nglkg) =
D =Dilution factor
Ws =Sample dry weight in kg
CEX =Quantity of the native compound in the extract in nanograms (ng/|iL *
extract volume in jiL)
Aqueous:
/" v n
EMPC (pg/L) =
Vs
D =Dilution factor
Vs =Sample volume in liters
CEX =Quantity of the native compound in the extract in picograms (pg/|iL * extract volume
in jiL)
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DEFINITIONS
Acronyms
CLP - Contract Laboratory Program
COC-Chain of Custody
DQO - Data Quality Objective
EMPC - Estimated Maximum Possible Concentration
EPA - Environmental Protection Agency
GC - Gas Chromatography
LCS - Laboratory Control Sample
LCSD - Laboratory Control Sample Duplicate
MS/MSD - Matrix Spike/Matrix Spike Duplicate
PCDD - Polychlorinated Dibenzodioxin
PCDF - Polychlorinated Dibenzofuran
PCDPE - Polychlorinated Diphenyl Ether
PFK - Perfluorokerosene
PQL - Practical Quantitation Limit
QA - Quality Assurance
QC - Quality Control
RF - Response Factor
RL - Reporting Limit
RPD - Relative Percent Difference
RSD - Relative Standard Deviation
SDG - Sample Delivery Group
SOW - Statement of Work
ANALYTICAL DATA VALIDATION - Analytical data validation is a systematic process,
performed external from the data generator, which applies a defined set of performance-based
criteria to a body of data that may result in physical qualification of the data. Data validation
occurs prior to drawing a conclusion from the body of data.
ANALYTICAL DATA VERIFICATION - Analytical data verification is a systematic process of
evaluating the completeness, correctness, consistency, and compliance of a set of facts against a
standard or contract, which is performed by either the data generator or by an entity external to
the data generator.
CASE - A finite, usually predetermined number of samples collected over a given time period
from a particular site. A case consists of one or more sample delivery groups.
CHAIN-OF-CUSTODY - The history of the transfer of samples from the time of sample
acquisition through archival and disposal of samples. Chain-of-Custody documentation is
required as evidence of sample integrity.
CONTRACT REQUIRED QUANTITATION LIMIT (CRQL) - The CRQL is the minimum
level of detection acceptable under the current CLP contract.
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DATA QUALITY OBJECTIVES - DQOs are qualitative and quantitative statements derived
from the outputs of each step of the DQO process, which specify the study objectives, domain,
limitations, most appropriate type of data to collect, and the levels of decision error that will be
acceptable for the decision.
HOLDING TIME - Holding time, as described in this procedure, is defined as the period of time
between sample collection and sample extraction.
LABORATORY CONTROL SAMPLE (LCS) - The LCS is a control sample of known
composition. Aqueous and solid laboratory control samples are analyzed using the same
preparation, reagents, and method employed for field samples.
LABORATORY DUPLICATE - The laboratory duplicate is a randomly chosen split of an
analytical sample into two aliquots prior to sample preparation. The purpose of a laboratory
duplicate is to monitor the precision of the analytical method.
MATRIX SPIKE - The matrix spike is a split of a field-originating analytical sample in which
one half of the split is spiked with a known amount of radionuclide of interest prior to sample
preparation. The purpose of a matrix spike is to measure the effect of interferences from the
sample matrix that will preclude accurate quantitation by the instrumentation.
METHOD BLANK - The method blank is a laboratory-generated sample of the same matrix as
the analytical samples, but in absence of the analyte of interest. The purpose of a method blank is
to monitor the presence of contamination of the analyte of interest in the sample preparation and
analysis processes.
RELATIVE PERCENT DIFFERENCE - RPD is the measure of precision between two values,
defined as the absolute value of the difference between two values divided by the mean of the
two values.
RELATIVE RESPONSE FACTOR (RRF) - RRF represents the response of a compound to an
analytical instrument relative to the response of an associated standard.
RELATIVE STANDARD DEVIATION (RSD) - RSD is the measure of precision between
multiple values, defined as the standard deviation of multiple values divided by the mean of the
values.
SAMPLE DELIVERY GROUP (SDG) - An SDG is defined by one of the following, whichever
occurs first: 1) Case of field samples; 2) Each 20 field samples within a case; 3) Each 14-day
calendar period during which field samples in a case are received, beginning with receipt of the
first sample in the SDG.
SAMPLE RESULT - A sample result, as described in this procedure, is a numeric denotation of
the concentration, amount, or activity of a specific analytical parameter uniquely associated with
an aliquot of environmental media.
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STANDARD REFERENCE MATERIAL (SRM) - A SRM is a material or substance of which
one or more properties of which are sufficiently well established to be used for the calibration of
an apparatus, the assessment of a measurement method, or for assigning values to materials. The
SRM is characterized by the U.S. National Institute of Standards and Technology (NIST) or
other certified testing authority, and issued with a certificate providing the results of the
characterization.
TRACEABLE REFERENCE MATERIAL (TRM) - A TRM is a NIST prepared standard
reference material or a sample of known activity or concentration prepared from a NIST standard
reference material (derived standard material).
VALIDATION QUALIFIER - A qualifier is an alphabetic character physically or electronically
associated with a discrete sample result during validation due to a data quality deficiency, which
provides guidance in data usability.
WELL CHARACTERIZED REFERENCE MATERIAL (WCRM) - The WCRM may be
derived from a field sample which has been well characterized through multiple analyses,
providing a high level of confidence of the concentration in the sample. The WCRM may be
submitted to NIST for characterization and classification as a TRM.
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REFERENCES
USEPA Contract Laboratory Program (CLP) National Functional Guidelines for Chlorinated
Dibenzo-p-Dioxins (CDDs) and Chlorinated Dibenzofurans (CDFs) Data Review, OSWER
9240.1-53, EPA-540-R-11-016, September 2011.
USEPA Guidance for Labeling Externally Validated Laboratory Analytical Data for Superfund
Use, OSWER 9200.1-85, EPA 540-R-08-005, January 2009.
USEPA Analytical Services Branch Statement of Work for the Analysis of Chlorinated Dibenzo-
p-Dioxins (CDDs) and Chlorinated Dibenzofurans (CDFs), Multi-Media, Multi-Concentration,
DLM02.2, December 2009.
USEPA Method 1613B: Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope
Dilution HRGC/HRMS, Revision B, October 1994.
USEPA SW-846 Method 8290A: Polychlorinated Dibenzo-p-Dioxins (PCDDs) and
Polychlorinated Dibenzofurans (PCDFs) by High-Resolution Gas Chromatography/High-
Resolution Mass Spectrometry (HRGC/HRMS), Revision 1, February 2007.
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United States
Environmental Protection
Agency
Region 10
1200 Sixth Avenue, Suite 900
Seattle, WA 98101-1128
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