Office of Superfund Remediation and Technology Innovation (OSRTI)
United States Environmental Protection Agency (USEPA)
Washington, DC 20460
OSWER 9240.1-48
USEPA-540-R-08-01
June 2008
USEPA Contract Laboratory Program
National
Functional
Guidelines
for Superfund Organic Methods Date Review
Final
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NOTICE
The policies and procedures set forth here are intended as guidance to the United States Environmental
Protection Agency (hereafter referred to as USEPA) and other Governmental employees. They do not
constitute rule-making by the USEPA, and may not be relied on to create a substantive or procedural right
enforceable by any other person. The Government may take action that is at a variance with the policies
and procedures in this manual.
This document can be obtained from the USEPA's Contract Laboratory Program (CLP) Web site at:
http://www.epa.gov/superfund/programs/clp/guidance.htm
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Table of Contents
INTRODUCTION 1
DATA QUALIFIER DEFINITIONS 2
DATA PACKAGE INSPECTION 3
PRELIMINARY REVIEW 4
DATA REVIEW NARRATIVE 5
TRACE VOLATILE DATA REVIEW 6
I. Preservation 7
II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check 9
III. Initial Calibration 17
IV. Continuing Calibration Verification (CCV) 21
V. Blanks 25
VI. Deuterated Monitoring Compounds (DMCs) 29
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs) 33
VIII. Regional Quality Assurance (QA) and Quality Control (QC) 35
IX. Internal Standards 36
X. Target Compound Identification 38
XI. Compound Quantitation and Reported Contract Required Quantitation Limits
(CRQLs) 40
XII. Tentatively Identified Compounds (TICs) 41
XIII. System Performance 44
XIV. Overall Assessment of Data 45
LOW/MEDIUM VOLATILE DATA REVIEW 46
I. Preservation 47
II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check 50
III. Initial Calibration 58
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IV. Continuing Calibration Verification (CCV) 62
V. Blanks 66
VI. Deuterated Monitoring Compounds (DMCs) 70
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs) 74
VIII. Regional Quality Assurance (QA) and Quality Control (QC) 76
IX. Internal Standards 77
X. Target Compound Identification 79
XI. Compound Quantitation and Reported Contract Required Quantitation Limits
(CRQLs) 81
XII. Tentatively Identified Compounds (TICs) 83
XIII. System Performance 86
XIV. Overall Assessment of Data 87
SEMIVOLATILE DATA REVIEW 88
I. Preservation 89
II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check 92
III. Initial Calibration 101
IV. Continuing Calibration Verification (CCV) 105
V. Blanks 109
VI. Deuterated Monitoring Compounds (DMCs) 113
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs) 118
VIII. Regional Quality Assurance (QA) and Quality Control (QC) 121
IX. Gel Permeation Chromatography (GPC) Performance Check 122
X. Internal Standards 124
XI. Target Compound Identification 126
XII. Compound Quantitation and Reported Contract Required Quantitation Limits
(CRQLs) 128
XIII. Tentatively Identified Compounds (TICs) 130
in
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XIV. System Performance 133
XV. Overall Assessment of Data 134
PESTICIDE DATA REVIEW 135
I. Preservation 136
II. Gas Chromatograph with Electron Capture Detector (GC/ECD) Instrument
Performance Check 139
III. Initial Calibration 145
IV. Continuing Calibration Verification (CCV) 151
V. Blanks 154
VI. Surrogate Spikes 158
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs) 161
VIII. Laboratory Control Samples (LCSs) 164
IX. Regional Quality Assurance (QA) and Quality Control (QC) 166
X. Florisil Cartridge Performance Check 167
XI. Gel Permeation Chromatography (GPC) Performance Check 169
XII. Target Compound Identification 171
XIII. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation 173
XIV. Compound Quantitation and Reported Contract Required Quantitation Limits
(CRQLs) 175
XV. Overall Assessment of Data 177
AROCLOR DATA REVIEW 178
I. Preservation 179
II. Initial Calibration 182
III. Continuing Calibration Verification (CCV) 186
IV. Blanks 189
V. Surrogate Spikes 193
VI. Matrix Spike/Matrix Spike Duplicates (MS/MSDs) 196
IV
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VII. Laboratory Control Samples (LCSs) 198
VIII. Regional Quality Assurance (QA) and Quality Control (QC) 200
IX. Gel Permeation Chromatography (GPC) Performance Check 201
X. Target Compound Identification 203
XI. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation 205
XII. Compound Quantitation and Reported Contract Required Quantitation Limits
(CRQLs) 206
XIII. Overall Assessment of Data 207
APPENDIX A: GLOSSARY A-l
APPENDIX B: ORGANIC DATA REVIEW SUMMARY B-l
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List of Tables
Table 1. Holding Time Actions for Trace Volatile Analyses 8
Table 2. Ion Abundance Criteria for Bromofluorobenzene (BFB) 15
Table 3. Volatile Compounds Exhibiting Poor Response 18
Table 4. Initial Calibration Actions for Trace Volatiles Analyses 20
Table 5. Continuing Calibration Verification (CCV) Actions for Trace Volatiles Analyses 23
Table 6. Blank Actions for Trace Volatiles Analyses 28
Table 7. Volatile Deuterated Monitoring Compounds (DMCs) and Recovery Limits 29
Table 8. Deuterated Monitoring Compound (DMC) Recovery Actions For Trace Volatiles
Analyses 31
Table 9. Volatile Deuterated Monitoring Compounds (DMCs) and the Associated Target
Compounds 32
Table 10. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Trace Volatiles
Analysis 34
Table 11. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD) Limits 34
Table 12. Internal Standard Actions for Trace Volatiles Analyses 37
Table 13. Holding Time Actions for Low/Medium Volatile Analyses 48
Table 14. Ion Abundance Criteria For Bromofluorobenzene (BFB) 56
Table 15. Volatile Compounds Exhibiting Poor Response 59
Table 16. Initial Calibration Actions for Low/Medium Volatiles Analyses 61
Table 17. Continuing Calibration Verification (CCV) Actions for Low/Medium Volatiles
Analyses 64
Table 18. Blank Actions for Low/Medium Volatiles Analyses 69
Table 19. Volatile Deuterated Monitoring Compounds (DMCs) and Recovery Limits 70
Table 20. Deuterated Monitoring Compound (DMC) Recovery Actions For Low/Medium
Volatiles Analyses 72
Table 21. Volatile Deuterated Monitoring Compounds (DMCs) and the Associated Target
Compounds 73
Table 22. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Low/Medium Volatiles
Analysis 75
Table 23. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD) Limits 75
Table 24. Internal Standard Actions for Low/Medium Volatiles Analyses 78
vi
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Table 25. Percent Moisture Actions for Low/Medium Volatiles Analysis For
Non-Aqueous Samples 82
Table 26. Holding Time Actions for Semivolatile Analyses 91
Table 27. Ion Abundance Criteria For Decafluorotriphenylphosphine (DFTPP) 98
Table 28. Semivolatile Target Compounds Exhibiting Poor Response 102
Table 29. Initial Calibration Actions for Semivolatile Analyses 104
Table 30. Continuing Calibration Verification (CCV) Actions for Semivolatile Analyses 108
Table 31. Blank Actions for Semivolatiles Analyses 112
Table 32. Semivolatile Deuterated Monitoring Compound (DMC) and Recovery Limits 114
Table 33. Deuterated Monitoring Compound (DMC) Recovery Actions For Semivolatile
Analyses 115
Table 34. Semivolatile Deuterated Monitoring Compounds (DMCs) and the Associated Target
Compounds 116
Table 35. Semivolatile Deuterated Monitoring Compounds (DMCs) for Selective Ion
Monitoring (SIM) and the Associated Target Compounds 117
Table 36. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Semivolatiles Analysis... 119
Table 37. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD) 120
Table 38. Internal Standard Actions For Semivolatiles Analyses 125
Table 39. Percent Moisture Actions for Semivolatiles Analyses for Non-Aqueous Samples 129
Table 40. Holding Time Actions for Pesticide Analyses 138
Table 41. Resolution Check Mixture Components 139
Table 42. Performance Evaluation Mixture (PEM) Components 140
Table 43. Individual Standard Mixtures A and B Components 141
Table 44. Individual Standard Mixture C Components 142
Table 45. Gas Chromatograph with Electron Capture Detector (GC/ECD) Instrument
Performance Check Actions 144
Table 46. Concentration Levels of Calibration Standards 146
Table 47. Initial Calibration Sequence 1 147
Table 48. Initial Calibration Sequence 2 148
Table 49. Initial Calibration Action for Pesticide Analyses 150
Table 50. Continuing Calibration Verification (CCV) Action for Pesticide Analyses 153
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Table 51. Blank Actions for Pesticide Analyses 157
Table 52. Surrogate Actions for Pesticide Analyses 160
Table 53. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Pesticide Analysis 162
Table 54. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD) 163
Table 55. Pesticides Laboratory Control Sample (LCS) Spike Compounds and Recovery
Limits 164
Table 56. Laboratory Control Sample (LCS) Recovery Actions 165
Table 57. Florisil Cartridge Performance Check Actions 168
Table 58. Gel Permeation Chromatography (GPC) Performance Check Actions 170
Table 59. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation Actions 174
Table 60. Percent Moisture Actions for Pesticides Analyses for Non-Aqueous Samples 176
Table 61. Holding Time Actions for Aroclor 181
Table 62. Initial Calibration Sequence 183
Table 63. Initial Calibration Action for Aroclor Analyses 185
Table 64. Continuing Calibration Verification (CCV) Action for Aroclor Analyses 188
Table 65. Blank Actions for Aroclor Analyses 192
Table 66. Surrogate Actions for Aroclor Analyses 195
Table 67. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Aroclor Analysis 197
Table 68. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD) Limits 197
Table 69. Aroclor Laboratory Control Sample (LCS) Recovery 198
Table 70. Laboratory Control Sample (LCS) Recovery Actions 199
Table 71. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation Actions 205
Table 72. Percent Moisture Actions for Aroclors Analyses for Non-Aqueous Samples 206
Vlll
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%D
%RSD
ARO
BFB
CCS
CCV
CF
CLP
CLPPO
COC
CRQL
CSF
DART
DAT
DCB
DFTPP
DMC
DQA
DQO
GC
GC/ECD
GC/MS
GPC
INDA
INDB
INDC
LCS
MS
MSD
OSRTI
Acronyms
Percent Difference
Percent Relative Standard Deviation
Aroclor
Bromofluorobenzene
Contract Compliance Screening
Continuing Calibration Verification
Calibration Factor
Contract Laboratory Program
Contract Laboratory Program Project Officer
Chain of Custody
Contract Required Quantitation Limit
Complete SDG File
Data Assessment Rapid Transmittal
Data Assessment Tool
Decachlorobiphenyl
Decafluorotriphenylphosphine
Deuterated Monitoring Compound
Data Quality Assessment
Data Quality Objective
Gas Chromatograph
Gas Chromatograph/Electron Capture Detector
Gas Chromatograph/Mass Spectrometer
Gel Permeation Chromatography
Individual Standard Mixture A
Individual Standard Mixture B
Individual Standard Mixture C
Laboratory Control Sample
Matrix Spike
Matrix Spike Duplicate
Office of Superfund Remediation and Technology Innovation
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Acronyms
PCBs Poly chlorinated Bipheny Is
PE Performance Evaluation
PEM Performance Evaluation Mixture
QA Quality Assurance
QAC Quality Assurance Coordinator
QAPP Quality Assurance Project Plan
QC Quality Control
RIC Reconstructed Ion Chromatogram
RPD Relative Percent Difference
RRF Relative Response Factor
pjy? Mean Relative Response Factor
RRT Relative Retention Time
RSCC Regional Sample Control Center
RSD Relative Standard Deviation
RT Retention Time
SAP Sampling and Analysis Plan
SCP Single Component Pesticide
SDG Sample Delivery Group
SIM Selected Ion Monitoring
SMO Sample Management Office
SOP Standard Operating Procedure
SOW Statement of Work
TCL Target Compound List
TCX Tetrachloro-m-xylene
TIC Tentatively Identified Compound
TR Traffic Report/Chain of Custody Record
USEPA United States Environmental Protection Agency
UV Ultraviolet
VTSR Validated Time of Sample Receipt
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Introduction
This document is designed to offer the data reviewer guidance in determining the usability of analytical
data generated through the Contract Laboratory Program's (CLP) Statement of Work (SOW) for Multi-
Media, Multi-Concentration Organics Analysis (SOM01.2), and any future editorial revisions of
SOM01.2, hereinafter referred to as the SOM01.2 SOW. The guidance is somewhat limited in scope and
is intended to be used as an aid in the formal technical review process. It should not be used to establish
specific contract compliance (use of this document to evaluate data generated under Organic SOWs other
than the SOM01.2 SOW is cautioned). Definitive guidance is provided where performance should be
fully under a laboratory's control (e.g., blanks, calibration standards, instrument performance checks),
while general guidance is provided for evaluating subjective data that is affected by the site conditions.
The guidelines presented in the document will aid the data reviewer in establishing: (a) if data meets the
specific technical and quality control (QC) criteria established in the SOW; and (b) the usability of any
data not meeting the specific technical and QC criteria established in the SOW. It must be understood by
the reviewer that acceptance of data not meeting technical requirements is based upon many factors,
including, but not limited to, site-specific technical requirements, the need to facilitate the progress of
specific projects, and availability for resampling. To make judgments at this level requires the reviewer
to have a complete understanding of the intended use of the data. The reviewer is strongly encouraged to
establish a dialogue with the user to discuss usability issues and to answer questions regarding the review,
prior to, and after data review. It should also be understood that in all cases, data which do not meet
specified criteria are never to be fully acceptable without qualification.
The data reviewer should note that while this document is to be used as an aid in the formal data review
process, other sources of guidance and information, as well as professional judgment, should also be used
to determine the ultimate usability of data, especially in those cases where all data does not meet specific
technical criteria. The reviewer should also be aware that minor modifications to the analytical methods
may be made through the CLP's Request For Quote For Modified Analysis form to meet site-specific
requirements, and that these modifications could affect certain validation criteria such as the Contract
Required Quantitation Limits (CRQLs), initial calibration levels, Continuing Calibration Verification
(CCV) levels, and Target Compound Lists (TCLs). A full copy of a request for modified analysis made
to the analytical method should be included in the data package by the laboratory.
June 2008 1 Final
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Data Qualifier Definitions
The following definitions provide brief explanations of the national qualifiers assigned to results in the
data review process. If the Regions choose to use additional qualifiers, a complete explanation of those
qualifiers should accompany the data review.
U
The analyte was analyzed for, but was not detected at a level greater than or equal to the level of the adjusted
Contract Required Quantitation Limit (CRQL) for sample and method.
The analyte was positively identified and the associated numerical value is the approximate concentration of the
analyte in the sample (due either to the quality of the data generated because certain quality control criteria were
not met, or the concentration of the analyte was below the CRQL).
NJ
The analysis indicates the presence of an analyte that has been "tentatively identified" and the associated
numerical value represents its approximate concentration.
UJ
The analyte was not detected at a level greater than or equal to the adjusted CRQL. However, the reported
adjusted CRQL is approximate and may be inaccurate or imprecise.
R
The sample results are unusable due to the quality of the data generated because certain criteria were not met. The
analyte may or may not be present in the sample.
This qualifier applies to pesticide and Aroclor results when the identification has been confirmed by Gas
Chromatograph/Mass Spectrometer (GC/MS).
This qualifier applies to pesticide and Aroclor results when GC/MS analysis was attempted but was unsuccessful.
June 2008
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Data Package Inspection
For data obtained through the CLP, the Data Assessment Tool (DAT) report is a useful tool in the data
review process. The DAT report incorporates Contract Compliance Screening (CCS) and computer-aided
data evaluation results and is transmitted via the Data Assessment Rapid Transmittal (DART) system.
For more information about the DAT report, please refer to the following USEPA Web site:
http://www.epa.gov/superfund/programs/clp/dat.htm
The DAT report will identify any missing and/or incorrect information in the data package. The CLP
laboratory may submit a reconciliation package for any missing items or to correct data.
To obtain the DAT report and/or the reconciliation package, or if there are any other concerns regarding
the data package, contact the Contract Laboratory Program Project Officer (CLP PO) from the Region
where the samples were taken. For personnel contact information, refer to the following USEPA Web
site:
http://www.epa.gov/superfund/programs/clp/contacts.htm
June 2008 3 Final
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Preliminary Review
This document is for the review of analytical data generated through the SOMO1.2 SOW and any future
editorial revisions of SOMO 1.2. To use this document effectively, the reviewer should have an
understanding of the analytical method used and a general overview of the Sample Delivery Group (SDG)
or sample Case at hand. The exact number of samples, their assigned numbers, their matrix, and the
number of laboratories involved in their analyses are essential information.
It is suggested that an initial review of the data package be performed, taking into consideration all
information specific to the data package (flexible analysis approval notices, Traffic Report/Chain of
Custody Records (TR/COCs), SDG Narratives, etc.).
The reviewer should also have a copy of the Quality Assurance Project Plan (QAPP) or similar document
for the project for which samples were analyzed. The reviewer should contact the appropriate Regional
Contract Laboratory Program Project Officer (CLP PO) to obtain copies of the QAPP and relevant site
information. This information is necessary in determining the final usability of the analytical data.
Sample Cases (SDGs) routinely have unique field quality control (QC) samples which require special
attention from the reviewer. These include field and trip blanks, field duplicates, and Performance
Evaluation (PE) samples which must be identified. The sampling records (e.g., TR/COC Records, field
logs, and/or contractor tables) should identify:
1. The Region where the samples were taken,
2. The Case number,
3. The complete list of samples, with information on:
a. Sample matrix;
b. Field Blanks (i.e., equipment blanks or rinsate blanks) and trip blanks;
c. Field duplicates;
d. Field spikes;
e. QC audit samples;
f Shipping dates;
g. Preservatives; and
h. Laboratories involved.
The TR/COC Record includes sample descriptions and date(s) of sampling. The reviewer must consider
lag times between sampling and start of analysis when assessing technical sample holding times.
The laboratory's SDG Narrative is another source of general information. Notable problems with
matrices, insufficient sample volume for analysis or re-analysis, samples received in broken containers,
preservation, and unusual events should be documented in the SDG Narrative. The reviewer should also
inspect any email correspondence, telephone, or other communication logs detailing any discussions of
sample preparation and/or analysis issues between the laboratory, CLP Sample Management Office
(SMO) and the USEPA Region.
June 2008 4 Final
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Data Review Narrative
A Data Review Narrative, including the Organic Data Review Summary form, (see Appendix B) must
accompany the laboratory data forwarded to the intended data recipient (client) or user to promote
communications. A copy of the Data Review Narrative should be submitted to the Contract Laboratory
Program Project Officer (CLP PO) assigned oversight responsibility for the laboratory producing the data.
The Data Review Narrative should include comments that clearly identify the problems associated with a
Case or SDG and state the limitations of the data. Documentation should include the CLP Sample
Number, analytical method, extent of the problem, and assigned qualifiers.
June 2008 5 Final
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Trace Volatiles Organic Analysis
TRACE VOLATILE DATA REVIEW
The data requirements to be checked are:
I. Preservation
II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check
III. Initial Calibration
IV. Continuing Calibration Verification (CCV)
V. Blanks
VI. Deuterated Monitoring Compounds (DMCs)
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
VIII. Regional Quality Assurance (QA) and Quality Control (QC)
IX. Internal Standards
X. Target Compound Identification
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XII. Tentatively Identified Compounds (TICs)
XIII. System Performance
XIV. Overall Assessment of Data
NOTE: Language specific to Selective Ion Monitoring (SIM) analyses is shown in italic.
June 2008 6 Final
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Trace Volatiles Organic Analysis
I. Preservation
A. Review Items:
Form I VOA-1, Form I VOA-2, Form I VOA-SIM, Form I VOA-TIC, Traffic Report/Chain of Custody
Records (TR/COCs), raw data, and the Sample Delivery Group (SDG) Narrative checking for:
1. pH
2. Sample temperature
3. Holding time
4. Other sample conditions (e.g., headspace)
B. Objective:
The objective is to ascertain the validity of the analytical results based on sample condition
(e.g., preservation, temperature, headspace) and the holding time of the sample from the time of collection
to the time of analysis.
C. Criteria:
The technical holding time criterion for aqueous samples are as follows:
For volatile compounds in properly cooled (4°C ± 2°C) aqueous samples that are acid-preserved (with
HC1 to a pH of 2 or below), the maximum holding time is 14 days from sample collection. For aqueous
samples that were properly cooled (4°C ± 2°C), but which have no indication of being preserved, the
maximum holding time is seven (7) days from sample collection.
D. Evaluation:
Technical holding times are established by comparing the sample collection dates on the TR/COC Record
with the dates of analysis on Form I VOA-1, Form I VOA-2, Form I VOA-SIM, Form I VOA-TIC and the
raw data. Information contained in the Complete SDG File (CSF) should also be considered in the
determination of holding times. Verify that the analysis dates on Form I(s) and the raw data/SDG file are
identical. Review the SDG Narrative to determine if the samples were preserved and arrived at the
laboratory in proper condition (e.g., received intact, appropriate sample temperature at receipt, pH,
absence of air bubbles or detectable headspace). If there is no indication in the SDG Narrative, the
TR/COC, or the sample records that there was a problem with the samples, the integrity of samples can be
assumed to be acceptable. If it is indicated that there were problems with the samples, the integrity of the
sample may have been compromised and professional judgment should be used to evaluate the effect of
the problem on the sample results.
E. Action:
1. Qualify sample results using preservation and technical holding time information as follows (see
Table 1):
a. If there is no evidence that the samples were properly preserved, but the samples were analyzed
within the technical holding time [seven (7) days from sample collection], no qualification of the
data is necessary.
June 2008 7 Final
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Trace Volatiles Organic Analysis
b. If there is no evidence that the samples were properly preserved, and the samples were analyzed
outside of the technical holding time [seven (7) days from sample collection], qualify detects for
all volatile compounds with a "J" and non-detects as unusable "R".
c. If the samples were properly preserved, and the samples were analyzed within the technical
holding time [14 days from sample collection], no qualification of the data is necessary.
d. If the samples were properly preserved, but were analyzed outside of the technical holding time
[14 days from sample collection], qualify detects with a "J" and non-detects as unusable "R".
Table 1. Holding Time Actions for Trace Volatile Analyses
Matrix
Aqueous
Aqueous
Aqueous
Aqueous
Preserved
No
No
Yes
Yes
Criteria
< 7 days
> 7 days
< 14 days
> 14 days
Action
Detected Associated
Compounds
Non-Detected Associated
Compounds
No qualification
J
R
No qualification
J
R
2. Whenever possible, the reviewer should comment on the effect of the holding time exceedance on the
resulting data in the Data Review Narrative.
3. Use professional judgment to qualify samples whose temperature upon receipt at the laboratory is
either below 2 degrees centigrade or above 6 degrees centigrade.
4. Note, for Contract Laboratory Program Project Officer (CLP PO) action, when technical holding
times are exceeded.
June 2008
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Trace Volatiles Organic Analysis
II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check
A. Review Items:
Form V VOA, bromofluorobenzene (BFB) mass spectra, and mass listing.
B. Objective:
GC/MS instrument performance checks are performed to ensure adequate mass resolution, identification,
and to some degree, sensitivity. These criteria are not sample-specific. Conformance is determined using
standard materials, therefore, these criteria should be met in all circumstances.
NOTE:
C. Criteria:
This requirement does not apply when samples are analyzed by the Selected Ion Monitoring (SIM)
technique.
1. The 12-hour clock begins with either the injection of BFB, or in cases where a closing Continuing
Calibration Verification (CCV) can be used as an opening CCV, the 12-hour clock begins with the
injection of the opening CCV.
2. Listed below are some, but not necessarily all, examples of acceptable analytical sequences
incorporating the use of the opening and/or closing CCV. Use these examples as a guide for the
possible analytical sequences that can be expected. The criteria associated with these analytical
sequences have been evaluated as part of the Contract Compliance Screening (CCS) process.
Conditions for When
Example Sequence is
Appropriate:
Acceptable Criteria That Must Be Met:
Notes:
Use Example 1 if time
remains on the 12-hour clock
after the initial calibration
sequence.
BFB tunes meet instrument
performance criteria.
The five Initial Calibration standards
meet initial calibration criteria.
CCV A meets both opening and
closing CCV criteria.
CCV B meets closing CCV criteria.
The requirement of starting the new 12-
hour clock for Analytical Sequence 2
with a new BFB tune is waived if CCV
A meets opening CCV criteria. If CCV
B meets opening CCV criteria, a method
blank and subsequent samples may be
analyzed immediately after CCV B.
Use Example 2 if time
remains on the 12-hour clock
after the initial calibration
sequence.
BFB tunes meet instrument
performance criteria.
The five Initial Calibration standards
meet initial calibration criteria.
CCV A meets closing CCV criteria
(but does not meet opening CCV
criteria).
CCV B meets opening CCV criteria.
CCV C meets closing CCV criteria.
CCV A does not meet opening CCV
criteria, therefore a new BFB tune must
be performed, immediately followed by
CCV B before a method blank and any
samples may be analyzed. In this case,
the new 12-hour clock and Analytical
Sequence 2 begins with the injection of
the new BFB tune.
June 2008
Final
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Trace Volatiles Organic Analysis
Conditions for When
Example Sequence is
Appropriate:
Acceptable Criteria That Must Be Met:
Notes:
Use Example 3 if more than
12-hours have elapsed since
the most recent initial
calibration or closing CCV,
OR
if the most recent closing
CCV was not or could not be
used as an opening CCV.
BFB tunes meet instrument
performance criteria.
CCV A meets opening CCV criteria.
CCV B meets both opening and
closing CCV criteria.
CCV C meets both opening and
closing CCV criteria.
The requirement of starting the new 12-
hour clock for Analytical Sequence 2
with a new BFB tune is waived if CCV B
meets opening CCV criteria. IfCCVC
meets opening CCV criteria, a method
blank and subsequent samples may be
analyzed immediately after CCV C.
Use Example 4 if more than
12-hours have elapsed since
the most recent initial
calibration or closing CCV,
OR
if the most recent closing
CCV was not or could not be
used as an opening CCV.
BFB tunes meet instrument
performance criteria.
CCV A meets opening CCV criteria.
CCV B meets closing CCV criteria
(but does not meet opening CCV
criteria).
CCV C meets opening CCV criteria.
CCV D meets both opening and
closing CCV criteria.
CCV B does not meet opening CCV
criteria, therefore a new BFB tune must
be performed, immediately followed by
CCV C before a method blank and any
samples may be analyzed. In this case,
the new 12-hour clock and Analytical
Sequence 2 begins with the injection of
the new BFB tune. The requirement of
starting the new 12-hour clock for
Analytical Sequence 3 with a new BFB
tune is waived if CCV D meets opening
CCV criteria. If CCV D meets opening
CCV criteria, a method blank and
subsequent samples may be analyzed
immediately after CCV D.
June 2008
10
Final
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Trace Volatiles Organic Analysis
Example 1:
Start of 12-hour clock for
Analytical Sequence 1
End of 12-hour clock for
Analytical Sequence I/
Beginning of 12-hour clock for
Analytical Sequence 2
Time Material Injected
Ohr BFB
Initial Calibration 0.5
Initial Calibration 1 .0
Initial Calibration 5.0
Initial Calibration 10
Initial Calibration 20
Method Blank
Subsequent Samples
•
•
•
•
12 hr CCV A (meets opening CCV criteria)
Analytical Sequence #
1
1
1
1
1
1
1
1
1
1
1
1
1/2
End of 12-hour clock for
Analytical Sequence 2/
Beginning of 12-hour clock for
Analytical Sequence 3
Method Blank
Subsequent Samples
24 hr CCV B (meets opening CCV criteria)
2
2
2
2
2
2
2/3
June 2008
11
Final
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Trace Volatiles Organic Analysis
Example 2: Time Material Injected
Start of 12-hour clock for _ , T-.-r.-n
, . , . . „ , 0 hr BFB
Analytical Sequence 1
Initial Calibration 0.5
Initial Calibration 1 .0
Initial Calibration 5.0
Initial Calibration 10
Initial Calibration 20
Method Blank
Subsequent Samples
•
•
•
•
Analytical Sequence #
1
1
1
1
1
1
1
1
1
1
1
1
End of 12-hour clock for
Analytical Sequence 1
Beginning of 12-hour clock for
Analytical Sequence 2
12 hr
13 hr
CCV A (meets closing CCV criteria; fails
opening CCV criteria)
BFB
CCV B (meets opening CCV criteria)
Method Blank
Subsequent Samples
End of 12-hour clock for
Analytical Sequence 2
25 hr CCV C (meets closing CCV criteria)
June 2008
12
Final
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Trace Volatiles Organic Analysis
Example 3:
Start of 12-hour clock for
Analytical Sequence 1
End of 12-hour clock for
Analytical Sequence 11
Beginning of 12-hour clock for
Analytical Sequence 2
End of 12-hour clock for
Analytical Sequence 2/
Beginning of 12-hour clock for
Analytical Sequence 3
Time
Ohr
Material Injected
BFB
CCV A (meets opening CCV criteria)
Method Blank
Subsequent Samples
12 hr CCV B (meets opening CCV criteria)
Method Blank
Subsequent Samples
24 hr CCV C (meets opening CCV criteria)
Analytical Sequence #
1
1
1
1
1
1
1
1
1/2
2
2
2
2
2
2/3
June 2008
13
Final
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Trace Volatiles Organic Analysis
Example 4:
Start of 12-hour clock for
Analytical Sequence 1
End of 12-hour clock for
Analytical Sequence 1
Beginning of 12-hour clock for
Analytical Sequence 2
End of 12-hour clock for
Analytical Sequence II
Beginning of 12-hour clock for
Analytical Sequence 3
Time
Ohr
Material Injected
BFB
CCV A (meets opening CCV criteria)
Method Blank
Subsequent Samples
Analytical Sequence #
1
1
1
1
1
1
1
12 hr
13hr
CCV B (meets closing CCV criteria; fails
opening CCV criteria)
BFB
CCV C (meets opening CCV criteria)
Method Blank
Subsequent Samples
25 hr CCV D (meets opening CCV criteria)
2
2
2
2
2
2
2/3
June 2008
14
Final
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Trace Volatiles Organic Analysis
3. Inject a sufficient amount of the instrument performance check solution (up to 50 ng BFB on-column)
at the beginning of each 12-hour period during which samples or standards are analyzed. The
instrument performance check, BFB for trace volatile analysis, must meet the ion abundance criteria
listed in Table 2. This criteria is waived in cases where a closing CCV can be used as an opening
CCV (i.e., a BFB instrument performance check analysis is not required when a closing CCV analysis
meets the requirements of an opening CCV analysis).
Table 2. Ion Abundance Criteria For Bromofluorobenzene (BFB)
Mass
50
75
95
96
173
174
175
176
177
Ion Abundance Criteria
15.0 -40.0% of mass 95
30.0 -80.0% of mass 95
Base peak, 100% relative abundance
5. 0-9.0% of mass 95*
Less than 2.0% of mass 174
50.0% -120% of mass 95
5. 0-9.0% of mass 174
95.0 -101% of mass 174
5. 0-9.0% of mass 176
* All ion abundances must be normalized to mass to charge (m/z) 95, the nominal base peak, even though the ion abundance of m/z 174
may be up to 120% that of m/z 95.
D. Evaluation:
1. Compare the data presented for each Instrument Performance Check (Form V VOA) with each mass
listing submitted to ensure the following:
a. Form V VOA is present and completed for each 12-hour period during which samples were
analyzed. In cases where a closing CCV is used as an opening CCV for the next 12-hour period,
an additional Form V VOA is not required.
b. The laboratory has not made transcription errors between the data and the form. If there are
major differences between the mass listing and the Form Vs, a more in-depth review of the data is
required. This may include obtaining and reviewing additional information from the laboratory.
c. The appropriate number of significant figures has been reported (number of significant figures
given for each ion in the ion abundance criteria column) and that rounding is correct.
d. The laboratory has not made any calculation errors.
2. Verify that samples were not analyzed before a valid instrument performance check or were not
analyzed 12 hours after the injection of the Instrument Performance Check Solution. This evaluation
is not to be performed in cases where a closing CCV is used as an opening CCV.
3. Verify from the raw data (mass spectral listing) that the mass assignment is correct and that the mass
listing is normalized to m/z 95.
4. Verify that the ion abundance criteria was met. The criteria for m/z 173, 175, 176, and 177 are
calculated by normalizing to the specified m/z.
June 2008
15
Final
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Trace Volatiles Organic Analysis
5. If possible, verify that spectra were generated using appropriate background subtraction techniques.
Since the BFB spectrum is obtained from chromatographic peaks that should be free from coelution
problems, background subtraction should be done in accordance with the following procedure:
a. Three scans (the peak apex scan and the scans immediately preceding and following the apex) are
acquired and averaged.
b. Background subtraction is required, and must be accomplished using a single scan no more than
20 scans prior to the elution of BFB. Do not subtract the BFB peak as part of the background.
NOTE: All mass spectrometer instrument conditions must be identical to those used during the sample
analysis. Background subtraction actions resulting in spectral distortions for the sole purpose of
meeting the method specifications are contrary to the Quality Assurance (QA) objectives, and are
therefore unacceptable.
For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the CCS process. Information regarding the laboratory's compliance with
these criteria can be obtained from the Data Assessment Tool (DAT) reports, and may be used as
part of the evaluation process.
E. Action:
1. If samples are analyzed without a preceding valid instrument performance check or are analyzed 12
hours after the Instrument Performance Check and are not preceded by an analysis of a closing CCV
that meets the opening CCV criteria, qualify all data in those samples as unusable "R".
2. If the laboratory has made minor transcription errors which do not significantly affect the data, the
data reviewer should make the necessary corrections on a copy of the form.
3. If the laboratory has failed to provide the correct forms or has made significant transcription or
calculation errors, the Region's designated representative should contact the laboratory and request
corrected data. If the information is not available, the reviewer must use professional judgment to
assess the data. Notify the laboratory's Contract Laboratory Program Project Officer (CLP PO).
4. If mass assignment is in error (e.g., m/z 96 is indicated as the base peak rather than m/z 95), classify
all associated data as unusable "R".
5. If ion abundance criteria are not met, professional judgment may be applied to determine to what
extent the data may be utilized. When applying professional judgment to this topic, the most
important factors to consider are the empirical results that are relatively insensitive to location on the
chromatographic profile and the type of instrumentation. Therefore, the critical ion abundance
criteria for BFB are the m/z 95/96, 174/175, 174/176, and 176/177 ratios. The relative abundances of
m/z 50 and 75 are of lower importance. This issue is more critical for Tentatively Identified
Compounds (TICs) than for target analytes.
6. Note, in the Data Review Narrative, decisions to use analytical data associated with BFB instrument
performance checks not meeting contract requirements.
7. If the reviewer has reason to believe that instrument performance check criteria were achieved using
techniques other than those described in Trace Volatiles Organic Analysis, Section II.D.5, obtain
additional information on the instrument performance checks. If the techniques employed are found
to be at variance with the contract requirements, the performance and procedures of the laboratory
may merit evaluation. Note, for CLP PO action, concerns or questions regarding laboratory
performance. For example, if the reviewer has reason to believe that an inappropriate technique was
used to obtain background subtraction (such as background subtracting from the solvent front or from
another region of the chromatogram rather than from the BFB peak), note this for CLP PO action.
June 2008 16 Final
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Trace Volatiles Organic Analysis
III. Initial Calibration
A. Review Items:
Form VIVOA-1, Form VI VOA-2, Form VIVOA-3, Form VI VOA-SIM, quantitation reports, and
chromatograms.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data for compounds on the
volatile Target Compound List (TCL). Initial calibration demonstrates that the instrument is capable of
acceptable performance in the beginning of the analytical run and of producing a linear calibration curve
and provides the Mean Relative Response Factors (RRFs) used for quantitation.
C. Criteria:
1. Initial calibration standards containing both volatile target compounds and Deuterated Monitoring
Compounds (DMCs) are analyzed at concentrations of 0.50, 1.0, 5.0, 10, and 20 (ig/L for non-
ketones, 5.0, 10, 50, 100 and 200 (ig/L for ketones at the beginning of each analytical sequence, or as
necessary if the continuing calibration verification acceptance criteria are not met. The initial
calibration (and any associated samples and blanks) must be analyzed within 12 hours of the
associated instrument performance check. All three xylene isomers (o-, m-, and p-xylene) must be
present in calibration standards. The o-xylene calibration standard concentrations must be at 0.50,
1.0, 5.0, 10 and 20 (ig/L, while the concentration of the m-, plus the p-xylene isomers must total 0.50,
1.0, 5.0, 10, and 20 (ig/L.
If analysis by the SIM technique is requested for compounds of interest, prepare calibration
standards containing the compounds of interest and their associated DMCs at concentrations ofO. 05,
0.1, 0.5, 1.0,and2.0fjg/L.
2. Initial calibration Relative Response Factors (RRFs) for the volatile target compounds listed in Table
3 and all DMCs must be greater than or equal to 0.010. The RRF for all other volatile target
compounds must be greater than or equal to 0.050.
3. The Percent Relative Standard Deviation (%RSD) of the initial calibration RRFs must be less than or
equal to 40.0% for the volatile target compounds listed in Table 3 and the associated DMCs (see
Table 9). The %RSD for all other volatile target compounds and associated DMCs must be less than
or equal to 30.0%.
NOTE: The flexibility clause in the method may impact some of the preceding criteria. A copy of the
flexibility clause should be present in the Sample Delivery Group (SDG). Refer to the Contract
Laboratory Program (CLP) home page at
http://www.epa.gov/oerrpage/superfund/programs/clp/modifledanalvses.htm for the specific
method flexibility requirements.
D. Evaluation:
1. Verify that the correct concentrations of standards were used for the initial calibration (i.e., 0.50, 1.0,
5.0, 10, and 20 (ig/L for non-ketones, 5.0, 10, 50, 100, and 200 (ig/L for ketones).
If analysis by the SIM technique is requested, verify that the correct concentrations of standards were
used for the initial calibration (i.e., 0.05, 0.1, 0.5, 1.0, and 2.0 /ug/L for all compounds and associated
DMCs).
June 2008 17 Final
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Trace Volatiles Organic Analysis
2. Verify that the RRF obtained from the associated initial calibration was used for calculating sample
results and the samples were analyzed within 12 hours of the associated instrument performance
check.
3. Evaluate the initial calibration RRFs and the RRFs for all volatile target compounds and DMCs:
a. Check and recalculate the RRFs and RRF for at least one volatile target compound associated
with each internal standard. Verify that the recalculated value(s) agrees with the laboratory
reported value(s).
b. Verify that for the volatile target compounds listed in Table 3 and for all DMCs, the initial
calibration RRFs are greater than or equal to 0.010, and for all other volatile target compounds,
RRFs are greater than or equal to 0.050.
Table 3. Volatile Compounds Exhibiting Poor Response
Volatile Compounds
Acetone
2-Butanone
Carbon disulfide
Chloroethane
Chloromethane
Cyclohexane
1 ,2-Dibromoethane
Dichlorodifluoromethane
cis-1 ,2-Dichloroethene
1 ,2-Dichloropropane
1 ,2-Dibromo-3-chloropropane
Isopropylbenzene
Methyl acetate
Methylene chloride
Methylcyclohexane
Methyl tert-butyl ether
trans- 1 ,2-Dichloroethene
4-Methyl-2-pentanone
2-Hexanone
Trichlorofluoromethane
1 , 1 ,2-Trichloro- 1 ,2,2-trifluoroethane
4. Evaluate the %RSD for all volatile target compounds and DMCs:
a. Check and recalculate the %RSD for one or more volatile target compound(s) and DMCs. Verify
that the recalculated value(s) agrees with the laboratory reported value(s).
b. If the %RSD is greater than the maximum criteria [40.0% for the volatile target compounds listed
in Table 3 and associated DMCs listed in Table 9, and 30.0% for all other volatile target
compounds and associated DMCs], the reviewer should use professional judgment to determine
the need to check the points on the curve for the cause of the non-linearity. This is checked by
eliminating either the high-point or the low-point and recalculating the %RSD (see Trace
Volatiles Organic Analysis, Section III.E.2).
5. If errors are detected in the calculations of either the RRFs or the %RSD, perform a more
comprehensive recalculation.
NOTE: For data obtained from the CLP, the preceding criteria are evaluated as part of the Contract
Compliance Screening (CCS) process. Information regarding the laboratory's compliance with
these criteria can be obtained from the Data Assessment Tool (DAT) reports, and may be used as
part of the evaluation process.
June 2008
18
Final
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Trace Volatiles Organic Analysis
E. Action:
1. Qualify all volatile target compounds, including the compounds exhibiting poor response listed in
Table 3, using the following criteria (see Table 4):
a. If any volatile target compound has an RRF value less than the minimum criterion (0.010 for the
compounds exhibiting poor response listed in Table 3, and 0.050 for all other volatile
compounds), use professional judgment for detects, based on mass spectral identification, to
qualify the data as a "J" or unusable "R".
b. If any volatile target compound has an RRF value less than the minimum criterion (0.010 for the
compounds exhibiting poor response listed in Table 3, and 0.050 for all other volatile
compounds), qualify non-detected compounds as unusable "R".
c. If any of the volatile target compounds listed in Table 3 has %RSD greater than 40.0%, qualify
detects with a "J", and non-detected compounds using professional judgment (see Trace Volatiles
Organic Analysis, Section III.E.2).
d. For all other volatile target compounds, if %RSD is greater than 30.0%, qualify detects with a "J",
and non-detected compounds using professional judgment (see Trace Volatiles Organic Analysis,
Section III.E.2).
e. If the volatile target compounds meet the acceptance criteria for RRF and the %RSD, no
qualification of the data is necessary.
f No qualification of the data is necessary on the DMC RRF and %RSD data alone. Use
professional judgment and follow the guidelines in Trace Volatiles Organic Analysis, Section
III.E.2, to evaluate the DMC RRF and %RSD data in conjunction with the DMC recoveries to
determine the need for qualification of data.
2. At the reviewer's discretion, and based on the project-specific Data Quality Objectives (DQOs), a
more in-depth review may be considered using the following guidelines:
a. If any volatile target compound has a %RSD greater than the maximum criterion (40.0% for the
compounds listed in Table 3, and 30.0% for all other volatile compounds), and if eliminating
either the high or the low-point of the curve does not restore the %RSD to less than or equal to
the required maximum:
i. Qualify detects for that compound(s) with a" J".
ii. Qualify non-detected volatile target compounds using professional judgment.
b. If the high-point of the curve is outside of the linearity criteria (e.g., due to saturation):
i. Qualify detects outside of the linear portion of the curve with a "J".
ii. No qualifiers are required for detects in the linear portion of the curve.
iii. No qualifiers are required for volatile target compounds that were not detected.
c. If the low-point of the curve is outside of the linearity criteria:
i. Qualify low-level detects in the area of non-linearity with a "J".
ii. No qualifiers are required for detects in the linear portion of the curve.
iii. For non-detected volatile compounds, use the lowest point of the linear portion of the curve
to determine the new quantitation limit.
3. If the laboratory has failed to provide adequate calibration information, the Region's designated
representative should contact the laboratory and request the necessary information. If the information
is not available, the reviewer must use professional judgment to assess the data.
June 2008 19 Final
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Trace Volatiles Organic Analysis
4. Note in the Data Review Narrative, whenever possible, the potential effects on the data due to
calibration criteria exceedance.
5. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if calibration criteria are
grossly exceeded.
Table 4. Initial Calibration Actions for Trace Volatiles Analyses
Criteria for Trace Analysis
RRF < 0.010 (target compounds listed in Table 3)
RRF < 0.050 (all other target compounds)
RRF > 0.010 (target compounds listed in Table 3)
RRF > 0.050 (all other target compounds)
% RSD < 40.0 (target compounds listed in Table 3)
% RSD < 30.0 (all other target compounds)
% RSD > 40.0 (target compounds listed in Table 3)
% RSD > 30.0 (all other target compounds)
Action
Detected Associated
Compounds
J or R (based on mass
spectral identification)
Non-Detected Associated
Compounds
R
No qualification
No qualification
J
Use professional judgment
June 2008
20
Final
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Trace Volatiles Organic Analysis
IV. Continuing Calibration Verification (CCV)
A. Review Items:
Form VII VOA-1, Form VII VOA-2, Form VII VOA-3, Form VII VOA-SIM, quantitation reports, and
chromatograms.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data. The CCV checks
satisfactory performance of the instrument on a day-to-day basis, however, quantitations are based on the
Mean Relative Response Factors (RRFs ) obtained from the initial calibration.
C. Criteria:
1. The 12-hour clock begins with either the injection of Bromofluorobenzene (BFB) or in cases where a
closing CCV can be used as an opening CCV, the 12-hour clock begins with the injection of the
opening CCV.
2. CCV standards containing both target compounds and Deuterated Monitoring Compounds (DMCs)
are analyzed both at the beginning (opening CCV) and end (closing CCV) of each 12-hour analysis
period following the analysis of the instrument performance check and prior to the analysis of the
method blank and samples. An instrument performance check is not required prior to the analysis of
a closing CCV or prior to a closing CCV which can be used as an opening CCV for the next 12-hour
period. If time remains in the 12-hour time period after initial calibration and samples are to be
analyzed, the mid-point standard from the initial calibration can be used as an opening CCV.
3. For an opening CCV, the Relative Response Factors (RRFs) for the volatile target compounds listed
in Table 3, and for all DMCs, must be greater than or equal to 0.010. The RRF for all other volatile
target compounds must be greater than or equal to 0.050.
4. For a closing CCV, the RRFs for all volatile target compounds and DMCs must be greater than or
equal to 0.010.
5. The Percent Difference (%D) between the initial calibration RRF and the opening CCV RRF must be
within ±40.0% for the volatile target compounds listed in Table 3 and associated DMCs listed in
Table 9. The Percent Difference for all other volatile target compounds and associated DMCs must
be within ±30.0%.
6. For a closing CCV, the Percent Difference between the initial calibration RRF and the CCV RRF must
be within ±50.0% for all volatile target compounds and associated DMCs.
D. Evaluation:
1. Verify that the CCV was run at the required frequency (an opening and closing CCV must be run
within a 12-hour period) and the CCV was compared to the correct initial calibration. If the mid-
point standard from the initial calibration is used as an opening CCV, verify that the result (RRF) of
the mid-point standard was compared to the RRF from the correct initial calibration.
2. Evaluate the CCV RRF for all volatile target compounds and DMCs:
June 2008 21 Final
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Trace Volatiles Organic Analysis
a. Check and recalculate the CCV RRF for at least one volatile target compound and DMC
associated with each internal standard. Verify that the recalculated value(s) agrees with the
laboratory reported value(s).
b. For an opening CCV, verify that all volatile target compounds listed in Table 3 and all DMCs
have CCV RRFs of greater than or equal to 0.010, and all other volatile target compounds have
RRFs greater than or equal to 0.050.
c. For a closing CCV, verify that all volatile target compounds and DMCs have CCV RRFs of
greater than or equal to 0.010.
3. Evaluate the Percent Difference between initial calibration RRF and CCV RRF (both opening and
closing RRF) for all volatile target compounds and DMCs:
a. Check and recalculate the Percent Difference for one or more volatile target compound(s) and
DMCs associated with each internal standard. Verify that the recalculated value(s) agrees with
the laboratory-reported value(s).
b. For an opening CCV, verify that the Percent Difference is within ±40.0% for the volatile target
compounds listed in Table 3 and DMCs listed in Table 9, and within ±30.0% for all other volatile
target compounds and associated DMCs.
c. For a closing CCV, verify that the Percent Difference is within ±50.0% for all volatile target
compounds and associated DMCs.
4. If errors are detected in the calculations of either the CCV (both opening and closing) RRF or the
Percent Difference, perform a more comprehensive recalculation.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If a CCV (opening and closing) was not run at the appropriate frequency, qualify all data as unusable
"R" (see Table 5).
2. Qualify all volatile target compounds, including the compounds exhibiting poor response listed in
Table 3 using the following criteria:
a. For an opening CCV, if any volatile target compound has an RRF value less than the minimum
criterion (0.010 for the compounds exhibiting poor response, and 0.050 for all other volatile
compounds), use professional judgment for detects, based on mass spectral identification, to
qualify the data as a "J" or unusable "R".
b. For a closing CCV, if any volatile target compound has an RRF value less than 0.010, use
professional judgment for detects based on mass spectral identification to qualify the data as a "J"
or unusable "R".
c. For an opening CCV, if any volatile target compound has an RRF value less than the minimum
criterion (0.010 for the compounds exhibiting poor response, and 0.050 for all other volatile
compounds), qualify non-detected compounds as unusable "R".
d. For a closing CCV, if any volatile target compound has an RRF value less than 0.010, qualify
non-detected compounds as unusable "R".
e. For an opening CCV, if the Percent Difference value for any of the volatile target compounds
listed in Table 3 is outside the ±40.0% criterion, qualify detects with a "J" and non-detected
compounds with an approximated "UJ".
June 2008 22 Final
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Trace Volatiles Organic Analysis
f. For a closing CCV, if the Percent Difference value for any of the volatile target compounds listed
in Table 3 is outside the ±50.0% criterion, qualify detects with a "J" and non-detected compounds
with an approximated "UJ".
g. For an opening CCV, if the Percent Difference value for any other volatile target compound is
outside the ±30.0% criterion, qualify detects with a "J" and non-detected compounds with an
approximated "UJ".
h. For a closing CCV, if the Percent Difference value for any other volatile target compound is
outside the ±50.0% criterion, qualify detects with a "J" and non-detected compounds with an
approximated "UJ".
i. If the volatile target compounds meet the acceptable criteria for RRF and the Percent Difference,
no qualification of the data is necessary.
j. No qualification of the data is necessary on the DMC RRF and the Percent Difference data alone.
Use professional judgment to evaluate the DMC RRF and Percent Difference data in conjunction
with the DMC recoveries to determine the need for qualification of data.
3. If the laboratory has failed to provide adequate calibration information, the Region's designated
representative should contact the laboratory and request the necessary information. If the information
is not available, the reviewer must use professional judgment to assess the data.
4. Note in the Data Review Narrative, whenever possible, the potential effects on the data due to
calibration criteria exceedance.
5. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if calibration criteria are
grossly exceeded.
Table 5. Continuing Calibration Verification (CCV) Actions for Trace Volatiles Analyses
Criteria for Opening CCV
Criteria for Closing CCV
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
RRF < 0.010 (volatile target compounds
listed in Table 3)
RRF < 0.050 (all other volatile target
compounds)
RRF < 0.010 (all volatile target
compounds)
J or R (based on
mass spectral
identification)
R
RRF > 0.010 (volatile target compounds
listed in Table 3)
RRF > 0.050 (all other volatile target
compounds)
RRF > 0.010 (all volatile target
compounds)
No qualification
%D > 40.0 or < -40.0 (volatile target
compounds listed in Table 3)
%D > 30.0 or < -30.0 (all other volatile
target compounds)
%D > 50.0 or < -50.0 (all volatile
target compounds)
UJ
%D < 40.0 and > -40.0 (volatile target
compounds listed in Table 3)
%D < 30.0 and > -30.0 (all other volatile
target compounds)
%D < 50.0 and >-50.0 (all
volatile target compounds)
No qualification
June 2008
23
Final
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Trace Volatiles Organic Analysis
Criteria for Opening CCV
Criteria for Closing CCV
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
Opening CCV not performed at required
frequency (see Trace Volatiles Organic
Analysis, Section I V.C.I)
Closing CCV not performed at
required frequency (see Trace
Volatile Organic Analysis,
Section I V.C.I)
R
June 2008
24
Final
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Trace Volatiles Organic Analysis
V. Blanks
A. Review Items:
Form I VOA-1, Form I VOA-2, Form I VOA-TIC, Form IVOA-SIM, Form IV VGA, Form IV VOA-
SIM, chromatograms, and quantitation reports.
B. Objective:
The purpose of laboratory, field, or trip blank analyses is to determine the existence and magnitude of
contamination resulting from laboratory, field, or sample transport activities. The purpose of the method
blank is to determine the levels of contamination associated with the processing and analysis of the
samples. The storage blank indicates whether contamination may have occurred during storage of
samples. The results from the instrument blank analysis indicate whether there is contamination from the
analysis of a previous sample. The criteria for evaluation of blanks apply to any blank associated with the
samples (e.g., method blanks, instrument blanks, storage blanks, field blanks, or trip blanks). If problems
with any blank exist, all associated data must be carefully evaluated to determine whether or not there is
an inherent variability in the data or if the problem is an isolated occurrence not affecting other data.
C. Criteria:
1. Method Blanks
A method blank analysis must be performed after the calibration standards and once for every 12-
hour time period.
The method blank must be analyzed on each Gas Chromatograph/Mass Spectrometer (GC/MS)
system used to analyze samples.
2. Storage Blanks
A storage blank must be prepared upon receipt of the first samples from a Sample Delivery Group
(SDG), and stored with the samples until analysis. The storage blank must be analyzed once per
SDG.
3. Instrument Blanks
An instrument blank must be analyzed immediately after any sample that has saturated ions (target
compounds that exceed the calibration range or non-target compounds that exceed 100 (ig/L) from a
given compound to check that the blank is free of interference and the system is not contaminated.
The concentration of each target compound in the instrument blank must be less than its Contract
Required Quantitation Limit (CRQL) listed in the method.
NOTE: The concentration of each target compound found in the storage, method, field, or trip blanks
must be less than its CRQL listed in the method, except for methylene chloride, acetone, and 2-
butanone, which must be less than 2x their respective CRQLs. The concentration of non-target
compounds in all blanks must be less than 2.0 ug/L.
D. Evaluation:
1. Review the results of all associated blanks on the forms and raw data (chromatograms and
quantitation reports) to evaluate the presence of target and non-target compounds in the blanks.
June 2008 25 Final
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Trace Volatiles Organic Analysis
2. Verify that a method blank analysis has been reported for each 12-hour time period on each GC/MS
system used to analyze volatile samples. The reviewer can use the Method Blank Summary (Form IV
VOA and Form IV VOA-SIM) to identify the samples associated with each method blank.
3. Verify that a storage blank has been analyzed and included with each SDG.
4. Verify that the instrument blank analysis has been performed following any sample analysis where a
target analyte(s) is/are reported at high concentration(s).
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process. Data concerning the field or
trip blanks are not evaluated as part of the CCS process. If field or trip blanks are present, the
data reviewer should evaluate this data in a similar fashion as the method blanks.
E. Action:
Action regarding unsuitable blank results depends on the circumstances and origin of the blank. In
instances where more than one of the same type of blank is associated with a given sample, qualification
should be based upon a comparison with the associated blank having the highest concentration of a
contaminant. Do not correct the results by subtracting any blank value.
1. If a volatile compound is found in a method blank, but not found in the sample, no qualification of the
data is necessary (see Table 6).
2. If the method blank concentration is less than the CRQL (less than 2x the CRQL for methylene
chloride, 2-butanone, and acetone) and:
a. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene chloride,
2-butanone, and acetone), report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), and less than 2x the CRQL (less than 4x
the CRQL for methylene chloride, 2-butanone, and acetone), use professional judgment.
c. the sample concentration is greater than or equal to 2x the CRQL (greater than or equal to 4x the
CRQL for methylene chloride, 2-butanone, and acetone), no qualification of the data is necessary.
3. If the method blank concentration is greater than the CRQL (greater than 2x the CRQL for methylene
chloride, 2-butanone, and acetone) and:
a. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene chloride,
2-butanone, and acetone), report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), and less than the blank concentration,
report the concentration of the compound in the sample at the same concentration found in the
blank and qualify with a "U", or the reviewer may elect to qualify the data as unusable "R".
c. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone) and greater than or equal to the blank
concentration, use professional judgment to qualify the data.
4. If the method blank concentration is equal to the CRQL (equal to 2x the CRQL for methylene
chloride, 2-butanone, and acetone) and:
a. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene chloride,
2-butanone, and acetone), report the CRQL value with a "U".
June 2008 26 Final
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Trace Volatiles Organic Analysis
b. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), use professional judgment to qualify the
data.
5. If gross contamination exists (i.e., saturated peaks by GC/MS), qualify all affected compounds in the
associated samples as unusable "R" due to interference. Note, for Contract Laboratory Program
Project Officer (CLP PO) action, if the contamination is suspected of having an effect on the sample
results.
6. Give the same consideration as the target compounds to the Tentatively Identified Compounds
(TICs), which are found in both the sample and associated blank(s) (see Trace Volatiles Organic
Analysis, Section XII, for TIC guidance).
7. If the contaminants found in the blank are interfering non-target compounds at concentrations greater
than 2 (ig/L, use professional judgment to qualify the data.
NOTE: There may be instances where little or no contamination was present in the associated blanks, but
qualification of the sample is deemed necessary. If the reviewer determines that the contamination
is from a source other than the sample, they should qualify the data. Contamination introduced
through dilution water is one example. Although it is not always possible to determine, instances
of this occurring can be detected when contaminants are found in the diluted sample result, but
are absent in the undiluted sample result.
8. If an instrument blank was not analyzed following a sample analysis which contained an analyte(s) at
high concentration(s), evaluate the sample analysis results immediately after the high concentration
sample for carryover. Use professional judgment to determine if instrument cross-contamination has
affected any positive compound identification(s). Note, for CLP PO action, if instrument cross-
contamination is suggested and suspected of having an effect on the sample results.
9. If contaminants are found in the storage, field, or trip blanks, the following is recommended:
a. Review the associated method blank data to determine if the contaminant(s) was also present in
the method blank.
i. If the analyte was present at a comparable level in the method blank, the source of the
contamination may be in the analytical system and the action recommended for the method
blank would apply.
ii. If the analyte was not present in the method blank, the source of contamination may be in the
storage area, in the field, or during sample transport. Consider all associated samples for
possible cross-contamination.
b. If the storage, field, or trip blanks contain a volatile Target Compound List (TCL) compound(s) at
a concentration less than the CRQL (less than 2x the CRQL for methylene chloride, 2-butanone,
and acetone), and:
i. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene
chloride, 2-butanone and acetone), report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to 2x the CRQL (greater than or equal to 4x
the CRQL for methylene chloride, 2-butanone and acetone), no qualification of the data is
necessary.
iii. the sample concentration is greater than or equal to the CRQL and less than 2x the CRQL
(less than 4x the CRQL for methylene chloride, 2-butanone and acetone), use professional
judgment to qualify the data.
c. If the storage, field, or trip blanks contain a volatile TCL compound(s) at a concentration equal to
the CRQL (2x the CRQL for methylene chloride, 2-butanone and acetone) and:
June 2008 27 Final
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Trace Volatiles Organic Analysis
i. the sample concentration is less than or equal to the CRQL (less than or equal to 2x the
CRQL for methylene chloride, 2-butanone and acetone), report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone and acetone), use professional judgment to qualify
the data.
d. If the storage, field, or trip blanks contain a volatile TCL compound(s) at a concentration greater
than the CRQL (greater than 2x the CRQL for methylene chloride, 2-butanone, and acetone), and:
i. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene
chloride, 2-butanone, and acetone), report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), and less than the blank
concentration, report the concentration of the compound in the sample at the same
concentration found in the blank and qualify with a "U", or the reviewer may elect to qualify
the data as unusable "R".
iii. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), and greater than or equal to the
blank concentration, use professional judgment to qualify the data.
e. If gross contamination [greater than 2x the CRQL (greater than 4x the CRQL for methylene
chloride, 2-butanone and acetone)] exists in the storage, field, or trip blank, positive sample
results may require rejection and be qualified as unusable "R". Non-detected volatile target
compounds do not require qualification unless the contamination is so high that it interferes with
the analyses of non-detected compounds.
f If the contaminants found in the blank are interfering non-target compounds at concentrations
greater than 2 (ig/L, use professional judgment to qualify the data.
Table 6. Blank Actions for Trace Volatiles Analyses
Blank Type
Method,
Storage, Field,
Trip,
Instrument***
Blank Result
Detects
< CRQL *
> CRQL *
— PT?rvr *
TIC >2 ng/L
Sample Result
Not detected
< CRQL*
> CRQL* and < 2x the CRQL**
>2x the CRQL**
< CRQL*
> CRQL* and < blank concentration
> CRQL* and > blank concentration
< CRQL*
> CRQL*
Detects
Action for Samples
No qualification
Report CRQL value with a U
Use professional judgment
No qualification
Report CRQL value with a U
Report the blank concentration for
the sample with a U or qualify the
data as unusable R
Use professional judgment
Report CRQL value with a U
Use professional judgment
Use professional judgment
2x the CRQL for methylene chloride, 2-butanone and acetone.
4x the CRQL for methylene chloride, 2-butanone, and acetone.
Qualifications based on instrument blank results affect only the sample analyzed immediately after the sample that has
target compounds that exceed the calibration range or non-target compounds that exceed 100 ug/L.
June 2008
28
Final
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Trace Volatiles Organic Analysis
VI. Deuterated Monitoring Compounds (DMCs)
A. Review Items:
Form II VOA-1, Form II VOA-2, Form II VOA-SIM1, Form II VOA-SIM2, quantitation reports, and
chromatograms.
B. Objective:
Laboratory performance on individual samples is established by means of spiking activities. All samples
are spiked with DMCs just prior to sample purging. The evaluation of the results of these DMCs is not
necessarily straightforward. The sample itself may produce effects due to such factors as interferences.
Since the effects of the sample matrix are frequently outside the control of the laboratory and may present
relatively unique problems, the evaluation and review of data based on specific sample results is
frequently subjective and requires analytical experience and professional judgment. Accordingly, this
section consists primarily of guidelines, in some cases with several optional approaches suggested.
C. Criteria:
The DMCs listed in Table 7 are added to all samples and blanks to measure their recovery in
environmental samples.
Table 7. Volatile Deuterated Monitoring Compounds (DMCs) and Recovery Limits
DMC
Vinyl chloride-d3
Chloroethane-d5
1 , 1 -Dichloroethene-d2
2-Butanone-d5
Chloroform-d
1 ,2-Dichloroethane-d4
Benzene-dg
Recovery Limits (%)
65-131
71-131
55 - 104
49-155
78 - 121
78 - 129
77 - 124
DMC
1 ,2-Dichloropropane-d,j
Toluene-d8
trans- 1 ,3-Dichloropropene-d4
2-Hexanone-d5
1 , 1 ,2,2-Tetrachloroethane-d2
1 ,2-Dichlorobenzene-d4
Recovery Limits (%)
79 - 124
77-121
73 - 121
28-135
73 - 125
80-131
Recoveries for DMCs in volatile samples and blanks must be within the limits specified in Table 7.
NOTE:
D. Evaluation:
The recovery limits for any of the compounds listed in Table 7 may be expanded at any time
during the period of performance if USEPA determines that the limits are too restrictive.
1. Check raw data (e.g., chromatograms and quantitation reports) to verify the recoveries on the
Deuterated Monitoring Compound Recovery Forms (Form II VOA-1, Form II VOA-2, Form II VOA-
3, Form IIVOA-4, Form IIVOA-SIM, and Form II VOA SIM2).
Check for any calculation or transcription errors; verify that the DMC recoveries were calculated
correctly using the equation in the method.
2. Whenever there are two or more analyses for a particular sample, the reviewer must determine which
are the most acceptable data to report. Considerations include, but are not limited to:
June 2008
29
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Trace Volatiles Organic Analysis
a. DMC recovery (marginal versus gross deviation).
b. Technical holding times.
c. Comparison of the values of the target compounds reported in each sample analysis.
d. Other Quality Control (QC) information, such as performance of internal standards.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
Table 9 lists the volatile DMCs and their associated target compounds. If any DMC recovery in the
volatiles fraction is out of specification, qualify the data considering the existence of interference in the
raw data (see Table 8). Considerations include, but are not limited to:
1. For any recovery greater than the upper acceptance limit:
a. Qualify detected associated volatile target compounds as a "J".
b. Do not qualify non-detected associated volatile target compounds.
2. For any recovery greater than or equal to 20%, and less than the lower acceptance limit:
a. Qualify detected associated volatile target compounds as a "J".
b. Qualify non-detected associated volatile target compounds as approximated "UJ".
3. For any recovery less than 20%:
a. Qualify detected associated volatile target compounds as a "J".
b. Qualify non-detected associated volatile target compounds as unusable "R".
4. For any recovery within acceptance limits, no qualification of the data is necessary.
5. In the special case of a blank analysis having DMCs out of specification, the reviewer must give
special consideration to the validity of associated sample data. The basic concern is whether the
blank problems represent an isolated problem with the blank alone, or whether there is a fundamental
problem with the analytical process. For example, if one or more samples in the batch show
acceptable DMC recoveries, the reviewer may choose to consider the blank problem to be an isolated
occurrence. However, even if this judgment allows some use of the affected data, note analytical
problems for Contract Laboratory Program Project Officer (CLP PO) action.
June 2008 30 Final
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Trace Volatiles Organic Analysis
Table 8. Deuterated Monitoring Compound (DMC) Recovery Actions For Trace Volatiles Analyses
Criteria
%R > Upper Acceptance Limit
20% %R < Lower Acceptance Limit
%R < 20%
Lower Acceptance Limit < %R < Upper Acceptance Limit
Action
Detected Associated
Compounds
J
J
J
Non-detected
Associated
Compounds
No qualification
UJ
R
No qualification
June 2008
31
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Trace Volatiles Organic Analysis
Table 9. Volatile Deuterated Monitoring Compounds (DMCs) and the Associated Target Compounds
Chloroethane-d5 (DMC)
Dichlorodifluoromethane
Chloromethane
Bromomethane
Chloroethane
Carbon disulfide
trans- 1 ,3-Dichloropropene-d4 (DMC)
cis-1 ,3-Dichloropropene
trans- 1 ,3-Dichloropropene
1 ,1 ,2-Trichloroethane
2-Butanone-d5 (DMC)
Acetone
2-Butanone
Vinyl chloride-d3 (DMC)
Vinyl chloride
l,2-Dichloroethane-d4 (DMC)
Trichlorofluoromethane
1 ,1 ,2-Trichloro-l ,2,2-trifluoroethane
Methyl acetate
Methylene chloride
Methyl-tert-butyl ether
1,1,1 -Trichloroethane
Carbon tetrachloride
1 ,2-Dibromoethane
1 ,2-Dichloroethane
l,2-Dichloropropane-d(5 (DMC)
Cyclohexane
Methylcyclohexane
1 ,2-Dichloropropane
Bromodichloromethane
Chloroform-d (DMC)
1 , 1 -Dichloroethane
Bromochloromethane
Chloroform
Dibromochloromethane
Bromoform
l,l-Dichloroethene-d2 (DMC)
trans- 1 ,2-Dichloroethene
1 , 1 -Dichloroethene
cis- 1 ,2-Dichloroethene
Benzene-d6 (DMC)
Benzene
l,2-Dichlorobenzene-d4 (DMC)
Chlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
1 ,2,4-Trichlorobenzene
1 ,2,3-Trichlorobenzene
2-Hexanone-d5 (DMC)
4-Methyl-2-pentanone
2-Hexanone
l,l,2,2-Tetrachloroethane-d2 (DMC)
1 ,1 ,2,2,-Tetrachlororethane
1 ,2-Dibromo-3-chloropropane
Toluene-d8 (DMC)
Trichloroethene
Toluene
Tetrachloroethene
Ethylbenzene
o-Xylene
m,p-Xylene
Styrene
Isopropylbenzene
June 2008
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Trace Volatiles Organic Analysis
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
A. Review Items:
Form III VOA-1, chromatograms, and quantitation reports.
NOTE: Data for MS and MSDs will not be present unless requested by the Region.
B. Objective:
Data for MS and MSDs are generated to determine long-term precision and accuracy of the analytical
method on the sample matrix and to demonstrate acceptable compound recovery by the laboratory at the
time of sample analysis. These data alone cannot be used to evaluate the precision and accuracy of
individual samples. However, when exercising professional judgment, this data should be used in
conjunction with other available Quality Control (QC) information.
C. Criteria:
1. If requested, MS and MSD samples are analyzed at a frequency of one MS and MSD per 20 or fewer
samples.
2. Spike recoveries should be within the advisory limits provided on Form III VOA-1.
3. Relative Percent Difference (RPD) between MS and MSD recoveries must be within the advisory
limits provided on Form III VOA-1.
D. Evaluation:
1. Verify that requested MS and MSD samples were analyzed at the required frequency and results are
provided for each sample.
2. Inspect results for the MS and MSD Recovery on Form III VOA-1 and verify that the results for
recovery and RPD are within the advisory limits.
3. Verify transcriptions from raw data and check calculations.
4. Verify that the MS and MSD recoveries and RPD were calculated correctly.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. No qualification of the data is necessary on MS and MSD data alone. However, using informed
professional judgment, the data reviewer may use the MS and MSD results in conjunction with other
QC criteria to determine the need for some qualification of the data. Table 11 lists the volatile target
compounds that are spiked into samples to test for matrix effects. If any MS and MSD Percent
Recovery or RPD in the volatiles fraction is out of specification, qualify data to include the
consideration of the existence of interference in the raw data (see Table 10). Considerations include,
but are not limited to:
a. For any recovery or RPD greater than the upper acceptance limit:
i. Qualify detected spiked volatile target compounds as a "J".
June 2008 33 Final
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Trace Volatiles Organic Analysis
ii. Do not qualify non-detected spiked volatile target compounds.
b. For any recovery greater than or equal to 20%, and less than the lower acceptance limit:
i. Qualify detected spiked volatile target compounds as a "J".
ii. Qualify non-detected spiked volatile target compounds as approximated "UJ".
c. For any recovery less than 20%:
i. Qualify detected spiked volatile target compounds as a "J".
ii. Qualify non-detected spiked volatile target compounds using professional judgment.
d. For any recovery or RPD within acceptance limits, no qualification of the data is necessary.
2. The data reviewer should first try to determine to what extent the results of the MS and MSB affect
the associated data. This determination should be made with regard to the MS and MSB sample
itself, as well as specific analytes for all samples associated with the MS and MSB.
3. In those instances where it can be determined that the results of the MS and MSB affect only the
sample spiked, limit qualification to this sample only. However, it may be determined through the
MS and MSB results that a laboratory is having a systematic problem in the analysis of one or more
analytes that affects all associated samples and the reviewer should use professional judgment to
qualify the data from all associated samples.
4. The reviewer must use professional judgment to determine the need for qualification of detects of
non-spiked compounds.
NOTE: Notify the Contract Laboratory Program Project Officer (CLP PO) if a field or trip blank was
used for the MS and MSB.
Table 10. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Trace Volatiles Analysis
Criteria
%R or RPD> Upper Acceptance Limit
20% < %R< Lower Acceptance Limit
%R < 20%
Lower Acceptance Limit < %R; RPD <
Upper Acceptance Limit
Action
Detected Spiked
Compounds
J
J
J
Non-detected Spiked
Compounds
No qualification
UJ
Use professional
judgment
No qualification
Table 11. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD) Limits
Compound
1 , 1 -Dichloroethene
Benzene
Trichloroethene
Toluene
Chlorobenzene
Percent Recovery
61 - 145
76 - 127
71 - 120
76 - 125
75 - 130
RPD
0-14
0-11
0-14
0-13
0-13
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Trace Volatiles Organic Analysis
VIII. Regional Quality Assurance (OA) and Quality Control (OC)
A. Review Items:
Form I VOA-1, Form I VOA-2, Form I VOA-SIM, chromatograms, Traffic Report/Chain of Custody
Record (TR/COC), quantitation reports, and other raw data from QA/QC samples.
B. Objective:
Regional QA/QC samples refer to any QA and/or QC samples initiated by the Region, including field
duplicates, Performance Evaluation (PE) samples, blind spikes, and blind blanks. The use of these
QA/QC samples is highly recommended (e.g., the use of field duplicates can provide information on
sampling precision and homogeneity).
C. Criteria:
Criteria are determined by each Region.
1. PE sample frequency may vary.
2. The analytes present in the PE sample must be correctly identified and quantified.
D. Evaluation:
1. Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data review.
Each Region will handle the evaluation of PE samples on an individual basis. Compare results for PE
samples to the acceptance criteria for the specific PE samples, if available.
2. Calculate Relative Percent Difference (RPD) between field duplicates. Provide this information in
the Data Review Narrative.
E. Action:
Any action must be in accordance with Regional specifications and the criteria for acceptable PE sample
results. Note, for Contract Laboratory Program Project Officer (CLP PO) action, unacceptable results for
PE samples.
June 2008 35 Final
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Trace Volatiles Organic Analysis
IX. Internal Standards
A. Review Items:
Form VIII VOA, Form VIII VOA-SIM, quantitation reports, and chromatograms.
B. Objective:
Internal standard performance criteria ensures that Gas Chromatograph/Mass Spectrometer (GC/MS)
sensitivity and response are stable during each analysis.
C. Criteria:
1. The internal standard area counts for all samples [including Matrix Spike and Matrix Spike Duplicate
(MS/MSD), and Performance Evaluation (PE) samples] and all blanks must not vary more than
±40.0% from the associated 12-hour calibration standard [opening Continuing Calibration
Verification (CCV) or mid-point standard from initial calibration].
2. The Retention Time (RT) of the internal standard in the sample or blank must not vary more than ±20
seconds from the RT of the internal standard in the associated 12-hour calibration standard (opening
CCV or mid-point standard from initial calibration).
D. Evaluation:
1. Check raw data (e.g., chromatograms and quantitation lists) to verify the internal standard RTs and
areas reported on the Internal Standard Area Summary (Form VIII VOA, Form VIII VOA-SIM).
2. Verify that all RTs and internal standard areas are within criteria for all samples and blanks.
3. If there are two analyses for a particular fraction, the reviewer must determine which are the best data
to report. Considerations include, but are not limited to:
a. Magnitude and direction of the internal standard area shift.
b. Magnitude and direction of the internal standard RT shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each fraction.
e. Other Quality Control (QC) information.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding the
laboratory's compliance with these criteria can be obtained from the Data Assessment Tool (DAT)
reports, and may be used as part of the evaluation process.
E. Action:
1. If an internal standard area count for a sample or blank is greater than 140.0% of the area for the
associated standard (opening CCV or mid-point standard from initial calibration) (see Table 12):
a. Qualify detects for compounds quantitated using that internal standard with a "J".
b. Do not qualify non-detected associated compounds.
2. If an internal standard area count for a sample or blank is less than 60.0% of the area for the
associated standard (opening CCV or mid-point standard from initial calibration):
June 2008 36 Final
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Trace Volatiles Organic Analysis
a. Qualify detects for compounds quantitated using that internal standard with a "J".
b. Qualify non-detected associated compounds as unusable "R".
3. If an internal standard area count for a sample or blank is greater than or equal to 60.0%, and less than
140% of the area for the associates standard opening CCV or mid-point standard from initial
calibration, no qualification of the data is necessary.
4. If an internal standard RT varies by more than 20.0 seconds:
Examine the chromatographic profile for that sample to determine if any false positives or negatives
exist. For shifts of a large magnitude, the reviewer may consider partial or total rejection of the data
for that sample fraction. Detects should not need to be qualified as unusable "R" if the mass spectral
criteria are met.
5. If an internal standard RT varies by less than or equal to 20.0 seconds, no qualification of the data is
necessary.
6. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if the internal standard
performance criteria are grossly exceeded. Note in the Data Review Narrative potential effects on the
data resulting from unacceptable internal standard performance.
Table 12. Internal Standard Actions for Trace Volatiles Analyses
Criteria
Area counts > 140% of 12-hour standard (opening CCV or mid-point
standard from initial calibration)
Area counts < 60% of 12-hour standard (opening CCV or mid-point
standard from initial calibration)
Area counts > 60% but < 140% of 12-hour standard (opening CCV or
mid-point standard from initial calibration)
RT difference > 20.0 seconds between samples and 12-hour standard
(opening CCV or mid-point standard from initial calibration)
RT difference < 20.0 seconds between samples and 12-hour standard
(opening CCV or mid-point standard from initial calibration)
Action
Detected
Associated
Compounds*
J
J
Non-detected
Associated
Compounds*
No qualification
R
No qualification
R**
No qualification
For volatile compounds associated to each internal standard, see Table 3 - Trace Volatile Target Compounds and Deuterated
Monitoring Compounds with Corresponding Internal Standards for Quantitation in SOM01.2. Exhibit D. available at:
http://www.epa.gov/superfund/programs/clp/soml.htm
See Trace Volatiles Organic Analysis, Section IX.E.4.
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X. Target Compound Identification
A. Review Items:
Form I VOA-1, Form I VOA-2, Form I VOA-SIM, quantitation reports, mass spectra, and
chromatograms.
B. Objective:
The objective of the criteria for Gas Chromatograph/Mass Spectrometer (GC/MS) qualitative analysis is
to minimize the number of erroneous compound identifications. An erroneous identification can either be
a false positive (reporting a compound present when it is not) or a false negative (not reporting a
compound that is present).
The identification criteria can be applied more easily in detecting false positives than false negatives.
More information is available for false positives due to the requirement for submittal of data supporting
positive identifications. Negatives, or non-detected compounds, on the other hand, represent an absence
of data and are, therefore, more difficult to assess. One example of the detection of false negatives is not
reporting a target compound that is reported as a Tentatively Identified Compound (TIC).
C. Criteria:
1. The Relative Retention Times (RRTs) must be within ±0.06 RRT units of the standard RRT [opening
Continuing Calibration Verification (CCV) or mid-point standard from initial calibration].
2. Mass spectra of the sample compound and a current laboratory-generated standard [i.e., the mass
spectrum from the associated calibration standard (opening CCV or mid-point standard from initial
calibration)] must match according to the following criteria:
a. All ions present in the standard mass spectrum at a relative intensity greater than 10% must be
present in the sample spectrum.
b. The relative intensities of these ions must agree within ±20% between the standard and sample
spectra (e.g., for an ion with an abundance of 50% in the standard spectrum, the corresponding
sample ion abundance must be between 30-70%).
c. Ions present at greater than 10% in the sample mass spectrum, but not present in the standard
spectrum, must be evaluated by a reviewer experienced in mass spectral interpretation.
D. Evaluation:
1. Check that the RRT of reported compounds is within ±0.06 RRT units of the standard RRT (opening
CCV or mid-point standard from the initial calibration).
2. Check the sample compound spectra against the laboratory standard spectra to verify that it meets the
specified criteria.
3. The reviewer should be aware of situations when sample carryover is a possibility and should use
professional judgment to determine if instrument cross-contamination has affected any positive
compound identification. The method specifies that an instrument blank must be run after samples
which contain target compounds at levels exceeding the initial calibration range (20 ug/L for non-
ketones, 200 ug/L for ketones), or non-target compounds at concentrations greater than 100 ug/L, or
saturated ions from a compound (excluding the compound peaks in the solvent front).
June 2008 38 Final
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Trace Volatiles Organic Analysis
4. Check the chromatogram to verify that peaks are identified. Major peaks are either identified as
target compounds, TICs, Deuterated Monitoring Compounds (DMCs), or internal standards.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. The application of qualitative criteria for GC/MS analysis of target compounds requires professional
judgment. It is up to the reviewer's discretion to obtain additional information from the laboratory. If
it is determined that incorrect identifications were made, qualify all such data as not detected "U" or
unusable "R".
2. Use professional judgment to qualify the data if it is determined that cross-contamination has
occurred.
3. Note in the Data Review Narrative any changes made to the reported compounds or concerns
regarding target compound identifications. Note, for Contract Laboratory Program Project Officer
(CLP PO) action, the necessity for numerous or significant changes.
June 2008 39 Final
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Trace Volatiles Organic Analysis
XL Compound Ouantitation and Reported Contract Required Ouantitation Limits (CRQLs)
A. Review Items:
Forms IVOA-1, Form I VOA-2, Form I VOA-SIM, sample preparation sheets, Sample Delivery Group
(SDG) Narrative, quantitation reports, and chromatograms.
B. Objective:
The objective is to ensure that the reported quantitation results and CRQLs are accurate.
C. Criteria:
1. Compound quantitation, as well as the adjustment of the CRQLs, must be calculated according to the
correct equation.
2. Compound Relative Response Factors (RRFs) must be calculated based on the internal standard
associated with that compound, as listed in the method. Quantitation must be based on the
quantitation ion (m/z) specified in the method for both the internal standards and target analytes. The
compound quantitation must be based on the average RRF from the associated initial calibration.
D. Evaluation:
1. Examine raw data to verify the correct calculation of all sample results reported by the laboratory.
Compare quantitation lists and chromatograms to the reported detects and non-detects sample results.
Check the reported values.
2. Verify that the correct internal standard, quantitation ion, and Mean Relative Response Factor (RRF)
were used to quantitate the compound. Verify that the same internal standard, quantitation ion, and
RRF are used consistently throughout, in both the calibration as well as the quantitation process.
3. Verify that the CRQLs have been adjusted to reflect all sample dilutions.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If any discrepancies are found, the Region's designated representative may contact the laboratory to
obtain additional information that could resolve any differences. If a discrepancy remains unresolved,
the reviewer must use professional judgment to decide which value is the most accurate. Under these
circumstances, the reviewer may determine that qualification of data is warranted. Note in the Data
Review Narrative a description of the reasons for data qualification and the qualification that is
applied to the data.
2. Note, for Contract Laboratory Program Project Officer (CLP PO) action, numerous or significant
failures to accurately quantify the target compounds or to properly evaluate and adjust CRQLs.
June 2008 40 Final
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Trace Volatiles Organic Analysis
XII. Tentatively Identified Compounds (TICs)
A. Review Items:
Form I VOA-TIC, chromatograms, library search printouts, and spectra for the TIC candidates.
B. Objective:
Chromatographic peaks in volatile fraction analyses that are not target analytes, Deuterated Monitoring
Compounds (DMCs), or internal standards are potential TICs. TICs must be qualitatively identified via a
forward search of the NIST/USEPA/NIH Mass Spectral Library (May 2002 release or later)1, and/or
Wiley Mass Spectral Library (1998 release or later)2, or the equivalent. The identifications must be
assessed by the data reviewer.
C. Criteria:
For each sample, the laboratory must conduct a mass spectral search of the NIST/USEPA/NIH (May 2002
release or later), and/or Wiley (1998 release or later), or equivalent mass spectral library, and report the
possible identity for 30 of the largest volatile fraction peaks which are not DMCs, internal standards, or
target compounds, but which have an area or height greater than 10% of the area or height of the nearest
internal standard. Estimated concentrations for TICs are calculated similarly to the Target Compound
List (TCL) compounds, using total ion areas for the TIC and the internal standard, and assuming a
Relative Response Factor (RRF) of 1.0. TIC results are reported for each sample on the Organic
Analyses Data Sheet (Form I VOA-TIC).
D. Evaluation:
1. Guidelines for tentative identification are as follows:
a. Major ions (greater than 10% Relative Intensity) in the reference spectrum should be present in
the sample spectrum.
b. The relative intensities of the major ions should agree within ±20% between the sample and the
reference spectra.
c. Molecular ions present in the reference spectrum should be present in the sample spectrum.
d. Review ions present in the sample spectrum, but not in the reference spectrum, for possible
background contamination, interference, or presence of coeluting compounds.
e. Review ions present in the reference spectrum, but not in the sample spectrum, for possible
subtraction from the sample spectrum because of background contamination or coeluting
compounds. Data system library reduction programs can sometimes create these discrepancies.
f Non-target compounds receiving a library search match of 85% or higher are considered a "likely
match". Report the compound unless the mass spectral interpretation specialist feels there is
evidence not to report the compound as identified by the library search program. Note in the
Sample Delivery Group (SDG) Narrative the justification for not reporting a compound as listed
by the search program.
'NIST/USEPA/NIH Mass Spectral Library (May 2002 release or later), National Institute of Standards and Technology, Gaithersburg,
Maryland.
Wiley Mass Spectral Library (1998 release or later) John Wiley & Sons, Inc., Hoboken, New Jersey.
June 2008 41 Final
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Trace Volatiles Organic Analysis
g. If the library search produces more than one compound greater than or equal to 85%, report the
compound with the highest percent match (report first compound if percent match is the same for
two or more compounds), unless the mass spectral interpretation specialist feels that the highest
match compound should not be reported or another compound with a lower match should be
reported. The laboratory should include the justification for not reporting the compound with the
highest spectral match within the SDG Narrative. Do not report DMCs, internal standards, and
volatile target compounds as TICs, unless the only compounds having a percent match of greater
than 85% are DMCs, internal standards, or volatile target compounds.
h. If the library search produces a series of obvious isomer compounds with library search matches
greater than or equal to 85%, report the compound with the highest library search percent match
(or the first compound if the library search matches are the same). Note in the SDG Narrative
that the exact isomer configuration, as reported, may not be accurate.
i. If the library search produces no matches greater than or equal to 85%, and in the technical
judgment of the mass spectral interpretation specialist, no valid tentative identification can be
made, report the compound as unknown. The mass spectral specialist should give additional
classification of the unknown compound, if possible (e.g., unknown aromatic, unknown
hydrocarbon, unknown acid type, unknown chlorinated compound). If probable molecular
weights can be distinguished, include them.
j. Alkanes are not to be reported as TICs on Form IVOA-TIC. An alkane is defined as any
hydrocarbon with the generic formula CnH2n+2 that contains only C-H and C-C single bonds.
When the preceding alkanes are tentatively identified, estimate the concentration(s) and report
them in the SDG Narrative as alkanes by class (i.e., straight-chain, branched, cyclic, as a series,
or as applicable). Report total alkanes concentration on Form I VOA-TIC.
2. Check the raw data to verify that the laboratory has generated a library search for all required peaks in
the chromatograms for samples and blanks.
3. Examine blank chromatograms to verify that TIC peaks present in samples are not found in blanks.
When a low-level, non-target compound that is a common artifact or laboratory contaminant is
detected in a sample, a thorough check of blank chromatograms may require looking for peaks which
are less than 10% of the internal standard height, but present in the blank chromatogram at a similar
Relative Retention Time (RRT).
4. Examine all mass spectra for every sample and blank.
5. Consider all reasonable choices, since TIC library searches often yield several candidate compounds
having a close matching score.
6. Be aware of common laboratory artifacts/contaminants and their sources (e.g., Aldol condensation
products, solvent preservatives, and reagent contaminants). These may be present in blanks and not
reported as sample TICs.
Examples:
Common laboratory contaminants include CO2 (m/z 44), siloxanes (m/z 73), diethyl ether,
hexane, certain freons, and phthalates at levels less than 100 (ig/L.
Solvent preservatives include cyclohexene, (a methylene chloride preservative). Related by-
products include cyclohexanone, cyclohexenone, cyclohexanol, cyclohexenol,
chlorocyclohexene, and chlorocyclohexanol.
Aldol condensation reaction products of acetone include: 4-hydroxy-4-methyl-2-pentanone, 4-
methyl-2-penten-2-one, and 5,5-dimethyl-2(5H)-furanone.
June 2008 42 Final
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Trace Volatiles Organic Analysis
7. A target compound may be identified in the proper analytical fraction by non-target library search
procedures, even though it was not found on the quantitation list (false negative). If the total area
quantitation method was used, request that the laboratory recalculate the result using the proper
quantitation ion and Relative Response Factor (RRF).
A non-target compound may be incorrectly identified by the instrument's target analyte data processor
as a target compound (false positive). When this happens, the non-target library search procedure
will not detect the false positive as a TIC. In this case, request that the laboratory properly identify
the compound and recalculate the result using the total area quantitation method and a RRF of 1.0.
Evaluate other sample chromatograms and check for both false negatives and false positives to
determine if the occurrence is isolated or systematic.
8. Target compounds may be identified in more than one fraction. Verify that quantitation is made from
the proper fraction.
9. Do not perform library searches on internal standards or DMCs.
10. Estimate TIC concentration assuming an RRF of 1.0.
E. Action:
1. Qualify all TIC results for which there is presumptive evidence of a match (e.g. greater than or equal
to 85% match) as "NJ", tentatively identified, with approximated concentrations.
2. General actions related to the review of TIC results are as follows:
a. If it is determined that a tentative identification of a non-target compound is unacceptable, change
the tentative identification to "unknown" or another appropriate identification, and qualify the
result with a "J".
b. If all contractually-required peaks were not library searched and quantitated, the Region's
designated representative may request these data from the laboratory.
3. In deciding whether a library search result for a TIC represents a reasonable identification, use
professional judgment. If there is more than one possible match, report the result as "either
compound X or compound Y". If there is a lack of isomer specificity, change the TIC result to a non-
specific isomer result (e.g., 1,3,5-trimethyl benzene to trimethyl benzene isomer) or to a compound
class (e.g., 2-methyl, 3-ethyl benzene to a substituted aromatic compound).
4. The reviewer may elect to report all similar compounds as a total (e.g., all alkanes may be
summarized and reported as total hydrocarbons).
5. Other Case factors may influence TIC judgments. If a sample TIC match is poor, but other samples
have a TIC with a valid library match, similar RRT, and the same ions, infer identification
information from the other sample TIC results.
6. Note in the Data Review Narrative any changes made to the reported data or any concerns regarding
TIC identifications.
7. Note, for Contract Laboratory Program Project Officer (CLP PO) action, failure to properly evaluate
and report TICs.
June 2008 43 Final
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Trace Volatiles Organic Analysis
XIII. System Performance
A. Review Items:
Form VIII VOA, Form VIII VOA-SIM, and chromatograms.
B. Objective:
During the period following Instrument Performance Quality Control (QC) checks (e.g., blanks, tuning,
calibration), changes may occur in the system that degrade the quality of the data. While this degradation
would not be directly shown by QC checks until the next required series of analytical QC runs, a thorough
review of the ongoing data acquisition can yield indicators of instrument performance.
C. Criteria:
There are no specific criteria for system performance. Use professional judgment to assess the system
performance.
D. Evaluation:
1. Abrupt discrete shifts in the Reconstructed Ion Chromatogram (RIC) baseline may indicate a change
in the instrument's sensitivity or the zero setting. A baseline "shift" could indicate a decrease in
sensitivity in the instrument or an increase in the instrument zero, possibly causing target compounds
at or near the detection limit to miss detection. A baseline "rise" could indicate problems such as a
change in the instrument zero, a leak, or degradation of the column.
2. Poor chromatographic performance affects both qualitative and quantitative results. Indications of
substandard performance include:
a. High RIC background levels or shifts in Absolute Retention Times (RTs) of internal standards.
b. Excessive baseline rise at elevated temperature.
c. Extraneous peaks.
d. Loss of resolution.
e. Peak tailing or peak splitting that may result in inaccurate quantitation.
3. A drift in instrument sensitivity may occur during the 12-hour time period and may be an indication
of possible internal standard spiking problems. This could be discerned by examination of the
internal standard area on Form VIII VOA for trends such as a continuous or near-continuous increase
or decrease in the internal standard area over time.
E. Action:
Use professional judgment to qualify the data if it is determined that system performance has degraded
during sample analyses. Note, for Contract Laboratory Program Project Officer (CLP PO) action, any
degradation of system performance which significantly affected the data.
June 2008 44 Final
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Trace Volatiles Organic Analysis
XIV. Overall Assessment of Data
A. Review Items:
Entire data package, data review results, and (if available), the Quality Assurance Project Plan (QAPP)
and Sampling and Analysis Plan (SAP).
B. Objective:
The overall assessment of a data package is a brief narrative in which the data reviewer expresses
concerns and comments on the quality and, if possible, the usability of the data.
C. Criteria:
Review all available materials to assess the overall quality of the data, keeping in mind the additive nature
of analytical problems.
D. Evaluation:
1. Evaluate any technical problems which have not been previously addressed.
2. If appropriate information is available, the reviewer may assess the usability of the data to help the
data user avoid inappropriate use of the data. Review all available information, including the QAPP
(specifically the acceptance and performance criteria), SAP, and communication with the data user
that concerns the intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which were not qualified
based on the Quality Control (QC) criteria previously discussed.
2. Write a brief narrative to give the user an indication of the analytical limitations of the data. Note, for
Contract Laboratory Program Project Officer (CLP PO) action, any inconsistency of the data with the
Sample Delivery Group (SDG) Narrative. If sufficient information on the intended use and required
quality of the data are available, the reviewer should include their assessment of the usability of the
data within the given context. This may be used as part of a formal Data Quality Assessment (DQA).
June 2008 45 Final
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Low/Medium Volatiles Organic Analysis
LOW/MEDIUM VOLATILE DATA REVIEW
The data requirements to be checked are:
I. Preservation
II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check
III. Initial Calibration
IV. Continuing Calibration Verification (CCV)
V. Blanks
VI. Deuterated Monitoring Compounds (DMCs)
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
VIII. Regional Quality Assurance (QA) and Quality Control (QC)
IX. Internal Standards
X. Target Compound Identification
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XII. Tentatively Identified Compounds (TICs)
XIII. System Performance
XIV. Overall Assessment of Data
June 2008 46 Final
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Low/Medium Volatiles Organic Analysis
I. Preservation
A. Review Items:
Form IVOA-1, Form IVOA-2, Form IVOA-TIC, Traffic Report/Chain of Custody Record (TR/COC),
raw data, and the Sample Delivery Group (SDG) Narrative checking for:
1. pH
2. Sample temperature
3. Holding time
4. Other sample conditions (e.g., headspace)
B. Objective:
The objective is to ascertain the validity of the analytical results based on sample condition (i.e.,
preservation, temperature, headspace) and the holding time of the sample from the time of collection to
the time of analysis.
C. Criteria:
The technical holding time criterion for aqueous samples are as follows:
For volatile compounds in properly cooled (4°C ± 2°C) aqueous samples that are acid-preserved
(with HC1 to a pH of 2 or below), the maximum holding time is 14 days from sample collection.
For aqueous samples that were properly cooled (4°C ± 2°C), but which have no indication of
being preserved, the maximum holding time is 7 days from sample collection.
The technical holding time criterion for non-aqueous samples are as follows:
For volatile components that are frozen (less than -7°C) or are properly cooled (4°C ± 2°C) and
preserved with NaHSO4, the maximum holding time is 14 days from sample collection.
D. Evaluation:
Technical holding times are established by comparing the sample collection dates on the TR/COC Record
with the dates of analysis on Form I VOA-1, Form I VOA-2, Form I VOA-TIC, and the raw data.
Information contained in the Complete SDG File (CSF) should also be considered in the determination of
holding times. Verify that the analysis dates on Form I(s) and the raw data/SDG file are identical.
Review the SDG Narrative to determine if samples were preserved and arrived at the laboratory in proper
condition (e.g., received intact, appropriate sample temperature at receipt, pH, absence of air bubbles or
detectable headspace). If there is no indication in the SDG Narrative, the TR/COC Record, or the sample
records that there was a problem with the samples, the integrity of samples can be assumed to be
acceptable. If it is indicated that there were problems with the samples, the integrity of the sample may
have been compromised and professional judgment should be used to evaluate the effect of the problem
on the sample results.
June 2008 47 Final
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Low/Medium Volatiles Organic Analysis
E. Action:
1. Qualify aqueous sample results using preservation and technical holding time information as follows
(see Table 13):
a. If there is no evidence that the samples were properly preserved, and the samples were analyzed
within the technical holding time (7 days from sample collection), no qualification of the data is
necessary.
b. If there is no evidence that the samples were properly preserved, and the samples were analyzed
outside of the technical holding time (7 days from sample collection), qualify detects for all
volatile compounds with a "J" and non-detects as unusable "R".
c. If the samples were properly preserved, and the samples were analyzed within the technical
holding time (14 days from sample collection), no qualification of the data is necessary.
d. If the samples were properly preserved, and were analyzed outside of the technical holding time
(14 days from sample collection), qualify detects with a "J" and non-detects as unusable "R".
2. Qualify non-aqueous sample results using the preservation and technical holding time information as
follows (see Table 13):
a. If there is no evidence that the samples were properly preserved, and the samples were analyzed
within technical holding time (14 days from sample collection) qualify detects for all volatile
compounds with a "J" and non-detects as unusable "R".
b. If the samples were properly preserved and the samples were analyzed within the technical
holding time (14 days from sample collection), no qualification of the data is necessary.
c. If there is no evidence that the samples were properly preserved, and the samples were analyzed
outside the technical holding time (14 days from sample collection), qualify detects for all
volatile compounds with a "J" and non-detects as unusable "R".
d. If the samples were properly preserved, and the samples were analyzed outside the technical
holding time (14 days from sample collection), qualify detects for all volatile compounds with a
"J" and non-detects as unusable "R".
Table 13. Holding Time Actions for Low/Medium Volatile Analyses
Matrix
Aqueous
Non-Aqueous
Preserved
No
No
Yes
Yes
No
Yes
Yes/No
Criteria
< 7 days
> 7 days
< 14 days
> 14 days
< 14 days
< 14 days
> 14 days
Action
Detected Associated Non-Detected Associated
Compounds Compounds
No qualification
J
R
No qualification
J
J
R
R
No qualification
J
R
3. Use professional judgment to qualify samples whose temperature upon receipt at the laboratory is
either below 2 degrees centigrade or above 6 degrees centigrade.
June 2008
48
Final
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Low/Medium Volatiles Organic Analysis
4. Due to limited information concerning holding times for non-aqueous samples, it is left to the
discretion of the data reviewer to apply aqueous holding times or other information that is available.
5. Note in the Data Review Narrative, whenever possible, the effect of the holding time exceedance on
the resulting data.
6. Note, for Contract Laboratory Program Project Officer (CLP PO) action, when technical holding
times are exceeded.
June 2008 49 Final
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Low/Medium Volatiles Organic Analysis
II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check
A. Review Items:
Form V VOA, bromofluorobenzene (BFB) mass spectra, and mass listing.
B. Objective:
GC/MS instrument performance checks are performed to ensure adequate mass resolution, identification,
and to some degree, sensitivity. These criteria are not sample-specific. Conformance is determined using
standard materials, therefore, these criteria should be met in all circumstances.
C. Criteria:
1. The 12-hour clock begins with either the injection of BFB, or in cases where a closing Continuing
Calibration Verification (CCV) can be used for an opening CCV, the 12-hour clock begins with the
injection of the opening CCV.
2. Listed below are some, but not necessarily all, examples of acceptable analytical sequences
incorporating the use of the opening and/or closing CCV. Use these examples as a guide for possible
analytical sequences that can be expected. The criteria associated with these analytical sequences
have been evaluated as part of the Contract Compliance Screening (CCS) process.
Conditions for When Example
Sequence is Appropriate:
Acceptable Criteria That Must Be Met:
Notes:
Use Example 1 if time remains
on the 12-hour clock after the
initial calibration sequence.
BFB tunes meet instrument
performance criteria.
The five Initial Calibration standards
meet initial calibration criteria.
CCV A meets both opening and
closing CCV criteria.
CCV B meets closing CCV criteria.
The requirement of starting the new
12-hour clock for Analytical Sequence
2 with a new BFB tune is waived if
CCV A meets opening CCV criteria.
If CCV B meets opening CCV criteria,
a method blank and subsequent
samples may be analyzed immediately
after CCV B.
Use Example 2 if time remains
on the 12-hour clock after the
initial calibration sequence.
BFB tunes meet instrument
performance criteria.
The five Initial Calibration standards
meet initial calibration criteria.
CCV A meets closing CCV criteria
(but does not meet opening CCV
criteria).
CCV B meets opening CCV criteria.
CCV C meets closing CCV criteria.
CCV A does not meet opening CCV
criteria, therefore, a new BFB tune
must be performed, immediately
followed by CCV B before the method
blank and any samples may be
analyzed. In this case, the new 12-
hour clock and Analytical Sequence 2
begins with the injection of the new
BFB tune.
June 2008
50
Final
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Low/Medium Volatiles Organic Analysis
Conditions for When Example
Sequence is Appropriate:
Acceptable Criteria That Must Be Met:
Notes:
Use Example 3 if more than 12-
hours have elapsed since the
most recent initial calibration or
closing CCV,
OR
if the most recent closing CCV
was not or could not be used as
an opening CCV.
BFB tunes meet instrument
performance criteria.
CCV A meets opening CCV criteria.
CCV B meets both opening and
closing CCV criteria.
CCV C meets both opening and
closing CCV criteria.
The requirement of starting the new
12-hour clock for Analytical Sequence
2 with a new BFB tune is waived if
CCV B meets opening CCV criteria.
If CCV C meets opening CCV criteria,
a method blank and subsequent
samples may be analyzed immediately
after CCV C.
Use Example 4 if more than 12-
hours have elapsed since the
most recent initial calibration or
closing CCV,
OR
if the most recent closing CCV
was not or could not be used as
an opening CCV.
BFB tunes meet instrument
performance criteria.
CCV A meets opening CCV criteria.
CCV B meets closing CCV criteria
(but does not meet opening CCV
criteria).
CCV C meets opening CCV criteria.
CCV D meets both opening and
closing CCV criteria.
Because CCV B does not meet
opening CCV criteria before the
method blank and any samples may be
analyzed, a new BFB tune must be
performed, immediately followed by
CCV C. In this case, the new 12-hour
clock and Analytical Sequence 2
begins with the injection of the new
BFB tune. The requirement of starting
the new 12-hour clock for Analytical
Sequence 3 with a new BFB tune is
waived if CCV D meets opening CCV
criteria. If CCV D meets opening
CCV criteria, a method blank and
subsequent samples may be analyzed
immediately after CCV D.
June 2008
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Final
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Low/Medium Volatiles Organic Analysis
Example 1: Time Material Injected
Start of 12-hour clock for „, T-.-r.-n
, . , . . „ , 0 hr BFB
Analytical Sequence 1
Initial Calibration 5.0
Initial Calibration 10
Initial Calibration 50
Initial Calibration 100
Initial Calibration 200
Method Blank
Subsequent Samples
•
•
•
•
Analytical Sequence #
1
1
1
1
1
1
1
1
1
1
1
1
End of 12-hour clock for
Analytical Sequence I/
Beginning of 12-hour clock for
Analytical Sequence 2
End of 12-hour clock for
Analytical Sequence II
Beginning of 12-hour clock for
Analytical Sequence 3
12 hr CC V A (meets opening CC V criteria)
Method Blank
Subsequent Samples
24 hr CCV B (meets opening CCV criteria)
1/2
2
2
2
2
2
2
2/3
June 2008
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Final
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Low/Medium Volatiles Organic Analysis
Example 2: Time Material Injected
Start of 12-hour clock for _ , T-.-r.-n
, . , . . „ , 0 hr BFB
Analytical Sequence 1
Initial Calibration 5.0
Initial Calibration 10
Initial Calibration 50
Initial Calibration 100
Initial Calibration 200
Method Blank
Subsequent Samples
•
•
•
•
Analytical Sequence #
1
1
1
1
1
1
1
1
1
1
1
1
End of 12-hour clock for
Analytical Sequence 1
Beginning of 12-hour clock for
Analytical Sequence 2
12 hr
13 hr
CCV A (meets closing CCV criteria, fails
opening CCV criteria)
BFB
CCV B (meets opening CCV criteria)
Method Blank
Subsequent Samples
End of 12-hour clock for
Analytical Sequence 2
25 hr CCV C (meets closing CCV criteria)
June 2008
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Final
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Low/Medium Volatiles Organic Analysis
Example 3:
Start of 12-hour clock for
Analytical Sequence 1
End of 12-hour clock for
Analytical Sequence 11
Beginning of 12-hour clock for
Analytical Sequence 2
Time Material Injected
Ohr BFB
CCV A (meets opening CCV criteria)
Method Blank
Subsequent Samples
•
•
•
•
12 hr CCV B (meets opening CCV criteria)
Analytical Sequence #
1
1
1
1
1
1
1
1
1/2
Method Blank
Subsequent Samples
End of 12-hour clock for
Analytical Sequence 2/
Beginning of 12-hour clock for
Analytical Sequence 3
24 hr CCV C (meets opening CCV criteria)
2
2
2
2
2
2/3
June 2008
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Final
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Low/Medium Volatiles Organic Analysis
Example 4:
Start of 12-hour clock for
Analytical Sequence 1
End of 12-hour clock for
Analytical Sequence 1
Beginning of 12-hour clock for
Analytical Sequence 2
Time Material Injected
Ohr BFB
CCV A (meets opening CCV criteria)
Method Blank
Subsequent Samples
•
•
•
•
. , CCV B (meets closing CCV criteria, fails
opening CCV criteria)
13 hr BFB
CCV C (meets opening CCV criteria)
Method Blank
Subsequent Samples
•
•
•
Analytical Sequence #
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
End of 12-hour clock for
Analytical Sequence II
Beginning of 12-hour clock for
Analytical Sequence 3
25 hr CCV D (meets opening CCV criteria)
2/3
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Low/Medium Volatiles Organic Analysis
3. Inject a sufficient amount of the instrument performance check solution (50 ng BFB on-column) at
the beginning of each 12-hour period during which samples or standards are analyzed. The
instrument performance check, BFB for volatile analysis, must meet the ion abundance criteria listed
in Table 14. This criteria is waived in cases where a closing CCV can be used as an opening CCV
(i.e., a BFB instrument performance check analysis is not required when a closing CCV analysis
meets the requirements of an opening CCV analysis).
Table 14. Ion Abundance Criteria For Bromofluorobenzene (BFB)
Mass
50
75
95
96
173
174
175
176
177
Ion Abundance Criteria
15. 0-40.0% of mass 95
30. 0-80.0% of mass 95
Base peak, 100% relative abundance
5. 0-9.0% of mass 95*
Less than 2.0% of mass 174
50.0% -120% of mass 95
5. 0-9.0% of mass 174
95. 0-101% of mass 174
5. 0-9.0% of mass 176
* All ion abundances must be normalized to mass to charge (m/z) 95, the nominal base peak, even though the ion abundance of m/z 174
may be up to 120% that of m/z 95.
D. Evaluation:
1. Compare the data presented for each Instrument Performance Check (Form V VOA) with each mass
listing submitted to ensure the following:
a. Form V VOA is present and completed for each 12-hour period during which samples were
analyzed. In cases where a closing CCV is used as an opening CCV for the next 12-hour period,
an additional Form V VOA is not required.
b. The laboratory has not made transcription errors between the data and the form. If there are
major differences between the mass listing and the Form Vs, a more in-depth review of the data is
required. This may include obtaining and reviewing additional information from the laboratory.
c. The appropriate number of significant figures has been reported (number of significant figures
given for each ion in the ion abundance criteria column) and that rounding is correct.
d. The laboratory has not made any calculation errors.
2. Verify that samples were not analyzed before a valid instrument performance check or were not
analyzed 12 hours after the injection of the Instrument Performance Check Solution. This evaluation
is not to be performed in cases where a closing CCV is used as an opening CCV.
3. Verify from the raw data (mass spectral listing) that the mass assignment is correct and that the mass
listing is normalized to m/z 95.
4. Verify that the ion abundance criteria were met. The criteria for m/z 173, 175, 176, and 177 are
calculated by normalizing to the specified m/z.
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Low/Medium Volatiles Organic Analysis
5. If possible, verify that spectra were generated using appropriate background subtraction techniques.
Since the BFB spectrum is obtained from chromatographic peaks that should be free from coelution
problems, background subtraction should be done in accordance with the following procedure:
a. Three scans (the peak apex scan and the scans immediately preceding and following the apex) are
acquired and averaged.
b. Background subtraction is required, and must be accomplished using a single scan no more than
20 scans prior to the elution of BFB. Do not subtract the BFB peak as part of the background.
NOTE: All mass spectrometer instrument conditions must be identical to those used during the sample
analysis. Background subtraction actions resulting in spectral distortions for the sole purpose of
meeting the contract specifications are contrary to the Quality Assurance (QA) objectives and are,
therefore, unacceptable.
For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the CCS process. Information regarding the laboratory's compliance with
these criteria can be obtained from the Data Assessment Tool (DAT) reports, and may be used as
part of the evaluation process.
E. Action:
1. If samples are analyzed without a preceding valid instrument check or are analyzed 12 hours after the
Instrument Performance Check and are not preceded by an analysis of a closing CCV that meets
opening CCV criteria, qualify all data for those samples as unusable "R".
2. If the laboratory has made minor transcription errors which do not significantly affect the data, the
data reviewer should make the necessary corrections on a copy of the form.
3. If the laboratory has failed to provide the correct forms or has made significant transcription or
calculation errors, the Region's designated representative should contact the laboratory and request
corrected data. If the information is not available, the reviewer must use professional judgment to
assess the data. Notify the laboratory's Contract Laboratory Program Project Officer (CLP PO).
4. If mass assignment is in error (e.g., m/z 96 is indicated as the base peak rather than m/z 95), classify
all associated data as unusable "R".
5. If ion abundance criteria are not met, professional judgment may be applied to determine to what
extent the data may be utilized. When applying professional judgment to this topic, the most
important factors to consider are the empirical results that are relatively insensitive to location on the
chromatographic profile and the type of instrumentation. Therefore, the critical ion abundance
criteria for BFB are the m/z 95/96, 174/175, 174/176, and 176/177 ratios. The relative abundances of
m/z 50 and 75 are of lower importance. This issue is more critical for Tentatively Identified
Compounds (TICs) than for target analytes.
6. Note in the Data Review Narrative decisions to use analytical data associated with BFB instrument
performance checks not meeting contract requirements.
7. If the reviewer has reason to believe that instrument performance check criteria were achieved using
techniques other than those described in Low/Medium Volatiles Organic Analysis, Section II.D.5,
obtain additional information on the instrument performance checks. If the techniques employed are
found to be at variance with the contract requirements, the procedures of the laboratory may merit
evaluation. Note, for CLP PO action, concerns or questions regarding laboratory performance. For
example, if the reviewer has reason to believe that an inappropriate technique was used to obtain
background subtraction (such as background subtracting from the solvent front or from another region
of the chromatogram rather than from the BFB peak), this should be noted for CLP PO action.
June 2008 57 Final
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Low/Medium Volatiles Organic Analysis
III. Initial Calibration
A. Review Items:
Form VI VOA-1, Form VI VOA-2, Form VI VOA-3, quantitation reports, and chromatograms.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data for compounds on the
volatile Target Compound List (TCL). Initial calibration demonstrates that the instrument is capable of
acceptable performance in the beginning of the analytical run and of producing a linear calibration curve
and provides the Mean Relative Response Factors (RRFs) used for quantitation.
C. Criteria:
1. Initial calibration standards containing both volatile target compounds and Deuterated Monitoring
Compounds (DMCs) are analyzed at concentrations of 5.0, 10, 50, 100, and 200 (ig/L for non-
ketones, 10, 20, 100, 200, and 400 (ig/L for ketones, and 100, 200, 1250, 2000, and 4000 (ig/L for
1,4-Dioxane at the beginning of each analytical sequence, or as necessary if the continuing calibration
verification acceptance criteria are not met. All three xylene isomers (o-, m-, and p-xylene) must be
present in the calibration standards. The o-xylene calibration standard concentrations must be at 5.0,
10, 50, 100, and 200 (ig/L, while the concentration of the m- plus the p-xylene isomers must total 5.0,
10, 50, 100, and 200 (ig/L. The initial calibration (and any associated samples and blanks) must be
analyzed within 12 hours of the associated instrument performance check.
2. Initial calibration standard Relative Response Factors (RRFs) for the volatile target compounds listed
in Table 15 and all DMCs must be greater than or equal to 0.010, except for 1,4-Dioxane and its
associated DMC (> 0.0050 advisory). The RRF for all other volatile target compounds must be
greater than or equal to 0.050.
3. The Percent Relative Standard Deviation (%RSD) of the initial calibration RRFs must be less than or
equal to 40.0% for the volatile target compounds and DMCs listed in Table 15 except for 1,4-Dioxane
and its associated DMC (50.0%). The %RSD for all other volatile target compounds and associated
DMCs must be less than or equal to 20.0%.
NOTE: The flexibility clause in the method may impact some of the criteria preceding. A copy of the
flexibility clause should be present in the Sample Delivery Group (SDG). Refer to the Contract
Laboratory Program (CLP) Web site at
http://www.epa.gov/oerrpage/superfund/programs/clp/modifledanalyses.htm for the specific
method flexibility requirements.
D. Evaluation:
1. Verify that the correct concentrations of standards were used for the initial calibration (i.e. 5.0, 10, 50,
100, and 200 (ig/L for non-ketones, 10, 20, 100, 200, and 400 (ig/L for ketones, and 100, 200, 1250,
2000, and 4000 (ig/L for 1,4-Dioxane).
2. Verify that the RRF obtained from the associated initial calibration was used for calculating sample
results and the samples were analyzed within 12 hours of the associated instrument performance
check.
3. Evaluate the initial calibration RRFs and the RRF for all volatile target compounds and DMCs:
June 2008 58 Final
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Low/Medium Volatiles Organic Analysis
a. Check and recalculate the RRFs and RRF for at least one volatile target compound associated with
each internal standard. Verify that the recalculated value(s) agrees with the laboratory reported
value(s).
b. Verify that for all volatile target compounds listed in Table 15 and for all DMCs, the initial
calibration RRFs are greater than or equal to 0.010, except for 1,4-Dioxane and its associated
DMC (> 0.0050 advisory), and for all other volatile target compounds, RRFs are greater than or
equal to 0.050.
Table 15. Volatile Compounds Exhibiting Poor Response
Volatile Compounds
Acetone
2-Butanone
Carbon disulfide
Chloroethane
Chloromethane
Cyclohexane
1 ,2-Dibromoethane
Dichlorodifluoromethane
1 ,2-Dichloropropane
cis-1 ,2-Dichloroethene
1 ,4-Dioxane
1 ,2-Dibromo-3-chloropropane
Isopropylbenzene
Methyl acetate
Methylene chloride
Methylcyclohexane
Methyl tert-butyl ether
trans- 1 ,2-Dichloroethene
4-Methyl-2-pentanone
2-Hexanone
Trichlorofluoromethane
1 , 1 ,2-Trichloro- 1 ,2,2-trifluoroethane
4. Evaluate the %RSD for all volatile target compounds and DMCs:
a. Check and recalculate the %RSD for one or more volatile target compound(s) and DMCs. Verify
that the recalculated value(s) agrees with the laboratory reported value(s).
b. If the %RSD is greater than the maximum criteria [40.0% for the volatile target compounds listed
in Table 15, and associated DMCs (see Table 21) except for 1,4-Dioxane (50.0%) and its
associated DMC, and 20.0% for all other volatile target compounds and associated DMCs], the
reviewer should use professional judgment to determine the need to check the points on the curve
for the cause of the non-linearity. This is checked by eliminating either the high-point or the low-
point and recalculating the %RSD (see Low/Medium Volatiles Organic Analysis, Section
III.E.2).
5. If errors are detected in the calculations of either the RRFs or the %RSD, perform a more
comprehensive recalculation.
NOTE:
E. Action:
For data obtained from the CLP, the preceding criteria are evaluated as part of the Contract
Compliance Screening (CCS) process. Information regarding the laboratory's compliance with
these criteria can be obtained from the Data Assessment Tool (DAT) reports, and may be used as
part of the evaluation process.
1. Qualify all volatile target compounds, including the compounds exhibiting poor response listed in
Table 15, using the following criteria (see Table 16):
June 2008
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Low/Medium Volatiles Organic Analysis
a. If any volatile target compound has an RRF value less than the minimum criterion [0.010 for the
compounds exhibiting poor response listed in Table 15, except for 1,4-Dioxane (0.0050 advisory)
and 0.050 for all other volatile compounds], use professional judgment for detects, based on mass
spectral identification, to qualify the data as a "J" or unusable "R".
b. If any volatile target compound has an RRF value less than the minimum criterion [0.010 for the
compounds exhibiting poor response listed in Table 15, except for 1,4-Dioxane (0.0050 advisory)
and 0.050 for all other volatile compounds], qualify non-detected compounds as unusable "R".
c. If any of the volatile target compounds listed in Table 15 has %RSD greater than 40.0%, except
for 1,4-Dioxane (50.0%), qualify detects with a "J" and non-detected compounds using
professional judgment (see Low/Medium Volatiles Organic Analysis, Section III.E.2).
d. For all other volatile target compounds, if %RSD is greater than 20.0%, qualify detects with a "J"
and non-detected compounds using professional judgment (see Low/Medium Volatiles Organic
Analysis, Section III.E.2).
e. If the volatile target compounds meet the acceptance criteria for RRF and %RSD, no qualification
of the data is necessary.
f No qualification of the data is necessary on the DMC RRF and %RSD data alone. Use
professional judgment and follow the guidelines in Low/Medium Volatiles Organic Analysis,
Section III.E.2, to evaluate the DMC RRF and %RSD data in conjunction with the DMC
recoveries for determination of the need for qualification of the data.
At the reviewer's discretion, and based on the project-specific Data Quality Objectives (DQOs), a
more in-depth review may be considered using the following guidelines:
a. If any volatile target compound has a %RSD greater than the maximum criterion [40.0% for the
compounds listed in Table 15, except for 1,4-Dioxane (50.0%), and 20.0% for all other volatile
compounds], and if eliminating either the high or the low-point of the curve does not restore the
%RSD to less than or equal to the required maximum:
i. Qualify detects for that compound(s) with a" J".
ii. Qualify non-detected volatile target compounds using professional judgment.
b. If the high-point of the curve is outside of the linearity criteria (e.g., due to saturation):
i. Qualify detects outside of the linear portion of the curve with a "J".
ii. No qualifiers are required for detects in the linear portion of the curve.
iii. No qualifiers are required for volatile target compounds that were not detected.
c. If the low-point of the curve is outside of the linearity criteria:
i. Qualify low-level detects in the area of non-linearity with a "J".
ii. No qualifiers are required for detects in the linear portion of the curve.
iii. For non-detected volatile compounds, use the lowest point of the linear portion of the curve
to determine the new quantitation limit.
If the laboratory has failed to provide adequate calibration information, the Region's designated
representative should contact the laboratory and request the necessary information. If the information
is not available, the reviewer must use professional judgment to assess the data.
Note in the Data Review Narrative, whenever possible, the potential effects on the data due to
calibration criteria exceedance.
June 2008 60 Final
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Low/Medium Volatiles Organic Analysis
5. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if calibration criteria are
grossly exceeded.
Table 16. Initial Calibration Actions for Low/Medium Volatiles Analyses
Criteria for Low/Med Analysis
Action
Detected Associated
Compounds
Non-Detected Associated
Compounds
RRF < 0.0050 (advisory for 1,4-Dioxane)
RRF < 0.010 (target compounds listed in Table 15)
RRF < 0.050 (all other target compounds)
J or R (based on mass spectral
identification)
R
RRF > 0.0050 (advisory for 1,4-Dioxane)
RRF > 0.010 (target compounds listed in Table 15)
RRF > 0.050 (all other target compounds)
No qualification
%RSD < 50.0 (1,4-Dioxane)
%RSD < 40.0 (target compounds listed in Table 15)
%RSD < 20.0 (all other target compounds)
No qualification
%RSD > 50.0 (1,4-Dioxane)
%RSD > 40.0 (target compounds listed in Table 15)
%RSD > 20.0 (all other target compounds)
Use professional judgment
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Low/Medium Volatiles Organic Analysis
IV. Continuing Calibration Verification (CCV)
A. Review Items:
Form VII VOA-1, Form VII VOA-2, Form VII VOA-3, quantitation reports, and chromatograms.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data. The CCV checks
satisfactory performance of the instrument on a day-to-day basis, however, quantitations are based on the
Mean Relative Response Factors (RRFs ) obtained from the initial calibration.
C. Criteria:
1. The 12-hour clock begins with either the injection of Bromofluorobenzene (BFB), or in cases where a
closing CCV can be used in an opening CCV, the 12-hour clock begins with the injection of the
opening CCV.
2. CCV standards containing both target compounds and associated Deuterated Monitoring Compounds
(DMCs) are analyzed both at the beginning (opening CCV) and end (closing CCV) of each 12-hour
analysis period following the analysis of the instrument performance check, and prior to the analysis
of the method blank and samples. An instrument performance check is not required prior to the
analysis of a closing CCV or prior to a closing CCV which can be used as an opening CCV for the
next 12-hour period. If time remains in the 12-hour time period after initial calibration and samples
are to be analyzed, the mid-point standard from the initial calibration can be used as the opening
CCV.
3. For an opening CCV, the Relative Response Factors (RRFs) for the volatile target compounds listed
in Table 15, and for all DMCs, must be greater than or equal to 0.010, except for 1,4-Dioxane and its
associated DMC (> 0.0050 advisory). The RRF for all other volatile target compounds must be
greater than or equal to 0.050.
4. For a closing CCV, the RRFs for all volatile target compounds and DMCs must be greater than or
equal to 0.010, except for 1,4-Dioxane and its associated DMC (> 0.0050 advisory).
5. The Percent Difference (%D) between the initial calibration RRF and the opening CCV RRF must be
within ±40.0% for the volatile target compounds listed in Table 15 and associated DMCs listed in
Table 21, except for l,4_Dioxane and its associated DMC (±50.0%). The Percent Difference for all
other volatile target compounds and associated DMCs must be within ±25.0%.
6. For the closing CCV, the Percent Difference between the initial calibration RRF and the CCV RRF
must be with ±50.0% for all volatile target compounds and associated DMCs.
D. Evaluation:
1. Verify that the CCV was run at the required frequency (an opening and closing CCV must be run
within a 12-hour period) and the CCV was compared to the correct initial calibration. If the mid-
point standard from the initial calibration is used as an opening CCV, verify that the result (RRF) of
the mid-point standard was compared to the RRF from the correct initial calibration.
2. Evaluate the CCV RRF for all volatile target compounds and DMCs:
June 2008 62 Final
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Low/Medium Volatiles Organic Analysis
a. Check and recalculate the CCV RRF for at least one volatile target compound and DMC
associated with each internal standard. Verify that the recalculated value(s) agrees with the
laboratory reported value(s).
b. For an opening CCV, verify that all volatile target compounds listed in Table 15 and all DMCs
have CCV RRFs of greater than or equal to 0.010, except for 1,4-Dioxane and its associated
DMC (> 0.0050 advisory), and all other volatile target compounds have RRFs greater than or
equal to 0.050.
c. For a closing CCV, verify that all volatile target compounds and DMCs have CCV RRFs of
greater than or equal to 0.010, except for 1,4-Dioxane and its associated DMC (> 0.0050
advisory).
3. Evaluate the Percent Difference between initial calibration RRF and CCV RRF (both opening and
closing) for all volatile target compounds and DMCs:
a. Check and recalculate the Percent Difference for one or more volatile target compound(s) and
DMCs associated with each internal standard. Verify that the recalculated value(s) agrees with
the laboratory-reported value(s).
b. For an opening CCV, verify that the Percent Difference is within ±40.0% for the volatile target
compounds listed in Table 15 and associated DMCs listed in Table 21, except for 1,4-Dioxane
and its associated DMC (±50.0%), and within ±25.0% for all other volatile target compounds and
associated DMCs.
c. For a closing CCV, verify that the Percent Difference is within ±50.0% for all volatile target
compounds and DMCs.
4. If errors are detected in the calculations of either the CCV (both opening and closing) RRF or the
Percent Difference, perform a more comprehensive recalculation.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If a CCV (opening and closing) was not run at the appropriate frequency, qualify all data as unusable
"R" (see Table 17).
2. Qualify all volatile target compounds, including the compounds exhibiting poor response listed in
Table 15 using the following criteria:
a. For an opening CCV, if any volatile target compound has an RRF value less than the minimum
criterion [0.010 for the compounds listed in Table 15, except 1,4-Dioxane (0.0050 advisory), and
0.050 for all other volatile compounds], use professional judgment for detects, based on mass
spectral identification, to qualify the data as a "J" or unusable "R".
b. For a closing CCV, if any volatile target compound has an RRF value less than 0.010, except 1,4-
Dioxane (< 0.0050 advisory), use professional judgment for detects based on mass spectral
identification to qualify the data as a "J" or unusable "R".
c. For an opening CCV, if any volatile target compound has an RRF value less than the minimum
criterion [0.010 for the compounds exhibiting poor response, except for 1,4-Dioxane (0.0050
advisory), and 0.050 for all other volatile compounds], qualify non-detected compounds as
unusable "R".
June 2008 63 Final
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Low/Medium Volatiles Organic Analysis
d. For a closing CCV, if any volatile target compound has an RRF value less than 0.010, except 1,4-
Dioxane (< 0.0050 advisory), qualify non-detected compounds as unusable "R".
e. For an opening CCV, if the Percent Difference value for any of the volatile target compounds
listed in Table 15 is outside the ±40.0% criterion, except for 1,4-Dioxane (±50.0%), qualify
detects with a "J" and non-detected compounds with an approximated "UJ".
f For a closing CCV, if the Percent Difference value for any of the volatile target compounds listed
in Table 15 is outside the ±50.0% criterion, qualify detects with a "J" and non-detected
compounds with an approximated "UJ".
g. For an opening CCV, if the Percent Difference value for any other volatile target compound is
outside the ±25.0% criterion, qualify detects with a "J" and non-detected compounds with an
approximated "UJ".
h. For a closing CCV, if the Percent Difference value for any other volatile target compound is
outside the ±50.0% criterion, qualify detects with a "J" and non-detected compounds with an
approximated "UJ".
i. If the volatile target compounds meet the acceptance criteria for RRF and Percent Difference, no
qualification of the data is necessary.
j. No qualification of the data is necessary on the DMC RRF and Percent Difference data alone.
However, use professional judgment to evaluate the DMC RRF and Percent Difference data in
conjunction with the DMC recoveries to determine the need for qualification of data.
3. If the laboratory has failed to provide adequate calibration information, the Region's designated
representative may contact the laboratory and request the necessary information. If the information is
not available, the reviewer must use professional judgment to assess the data.
4. Note in the Data Review Narrative, whenever possible, the potential effects on the data due to
calibration criteria exceedance.
5. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if calibration criteria are
grossly exceeded.
Table 17. Continuing Calibration Verification (CCV) Actions for Low/Medium Volatiles Analyses
Criteria for Opening CCV
Criteria for Closing CCV
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
RRF < 0.0050 (advisory for 1,4-Dioxane)
RRF < 0.010 (target compounds listed in
Table 15)
RRF < 0.050 (all other target compounds)
RRF < 0.0050 (advisory for 1,4-
Dioxane)
RRF < 0.010 (all volatile target
compounds)
J or R (based on
mass spectral
identification)
R
RRF > 0.0050 (advisory for 1,4-Dioxane)
RRF > 0.010 (target compounds listed in
Table 15)
RRF > 0.050 (all other target compounds)
RRF > 0.0050 (advisory for 1,4-
Dioxane)
RRF > 0.010 (all volatile target
compounds)
No qualification
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Low/Medium Volatiles Organic Analysis
Criteria for Opening CCV
Criteria for Closing CCV
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
%D > 50.0 or < -50.0 (1,4-Dioxane)
%D > 40.0 or < -40.0 (target compounds
listed in Table 15)
%D > 25.0 or < -25.0 (all other target
compounds)
%D > 50.0 or <-50.0 (all volatile
target compounds)
UJ
%D < 50.0 and >-50.0 (1,4-Dioxane)
%D < 40.0 and > -40.0 (target compounds
listed in Table 15)
%D < 25.0 and > -25.0 (all other target
compounds)
%D < 50.0 and > -50.0 (all volatile
target compounds)
No qualification
Opening CCV not performed at required
frequency (see Low/Medium Volatiles
Organic Analysis, Section IV.C.l)
Closing CCV not performed at
required frequency (see
Low/Medium Volatiles Organic
Analysis, Section IV.C.l)
R
June 2008
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Low/Medium Volatiles Organic Analysis
V. Blanks
A. Review Items:
Form I VOA-1, Form I VOA-2, Form I VOA-TIC, Form IV VOA, chromatograms, and quantitation
reports.
B. Objective:
The purpose of laboratory, field, or trip blank analyses is to determine the existence and magnitude of
contamination resulting from laboratory, field, or sample transport activities. The purpose of the method
blank is to determine the levels of contamination associated with the processing and analysis of samples.
The storage blank indicates whether contamination may have occurred during storage of samples. The
results from the instrument blank analysis indicate whether there is contamination from the analysis of a
previous sample. The criteria for evaluation of blanks apply to any blank associated with the samples
(e.g., method blanks, instrument blanks, storage blanks, field blanks, or trip blanks). If problems with any
blank exist, all associated data must be carefully evaluated to determine whether or not there is an
inherent variability in the data or if the problem is an isolated occurrence not affecting other data.
C. Criteria:
1. Method Blanks
A method blank analysis must be performed after the calibration standards and once for every 12-
hour time period.
The method blank must be analyzed on each Gas Chromatograph/Mass Spectrometer (GC/MS)
system used to analyze samples. The method blank must be matrix specific (i.e., a non-aqueous
method blank is required for non-aqueous samples, and an aqueous method blank is required for
aqueous samples).
2. Storage Blanks
A storage blank must be prepared upon receipt of the first samples from a Sample Delivery Group
(SDG), and stored with the samples until analysis. The storage blank must be analyzed once per
SDG.
3. Instrument Blank
An instrument blank must be analyzed after any sample that has saturated ions from a given
compound to check that the blank is free of interference and the system is not contaminated. The
concentration of each target compound in the instrument blank must be less than its Contract
Required Quantitation Limit (CRQL) listed in the method.
NOTE: The concentration of each target compound found in the storage, method, field, or trip blanks
must be less than its CRQL listed in the method, except for methylene chloride, acetone, and 2-
butanone which must be less than 2 times (2x) their respective CRQLs.
D. Evaluation:
1. Review the results of all associated blanks on the forms and raw data (chromatograms and
quantitation reports) to evaluate the presence of target and non-target compounds in the blanks.
June 2008 66 Final
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Low/Medium Volatiles Organic Analysis
2. Verify that a method blank analysis has been reported for each 12-hour time period on each GC/MS
system used to analyze volatile samples. The reviewer can use the Method Blank Summary (Form IV
VOA) to identify the samples associated with each method blank.
3. Verify that a method blank has been analyzed for each matrix present (i.e. if non-aqueous samples are
present, verify that there is a non-aqueous method blank).
4. Verify that a storage blank has been analyzed and included with each SDG.
5. Verify that the instrument blank analysis has been performed following any sample analysis where a
target analyte(s) is/are reported at high concentration(s).
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process. Data concerning the field or
trip blanks are not evaluated as part of the CCS process. If field or trip blanks are present, the
data reviewer should evaluate this data in a similar fashion as method blanks.
E. Action:
Action regarding unsuitable blank results depends on the circumstances and origin of the blank. In
instances where more than one of the same type of blank is associated with a given sample, qualification
should be based upon a comparison with the associated blank having the highest concentration of a
contaminant. Do not correct the results by subtracting any blank value (see Table 18).
1. If a volatile compound is found in a method blank, but not found in the sample, no qualification of the
data is necessary.
2. If the method blank concentration is less than the CRQL (less than 2x the CRQL for methylene
chloride, 2-butanone, and acetone) and:
a. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene chloride,
2-butanone, and acetone), report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), use professional judgment to qualify the
data.
3. If the method blank concentration is greater than the CRQL (greater than 2x the CRQL for methylene
chloride, 2-butanone, and acetone) and:
a. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene chloride,
2-butanone, and acetone), report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), and less than the blank concentration,
report the concentration of the compound in the sample at the same concentration found in the
blank and qualify with a "U", or the reviewer may elect to qualify the data as unusable "R".
c. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), and greater than or equal to the blank
concentration, use professional judgment to qualify the data.
4. If the method blank concentration is equal to the CRQL (equal to 2x the CRQL for methylene
chloride, 2-butanone, and acetone) and:
a. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene chloride,
2-butanone, and acetone), report the CRQL value with a "U".
June 2008 67 Final
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b. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), use professional judgment to qualify the
data.
5. If gross contamination exists (i.e., saturated peaks by GC/MS), qualify all affected compounds in the
associated samples as unusable "R" due to interference. Note, for Contract Laboratory Program
Project Officer (CLP PO) action, if the contamination is suspected of having an effect on the sample
results.
6. Give the same consideration as the target compounds to the Tentatively Identified Compounds
(TICs), which are found in both the sample and associated blank(s) (see Low/Medium Volatiles
Organic Analysis, Section XII, for TIC guidance).
7. If the contaminants found in the blank are interfering non-target compounds at concentrations greater
than 10 (ig/L, use professional judgment to qualify the data.
NOTE: There may be instances where little or no contamination was present in the associated blanks, but
qualification of the sample is deemed necessary. If the reviewer determines that the contamination
is from a source other than the sample, they should qualify the data. Contamination introduced
through dilution water is one example. Although it is not always possible to determine, instances
of this occurring can be detected when contaminants are found in the diluted sample result, but
are absent in the undiluted sample result.
8. If an instrument blank was not analyzed following a sample analysis which contained an analyte(s) at
high concentration(s), evaluate the sample analysis results immediately after the high concentration
sample for carryover. Use professional judgment to determine if instrument cross-contamination has
affected any positive compound identification(s). Note, for CLP PO action, if instrument cross-
contamination is suggested and is suspected of having an effect on the sample results.
9. If contaminants are found in the storage, field, or trip blanks, the following is recommended:
a. Review the associated method blank data to determine if the contaminant(s) was also present in
the method blank.
i. If the analyte was present at a comparable level in the method blank, the source of the
contamination may be in the analytical system and the action recommended for the method
blank would apply.
ii. If the analyte was not present in the method blank, the source of contamination may be in the
storage area, in the field, or during sample transport, consider all associated samples for
possible cross-contamination.
b. If the storage, field, or trip blanks contain a volatile Target Compound List (TCL) compound(s) at
a concentration less than the CRQL (less than 2x the CRQL for methylene chloride, 2-butanone,
and acetone) and:
i. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene
chloride, 2-butanone, and acetone), report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), use professional judgment to
qualify the data.
c. If the storage, field, or trip blanks contain a volatile TCL compound(s) at a concentration greater
than the CRQL (greater than 2x the CRQL for methylene chloride, 2-butanone, and acetone) and:
i. the sample concentration is less than the CRQL (less than 2x the CRQL for methylene
chloride, 2-butanone, and acetone), report the CRQL value with a "U".
June 2008 68 Final
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Low/Medium Volatiles Organic Analysis
e.
ii. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone), and less than the blank
concentration, report the concentration of the compound in the sample at the same
concentration found in the blank and qualify with a "U", or the reviewer may elect to qualify
the data as unusable "R".
iii. the sample concentration is greater than or equal to the CRQL (greater than or equal to 2x the
CRQL for methylene chloride, 2-butanone, and acetone) and greater than or equal to the
blank concentration, use professional judgment to qualify the data.
If the storage, field, or trip blanks contain a volatile TCL compound(s) at a concentration equal to
the CRQL (2x the CRQL for methylene chloride, 2-butanone, and acetone) and:
i. the sample concentration is less than the CRQL (2x the CRQL for methylene chloride, 2-
butanone, and acetone), report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL (2x the CRQL for methylene
chloride, 2-butanone, and acetone), use professional judgment to qualify the data.
If gross contamination (i.e., saturated by GC/MS) exists in the storage, field or trip blank, positive
sample results may require rejection and be qualified as unusable "R". Non-detected volatile
target compounds do not require qualification unless the contamination is so high that it interferes
with the analyses of non-detected compounds.
Table 18. Blank Actions for Low/Medium Volatiles Analyses
Blank Type
Method, Storage,
Field, Trip,
Instrument **
Blank Result
Detects
< PT? DT *
> CRQL*
— pwnT *
Gross contamination
Sample Result
Not detected
< CRQL*
> CRQL*
< CRQL*
> CRQL* and < blank
concentration
> CRQL* and > blank
concentration
< CRQL*
> CRQL*
Detects
Action for Samples
No qualification
Report CRQL value with a U
Use professional judgment
Report CRQL value with a U
Report the blank concentration for the
sample with a U or qualify the data as
unusable R
Use professional judgment
Report CRQL value with a U
Use professional judgment
Qualify results as unusable R
2xthe CRQL for methylene chloride, 2-butanone, and acetone.
Qualifications based on instrument blank results affect only the sample analyzed immediately after the sample that has
target compounds that exceed the calibration range or non-target compounds that exceed 100 ug/L.
June 2008
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VI. Deuterated Monitoring Compounds (DMCs)
A. Review Items:
Form II VOA-1, Form II VOA-2, Form II VOA-3, Form II VOA-4, quantitation reports, and
chromatograms.
B. Objective:
Laboratory performance on individual samples is established by means of spiking activities. All samples
are spiked with DMCs just prior to sample purging. The evaluation of the results of these DMCs is not
necessarily straightforward. The sample itself may produce effects due to such factors as interferences.
Since the effects of the sample matrix are frequently outside the control of the laboratory and may present
relatively unique problems, the evaluation and review of data based on specific sample results is
frequently subjective and requires analytical experience and professional judgment. Accordingly, this
section consists primarily of guidelines, in some cases with several optional approaches suggested.
C. Criteria:
1. The DMCs listed in Table 19 are added to all samples and blanks to measure their recovery in
environmental samples.
Table 19. Volatile Deuterated Monitoring Compounds (DMCs) and Recovery Limits
DMC
Vinyl chloride-d3
Chloroethane-d5
1 , 1 -Dichloroethene-d2
2-Butanone-d5
Chloroform-d
1 ,2-Dichloroethane-d4
Benzene-d,;
1 ,2-Dichloropropane-dg
Toluene-d8
trans-1 ,3-Dichloropropene-d4
2-Hexanone-d5
l,4-Dioxane-d8
1 , 1 ,2,2-Tetrachloroethane-d2
1 ,2-Dichlorobenzene-d4
Recovery Limits (%)
for Water Samples
65-131
71-131
55 - 104
49-155
78-121
78 - 129
77 - 124
79 - 124
77-121
73 - 121
28-135
50-150
73 - 125
80-131
Recovery Limits (%)
for Soil Samples
68 - 122
61 - 130
45 - 132
20 - 182
72 - 123
79 - 122
80 - 121
74 - 124
78 - 121
72 - 130
17-184
50-150
56-161
70-131
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Low/Medium Volatiles Organic Analysis
2. Recoveries for DMCs in volatile samples and blanks must be within the limits specified in Table 19.
NOTE: The recovery limits for any of the compounds listed in Table 19 may be expanded at any time
during the period of performance if USEPA determines that the limits are too restrictive.
D. Evaluation:
1. Check raw data (e.g., chromatograms and quantitation reports) to verify the recoveries on the
Deuterated Monitoring Compound Recovery Forms (Form II VOA-1, Form II VOA-2, Form II VOA-
3, and Form IIVOA-4).
Check for any calculation or transcription errors; verify that the DMC recoveries were calculated
correctly using the equation in the method.
2. Whenever there are two or more analyses for a particular sample, the reviewer must determine which
are the most acceptable data to report. Considerations include, but are not limited to:
a. DMC recovery (marginal versus gross deviation).
b. Technical holding times.
c. Comparison of the values of the target compounds reported in each sample analysis.
d. Other Quality Control (QC) information, such as performance of internal standards.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
Table 21 lists the volatile DMCs and their associated target compounds. If any DMC recovery in the
volatiles fraction is out of specification, qualify data considering the existence of interference in the raw
data (see Table 20). Considerations include, but are not limited to:
1. For any recovery greater than the upper acceptance limit:
a. Qualify detected associated volatile target compounds as a "J".
b. Do not qualify non-detected associated volatile target compounds.
2. For any recovery greater than or equal to 20%, and less than the lower acceptance limit:
a. Qualify detected associated volatile target compounds as a "J".
b. Qualify non-detected associated volatile target compounds as approximated "UJ".
3. For any recovery less than 20%:
a. Qualify detected associated volatile target compounds as a "J".
b. Qualify non-detected associated volatile target compounds as unusable "R".
4. For any recovery within acceptance limits, no qualification of the data is necessary.
5. In the special case of a blank analysis having DMCs out of specification, the reviewer must give
special consideration to the validity of associated sample data. The basic concern is whether the
blank problems represent an isolated problem with the blank alone, or whether there is a fundamental
problem with the analytical process. For example, if one or more samples in the batch show
acceptable DMC recoveries, the reviewer may choose to consider the blank problem to be an isolated
occurrence. However, even if this judgment allows some use of the affected data, note analytical
problems for Contract Laboratory Program Project Officer (CLP PO) action.
June 2008 71 Final
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Table 20. Deuterated Monitoring Compound (DMC) Recovery Actions For Low/Medium Volatiles Analyses
Criteria
%R > Upper Acceptance Limit
20% < %R < Lower Acceptance Limit
%R < 20%
Lower Acceptance Limit < %R < Upper Acceptance Limit
Action
Detected Associated
Compounds
J
J
J
Non-detected Associated
Compounds
No qualification
UJ
R
No qualification
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Table 21. Volatile Deuterated Monitoring Compounds (DMCs) and the Associated Target Compounds
Chloroethane-dj (DMC)
Dichlorodifluoromethane
Chloromethane
Bromomethane
Chloroethane
Carbon disulfide
l,4-Dioxane-d8(DMC)
1 ,4-Dioxane
2-Butanone-d5 (DMC)
Acetone
2-Butanone
Vinyl chloride-d3 (DMC)
Vinyl chloride
l,2-Dichloroethane-d4 (DMC)
Trichlorofluoromethane
1,1,2-Trichloro- 1,2,2-
trifluoroethane
Methyl acetate
Methylene chloride
Methyl-tert-butyl ether
1,1,1 -Trichloroethane
Carbon tetrachloride
1 ,2-Dibromoethane
1 ,2-Dichloroethane
l,2-Dichloropropane-d6 (DMC)
Cyclohexane
Methylcyclohexane
1 ,2-Dichloropropane
Bromodichloromethane
trans-l,3-Dichloropropene-d4 (DMC)
cis- 1 ,3-Dichloropropene
trans-1 ,3-Dichloropropene
1 , 1 ,2-Trichloroethane
l,l-Dichloroethene-d2 (DMC)
trans-1 ,2-Dichloroethene
1 , 1 -Dichloroethene
cis- 1 ,2-Dichloroethene
Benzene-d6 (DMC)
Benzene
l,2-Dichlorobenzene-d4 (DMC)
Chlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
1 ,2,4-Trichlorobenzene
1 ,2,3-Trichlorobenzene
Chloroform-d (DMC)
1 , 1 -Dichloroethane
Bromochloromethane
Chloroform
Dibromochloromethane
Bromoform
2-Hexanone-d5 (DMC)
4-Methyl-2-pentanone
2-Hexanone
l,l,2,2-Tetrachloroethane-d2 (DMC)
1 ,1 ,2,2,-Tetrachlororethane
1 ,2-Dibromo-3-chloropropane
Toluene-d8 (DMC)
Trichloroethene
Toluene
Tetrachloroethene
Ethylbenzene
o-Xylene
m,p-Xylene
Styrene
Isopropylbenzene
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Low/Medium Volatiles Organic Analysis
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
A. Review Items:
Form III VOA-1, Form III VOA-2, chromatograms, and quantitation reports.
NOTE: Data for MS and MSDs will not be present unless requested by the Region.
B. Objective:
Data for MS and MSDs are generated to determine long-term precision and accuracy of the analytical
method on the sample matrix and to demonstrate acceptable compound recovery by the laboratory at the
time of sample analysis. These data alone cannot be used to evaluate the precision and accuracy of
individual samples. However, when exercising professional judgment, this data should be used in
conjunction with other available Quality Control (QC) information.
C. Criteria:
1. If requested, MS and MSD samples are analyzed at a frequency of one MS and MSD per 20 or fewer
samples per sample matrix and concentration level.
2. Spike recoveries should be within the advisory limits provided on Form III VOA-1 and Form III
VOA-2.
3. Relative Percent Difference (RPD) between MS and MSD recoveries must be within the advisory
limits provided on Form III VOA-1 and Form III VOA-2.
D. Evaluation:
1. Verify that requested MS and MSD samples were analyzed at the required frequency and results are
provided for each sample.
2. Inspect results for the MS and MSD Recovery on Form III VOA-1 and Form III VOA-2 and verify
that the results for recovery and RPD are within the advisory limits.
3. Verify transcriptions from raw data and check calculations.
4. Verify that the MS recoveries and RPD were calculated correctly.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. No qualification of the data is necessary on MS and MSD data alone. However, using informed
professional judgment, the data reviewer may use the MS and MSD results in conjunction with other
QC criteria to determine the need for some qualification of the data. Table 23 lists the volatile target
compounds that are spiked into samples to test for matrix effects. If any MS and MSD Percent
Recovery or RPD in the volatiles fraction is out of specification, qualify data to include the
consideration of the existence of interference in the raw data (see Table 22). Considerations include,
but are not limited to:
a. For any recovery or RPD greater than the upper acceptance limit:
i. Qualify detected spiked volatile target compounds as a "J".
June 2008 74 Final
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Low/Medium Volatiles Organic Analysis
ii. Do not qualify non-detected spiked volatile target compounds.
b. For any recovery greater than or equal to 20%, and less than the lower acceptance limit:
i. Qualify detected spiked volatile target compounds as a "J".
ii. Qualify non-detected spiked volatile target compounds as approximated "UJ".
c. For any recovery less than 20%:
i. Qualify detected spiked volatile target compounds as a "J".
ii. Use professional judgment to qualify non-detected spiked volatile target compounds.
d. For any recovery or RPD within acceptance limits, no qualification of the data is necessary.
2. The data reviewer should first try to determine to what extent the results of the MS and MSB affect
the associated data. This determination should be made with regard to the MS and MSB sample
itself, as well as specific analytes for all samples associated with the MS and MSB.
3. In those instances where it can be determined that the results of the MS and MSB affect only the
sample spiked, limit qualification to this sample only. However, it may be determined through the
MS and MSB results that a laboratory is having a systematic problem in the analysis of one or more
analytes that affects all associated samples, and the reviewer must use professional judgment to
qualify the data from all associated samples.
4. The reviewer must use professional judgment to determine the need for qualification of detects of
non-spiked compounds.
NOTE: Notify the Contract Laboratory Program Project Officer (CLP PO) if a field or trip blank was
used for the MS and MSB.
Table 22. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Low/Medium Volatiles Analysis
Criteria
%R or RPD > Upper Acceptance Limit
20% < %R < Lower Acceptance Limit
%R < 20%
Lower Acceptance Limit < %R; RPD < Upper Acceptance Limit
Action
Detected Spiked
Compounds
J
J
J
Non-detected Spiked
Compounds
No qualification
UJ
Use professional
judgment
No qualification
Table 23. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD) Limits
Compound
1 , 1 -Dichloroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
% Recovery for
Water Samples
61 - 145
71 - 120
76 - 127
76 - 125
75-130
RPD for Water
Samples
0-14
0-14
0-11
0-13
0-13
% Recovery for
Soil/Sediment
Samples
59 - 172
62-137
66 - 142
59-139
60-133
RPD for
Soil/Sediment
Samples
0-22
0-24
0-21
0-21
0-21
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Low/Medium Volatiles Organic Analysis
VIII. Regional Quality Assurance (OA) and Quality Control (OC)
A. Review Items:
Form I VOA-1, Form I VOA-2, chromatograms, Traffic Report/Chain of Custody Record (TR/COC),
quantitation reports, and other raw data from QA/QC samples.
B. Objective:
Regional QA/QC samples refer to any QA and/or QC samples initiated by the Region, including field
duplicates, Performance Evaluation (PE) samples, blind spikes, and blind blanks. The use of these
QA/QC samples is highly recommended (e.g., the use of field duplicates can provide information on
sampling precision and homogeneity).
C. Criteria:
Criteria are determined by each Region.
1. PE sample frequency may vary.
2. The analytes present in the PE sample must be correctly identified and quantified.
D. Evaluation:
1. Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data review.
Each Region will handle the evaluation of PE samples on an individual basis. Compare results for PE
samples to the acceptance criteria for the specific PE samples, if available.
2. Calculate Relative Percent Difference (RPD) between field duplicates. Provide this information in
the Data Review Narrative.
E. Action:
Any action must be in accordance with Regional specifications and the criteria for acceptable PE sample
results. Note, for Contract Laboratory Program Project Officer (CLP PO) action, unacceptable results for
PE samples.
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Low/Medium Volatiles Organic Analysis
IX. Internal Standards
A. Review Items:
Form VIII VOA, quantitation reports, and chromatograms.
B. Objective:
Internal standard performance criteria ensures that Gas Chromatograph/Mass Spectrometer (GC/MS)
sensitivity and response are stable during each analysis.
C. Criteria:
1. The internal standard area counts for all samples [including Matrix Spike/Matrix Spike Duplicate
(MS/MSD) and Performance Evaluation (PE) samples] and all blanks must be within the inclusive
range of 50.0% and 200% of its response from the associated 12-hour calibration standard [opening
Continuing Calibration Verification (CCV) or mid-point standard from the initial calibration].
2. The Retention Time (RT) of the internal standard in the sample or blank must not vary more than ±30
seconds from the RT of the internal standard in the associated 12-hour calibration standard (opening
CCV or mid-point standard from initial calibration).
D. Evaluation:
1. Check raw data (e.g., chromatograms and quantitation lists) to verify the internal standard RTs and
areas reported on the Internal Standard Area Summary (Form VIII VOA).
2. Verify that all RTs and internal standard areas are within criteria for all samples and blanks.
3. If there are two analyses for a particular fraction, the reviewer must determine which are the best data
to report. Considerations include, but are not limited to:
a. Magnitude and direction of the internal standard area shift.
b. Magnitude and direction of the internal standard RT shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each fraction.
e. Other Quality Control (QC) information.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
June 2008 77 Final
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Low/Medium Volatiles Organic Analysis
E. Action:
1. If an internal standard area count for a sample or blank is greater than 200% of the area for the
associated standard (opening CCV or mid-point standard from the initial calibration) (see Table 24):
a. Qualify detects for compounds quantitated using that internal standard with a "J".
b. Do not qualify non-detected associated compounds.
2. If an internal standard area count for a sample or blank is less than 50.0% of the area for the
associated standard (opening CCV or mid-point standard from initial calibration):
a. Qualify detects for compounds quantitated using that internal standard with a "J".
b. Qualify non-detected associated compounds as unusable "R".
3. If an internal standard area count for a sample or blank is greater than or equal to 50.0%, and less than
or equal to 200% of the area for the associated standard opening CCV or mid-point standard from
initial calibration, no qualification of the data is necessary.
4. If an internal standard RT varies by more than 30.0 seconds:
Examine the chromatographic profile for that sample to determine if any false positives or negatives
exist. For shifts of a large magnitude, the reviewer may consider partial or total rejection of the data
for that sample fraction. Detects should not need to be qualified as unusable "R" if the mass spectral
criteria are met.
5. If an internal standard RT varies by less than or equal to 30.0 seconds, no qualification of the data is
necessary.
6. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if the internal standard
performance criteria are grossly exceeded. Note in the Data Review Narrative potential effects on the
data resulting from unacceptable internal standard performance.
Table 24. Internal Standard Actions for Low/Medium Volatiles Analyses
Criteria
Area counts < 50.0% of 12-hour standard (opening CCV or mid-point
standard from the initial calibration)
Area counts > 50.0% and < 200% of 12-hour standard (opening CCV or mid-
point standard from the initial calibration)
Area counts > 200% of 12-hour standard (opening CCV or mid-point
standard from the initial calibration)
RT Difference < 30.0 seconds between samples and 12-hour standard
(opening CCV or mid-point standard from the initial calibration)
RT Difference > 30.0 seconds between samples and 12-hour standard
(opening CCV or mid-point standard from the initial calibration)
Action
Detected
Associated
Compounds*
J
Non-Detected
Associated
Compounds*
R
No qualification
J
No qualification
No qualification
R**
R
For volatile compounds associated with each internal standard, see Table 3 - Volatile Target Compounds and Deuterated Monitoring
Compounds with Corresponding Internal Standards for Quantitation in SOM01.2. Exhibit D. available at:
http://www.epa.gov/superfund/programs/clp/soml.htm
See Low/Medium Volatiles Organic Analysis, Section IX.E.4 for exceptions.
June 2008
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Low/Medium Volatiles Organic Analysis
X. Target Compound Identification
A. Review Items:
Form I VOA-1, Form I VOA-2, quantitation reports, mass spectra, and chromatograms.
B. Objective:
The objective of the criteria for Gas Chromatograph/Mass Spectrometer (GC/MS) qualitative analysis is
to minimize the number of erroneous compound identifications. An erroneous identification can either be
a false positive (reporting a compound present when it is not) or a false negative (not reporting a
compound that is present).
The identification criteria can be applied more easily in detecting false positives than false negatives.
More information is available for false positives due to the requirement for submittal of data supporting
positive identifications. Negatives, or non-detected compounds, on the other hand, represent an absence
of data and are, therefore, more difficult to assess. One example of the detection of false negatives is not
reporting a target compound that is reported as a Tentatively Identified Compound (TIC).
C. Criteria:
1. The Relative Retention Times (RRTs) must be within ±0.06 RRT units of the standard RRT [opening
Continuing Calibration Verification (CCV) or mid-point standard from the initial calibration].
2. Mass spectra of the sample compound and a current laboratory-generated standard [i.e., the mass
spectrum from the associated calibration standard (opening CCV or mid-point standard from initial
calibration)] must match according to the following criteria:
a. All ions present in the standard mass spectrum at a relative intensity greater than 10% must be
present in the sample spectrum.
b. The relative intensities of these ions must agree within ±20% between the standard and sample
spectra (e.g., for an ion with an abundance of 50% in the standard spectrum, the corresponding
sample ion abundance must be between 30-70%).
c. Ions present at greater than 10% in the sample mass spectrum, but not present in the standard
spectrum, must be evaluated by a reviewer experienced in mass spectral interpretation.
D. Evaluation:
1. Check that the RRT of reported compounds is within ±0.06 RRT units of the standard RRT (opening
CCV or mid-point standard from the initial calibration).
2. Check the sample compound spectra against the laboratory standard spectra to verify that it meets the
specified criteria.
3. Be aware of situations when sample carryover is a possibility and use professional judgment to
determine if instrument cross-contamination has affected any positive compound identification. The
method specifies that an instrument blank must be run after samples which contain target compounds
at levels exceeding the initial calibration range (200 ug/L for non-ketones, 400 ug/L for ketones, and
4000 ug/L for 1,4-Dioxane).
4. Check the chromatogram to verify that peaks are identified. Major peaks are either identified as
target compounds, TICs, Deuterated Monitoring Compounds (DMCs), or internal standards.
June 2008 79 Final
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NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. The application of qualitative criteria for GC/MS analysis of target compounds requires professional
judgment. It is up to the reviewer's discretion to obtain additional information from the laboratory. If
it is determined that incorrect identifications were made, qualify all such data as not detected "U" or
unusable "R".
2. Use professional judgment to qualify the data if it is determined that cross-contamination has
occurred.
3. Note in the Data Review Narrative any changes made to the reported compounds or concerns
regarding target compound identifications. Note, for Contract Laboratory Program Project Officer
(CLP PO) action, the necessity for numerous or significant changes.
June 2008 80 Final
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Low/Medium Volatiles Organic Analysis
XL Compound Ouantitation and Reported Contract Required Ouantitation Limits (CRQLs)
A. Review Items:
Forms IVOA-1, Form IVOA-2, sample preparation sheets, Sample Delivery Group (SDG) Narrative,
quantitation reports, and chromatograms.
B. Objective:
The objective is to ensure that the reported quantitation results and CRQLs are accurate.
C. Criteria:
1. Compound quantitation, as well as the adjustment of the CRQLs, must be calculated according to the
correct equation.
2. Compound Relative Response Factors (RRFs) must be calculated based on the internal standard
associated with that compound, as listed in the method. Quantitation must be based on the
quantitation ion (m/z) specified in the method for both the internal standards and target analytes. The
compound quantitation must be based on the average RRF from the associated initial calibration.
D. Evaluation:
1. Examine raw data to verify the correct calculation of all sample results reported by the laboratory.
Compare quantitation lists and chromatograms to the reported detects and non-detects sample results.
Check the reported values.
2. Verify that the correct internal standard, quantitation ion, and Mean Relative Response Factor (RRF)
were used to quantitate the compound. Verify that the same internal standard, quantitation ion,
and RRF were used consistently throughout, in both the calibration as well as the quantitation process.
3. Verify that the CRQLs have been adjusted to reflect all sample dilutions and dry weight factors (for
non-aqueous samples).
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If any discrepancies are found, the Region's designated representative may contact the laboratory to
obtain additional information that could resolve any differences. If a discrepancy remains unresolved,
the reviewer must use professional judgment to decide which value is the most accurate value. Under
these circumstances, the reviewer may determine that qualification of data is warranted. Note in the
Data Review Narrative a description of the reasons for data qualification and the qualification that is
applied to the data.
2. For non-aqueous samples, if the Percent Moisture is less than 70.0%, no qualification of the data is
necessary. If the Percent Moisture is greater than or equal to 70.0% and less than 90.0%, qualify
detects as "J" and non-detects as approximated "UJ". If the Percent Moisture is greater than or equal
to 90.0%, qualify detects as "J" and non-detects as unusable "R" (see Table 25).
June 2008 81 Final
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Low/Medium Volatiles Organic Analysis
Table 25. Percent Moisture Actions for Low/Medium Volatiles Analysis For Non-Aqueous Samples
Criteria
% Moisture < 70.0
70.0 <% Moisture < 90.0
% Moisture > 90.0
Action
Detected Associated Compounds
Non-detected Associated
Compounds
No qualification
J
J
UJ
R
NOTE: For Contract Laboratory Program Project Officer (CLP PO) action, numerous or significant
failures to accurately quantify the target compounds or to properly evaluate and adjust CRQLs.
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Low/Medium Volatiles Organic Analysis
XII. Tentatively Identified Compounds (TICs)
A. Review Items:
Form I VOA-TIC, chromatograms, library search printouts, and spectra for the TIC candidates.
B. Objective:
Chromatographic peaks in volatile fraction analyses that are not target analytes, Deuterated Monitoring
Compounds (DMCs), or internal standards are potential TICs. TICs must be qualitatively identified via a
forward search of the NIST/USEPA/NIH Mass Spectral Library (May 2002 release or later)3, and/or
Wiley Mass Spectral Library (1998 release or later)4, or the equivalent. The identifications must be
assessed by the data reviewer.
C. Criteria:
For each sample, the laboratory must conduct a mass spectral search of the NIST/USEPA/NIH (May 2002
release or later), and/or Wiley (1998 release or later), or equivalent mass spectral library, and report the
possible identity for 30 of the largest volatile fraction peaks which are not DMCs, internal standards, or
target compounds, but which have an area or height greater than 10% of the area or height of the nearest
internal standard. Estimated concentrations for TICs are calculated similarly to the Target Compound
List (TCL) compounds, using total ion areas for the TIC and the internal standard, and assuming a
Relative Response Factor (RRF) of 1.0. TIC results are reported for each sample on the Organic
Analyses Data Sheet (Form I VOA-TIC).
D. Evaluation:
1. Guidelines for tentative identification are as follows:
a. Major ions (greater than 10% Relative Intensity) in the reference spectrum should be present in
the sample spectrum.
b. The relative intensities of the major ions should agree within ±20% between the sample and the
reference spectra.
c. Molecular ions present in the reference spectrum should be present in the sample spectrum.
d. Review ions present in the sample spectrum, but not in the reference spectrum, for possible
background contamination, interference, or presence of coeluting compounds.
e. Review ions present in the reference spectrum, but not in the sample spectrum, for possible
subtraction from the sample spectrum because of background contamination or coeluting
compounds. Data system library reduction programs can sometimes create these discrepancies.
f Non-target compounds receiving a library search match of 85% or higher are considered a "likely
match". Report the compound unless the mass spectral interpretation specialist feels there is
evidence not to report the compound as identified by the library search program. Note in the
Sample Delivery Group (SDG) Narrative the justification for not reporting a compound as listed
by the search program.
3NIST/USEPA/NIH Mass Spectral Library (May 2002 release or later), National Institute of Standards and Technology, Gaithersburg,
Maryland.
4Wiley Mass Spectral Library (1998 release or later), John Wiley & Sons, Inc., Hoboken, New Jersey.
June 2008 83 Final
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Low/Medium Volatiles Organic Analysis
g. If the library search produces more than one compound greater than or equal to 85%, report the
compound with the highest percent match (report first compound if percent match is the same for
two or more compounds), unless the mass spectral interpretation specialist feels that the highest
match compound should not be reported or another compound with a lower match should be
reported. The laboratory should include the justification for not reporting the compound with the
highest spectral match within the SDG Narrative. Do not report DMCs, internal standards, and
volatile target compounds as TICs, unless the only compounds having a percent match of greater
than 85% are DMCs, internal standards, or volatile target compounds.
h. If the library search produces a series of obvious isomer compounds with library search matches
greater than or equal to 85%, report the compound with the highest library search percent match
(or the first compound if the library search matches are the same). Note in the SDG Narrative
that the exact isomer configuration, as reported, may not be accurate.
i. If the library search produces no matches greater than or equal to 85%, and in the technical
judgment of the mass spectral interpretation specialist, no valid tentative identification can be
made, report the compound as unknown. The mass spectral specialist should give additional
classification of the unknown compound, if possible (e.g., unknown aromatic, unknown
hydrocarbon, unknown acid type, unknown chlorinated compound). If probable molecular
weights can be distinguished, include them.
j. Alkanes are not to be reported as TICs on Form IVOA-TIC. An alkane is defined as any
hydrocarbon with the generic formula CnH2n+2 that contains only C-H and C-C single bonds.
When the preceding alkanes are tentatively identified, estimate the concentration(s) and report
them in the SDG Narrative as alkanes by class (i.e., straight-chain, branched, cyclic, as a series,
or as applicable). Report total alkanes concentration on Form I VOA-TIC.
2. Check the raw data to verify that the laboratory has generated a library search for all required peaks in
the chromatograms for samples and blanks.
3. Examine blank chromatograms to verify that TIC peaks present in samples are not found in blanks.
When a low-level, non-target compound that is a common artifact or laboratory contaminant is
detected in a sample, a thorough check of blank chromatograms may require looking for peaks which
are less than 10% of the internal standard height, but present in the blank chromatogram at a similar
Relative Retention Time (RRT).
4. Examine all mass spectra for every sample and blank.
5. Consider all reasonable choices since TIC library searches often yield several candidate compounds
having a close matching score.
6. Be aware of common laboratory artifacts/contaminants and their sources (e.g., Aldol condensation
products, solvent preservatives, and reagent contaminants). These may be present in blanks and not
reported as sample TICs.
a. Examples:
i. Common laboratory contaminants include CO2 (m/z 44), siloxanes (m/z 73), diethyl ether,
hexane, certain freons, and phthalates at levels less than 100 (ig/L.
ii. Solvent preservatives include cyclohexene (a methylene chloride preservative). Related by-
products include cyclohexanone, cyclohexenone, cyclohexanol, cyclohexenol,
chlorocyclohexene, and chlorocyclohexanol.
iii. Aldol condensation reaction products of acetone include 4-hydroxy-4-methyl-2-pentanone, 4-
methyl-2-penten-2-one, and 5,5-dimethyl-2(5H)-furanone.
June 2008 84 Final
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Low/Medium Volatiles Organic Analysis
7. A target compound may be identified in the proper analytical fraction by non-target library search
procedures, even though it was not found on the quantitation list (false negative). If the total area
quantitation method was used, request that the laboratory recalculate the result using the proper
quantitation ion and Relative Response Factor (RRF).
A non-target compound may be incorrectly identified by the instrument's target analyte data processor
as a target compound (false positive). When this happens, the non-target library search procedure
will not detect the false positive as a TIC. In this case, request that the laboratory properly identify
the compound and recalculate the result using the total area quantitation method and a RRF of 1.0.
Evaluate other sample chromatograms and check for both false negatives and false positives to
determine if the occurrence is isolated or systematic.
8. Target compounds may be identified in more than one fraction. Verify that quantitation is made from
the proper fraction.
9. Do not perform library searches on internal standards or DMCs.
10. Estimate TIC concentration assuming an RRF of 1.0.
E. Action:
1. Qualify all TIC results for which there is presumptive evidence of a match (e.g., greater than or equal
to 85% match) as "NJ", tentatively identified, with approximated concentrations.
2. General actions related to the review of TIC results are as follows:
a. If it is determined that a tentative identification of a non-target compound is unacceptable, change
the tentative identification to "unknown" or another appropriate identification, and qualify the
result with a "J".
b. If all contractually-required peaks were not library searched and quantitated, the Region's
designated representative may request these data from the laboratory.
3. In deciding whether a library search result for a TIC represents a reasonable identification, use
professional judgment. If there is more than one possible match, report the result as "either
compound X or compound Y". If there is a lack of isomer specificity, change the TIC result to a non-
specific isomer result (e.g., 1,3,5-trimethyl benzene to trimethyl benzene isomer) or to a compound
class (e.g., 2-methyl, 3-ethyl benzene to a substituted aromatic compound).
4. The reviewer may elect to report all similar compounds as a total (e.g., all alkanes may be
summarized and reported as total hydrocarbons).
5. Other Case factors may influence TIC judgments. If a sample TIC match is poor, but other samples
have a TIC with a valid library match, similar RRT, and the same ions, infer identification
information from the other sample TIC results.
6. Note in the Data Review Narrative any changes made to the reported data or any concerns regarding
TIC identifications.
7. Note, for Contract Laboratory Program Project Officer (CLP PO) action, failure to properly evaluate
and report TICs.
June 2008 85 Final
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Low/Medium Volatiles Organic Analysis
XIII. System Performance
A. Review Items:
Form VIII VOA and chromatograms.
B. Objective:
During the period following Instrument Performance Quality Control (QC) checks (e.g., blanks, tuning,
calibration), changes may occur in the system that degrade the quality of the data. While this degradation
would not be directly shown by QC checks until the next required series of analytical QC runs, a thorough
review of the ongoing data acquisition can yield indicators of instrument performance.
C. Criteria:
There are no specific criteria for system performance. Professional judgment should be applied to assess
the system performance.
D. Evaluation:
1. Abrupt discrete shifts in the Reconstructed Ion Chromatogram (RIC) baseline may indicate a change
in the instrument's sensitivity or the zero setting. A baseline "shift" could indicate a decrease in
sensitivity in the instrument or an increase in the instrument zero, possibly causing target compounds,
at or near the detection limit, to miss detection. A baseline "rise" could indicate problems such as a
change in the instrument zero, a leak, or degradation of the column.
2. Poor chromatographic performance affects both qualitative and quantitative results. Indications of
substandard performance include:
a. High RIC background levels or shifts in Absolute Retention Times (RTs) of internal standards.
b. Excessive baseline rise at elevated temperature.
c. Extraneous peaks.
d. Loss of resolution.
e. Peak tailing or peak splitting that may result in inaccurate quantitation.
3. A drift in instrument sensitivity may occur during the 12-hour time period and may be an indication
of internal standard spiking problems. This could be discerned by examination of the internal
standard area on Form VIII VOA for trends such as a continuous or near-continuous increase or
decrease in the internal standard area over time.
E. Action:
Use professional judgment to qualify the data if it is determined that system performance has degraded
during sample analyses. Note, for Contract Laboratory Program Project Officer (CLP PO) action, any
degradation of system performance which significantly affected the data.
June 2008 86 Final
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Low/Medium Volatiles Organic Analysis
XIV. Overall Assessment of Data
A. Review Items:
Entire data package, data review results, and (if available) the Quality Assurance Project Plan (QAPP)
and Sampling and Analysis Plan (SAP).
B. Objective:
The overall assessment of a data package is a brief narrative in which the data reviewer expresses
concerns and comments on the quality and, if possible, the usability of the data.
C. Criteria:
Review all available materials to assess the overall quality of the data, keeping in mind the additive nature
of analytical problems.
D. Evaluation:
1. Evaluate any technical problems which have not been previously addressed.
2. If appropriate information is available, the reviewer may assess the usability of the data to help the
data user avoid inappropriate use of the data. Review all available information, including the QAPP
(specifically the acceptance and performance criteria), SAP, and communication with the data user
that concerns the intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which were not qualified
based on the Quality Control (QC) criteria previously discussed.
2. Write a brief narrative to give the user an indication of the analytical limitations of the data. Note, for
Contract Laboratory Program Project Officer (CLP PO) action, any inconsistency of the data with the
Sample Delivery Group (SDG) Narrative. If sufficient information on the intended use and required
quality of the data are available, the reviewer should include their assessment of the usability of the
data within the given context. This may be used as part of a formal Data Quality Assessment (DQA).
June 2008 87 Final
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Semivolatiles Organic Analysis
SEMIVOLATILE DATA REVIEW
The semivolatile data requirements to be checked are:
I. Preservation
II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check
III. Initial Calibration
IV. Continuing Calibration Verification (CCV)
V. Blanks
VI. Deuterated Monitoring Compounds (DMCs)
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
VIII. Regional Quality Assurance (QA) and Quality Control (QC)
IX. Gel Permeation Chromatography (GPC) Performance Check
X. Internal Standards
XI. Target Compound Identification
XII. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XIII. Tentatively Identified Compounds (TICs)
XIV. System Performance
XV. Overall Assessment of Data
NOTE: Language specific to Selective Ion Monitoring (SIM) analyses is shown in italic.
June 2008 88 Final
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Semivolatiles Organic Analysis
I. Preservation
A. Review Items:
Form I SV-1, Form I SV-2, Form SV-SIM, Form I SV-TIC, Traffic Report/Chain of Custody Record
(TR/COC), raw data, sample extraction sheets, and the Sample Delivery Group (SDG) Narrative checking
for:
1. pH
2. Sample temperature
3. Holding time
4. Other sample conditions
B. Objective:
The objective is to ascertain the validity of the analytical results based on sample condition (e.g.,
preservation and temperature) and the holding time of the sample from time of collection to time of
sample extraction and analysis.
C. Criteria:
The technical holding time criteria for aqueous samples are as follows:
For semivolatile compounds in properly cooled (4°C ± 2°C) aqueous samples, the maximum
holding time for extraction is seven (7) days from sample collection, and the maximum holding
time for analysis is 40 days from sample extraction.
The technical holding time criteria for non-aqueous samples are as follows:
For semivolatile compounds in properly cooled (4°C ± 2°C) non-aqueous samples, the maximum
holding time for extraction is 14 days from sample collection, and the maximum holding time for
analysis is 40 days from sample extraction.
D. Evaluation:
Technical holding times for sample extraction are established by comparing the sample collection dates
on the TR/COC Record with the dates of extraction on Form I SV-1, Form I SV-2, Form I SV-SIM, Form
I SV-TIC, and the sample extraction sheets. To determine if the samples were analyzed within the
holding time after extraction, compare the dates of extraction on the sample extraction sheets with the
dates of analysis on Form I SV-1, Form I SV-2, Form 1SV-SIMand Form I SV-TIC. Verify that the
analysis dates on Form I(s) and the raw data/SDG File are identical. Review the SDG Narrative and the
TR/COC Record to determine if the samples were received intact and iced. If there is no indication in the
SDG Narrative, the TR/COC Record, or the sample records that there was a problem with the samples,
the integrity of the samples can be assumed to be acceptable. If it is indicated that there were problems
with the samples, the integrity of the sample may have been compromised and professional judgment
should be used to evaluate the effect of the problem on the sample results.
June 2008 89 Final
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Semivolatiles Organic Analysis
E. Action:
1. Qualify aqueous sample results using preservation and technical holding time information as follows
(see Table 26):
a. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed within the technical holding times [seven (7) days from
sample collection for extraction; 40 days from sample collection for analysis], use professional
judgment to qualify the data.
b. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed outside the technical holding times [seven (7) days from
sample collection for extraction; 40 days from sample collection for analysis], use professional
judgment to qualify the data.
c. If the samples were properly preserved, and were extracted and analyzed within the technical
holding times [seven (7) days from sample collection for extraction; 40 days from sample
collection for analysis], no qualification of the data is necessary.
d. If the samples were properly preserved, and were extracted or analyzed outside the technical
holding times [seven (7) days from sample collection for extraction; 40 days from sample
collection for analysis], qualify detects with a "J" and non-detects as estimated with an
approximated "UJ". Note in the Data Review Narrative that holding times were exceeded and the
effect of exceeding the holding time on the resulting data.
2. Qualify non-aqueous sample results using preservation and technical holding time information as
follows (see Table 26):
a. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed within the technical holding time [14 days from sample
collection for extraction; 40 days from sample collection for analysis], use professional judgment
to qualify the data.
b. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed outside the technical holding time [14 days from sample
collection for extraction; 40 days from sample collection for analysis], use professional judgment
to qualify the data.
c. If the samples were properly preserved, and were extracted and analyzed within the technical
holding time [14 days from sample collection for extraction; 40 days from sample collection for
analysis], no qualification of the data is necessary.
d. If the samples were properly preserved, and were extracted or analyzed outside the technical
holding time [14 days from sample collection for extraction; 40 days from sample collection for
analysis], qualify detects with a "J" and non-detects as estimated with an approximated "UJ".
Note in the Data Review Narrative that holding times were exceeded and the effect of exceeding
the holding time on the resulting data.
3. Use professional judgment to qualify samples whose temperature upon receipt at the laboratory is
either below 2 degrees centigrade or above 6 degrees centigrade.
4. If technical holding times are grossly exceeded, qualify all detects as estimated with a "J" and use
professional judgment to qualify sample non-detects as "UJ" or "R".
June 2008 90 Final
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Semivolatiles Organic Analysis
5. Note in the Data Review Narrative, whenever possible, the effect of exceeding the holding time on
the resulting data.
6. Note, for Contract Laboratory Program Project Officer (CLP PO) action, when technical holding
times are grossly exceeded.
Table 26. Holding Time Actions for Semivolatile Analyses
Matrix
Aqueous
Non-aqueous
Preserved
No
No
Yes
Yes
Yes/No
No
No
Yes
Yes
Yes/No
Criteria
< 7 days (for extraction) and
< 40 days (for analysis)
> 7 days (for extraction) and
> 40 days (for analysis)
< 7 days (for extraction) and
< 40 days (for analysis)
> 7 days (for extraction) and
> 40 days (for analysis)
Grossly Exceeded
< 14 days (for extraction) and
< 40 days (for analysis)
> 14 days (for extraction) and
> 40 days (for analysis)
< 14 days (for extraction) and
< 40 days (for analysis)
> 14 days (for extraction) and
> 40 days (for analysis)
Grossly Exceeded
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
Use professional judgment
Use professional judgment
No qualification
J
J
UJ
UJorR
Use professional judgment
Use professional judgment
No qualification
J
J
UJ
UJorR
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II. Gas Chromatograph/Mass Spectrometer (GC/MS) Instrument Performance Check
A. Review Items:
Form V SV, decafluorotriphenylphosphine (DFTPP) mass spectra, and mass listing.
B. Objective:
GC/MS instrument performance checks are performed to ensure adequate mass resolution, identification,
and to some degree, sensitivity. These criteria are not sample-specific. Conformance is determined using
standard materials, therefore, these criteria should be met in all circumstances.
NOTE:
C. Criteria:
This requirement does not apply when samples are analyzed by the Selected Ion Monitoring (SIM)
technique.
1. The 12-hour clock begins with either the injection of DFTPP or in cases where a closing Continuing
Calibration Verification (CCV) can be used as an opening CCV, the 12-hour clock begins with the
injection of the opening CCV.
2. Listed below are some, but not necessarily all, examples of acceptable analytical sequences
incorporating the use of the opening and/or closing CCV. Use these examples as a guide for possible
analytical sequences that can be expected. The criteria associated with these analytical sequences
have been evaluated as part of the Contract Compliance Screening (CCS) process.
Conditions for When
Example Sequence is
Appropriate:
Acceptable Criteria That Must Be Met:
Notes:
Use Example 1 if time
remains on the 12-hour clock
after the initial calibration
sequence.
DFTPP tunes meet instrument
performance criteria.
The five Initial Calibration standards
meet initial calibration criteria.
CCV A meets both opening and
closing CCV criteria.
CCV B meets closing CCV criteria.
The requirement of starting the new 12-
hour clock for Analytical Sequence 2
with a new DFTPP tune is waived if
CCV A meets opening CCV criteria. If
CCV B meets opening CCV criteria, a
method blank and subsequent samples
may be analyzed immediately after
CCVB.
Use Example 2 if time
remains on the 12-hour clock
after the initial calibration
sequence.
DFTPP tunes meet instrument
performance criteria.
The five Initial Calibration standards
meet initial calibration criteria.
CCV A meets closing CCV criteria
(but does not meet opening CCV
criteria).
CCV B meets opening CCV criteria.
CCV C meets closing CCV criteria.
CCV A does not meet opening CCV
criteria, therefore a new DFTPP tune
must be performed, immediately
followed by CCV B, before the method
blank and any samples may be analyzed.
In this case, the new 12-hour clock and
Analytical Sequence 2 begins with the
injection of the new DFTPP tune.
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Conditions for When
Example Sequence is
Appropriate:
Acceptable Criteria That Must Be Met:
Notes:
Use Example 3 if more than
12-hours have elapsed since
the most recent initial
calibration or closing CCV,
OR
if the most recent closing
CCV was not or could not be
used as an opening CCV.
DFTPP tunes meet instrument
performance criteria.
CCV A meets opening CCV criteria.
CCV B meets both opening and
closing CCV criteria.
CCV C meets both opening and
closing CCV criteria.
The requirement of starting the new 12-
hour clock for Analytical Sequence 2
with a new DFTPP tune is waived if
CCV B meets opening CCV criteria. If
CCV C meets opening CCV criteria, a
method blank and subsequent samples
may be analyzed immediately after
CCVC.
Use Example 4 if more than
12-hours have elapsed since
the most recent initial
calibration or closing CCV,
OR
if the most recent closing
CCV was not or could not be
used as an opening CCV.
DFTPP tunes meet instrument
performance criteria.
CCV A meets opening CCV criteria.
CCV B meets closing CCV criteria
(but does not meet opening CCV
criteria).
CCV C meets opening CCV criteria.
CCV D meets both opening and
closing CCV criteria.
CCV B does not meet opening CCV
criteria, therefore a new DFTPP tune
must be performed, immediately
followed by CCV C, before the method
blank and any samples may be analyzed.
In this case, the new 12-hour clock and
Analytical Sequence 2 begins with the
injection of the new DFTPP tune. The
requirement of starting the new 12-hour
clock for Analytical Sequence 3 with a
new DFTPP tune is waived if CCV D
meets opening CCV criteria. If CCV D
meets opening CCV criteria, a method
blank and subsequent samples may be
analyzed immediately after CCV D.
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Example 1: Time Material Injected
Start of 12-hour clock for „,
, . , . . „ , 0 hr DFTPP
Analytical Sequence 1
Initial Calibration 5.0
Initial Calibration 10
Initial Calibration 20
Initial Calibration 40
Initial Calibration 80
Method Blank
Subsequent Samples
•
•
•
•
Analytical Sequence #
1
1
1
1
1
1
1
1
1
1
1
1
End of 12-hour clock for
Analytical Sequence I/
Beginning of 12-hour clock for
Analytical Sequence 2
End of 12-hour clock for
Analytical Sequence II
Beginning of 12-hour clock for
Analytical Sequence 3
12 hr CC V A (meets opening CC V criteria)
Method Blank
Subsequent Samples
24 hr CCV B (meets opening CCV criteria)
1/2
2
2
2
2
2
2
2/3
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Example 2: Time Material Injected
Start of 12-hour clock for _ ,
, . , . . „ , 0 hr DFTPP
Analytical Sequence 1
Initial Calibration 5.0
Initial Calibration 10
Initial Calibration 20
Initial Calibration 40
Initial Calibration 80
Method Blank
Subsequent Samples
•
•
•
•
Analytical Sequence #
1
1
1
1
1
1
1
1
1
1
1
1
End of 12-hour clock for
Analytical Sequence 1
Beginning of 12-hour clock for
Analytical Sequence 2
12 hr
13 hr
CCV A (meets closing CCV criteria, fails
opening CCV criteria)
DFTPP
CCV B (meets opening CCV criteria)
Method Blank
Subsequent Samples
End of 12-hour clock for
Analytical Sequence 2
25 hr CCV C (meets closing CCV criteria)
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Semivolatiles Organic Analysis
Example 3:
Start of 12-hour clock for
Analytical Sequence 1
End of 12-hour clock for
Analytical Sequence 11
Beginning of 12-hour clock for
Analytical Sequence 2
Time Material Injected
0 hr DFTPP
CCV A (meets opening CCV criteria)
Method Blank
Subsequent Samples
•
•
•
•
12 hr CCV B (meets opening CCV criteria)
Analytical Sequence #
1
1
1
1
1
1
1
1
1/2
Method Blank
Subsequent Samples
End of 12-hour clock for
Analytical Sequence 2/
Beginning of 12-hour clock for
Analytical Sequence 3
24 hr CCV C (meets opening CCV criteria)
2
2
2
2
2
2/3
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Example 4:
Start of 12-hour clock for
Analytical Sequence 1
End of 12-hour clock for
Analytical Sequence 1
Beginning of 12-hour clock for
Analytical Sequence 2
End of 12-hour clock for
Analytical Sequence II
Beginning of 12-hour clock for
Analytical Sequence 3
Time
Ohr
12 hr
13hr
Material Injected
DFTPP
CCV A (meets opening CCV criteria)
Method Blank
Subsequent Samples
Analytical Sequence #
1
1
1
1
1
1
1
CCV B (meets closing CCV criteria, fails
opening CCV criteria)
DFTPP
CCV C (meets opening CCV criteria)
Method Blank
Subsequent Samples
25 hr CCV D (meets opening CCV criteria)
2
2
2
2
2
2
2/3
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3. Inject a sufficient amount of the instrument performance check solution (50 ng DFTPP on-column) at
the beginning of each 12-hour period during which samples or standards are analyzed. This
requirement is waived if a closing CCV can be used as an opening CCV. The instrument
performance check, DFTPP for semivolatile analysis, must meet the ion abundance criteria provided
in Table 27.
Table 27. Ion Abundance Criteria For Decafluorotriphenylphosphine (DFTPP)
Mass
51
68
69
70
127
197
198
199
275
365
441
442
443
Ion Abundance Criteria
10.0 -80.0% of mass 198
Less than 2.0% of mass 69
Present
Less than 2.0% of mass 69
10.0- 80.0% of mass 198
Less than 2.0% of mass 198
Base peak, 100% relative abundance*
5. 0-9.0% of mass 198
10.0 -60.0% of mass 198
Greater than 1.0% of mass 198
Present, but less than mass 443
50.0 -100% of mass 198
15.0 -24.0% of mass 442
* All ion abundances must be normalized to m/z 198, the nominal base peak, even though the ion abundance of m/z 442 may be up to 100%
thatofm/z 198.
D. Evaluation:
1. Compare the data presented on each GC/MS Instrument Performance Check (Form V SV) with each
mass listing submitted and ensure the following:
a. Form V SV is present and completed for each 12-hour period during which samples were
analyzed. In cases where a closing CCV is used as an opening CCV for the next 12-hour period,
an additional Form V SV is not required.
b. The laboratory has not made any transcription errors between the data and the form. If there are
major differences between the mass listing and the Form Vs, a more in-depth review of the data is
required. This may include obtaining and reviewing additional information from the laboratory.
c. The appropriate number of significant figures has been reported (number of significant figures
given for each ion in the ion abundance criteria column) and that rounding is correct.
d. The laboratory has not made any calculation errors.
2. Verify that samples were not analyzed before a valid instrument performance check or were not
analyzed 12 hours after the injection of the Instrument Performance Check Solution. This evaluation
is not to be performed in cases where a closing CCV is used as an opening CCV.
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3. Verify from the raw data (mass spectral listing) that the mass assignment is correct and the mass is
normalized to m/z 198.
4. Verify that the ion abundance criteria were met. The criteria for m/z 68, 70, 441, and 443 are
calculated by normalizing to the specified m/z.
5. If possible, verify that spectra were generated using appropriate background subtraction techniques.
Since the DFTPP spectrum is obtained from chromatographic peaks that should be free from
coelution problems, background subtraction should be done in accordance with the following
procedure:
a. Three scans (the peak apex scan and the scans immediately preceding and following the apex) are
acquired and averaged.
b. Background subtraction is required, and must be accomplished using a single scan acquired no
more than 20 scans prior to the elution of DFTPP. Do not subtract the DFTPP peak as part of the
background.
NOTE: All mass spectrometer instrument conditions must be identical to those used during the sample
analysis. Background subtraction actions resulting in spectral distortions for the sole purpose of
meeting the contract specifications are contrary to the Quality Assurance (QA) objectives and are,
therefore, unacceptable.
For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the CCS process. Information regarding the laboratory's compliance with
these criteria can be obtained from the Data Assessment Tool (DAT) reports, and may be used as
part of the evaluation process.
E. Action:
1. If samples are analyzed without a preceding valid instrument performance check or are analyzed 12
hours after the Instrument Performance Check and are not preceded by an analysis of a closing CCV
that meets the opening CCV criteria, qualify all data in those samples as unusable "R".
2. If the laboratory has made minor transcription errors that do not significantly affect the data, the data
reviewer should make the necessary corrections on a copy of the form.
3. If the laboratory has failed to provide the correct forms or has made significant transcription or
calculation errors, the Region's designated representative should contact the laboratory and request
corrected data. If the information is not available, the reviewer must use professional judgment to
assess the data. Notify the laboratory's Contract Laboratory Program Project Officer (CLP PO).
4. If mass assignment is in error (e.g., m/z 199 is indicated as the base peak rather than m/z 198),
classify all associated data as unusable "R".
5. If ion abundance criteria are not met, use professional judgment to determine to what extent the data
may be utilized. Guidelines to aid in the application of professional judgment in evaluating ion
abundance criteria are discussed as follows:
a. Some of the most critical factors in the DFTPP criteria are the non-instrument specific
requirements that are also not unduly affected by the location of the spectrum on the
chromatographic profile. The m/z ratios for 198/199 and 442/443 are critical. These ratios are
based on the natural abundances of carbon 12 and carbon 13 and should always be met.
Similarly, the relative abundances for m/z 68, 70, 197, and 441 indicate the condition of the
instrument and the suitability of the resolution adjustment. Note that all of the foregoing
abundances relate to adjacent ions; they are relatively insensitive to differences in instrument
design and position of the spectrum on the chromatographic profile.
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b. For the ions at m/z 51, 127, and 275, the actual relative abundance is not as critical. For
instance, if m/z 275 has 80.0% relative abundance (criteria: 10.0-60.0%) and other criteria are
met, the deficiency is minor.
c. The relative abundance of m/z 365 is an indicator of suitable instrument zero adjustment. If
relative abundance for m/z 365 is zero, minimum detection limits may be affected. On the other
hand, if m/z 365 is present, but less than the 0.75% minimum abundance criteria, the deficiency is
not as serious.
6. Note in the Data Review Narrative decisions to use analytical data associated with DFTPP instrument
performance checks not meeting method requirements.
7. If the reviewer has reason to believe that instrument performance check criteria were achieved using
techniques other than those specified in Semivolatiles Organic Analysis, Section II.D.5, obtain
additional information on the DFTPP instrument performance checks. If the techniques employed are
found to be at variance with contract requirements, the procedures of the laboratory may merit
evaluation. Note, for CLP PO action, concerns or questions regarding laboratory performance. For
example, if the reviewer has reason to believe that an inappropriate technique was used to obtain
background subtraction (such as background subtracting from the solvent front or from another region
of the chromatogram rather than from the DFTPP peak), this should be noted for CLP PO action.
June 2008 100 Final
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III. Initial Calibration
A. Review Items:
Form VI SV-1, Form VI SV-2, Form VI SV-3, Form VISV-SIM, quantitation reports, and
chromatograms.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data for compounds on the
semivolatile Target Compound List (TCL). Initial calibration demonstrates that the instrument is capable
of acceptable performance in the beginning of the analytical run and of producing a linear calibration
curve, and provides the Mean Relative Response Factors (RRFs) used for quantitation.
C. Criteria:
1. Initial calibration standards containing both semivolatile target compounds and Deuterated
Monitoring Compounds (DMCs) are analyzed. All target compounds (except the seven compounds
listed below) and the DMCs are analyzed at concentrations of 5.0, 10, 20, 40, and 80 ng/(iL at the
beginning of each analytical sequence or as necessary if the continuing calibration verification
acceptance criteria are not met. The seven compounds are: 2,4-dinitrophenol; pentachlorophenol; 2-
nitroaniline; 3-nitroaniline; 4-nitroaniline; 4-nitrophenol, and 4,6-dinitro-2-methylphenol. These
compounds require a 4-point calibration at 10, 20, 40, and 80 ng/(iL. The initial calibration (and any
associated samples and blanks) must be analyzed within 12 hours of the associated instrument
performance check.
If analysis by the Selected Ion Monitoring (SIM) technique is requested for
PAHs/pentachlorophenols, calibration standards are analyzed at 0.10, 0.20, 0.40, 0.80, and 1.0
ng/juLfor each target compound of interest and the associated DMCs (see Table 34).
Pentachlorophenol will require only a four-point initial calibration at 0.20, 0.40, 0.80, and 1.0
ng/fiL.
2. Initial calibration standard Relative Response Factors (RRFs) for the semivolatile target compounds
listed in Table 28 and for all DMCs must be greater than or equal to 0.010. The RRF for all other
semivolatile target compounds must be greater than or equal to 0.050.
3. The Percent Relative Standard Deviation (%RSD) of the initial calibration RRFs must be less than or
equal to 40.0% for the semivolatile target compounds and associated DMCs listed in Table 28. The
%RSD for all other semivolatile target compounds and associated DMCs must be less than or equal to
20.0%.
NOTE: The flexibility clause in the method may impact some of the preceding criteria. A copy of the
flexibility clause should be present in the Sample Delivery Group (SDG). Refer to the Contract
Laboratory Program (CLP) Web site at
http://www.epa.gov/oerrpage/superfund/programs/clp/modifledanalvses.htm for the specific
method flexibility requirements.
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D. Evaluation:
1. Verify that the correct concentrations of standards were used for the initial calibration (i.e., 5.0, 10,
20, 40, and 80 ng/(iL). For the seven compounds with higher Contract Required Quantitation Limits
(CRQLs) listed in Semivolatiles Organic Analysis, Section III.C.I, verify that a four-point initial
calibration at 10, 20, 40, 80 ng/(iL was performed.
If analysis by the SIM technique is requested, verify that the correct concentrations of standards were
used for the initial calibration (i.e., 0.10, 0.20, 0.40, 0.80, and 1.0 ng/^L. The 0.10 standard is not
required for pentachlorophenol).
2. Verify that the RRF obtained from the associated initial calibration was used for calculating sample
results and the samples were analyzed within 12 hours of the associated instrument performance
check.
3. Evaluate the initial calibration RRFs and the RRFs for all semi volatile target compounds and DMCs:
a. Check and recalculate the RRFs and RRFs for at least one semivolatile target compound
associated with each internal standard. Verify that the recalculated value(s) agrees with the
laboratory reported value(s).
b. Verify that for the semivolatile target compounds listed in Table 28 and for all DMCs, the initial
calibration RRFs are greater than or equal to 0.010, and for all other semivolatile target
compounds, RRFs are greater than or equal to 0.050.
Table 28. Semivolatile Target Compounds Exhibiting Poor Response
Compounds
2,2'-Oxybis-(l-chloropropane)
4-Chloroaniline
Hexachlorobutadiene
Hexachlorocyclopentadiene
2-Nitroaniline
3-Nitroaniline
2,4-Dinitrophenol
4-Nitrophenol
Acetophenone
Caprolactam
Atrazine
Di-n-butylphthalate
Bis(2-ethylhexyl)phthalate
Benzaldehyde
4-Nitroaniline
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
3-3'-Dichlorobenzidine
l,l'-Biphenyl
Dimethy Iphthalate
Diethylphthalate
1 ,2,4,5-Tetrachlorobenzene
Carbazole
Butylbenzylphthalate
Di-n-octylphthalate
4. Evaluate the %RSD for all semivolatile target compounds and DMCs:
a. Check and recalculate the %RSD for one or more semivolatile target compound(s) and DMCs.
Verify that the recalculated value(s) agrees with the laboratory reported value(s).
b. If the %RSD is greater than the maximum criteria (40.0% for the semivolatile target compounds
listed in Table 28 and associated DMCs (see Table 34), and 20.0% for all other semivolatile
June 2008
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Semivolatiles Organic Analysis
target compounds and associated DMCs), the reviewer should use professional judgment to
determine the need to check the points on the curve for the cause of the non-linearity. This is
checked by eliminating either the high-point or the low-point and re-calculating the %RSD (see
Semivolatiles Organic Analysis, Section III.E.2).
5. If errors are detected in the calculations of either the RRF or the %RSD, perform a more
comprehensive recalculation.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. Qualify all semivolatile target compounds, including the compounds exhibiting poor response listed
in Table 28, using the following criteria (see Table 29):
a. If any semivolatile target compound has an RRF value less than the minimum criterion (0.010 for
the target compounds exhibiting poor response listed in Table 28, and 0.050 for all other
semivolatile compounds), use professional judgment for detects, based on mass spectral
identification, to qualify the data as a "J" or unusable "R".
b. If any semivolatile target compound has an RRF value less than the minimum criterion (0.010 for
the target compounds exhibiting poor response listed in Table 28, and 0.050 for all other
semivolatile compounds), qualify non-detected compounds as unusable "R".
c. If any of the semivolatile target compounds listed in Table 28 has %RSD greater than 40.0%,
qualify detects with a "J" and non-detected compounds using professional judgment (see
Semivolatiles Organic Analysis, Section III.E.2).
d. For all other semivolatile target compounds, if %RSD is greater than 20.0%, qualify detects with
a "J" and non-detected compounds using professional judgment (see Semivolatiles Organic
Analysis, Section III.E.2).
e. If the semivolatile target compounds meet the acceptance criteria for RRF and %RSD, no
qualification of the data is necessary.
f No qualification of the data is necessary on the DMC RRF and %RSD data alone. However, use
professional judgment and follow the guidelines in Semivolatiles Organic Analysis, Section
III.E.2, to evaluate the DMC RRF and %RSD data in conjunction with the DMC recoveries to
determine the need for qualification of data.
2. At the reviewer's discretion, and based on the project-specific data quality objectives, a more in-depth
review may be considered using the following guidelines:
a. If any semivolatile target compound has a %RSD greater than the maximum criterion (40.0% for
the target compounds listed in Table 28, and 20.0% for all other semivolatile compounds), and if
eliminating either the high or the low-point of the curve does not restore the %RSD to less than or
equal to the required maximum:
i. Qualify detects for that compound(s) with a" J".
ii. Qualify non-detected semivolatile target compounds using professional judgment.
b. If the high-point of the curve is outside of the linearity criteria (e.g., due to saturation):
i. Qualify detects outside of the linear portion of the curve with a "J".
ii. No qualifiers are required for detects in the linear portion of the curve.
June 2008 103 Final
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Semivolatiles Organic Analysis
iii. No qualifiers are required for semivolatile target compounds that were not detected.
c. If the low-point of the curve is outside of the linearity criteria:
i. Qualify low-level detects in the area of non-linearity with a "J".
ii. No qualifiers are required for detects in the linear portion of the curve.
iii. For non-detected semivolatile compounds, use the lowest point of the linear portion of the
curve to determine the new quantitation limit.
3. If the laboratory has failed to provide adequate calibration information, the Region's designated
representative may contact the laboratory and request the necessary information. If the information is
not available, the reviewer must use professional judgment to assess the data.
4. Note in the Data Review Narrative, whenever possible, the potential effects on the data due to
calibration criteria exceedance.
5. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if calibration criteria are
grossly exceeded.
Table 29. Initial Calibration Actions for Semivolatile Analyses
Criteria for Semivolatile Analysis
RRF < 0.010 (target compounds listed in Table 28)
RRF < 0.050 (all other target compounds)
RRF > 0.010 (target compounds listed in Table 28)
RRF > 0.050 (all other target compounds)
%RSD < 40.0 (target compounds listed in Table 28)
%RSD < 20.0 (all other target compounds)
%RSD > 40.0 (target compounds listed in Table 28)
%RSD > 20.0 (all other target compounds)
Action
Detected Associated
Compounds
J or R (based on mass
spectral identification)
Non-Detected Associated
Compounds
R
No qualification
No qualification
J
Use professional judgment
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IV. Continuing Calibration Verification (CCV)
A. Review Items:
Form VII SV-1, Form VII SV-2, Form VII SV-3, Form VIISV-SIM, quantitation reports, and
chromatograms.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data. The CCV checks
satisfactory performance of the instrument on a day-to-day basis, however quantitations are based on the
Mean Relative Response Factors (RRFs ) obtained from the initial calibration.
C. Criteria:
1. The 12-hour clock begins with either the injection of Decafluorotriphenylphosphine (DFTPP), or in
cases where a closing CCV can be used as on opening CCV, the 12-hour clock begins with the
injection of the opening CCV.
2. CCV standards containing both target compounds and associated Deuterated Monitoring Compounds
(DMCs) are analyzed both at the beginning (opening CCV) and end (closing CCV) of each 12-hour
analysis period following the analysis of the instrument performance check, and prior to the analysis
of the method blank and samples. An instrument performance check is not required prior to the
analysis of a closing CCV or prior to a closing CCV which can be used as an opening CCV for the
next 12-hour period. If time remains in the 12-hour time period after initial calibration and samples
are to be analyzed, the mid-point standard from the initial calibration can be used as an opening CCV.
3. For an opening CCV, the Relative Response Factors (RRFs) for the semivolatile target compounds
listed in Table 28, and for all associated DMCs, must be greater than or equal to 0.010. The RRF for
all other semivolatile target compounds must be greater than or equal to 0.050.
4. For a closing CCV, RRFs must be greater than or equal to 0.010 for all semivolatile target
compounds and associated DMCs.
5. For an opening CCV, the Percent Difference (%D) between the initial calibration RRF and the
opening CCV RRF must be within ±40.0% for the semivolatile target compounds and associated
DMCs listed in Table 28. For an opening CCV, the Percent Difference for all other semivolatile
target compounds and associated DMCs must be within ±25.0%.
6. For a closing CCV, the Percent Difference between the initial calibration RRF and the opening CCV
RRF must be within ±50.0% for all semivolatile target compounds and associated DMCs.
D. Evaluation:
1. Verify that the CCV was run at the required frequency (an opening and closing CCV must be run
within a 12-hour period) and the CCV was compared to the correct initial calibration. If the mid-
point standard from the initial calibration is used as an opening CCV, verify that the result (RRF) of
the mid-point standard was compared to the RRF from the correct initial calibration.
2. Evaluate the CCV RRF for all semivolatile target compounds and DMCs:
June 2008 105 Final
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Semivolatiles Organic Analysis
a. Check and recalculate the CCV RRF for at least one semivolatile target compound and DMC
associated with each internal standard. Verify that the recalculated value(s) agrees with the
laboratory reported value(s).
b. For an opening CCV, verify that all semivolatile target compounds listed in Table 28 and all
DMCs have CCV RRFs of greater than or equal to 0.010, and all other semivolatile target
compounds have RRFs of greater than or equal to 0.050.
c. For a closing CCV, verify that all semivolatile target compounds and DMCs have CCV RRFs of
greater than or equal to 0.010.
3. Evaluate the Percent Difference between initial calibration RRF and CCV (both opening and closing)
RRF for one or more semivolatile target compound(s) and DMCs:
a. Check and recalculate the Percent Difference for one or more semivolatile target compound(s)
and DMCs associated with each internal standard. Verify that the recalculated value(s) agrees
with the laboratory-reported value (s).
b. For an opening CCV, verify that the Percent Difference is within ±40.0% for the semivolatile
target compounds and associated DMCs listed in Table 28, and within ±25.0% for all other
semivolatile target compounds and associated DMCs.
c. For a closing CCV, verify that the Percent Difference is within ±50.0% for all semivolatile target
compounds and DMCs.
4. If errors are detected in the calculations of either the CCV (both opening and closing) RRF or the
Percent Difference, perform a more comprehensive recalculation.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If a CCV (opening and closing) was not run at the appropriate frequency, qualify all data as unusable
"R" (see Table 30).
2. Qualify all semivolatile target compounds, including the compounds exhibiting poor response listed
in Table 28, using the following criteria:
a. For an opening CCV, if any semivolatile target compound has an RRF value less than the
minimum criterion (0.010 for the compounds listed in Table 28 and 0.050 for all other
semivolatile compounds), use professional judgment for detects, based on mass spectral
identification, to qualify the data as a "J" or unusable "R".
b. For a closing CCV, if any semivolatile target compound has an RRF value less than 0.010, use
professional judgment for detects based on mass spectral identification to qualify the data as a "J"
or unusable "R".
c. For an opening CCV, if any semivolatile target compound has an RRF value less than the
minimum criterion (0.010 for the compounds listed in Table 28 and 0.050 for all other
semivolatile compounds), qualify non-detected compounds as unusable "R".
d. For a closing CCV, if any semivolatile target compound has an RRF of less than 0.010, qualify
non-detected compounds as unusable "R".
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Semivolatiles Organic Analysis
e. For an opening CCV, if the Percent Difference value for any of the semivolatile target
compounds listed in Table 28 is outside the ±40.0% criterion, qualify detects with a "J" and non-
detected compounds with an approximated "UJ".
f For a closing CCV, if the Percent Difference value for any of the semivolatile target compounds
exhibiting poor response is outside the ±50.0% criterion, qualify detects with a "J" and non-
detected compounds with an approximated "UJ".
g. For an opening CCV, if the Percent Difference value for any other semivolatile target compound
is outside the ±25.0% criterion, qualify detects with a "J" and non-detected compounds with an
approximated "UJ".
h. For a closing CCV, if the Percent Difference value for any other semivolatile target compound is
outside the ±50.0% criterion, qualify detects with a "J" and non-detected compounds with an
approximated "UJ".
i. No qualification of the data is necessary on the DMC RRF and Percent Difference data alone.
However, use professional judgment to evaluate the DMC RRF and Percent Difference data in
conjunction with the DMC recoveries to determine the need for qualification of data.
j. If the semivolatile target compounds meet the acceptance criteria for RRF and the Percent
Difference, no qualification of the data is necessary.
3. If the laboratory has failed to provide adequate calibration information, the Region's designated
representative may contact the laboratory and request the necessary information. If the information is
not available, the reviewer must use professional judgment to assess the data.
4. Note in the Data Review Narrative, whenever possible, the potential effects on the data due to
calibration criteria exceedance.
5. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if calibration criteria are
grossly exceeded.
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Table 30. Continuing Calibration Verification (CCV) Actions for Semivolatile Analyses
Criteria for Opening CCV
Criteria for Closing CCV
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
Opening CCV not performed at required
frequency (see Semivolatile Organic
Analysis, Section IV C.I)
Closing CCV not performed at
required frequency (see
Semivolatile Organic Analysis,
Section IV C.I)
R
RRF < 0.010 (target compounds listed in
Table 28)
RRF < 0.050 (all other target compounds)
RRF < 0.010 (all target
compounds)
JorR
R
RRF > 0.010 (target compounds listed in
Table 28)
RRF > 0.050 (all other target compounds)
RRF > 0.010 (all target
compounds)
No qualification
% D < 40.0 or > -40.0 (target compounds
listed in Table 28)
%D < 25.0 or >-25.0 (all other target
compounds)
% D < 50.0 or > -50.0 (all target
compounds)
No qualification
% D > 40.0 or < -40.0 (target compounds
listed in Table 28)
%D > 25.0 or < -25.0 (all other target
compounds)
% D > 50.0 or < -50.0 (all target
compounds)
UJ
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Semivolatiles Organic Analysis
V. Blanks
A. Review Items:
Form I SV-1, Form I SV-2, Form I SV-TIC, Form ISV-SIM, Form IV SV, Form IV SV-SIM,
chromatograms, and quantitation reports.
B. Objective:
The purpose of laboratory or field blank analyses is to determine the existence and magnitude of
contamination resulting from laboratory, field, or sample transport activities. The purpose of the method
blank is to determine the levels of contamination associated with the processing and analysis of the
samples. The criteria for evaluation of blanks apply to any blank associated with samples (e.g., method
blanks and field blanks). If problems with a blank exist, all associated data must be carefully evaluated to
determine whether or not there is any variability in the data, or if the problem is an isolated occurrence
not affecting other data.
C. Criteria:
1. Method Blanks
A method blank must be extracted each time samples are extracted. A method blank is required per
matrix (e.g., a non-aqueous method blank is required for non-aqueous samples and an aqueous
method blank is required for aqueous samples) and concentration level (e.g., low or medium). The
number of samples extracted with each method blank shall not exceed 20 field samples [excluding
Matrix Spike/Matrix Spike Duplicates (MS/MSDs) and Performance Evaluation (PE) samples]. The
method blank must be analyzed on each Gas Chromatograph/Mass Spectrometer (GC/MS) system
used to analyze the set of samples prepared with the method blank.
For low-level non-aqueous and aqueous samples, the concentration of each target compound [except
bis(2-ethylhexyl)phthalate] found in the method blank must be less than its Contract Required
Quantitation Limit (CRQL) listed in the method. The concentration of bis(2-ethylhexyl)phthalate
found in the method blank must be less than five times (5x) its respective CRQL listed in the method.
For medium-level non-aqueous samples, the concentration of each target compound found in the
method blank must be less than its CRQL listed in the method.
NOTE: The concentration of non-target compounds in all blanks must be less than or equal to 10 u,g/L.
D. Evaluation:
1. Review the results of blanks on the forms and raw data (chromatograms and quantitation reports) to
evaluate the presence of target and non-target compounds in the blanks.
2. Verify that a method blank analysis has been reported for each extraction batch and for each GC/MS
system used to analyze semivolatile samples. There must be a method blank per sample matrix (i.e.,
if non-aqueous samples are present, verify that there is a non-aqueous method blank) and
concentration level. The reviewer may use the Method Blank Summary (Form IV SV and Form IV
SV-SIM) to identify the samples associated with each method blank.
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Semivolatiles Organic Analysis
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process. Data concerning the field
blanks are not evaluated as part of the CCS process. If field blanks are present, the data reviewer
should evaluate this data in a similar fashion as the method blanks.
E. Action:
Action regarding unsuitable blank results depends on the circumstances and origin of the blank. In
instances where more than one of the same type of blank is associated with a given sample, qualification
should be based upon a comparison with the associated blank having the highest concentration of a
contaminant. Do not correct the sample results by subtracting any blank value (see Table 31).
1. If a semivolatile compound is found in a method blank, but not found in the sample, no qualification
of the data is necessary.
2. If the method blank concentration is less than the CRQL [less than 5x the CRQL for bis(2-
ethylhexyl)phthalate in low-level non-aqueous and aqueous samples] and:
a. the sample concentration is less than the CRQL [less than 5x the CRQL for bis(2-
ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], report the CRQL value
with a "U".
b. the sample concentration is greater than or equal to the CRQL [greater than or equal to 5x the
CRQL for bis(2-ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], use
professional judgment to qualify the data.
3. If the method blank concentration is greater than the CRQL [greater than 5x the CRQL for bis(2-
ethylhexyl)phthalate in low-level non-aqueous and aqueous samples] and:
a. the sample concentration is less than the CRQL [less than 5x the CRQL for bis(2-
ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], report the CRQL value
with a "U".
b. the sample concentration is greater than or equal to the CRQL [greater than or equal to 5x the
CRQL for bis(2-ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], and less
than the blank concentration, report the concentration of the compound in the sample at the same
concentration found in the blank with a "U", or the reviewer may elect to qualify the data as
unusable "R".
c. the sample concentration is greater than or equal to the CRQL [greater than or equal to 5x the
CRQL for bis(2-ethylhexyl)phthalate in low-level non-aqueous and aqueous samples] and greater
than or equal to the blank concentration, use professional judgment to qualify the data.
4. If the method blank concentration is equal to the CRQL [equal to 5x the CRQL for bis(2-
ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], and:
a. the sample concentration is less than the CRQL [less than 5x the CRQL for bis(2-
ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], report the CRQL value
with a "U".
b. the sample concentration is greater than or equal to the CRQL [greater than or equal to 5x the
CRQL for bis(2-ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], use
professional judgment to qualify the data.
5. If gross contamination exists (i.e., saturated peaks by GC/MS), qualify all affected compounds in the
associated samples as unusable "R", due to interference. Note, for Contract Laboratory Program
June 2008 110 Final
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Semivolatiles Organic Analysis
Project Officer (CLP PO) action, if the contamination is suspected of having an effect on the sample
results.
6. Give the same consideration as the target compounds to the Tentatively Identified Compounds
(TICs), which are found in both the sample and associated blank(s) (see Semivolatiles Organic
Analysis, Section XIII, for TIC guidance).
7. If the contaminants found in the blank are interfering non-target compounds at concentrations greater
than 10 ug/L, the reviewer may use professional judgment to qualify the data.
NOTE: There may be instances where little or no contamination was present in the associated blanks, but
qualification of the sample is deemed necessary. If the reviewer determines that the contamination
is from a source other than the sample, they should qualify the data. Contamination introduced
through dilution water is one example. Although it is not always possible to determine, instances
of this occurring can be detected when contaminants are found in the diluted sample result, but
are absent in the undiluted sample result.
8. If contaminants are found in the field blanks, the following is recommended:
a. Review the associated method blank data to determine if the contaminant(s) was also present in
the method blank.
i. If the analyte was present at a comparable level in the method blank, the source of the
contamination may be in the analytical system and the action recommended for the method
blank would apply.
ii. If the analyte was not present in the method blank, the source of contamination may be in the
field. Consider all associated samples for possible cross-contamination.
b. If the field blank contains a semivolatile Target Compound List (TCL) compound(s) at a
concentration greater than the CRQL [greater than 5x the CRQL for bis(2-ethylhexyl)phthalate in
low-level non-aqueous and aqueous samples], and:
i. the sample concentration is less than the CRQL [less than 5x the CRQL for bis(2-
ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], report the CRQL value
with a "U".
ii. the sample concentration is greater than or equal to the CRQL [greater than or equal to 5x the
CRQL for bis(2-ethylhexyl)phthalate in low-level non-aqueous and aqueous samples], and
less than the blank concentration, report the concentration of the compound in the sample at
the same concentration found in the blank and qualify with a "U", or the reviewer may elect
to qualify the data as unusable "R".
iii. the sample concentration is greater than the CRQL [greater than 5x the CRQL for bis(2-
ethylhexyl)phthalate in low-level non-aqueous and aqueous samples]and greater than or equal
to the blank concentration, use professional judgment to qualify the data.
c. If the field blanks contain a semivolatile TCL compound(s) at a concentration less than the CRQL
[less than 5x the CRQL for bis(2-ethylhexyl)phthalate in low-level non-aqueous and aqueous
samples], and:
i. the sample concentration is less than the CRQL [less than 5x the CRQL for bis(2-
ethylhexyl)phthalate for low-level non-aqueous and aqueous samples], report the CRQL
value with a "U".
ii. the sample concentration is greater than or equal to the CRQL [greater than or equal to 5x the
CRQL for bis(2-ethylhexyl)phthalate for low-level non-aqueous and aqueous samples], no
qualification of the data is necessary.
June 2008 111 Final
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Semivolatiles Organic Analysis
d. If the field blanks contain a semivolatile TCL compound(s) at a concentration equal to the CRQL
[equal to 5x the CRQL for bis(2-ethylhexyl)phthalate for low-level non-aqueous and aqueous
samples] and:
i. the sample concentration is less than the CRQL [less than 5x the CRQL for bis(2-
ethylhexyl)phthalate for low-level non-aqueous and aqueous samples], report the CRQL
value with a "U".
ii. the sample concentration is greater than or equal to the CRQL [greater than or equal to 5x the
CRQL for bis(2-ethylhexyl)phthalate for low-level non-aqueous and aqueous samples], use
professional judgment to qualify the data.
e. If gross contamination (i.e., saturated peaks by GC/MS) exists in the field blank, positive sample
results may require rejection and be qualified as unusable "R". Non-detected semivolatile target
compounds do not require qualification unless the contamination is so high that it interferes with
the analyses of non-detected compounds.
f If the contaminants found in the field blank are interfering non-target compounds at
concentrations greater than 10 (ig/L (for aqueous blanks) or 330 (ig/kg (for non-aqueous blanks),
use professional judgment to qualify the data.
Table 31. Blank Actions for Semivolatiles Analyses
Blank
Type
Method,
Field
Blank Result
Detects
^ PDDT *
> CRQL*
— pwnT *
Gross contamination
TIC > 10 |ig/L (for aqueous
blanks)
TIC> 330 jig/kg (for non-
aqueous blanks)
Sample Result
Not detected
< CRQL*
> CRQL*
< CRQL*
> CRQL* and CRQL* and > blank concentration
< CRQL*
> CRQL*
Detects
Detects
Action for Samples
No qualification
Report CRQL value with a U
Use professional judgment
Report CRQL value with a U
Report the blank concentration
for the sample with a U or
qualify the data as unusable R
Use professional judgment
Report CRQL with a U
Use professional judgment
Qualify results as unusable R
Use professional judgment
5x the CRQL for bis(2-ethylhexyl)phthalate for low-level non-aqueous and aqueous samples.
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VI. Deuterated Monitoring Compounds (DMCs)
A. Review Items:
Form II SV-1, Form II SV-2, Form II SV-3, Form II SV-4, Form IISV-SIM1, Form IISV-SIM2,
chromatograms, and quantitation reports.
B. Objective:
Laboratory performance on individual samples is established by means of spiking activities. All samples
are spiked with DMCs prior to sample preparation. The evaluation of the results of these DMCs is not
necessarily straightforward. The sample itself may produce effects due to factors such as interferences.
Since the effects of the sample matrix are frequently outside laboratory control and may present relatively
unique problems, the evaluation and review of data based on specific sample results is frequently
subjective and requires analytical experience and professional judgment. Accordingly, this section
consists primarily of guidelines, in some cases with several optional approaches suggested.
C. Criteria:
1. The DMCs listed in Table 32 are added to all samples and blanks to measure their recovery in
environmental samples.
June 2008 113 Final
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Semivolatiles Organic Analysis
Table 32. Semivolatile Deuterated Monitoring Compound (DMC) and Recovery Limits
DMC
Phenol-d5
Bis-(2-chloroethyl) ether-d8
2-Chlorophenol-d4
4-Methylphenol-d8
Nitrobenzene-d5
2-Nitrophenol-d4
2,4-Dichlorophenol-d3
4-Chloroaniline-d4
Dimethylphthalate-d<5
Acenaphthylene-d8
4-Nitrophenol-d4
Fluorene-d10
4,6-Dinitro-2-methylphenol-d2
Anthracene-d10
Pyrene-d10
Benzo(a)pyrene-d12
Fluoranthene-d10 (SIM)
2-Methylnaphthalene-d10 (SIM)
Recovery Limits
(%) for Water
Samples
39-106
40 - 105
41 - 106
25-111
43 - 108
40 - 108
37-105
1-145
47-114
41 - 107
33-116
42-111
22 - 104
44-110
52-119
32-121
50-150
50-150
Recovery Limits
(%) for
Soil/Sediment
Samples
17-103
12-98
13-101
8-100
16-103
16-104
23 - 104
1 -145
43-111
20-97
16-166
40-108
1 -121
22-98
51 - 120
43-111
50-150
50-150
2. Recoveries for DMCs in semivolatile samples and blanks must be within the limits specified in
Table 32.
NOTE:
D. Evaluation:
The recovery limits for any of the compounds listed in Table 32 may be expanded at any time
during the period of performance if USEPA determines that the limits are too restrictive.
1. Check raw data (e.g., chromatograms and quantitation reports) to verify the recoveries on the
Deuterated Monitoring Compound Recovery Forms (Form II SV-1, Form II SV-2, Form II SV-3,
Form II SV-4, Form IISV-SIM1, and Form IISV-SIM2).
Check for any calculation or transcription errors; verify that the DMC recoveries were calculated
correctly using the equation in the method.
2. Whenever there are two or more analyses for a particular sample, the reviewer must determine which
are the most acceptable data to report. Considerations include, but are not limited to:
a. DMC recovery (marginal versus gross deviation).
b. Technical holding times.
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Semivolatiles Organic Analysis
c. Comparison of the values of the target compounds reported in each sample analysis.
d. Other Quality Control (QC) information, such as performance of internal standards.
NOTE:
E. Action:
For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
Table 34 and Table 35 (SIMAnalysis) list the semivolatile DMCs and their associated target compounds.
If any DMC recovery in the semivolatiles fraction is out of specification, qualify data considering the
existence of interference in the raw data (see Table 33). Considerations include, but are not limited to:
1. For any recovery greater than the upper acceptance limit:
a. Qualify detected associated semivolatile target compounds as a "J".
b. Do not qualify non-detected associated semivolatile target compounds.
2. For any recovery less than the lower acceptance limit:
a. Qualify detected associated semivolatile target compounds as a "J".
b. Qualify non-detected associated semivolatile target compounds as approximated "UJ" or unusable
"R".
3. For any recovery within acceptance limits, no qualification of the data is necessary.
4. In the special case of a blank analysis having DMCs out of specification, the reviewer must give
special consideration to the validity of associated sample data. The basic concern is whether the
blank problems represent an isolated problem with the blank alone, or whether there is a fundamental
problem with the analytical process. For example, if one or more samples in the batch show
acceptable DMC recoveries, the reviewer may choose to consider the blank problem to be an isolated
occurrence. Note, for Contract Laboratory Program Project Officer (CLP PO) action, analytical
problems, even if this judgment allows some use of the affected data.
Table 33. Deuterated Monitoring Compound (DMC) Recovery Actions For Semivolatile Analyses
Criteria
%R > Upper Acceptance Limit
%R < Lower Acceptance Limit
Lower Acceptance < %R < Upper Acceptance Limit
Action
Detected Associated
Compounds
J
J
Non-Detected
Associated
Compounds
No qualification
UJorR
No qualification
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Table 34. Semivolatile Deuterated Monitoring Compounds (DMCs) and the Associated Target Compounds
Phenol-dj (DMC)
Benzaldehyde
Phenol
bis(2-Chloroethyl) ether-ds (DMC)
bis-(2-Chloroethyl) ether
2,2'-oxybis( 1 -Chloropropane)
bis(2-Chloroethoxy) methane
Nitrobenzene-ds (DMC)
Acetophenone
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
2,6-Dinitrotoluene
2,4-Dinitrotoluene
N-Nitrosodiphenylamine
Fluorene-d10 (DMC)
Dibenzofuran
Fluorene
4-Chlorophenyl-phenylether
4-Bromophenyl-phenylether
Carbazole
Acenaphthylene-d8 (DMC)
Naphthalene
2-Methylnaphthalene
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
4,6-Dinitro-2-methylphenol-d2(DMC)
4,6-Dinitro-2-methylphenol
2-Chlorophenol-d4 (DMC)
2-Chlorophenol
4-Methylphenol-d8 (DMC)
2-Methylphenol
4-Methylphenol
2,4-Dimethylphenol
2,4-Dichlorophenol-d3 (DMC)
2,4-Dichlorophenol
Hexachlorobutadiene
4-Chloro-3-methylphenol
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
1 ,2,4,5-Tetrachlorobenzene
Pentachlorophenol
2,3,4 ,6-Tetrachlorophenol
Anthracene-d10 (DMC)
Hexachlorobenzene
Atrazine
Phenanthrene
Anthracene
4-Nitrophenol-d4 (DMC)
2-Nitroaniline
3-Nitroaniline
2,4-Dinitrophenol
4-Nitrophenol
4-Nitroaniline
2-Nitrophenol-d4 (DMC)
Isophorone
2-Nitrophenol
4-Chloroaniline-d4 (DMC)
4-Chloroaniline
Hexachlorocyclopentadiene
3,3' -Dichlorobenzidine
Dimethylphthalate-d6 (DMC)
Caprolactam
l,l'-Biphenyl
Dimethylphthalate
Diethylphthalate
Di-n-butylphthalate
Butylbenzylphthalate
bis(2-ethylhexyl)phthalate
Di-n-octylphthalate
Pyrene-d10 (DMC)
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo (a) pyrene-d12 (DMC)
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno( 1 ,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
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Table 35. Semivolatile Deuterated Monitoring Compounds (DMCs) for Selective Ion Monitoring (SIM) and the
Associated Target Compounds
Fluoranthene-d10 (DMC)
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno( 1 ,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
2-Methylnapthalene-d10 (DMC)
Napthalene
2-Methylnapthalene
Acenapthylene
Acenaphthene
Fluorene
Pentachlorophenol
Phenanthrene
Anthracene
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Semivolatiles Organic Analysis
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
A. Review Items:
Form III SV-1, Form III SV-2, Form III SV-SIM1 and Form IIISV-SIM2, chromatograms, and
quantitation reports.
NOTE: Data for MS and MSDs will not be present unless requested by the Region.
B. Objective:
Data for MS and MSDs are generated to determine long-term precision and accuracy of the analytical
method on the sample matrix and to demonstrate acceptable compound recovery by the laboratory at the
time of sample analysis. These data alone cannot be used to evaluate the precision and accuracy of
individual samples. However, when exercising professional judgment, this data should be used in
conjunction with other available Quality Control (QC) information.
C. Criteria:
1. If requested, MS and MSD samples are analyzed at a frequency of one MS and MSD per 20 or fewer
samples per sample matrix and concentration level.
2. Spike recoveries should be within the advisory limits provided on Form III SV-1, Form III SV-2,
Form III SV-SIM, and Form III SV-SIM2.
3. Relative Percent Differences (RPDs) between MS and MSD recoveries must be within the advisory
limits provided on Form III SV-1, Form III SV-2, Form III SV-SIM, and Form III SV-SIM2.
D. Evaluation:
1. Verify that requested MS and MSD samples were analyzed at the required frequency and that results
are provided for each sample.
2. Inspect results for the MS and MSD Recovery on Form III SV, Form III SV-1, Form III SV-2, Form
III SV-SIM and Form III SV-SIM2 and verify that the results for recovery and RPD are within the
advisory limits.
3. Verify transcriptions from raw data and verify calculations.
4. Check that the MS recoveries and RPD were calculated correctly.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. No qualification of the data is necessary on MS and MSD data alone. However, using informed
professional judgment, the data reviewer may use the MS and MSD results in conjunction with other
QC criteria to determine the need for some qualification of the data (see Table 36). Table 37 lists the
semivolatile target compounds that are spiked into samples to test for matrix effects. If any MS and
MSD Percent Recovery or RPD in the semivolatiles fraction is out of specification (see Table 37),
qualify data to include the consideration of the existence of interference in the raw data.
Considerations include, but are not limited to:
June 2008 118 Final
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Semivolatiles Organic Analysis
a. For any recovery or RPD greater than the upper acceptance limit:
i. Qualify detected spiked semivolatile target compounds as a "J".
ii. Do not qualify non-detected spiked semivolatile target compounds.
b. For any recovery less than the lower acceptance limit:
i. Qualify detected spiked semivolatile target compounds as a "J".
ii. Use professional judgment to qualify non-detected spiked semivolatile target compounds.
c. For any recovery or RPD within acceptance limits, no qualification of the data is necessary.
2. The data reviewer should first try to determine to what extent the results of the MS and MSD affect
the associated data. This determination should be made with regard to the MS and MSD sample
itself, as well as specific analytes for all samples associated with the MS and MSD.
3. In those instances where it can be determined that the results of the MS and MSD affect only the
sample spiked, limit qualification to this sample only. However, it may be determined through the
MS and MSD results that a laboratory is having a systematic problem in the analysis of one or more
analytes, that affects all associated samples. Use professional judgment to qualify the data from all
associated samples.
4. Use professional judgment to determine the need for qualification of detects of non-spiked
compounds.
NOTE: Note, for Contract Laboratory Program Project Officer (CLP PO) action, if a field blank was used
for the MS and MSD.
Table 36. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Semivolatiles Analysis
Criteria
%R or RPD > Upper Acceptance Limit
%R < Lower Acceptance Limit
Lower Acceptance Limit < %R;
RPD < Upper Acceptance Limit
Action
Detected Spiked Compounds
J
J
Non-detected Spiked
Compounds
No qualification
Use professional judgment
No qualification
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Table 37. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD)
Compound
Phenol
2-Chlorophenol
N-Nitroso-di-n-propylamine
4-Chloro-3-methylphenol
Acenaphthene
4-Nitrophenol
2,4-Dinitrotoluene
Pentachlorophenol
Pyrene
% Recovery for
Water Samples
12-110
27-123
41-116
23-97
46-118
10-80
24-96
9-103
26 - 127
RPD for Water
Samples
0-42
0-40
0-38
0-42
0-31
0-50
0-38
0-50
0-31
% Recovery for
Soil/Sediment
Samples
26-90
25 - 102
41 - 126
26 - 103
31-137
11-114
28-89
17-109
35 - 142
RPD for
Soil/Sediment
Samples
0-35
0-50
0-38
0-33
0-19
0-50
0-47
0-47
0-36
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VIII. Regional Quality Assurance (OA) and Quality Control (OC)
A. Review Items:
Form I SV-1, Form I SV-2, Form ISV-SIM, chromatograms, Traffic Report/Chain of Custody Record
(TR/COC), quantitation reports, and other raw data from QA/QC samples.
B. Objective:
Regional QA/QC refers to any QA and/or QC samples initiated by the Region, including field duplicates,
Performance Evaluation (PE) samples, blind spikes, and blind blanks. The use of these QA/QC samples
is highly recommended (e.g., the use of field duplicates can provide information on sampling precision
and homogeneity).
C. Criteria:
Criteria are determined by each Region.
1. PE sample frequency may vary.
2. The analytes present in the PE sample must be correctly identified and quantified.
D. Evaluation:
1. Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data review.
Each Region will handle the evaluation of PE samples on an individual basis. Compare results for PE
samples to the acceptance criteria for the specific PE samples, if available.
2. Calculate Relative Percent Difference (RPD) between field duplicates. Provide this information in
the Data Review Narrative.
E. Action:
Any action must be in accordance with Regional specifications and the criteria for acceptable PE sample
results. Note, for Contract Laboratory Program Project Officer (CLP PO) action, unacceptable results for
PE samples.
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IX. Gel Permeation Chromatography (GPC) Performance Check
A. Review Items:
Two ultraviolet (UV) traces, GPC cleanup blank quantitation reports, and chromatograms.
B. Objective:
GPC is used to remove high molecular weight contaminants that can interfere with the analysis of target
analytes. GPC cleanup procedures are checked by adding the GPC calibration mixture to the GPC cleanup
columns and setting the appropriate elution window, and verifying the recovery of target compounds
through the cleanup procedure by the analysis of a cleanup blank.
C. Criteria:
1. GPC is used for the cleanup of all non-aqueous sample extracts and for aqueous sample extracts that
contain high molecular weight components that interfere with the analysis of the target analytes.
2. At least once every seven (7) days, the calibration of the GPC unit must be checked by injecting the
calibration solution.
3. The GPC calibration is acceptable if the two UV traces meet the following requirements:
a. Peaks must be observed and symmetrical for all compounds in the calibration solution.
b. Corn oil and the phthalate peaks exhibit greater than 85% resolution.
c. The phthalate and methoxychlor peaks exhibit greater than 85% resolution.
d. Methoxychlor and perylene peaks exhibit greater than 85% resolution.
e. Perylene and sulfur peaks must not be saturated and should exhibit greater than 90% baseline
resolution.
f The Retention Time (RT) shift is less than 5% between UV traces for bis(2-ethylhexyl)phthalate
and perylene.
4. A GPC blank must be analyzed after each GPC calibration and is acceptable if the blank does not
exceed the Contract Required Quantitation Limits (CRQL) for any target analytes, except for bis(2-
ethylhexyl)phthalate, which must be less than 5x the CRQL.
D. Evaluation
1. Verify that there are two UV traces present and that the RT shift for bis(2-ethylhexyl)phthalate and
perylene is less than 5%.
2. Verify that the compounds listed in Semivolatiles Organic Analysis, Section IX.C.3, are present and
symmetrical in both UV traces and that the compound pairs meet the minimum resolution
requirements.
3. Verify that no target compound exceeds the CRQL except for bis(2-ethylhexyl)phthalate, which must
not exceed 5x the CRQL.
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E. Action:
1. If GPC criteria are not met, examine the raw data for the presence of high molecular weight
contaminants; examine subsequent sample data for unusual peaks; and use professional judgment in
qualifying the data. Notify the Contract Laboratory Program Project Officer (CLP PO) if the
laboratory chooses to analyze samples under unacceptable GPC criteria.
2. Note in the Data Review Narrative potential effects on the sample data resulting from the GPC
cleanup analyses not yielding acceptable results.
June 2008 123 Final
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Semivolatiles Organic Analysis
X. Internal Standards
A. Review Items:
Form VIII SV-1, Form VIII SV-2, Form VIIISV-SIM1, Form VIIISV-SIM2, quantitation reports, and
chromatograms.
B. Objective:
Internal standards performance criteria ensure that Gas Chromatograph/Mass Spectrometer (GC/MS)
sensitivity and response are stable during each analysis.
C. Criteria:
1. Internal standard area counts for all samples [including Matrix Spike/Matrix Spike Duplicate
(MS/MSD), or Performance Evaluation (PE) samples] and all blanks must be within the inclusive
range of 50.0% and 200% of its response from the associated 12-hour calibration standard [opening
Continuing Calibration Verification (CCV) or mid-point standard from the initial calibration].
2. The Retention Time (RT) of the internal standard in the sample or blank must not vary by more than
±30.0 seconds from the RT of the internal standard in the associated 12-hour calibration standard
[opening CCV or mid-point standard from the initial calibration].
D. Evaluation:
1. Check raw data (e.g., chromatograms and quantitation lists) to verify the internal standard RTs and
areas reported on the Internal Standard Area Summary (Form VIII SV-1, Form VIII SV-2, Form VIII
SV-SIM1, and Form VIIISV-SIM2}.
2. Verify that all RTs and internal standard areas are within the required criteria for all samples and
blanks.
3. If there are two analyses for a particular fraction, the reviewer must determine which are the most
accurate data to report. Considerations include, but are not limited to:
a. Magnitude and direction of the internal standard area shift.
b. Magnitude and direction of the internal standard RT shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each fraction.
e. Other Quality Control (QC) information.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance screening (CCS) process. Information regarding the
laboratory's compliance with these criteria can be obtained from the Data Assessment Tool (DAT)
reports, and may be used as part of the evaluation process.
E. Action:
1. If an internal standard area count for a sample or blank is greater than 200% of the area for the
associated standard (opening CCV or mid-point standard from the initial calibration) (see Table 38):
a. Qualify detects for compounds quantitated using that internal standard with a "J".
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Semivolatiles Organic Analysis
b. Do not qualify non-detected associated compounds.
2. If an internal standard area count for a sample or blank is less than 50.0% of the area for the
associated standard (opening CCV or mid-point standard from the initial calibration):
a. Qualify detects for compounds quantitated using that internal standard with a "J".
b. Qualify non-detected associated compounds as unusable "R**".
3. If an internal standard area count for a sample or a blank is greater than or equal to 50.0%, and less
than or equal to 200% of the area for the associated standard opening CCV or mid-point standard
from the initial calibration, no qualification is necessary.
4. Absolute RTs of internal standards should not vary dramatically between samples and the associated
12-hour calibration standard (opening CCV or mid-point standard from the initial calibration).
Examine the chromatographic profile for that sample to determine if any false positives or negatives
exist. For shifts of a large magnitude, the reviewer may consider partial or total rejection of the data
for that sample fraction. Detects should not need to be qualified as unusable "R" if the mass spectral
criteria are met.
5. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if the internal standard
performance criteria are grossly exceeded. Note in the Data Review Narrative potential effects on the
data resulting from unacceptable internal standard performance.
Table 38. Internal Standard Actions For Semivolatiles Analyses
Criteria
Area counts >200% of 12-hour standard (opening CCV or mid-point
standard from the initial calibration)
Area counts <50.0% of 12-hour standard (opening CCV or mid-point
standard from the initial calibration)
Area counts > 50.0% and < 200% of 12-hour standard (opening CCV or
mid-point standard from the initial calibration)
RT difference > 30.0 seconds between samples and 12-hour standard
(opening CCV or mid-point standard from the initial calibration)
RT difference < 30.0 seconds between samples and 12-hour standard
(opening CCV or mid-point standard from the initial calibration)
Action
Detected Associated
Compounds*
J
J
Non-Detected
Associated
Compounds*
No qualification
R**
No qualification
R
No qualification
For semivolatile compounds associated to each internal standard, see Table 2 - Semivolatile Internal Standards with Corresponding
Target and Deuterated Monitoring Compounds Assigned for Quantitation in SOM01.2. Exhibit D. available at:
http://www.epa.gov/superfund/programs/clp/soml.htm
For area counts in the range of 20-50%, nondetected compounds may be qualified as UJ based on further evaluations on the data. The
evaluations may include but are not limited to review of the chromatograms, mass spectra and statistical studies of signal-to-noise
ratios. Such data qualifications shall be performed on a project-by-project basis.
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XL Target Compound Identification
A. Review Items:
Form I SV-1, Form I SV-2, Form ISV-SIM, quantitation reports, mass spectra, and chromatograms.
B. Objective:
The objective of the criteria for Gas Chromatograph/Mass Spectrometer (GC/MS) qualitative analysis is
to minimize the number of erroneous identifications of compounds. An erroneous identification can
either be a false positive (reporting a compound present when it is not) or a false negative (not reporting a
compound that is present).
The identification criteria can be applied much more easily in detecting false positives than false
negatives. More information is available for false positives due to the requirement for submittal of data
supporting positive identifications. Negatives, or non-detected compounds, represent an absence of data
and are, therefore, much more difficult to assess. One example of the detection of false negatives is not
reporting a target compound that is reported as a Tentatively Identified Compound (TIC).
C. Criteria:
1. The Relative Retention Times (RRTs) must be within ±0.06 RRT units of the standard RRT [opening
Continuing Calibration Verification (CCV) or mid-point standard from the initial calibration].
2. Mass spectra of the sample compound and a current laboratory-generated standard [i.e., the mass
spectrum from the associated calibration standard (opening CCV or mid-point standard from initial
calibration)] must match according to the following criteria:
a. All ions present in the standard mass spectrum at a relative intensity greater than 10% must be
present in the sample spectrum.
b. The relative intensities of these ions must agree within ±20% between the standard and sample
spectra (e.g., for an ion with an abundance of 50% in the standard spectrum, the corresponding
sample ion abundance must be between 30-70%).
c. Ions present at greater than 10% in the sample mass spectrum, but not present in the standard
spectrum, must be evaluated by a reviewer experienced in mass spectral interpretation.
D. Evaluation:
1. Check that the RRT of reported compounds is within ±0.06 RRT units of the standard RRT (opening
CCV or mid-point standard from the initial calibration).
2. Check the sample compound spectra against the laboratory standard spectra to verify that it meets the
specified criteria.
3. Be aware of situations when sample carryover is a possibility and use professional judgment to
determine if instrument cross-contamination has affected any positive compound identification.
4. Check the chromatogram to verify that peaks are identified. Major peaks are either identified as
target compounds, TICs, Deuterated Monitoring Compounds (DMCs), or internal standards.
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Semivolatiles Organic Analysis
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. The application of qualitative criteria for GC/MS analysis of target compounds requires professional
judgment. It is up to the reviewer's discretion to obtain additional information from the laboratory. If
it is determined that incorrect identifications were made, qualify all such data as not detected "U" or
unusable "R".
2. Use professional judgment to qualify the data if it is determined that cross-contamination has
occurred.
3. Note in the Data Review Narrative any changes made to the reported compounds or concerns
regarding target compound identifications. Note, for Contract Laboratory Program Project Officer
(CLP PO) action, the necessity for numerous or significant changes.
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Semivolatiles Organic Analysis
XII. Compound Ouantitation and Reported Contract Required Ouantitation Limits (CRQLs)
A. Review Items:
Form I SV-1, Form I SV-2, Form ISV-SIM, sample preparation sheets, Sample Delivery Group (SDG)
Narrative, quantitation reports, and chromatograms.
B. Objective:
The objective is to ensure that the reported quantitation results and CRQLs are accurate.
C. Criteria:
1. Compound quantitation, adjustment of the CRQL, and Percent Moisture (for non-aqueous samples)
must be calculated according to the correct equation.
2. Compound Relative Response Factors (RRFs) must be calculated based on the internal standard
associated with that compound, as listed in the method. Quantitation must be based on the
quantitation ion (m/z) specified in the method for both the internal standard and target analytes. The
compound quantitation must be based on the average RRF from the associated initial calibration.
D. Evaluation:
1. Examine raw data to verify the correct calculation of all sample results reported by the laboratory.
Compare quantitation lists and chromatograms to the reported detect and non-detect sample results.
Check the reported values.
2. Verify that the correct internal standard, quantitation ion, and Mean Relative Response Factor (RRF)
were used to quantitate the compound. Verify that the same internal standard, quantitation ion, and
RRF are used consistently throughout, in both the calibration as well as quantitation process.
3. Verify that the CRQLs have been adjusted to reflect all sample dilutions and Percent Moisture factors
(for non-aqueous samples).
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. For non-aqueous samples, if the Percent Moisture is less the 70.0%, no qualification of the data is
necessary. If the Percent Moisture is greater than or equal to 70.0% and less than 90.0%, qualify
detects as "J" and non-detects as approximated "UJ". If the Percent Moisture is greater than or equal
to 90.0%, qualify detects as "J" and non-detects as unusable "R" (see Table 39).
2. If any discrepancies are found, the Region's designated representative may contact the laboratory to
obtain additional information that could resolve any differences. If a discrepancy remains unresolved,
the reviewer must use professional judgment to decide which value is the most accurate value. Under
these circumstances, the reviewer may determine that qualification of data is warranted. Note in the
Data Review Narrative a description of the reasons for data qualification and the qualification that is
applied to the data.
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Semivolatiles Organic Analysis
3. Note, for Contract Laboratory Program Project Officer (CLP PO) action, numerous or significant
failures to accurately quantify the target compound or to properly evaluate and adjust CRQLs.
Table 39. Percent Moisture Actions for Semivolatiles Analyses for Non-Aqueous Samples
Criteria
%Moisture < 70.0%
70.0% < %Moisture < 90.0%
%Moisture > 90.0%
Action
Detected Associated Compounds
Non-Detected Associated
Compounds
No qualification
J
J
UJ
R
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XIII. Tentatively Identified Compounds (TICs)
A. Review Items:
Form I SV-TIC, chromatograms, library search printouts, and spectra for the TIC candidates.
B. Objective:
Chromatographic peaks in semivolatile fraction analyses that are not target analytes, Deuterated
Monitoring Compounds (DMCs), or internal standards are potential TICs. TICs must be qualitatively
identified via a forward search of the NIST/USEPA/NIH Mass Spectral Library (May 2002 release or
later)5, and/or Wiley Mass Spectral Library (1998 release or later)6, or equivalent. The identifications
must be assessed by the data reviewer.
C. Criteria:
For each sample, the laboratory must conduct a mass spectral search of the NIST/USEPA/NIH (May 2002
release or later), and/or Wiley (1998 release or later), or equivalent mass spectral library, and report the
possible identity for 30 of the largest semivolatile fraction peaks which are not DMCs, internal standards,
or target compounds, but which have area or height greater than 10% of the area or height of the nearest
internal standard. Estimated concentrations for TICs are calculated similarly to the Target Compound
List (TCL) compounds, using total ion areas for the TIC and the internal standard, and assuming a
Relative Response Factor (RRF) of 1.0. TIC results are reported for each sample on the Organic
Analyses Data Sheet (Form I SV-TIC).
D. Evaluation:
1. Guidelines for tentative identification are as follows:
a. Major ions (greater than 10% Relative Intensity) in the reference spectrum should be present in
the sample spectrum.
b. The relative intensities of the major ions should agree within ±20% between the sample and the
reference spectra.
c. Molecular ions present in the reference spectrum should be present in the sample spectrum.
d. Review ions present in the sample spectrum, but not in the reference spectrum, for possible
background contamination, interference, or presence of coeluting compounds.
e. Review ions present in the reference spectrum, but not in the sample spectrum, for possible
subtraction from the sample spectrum because of background contamination or coeluting
compounds. Data system library reduction programs can sometimes create these discrepancies.
f Non-target compounds receiving a library search match of 85% or higher are a "likely match".
Report the compound unless the mass spectral interpretation specialist feels there is evidence not
to report the compound as identified by the library search program. Note in the Sample Delivery
Group (SDG) Narrative the justification for not reporting a compound as listed by the search
program.
5NIST/USEPA/NIH Mass Spectral Library (May 2002 release or later), National Institute of Standards and Technology, Gaithersburg,
Maryland.
6Wiley Mass Spectral Library (1998 release or later) John Wiley & Sons, Inc., Hoboken, New Jersey.
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Semivolatiles Organic Analysis
g. If the library search produces more than one compound greater than or equal to 85%, report the
compound with the highest percent match (report first compound if percent match is the same for
two or more compounds), unless the mass spectral interpretation specialist feels that the highest
match compound should not be reported or another compound with a lower match should be
reported. The laboratory should include the justification for not reporting the compound with the
highest spectral match within the SDG Narrative. Do not report DMCs, internal standards, and
volatile target compounds as TICs, unless the only compounds having a percent match of greater
than 85% are DMCs, internal standards, or volatile target compounds.
h. If the library search produces a series of obvious isomer compounds with library search matches
greater than or equal to 85% (e.g., tetramethyl naphthalenes), report the compound with the
highest library search percent match (or the first compound if the library search matches are the
same). Note in the SDG Narrative that the exact isomer configuration, as reported, may not be
accurate.
i. If the library search produces no matches greater than or equal to 85%, and in the technical
judgment of the mass spectral interpretation specialist, no valid tentative identification can be
made, report the compound as unknown. The mass spectral specialist should give additional
classification of the unknown compound, if possible (e.g., unknown phthalate, unknown
hydrocarbon, unknown acid type, unknown chlorinated compound). If probable molecular
weights can be distinguished, include them.
j. Alkanes are not to be reported as TICs on Form I SVOA-TIC. An alkane is defined as any
hydrocarbon with the generic formula CnH2n+2 that contains only C-H and C-C single bonds.
When the preceding alkanes are tentatively identified, estimate the concentration(s) and report
them in the SDG Narrative as alkanes by class (i.e., straight-chain, branched, cyclic, as a series,
or as applicable). Report total alkanes concentration on Form IVOA-TIC.
2. Check the raw data to verify that the laboratory has generated a library search for all required peaks in
the chromatograms for samples and blanks.
3. Examine blank chromatograms to verify that TIC peaks present in samples are not found in blanks.
When a low-level, non-target compound that is a common artifact or laboratory contaminant is
detected in a sample, a thorough check of blank chromatograms may require looking for peaks which
are less than 10% of the internal standard height, but present in the blank chromatogram at a similar
Relative Retention Time (RRT).
4. Examine all mass spectra for each sample and blank.
5. Consider all reasonable choices since TIC library searches often yield several candidate compounds
having a close matching score.
6. Be aware of common laboratory artifacts/contaminants and their sources (e.g., Aldol condensation
products, solvent preservatives, and reagent contaminants). These may be present in blanks and not
reported as sample TICs.
a. Examples:
i. Common laboratory contaminants include CO2 (m/z 44), siloxanes (m/z 73), diethyl ether,
hexane, certain freons, and phthalates at levels less than 100 (ig/L.
ii. Solvent preservatives include cyclohexene (a methylene chloride preservative). Related by-
products include cyclohexanone, cyclohexenone, cyclohexanol, cyclohexenol,
chlorocyclohexene, and chlorocyclohexanol.
iii. Aldol condensation reaction products of acetone include 4-hydroxy-4-methyl-2-pentanone, 4-
methyl-2-penten-2-one, and 5,5-dimethyl-2(5H)-furanone.
June 2008 131 Final
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Semivolatiles Organic Analysis
7. A target compound may be identified in the proper analytical fraction by non-target library search
procedures, even though it was not found on the quantitation list (false negative). If the total area
quantitation method was used, request that the laboratory recalculate the result using the proper
quantitation ion and Relative Response Factor (RRF).
A non-target compound may be incorrectly identified by the instrument's target analyte data processor
as a target compound (false positive). When this happens, the non-target library search procedure
will not detect the false positive as a TIC. In this case, request that the laboratory properly identify
the compound and recalculate the result using the total area quantitation method and a RRF of 1.0.
Evaluate other sample chromatograms and check for both false negatives and false positives to
determine if the occurrence is isolated or systematic.
8. Target compounds may be identified in more than one fraction. Verify that quantitation is made from
the proper fraction.
9. Do not perform library searches on internal standards or DMCs.
10. Estimate TIC concentration assuming an RRF of 1.0.
E. Action:
1. Qualify all TIC results for which there is presumptive evidence of a match (i.e., greater than or equal
to 85% match) as "NJ", tentatively identified, with approximated concentrations.
2. General actions related to the review of TIC results are as follows:
a. If it is determined that a tentative identification of a non-target compound is unacceptable, change
the tentative identification to "unknown" or another appropriate identification and qualify the
result with a "J".
b. If all contractually-required peaks were not library searched and quantitated, the Region's
designated representative may request these data from the laboratory.
3. In deciding whether a library search result for a TIC represents a reasonable identification, use
professional judgment. If there is more than one possible match, report the result as "either
compound X or compound Y". If there is a lack of isomer specificity, change the TIC result to a non-
specific isomer result (e.g., 1,3,5-trimethyl benzene to trimethyl benzene isomer), or to a compound
class (e.g., 2-methyl, 3-ethyl benzene to a substituted aromatic compound).
4. The reviewer may elect to report all similar isomers as a total (e.g., all alkanes may be summarized
and reported as total hydrocarbons).
5. Other Case factors may influence TIC judgments. If a sample TIC match is poor, but other samples
have a TIC with a good library match, similar RRT, and the same ions, infer identification
information from the other sample TIC results.
6. Note in the Data Review Narrative any changes made to the reported data or any concerns regarding
TIC identifications.
7. Note, for Contract Laboratory Program Project Officer (CLP PO) action, failure to properly evaluate
and report TICs.
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Semivolatiles Organic Analysis
XIV. System Performance
A. Review Items:
Form VIII SV-1, Form VIII SV-2, Form VIIISV-SIM1, Form VIIISV-SIM2, and chromatograms.
B. Objective:
During the period following Instrument Performance Quality Control (QC) checks (e.g., blanks, tuning,
calibration), changes may occur in the system that degrade the quality of the data. While this degradation
would not be directly shown by QC checks until the next required series of analytical QC runs, a thorough
review of the ongoing data acquisition can yield indicators of instrument performance.
C. Criteria:
There are no specific criteria for system performance. Use professional judgment to assess the system
performance.
D. Evaluation:
1. Abrupt discrete shifts in the Reconstructed Ion Chromatogram (RIC) baseline may indicate a change
in the instrument's sensitivity or the zero setting. A baseline "shift" could indicate a decrease in
sensitivity in the instrument or an increase in the instrument zero, possibly causing target compounds,
at or near the detection limit, to miss detection. A baseline "rise" could indicate problems such as a
change in the instrument zero, a leak, or degradation of the column.
2. Poor chromatographic performance affects both qualitative and quantitative results. Indications of
substandard performance include:
a. High RIC background levels or shifts in Absolute Retention Times (RTs) of internal standards.
b. Excessive baseline rise at elevated temperature.
c. Extraneous peaks.
d. Loss of resolution.
e. Peak tailing or peak splitting that may result in inaccurate quantitation.
3. A drift in instrument sensitivity may occur during the 12-hour time period and may be an indication
of internal standard spiking problems. This could be discerned by examination of the internal
standards area on Form VIII SV-1, Form VIII SV-2, Form VIII SV-SIM1, and Form VIII SV-SIM2,
for trends such as a continuous or near-continuous increase or decrease in the internal standard area
overtime.
E. Action:
Use professional judgment to qualify the data if it is determined that system performance has degraded
during sample analyses. Note, for Contract Laboratory Program Project Officer (CLP PO) action, any
degradation of system performance which significantly affected the data.
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Semivolatiles Organic Analysis
XV. Overall Assessment of Data
A. Review Items:
Entire data package, data review results, and (if available) Quality Assurance Project Plan (QAPP), and
Sampling and Analysis Plan (SAP).
B. Objective:
The overall assessment of a data package is a brief narrative in which the data reviewer expresses
concerns and comments on the quality and, if possible, the usability of the data.
C. Criteria:
Review all available materials to assess the overall quality of the data, keeping in mind the additive nature
of analytical problems.
D. Evaluation:
1. Evaluate any technical problems that have not been previously addressed.
2. If appropriate information is available, the reviewer may assess the usability of the data to help the
data user in avoiding inappropriate use of the data. Review all available information, including the
QAPP (specifically the acceptance or performance criteria), SAP, and communication with the data
user that concerns the intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which were not qualified
based on the Quality Control (QC) criteria previously discussed.
2. Write a brief narrative to give the user an indication of the analytical limitations of the data. Note, for
Contract Laboratory Program Project Officer (CLP PO) action, any inconsistency of the data with the
Sample Delivery Group (SDG) Narrative. If sufficient information on the intended use and required
quality of the data are available, the reviewer should include their assessment of the usability of the
data within the given context. This may be used as part of a formal Data Quality Assessment (DQA).
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Pesticides Organic Analysis
PESTICIDE DATA REVIEW
The pesticide data requirements to be checked are:
I. Preservation
II. Gas Chromatograph/Electron Capture Detector (GC/ECD) Instrument Performance Check
III. Initial Calibration
IV. Continuing Calibration Verification (CCV)
V. Blanks
VI. Surrogate Spikes
VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
VIII. Laboratory Control Samples (LCSs)
IX. Regional Quality Assurance (QA) and Quality Control (QC)
X. Florisil Cartridge Performance Check
XI. Gel Permeation Chromatography (GPC) Performance Check
XII. Target Compound Identification
XIII. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation
XIV. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XV. Overall Assessment of Data
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Pesticides Organic Analysis
I. Preservation
A. Review Items:
Form I PEST, Traffic Report/Chain of Custody Record (TR/COC), raw data, sample extraction sheets,
and Sample Delivery Group (SDG) Narrative checking for:
1. pH
2. Sample temperature
3. Holding time
4. Other sample conditions
B. Objective:
The objective is to ascertain the validity of the analytical results based on sample condition (e.g.,
preservation and temperature) and the holding time of the sample from time of collection to time of
sample extraction and analysis.
C. Criteria:
The technical holding time criteria for aqueous samples are as follows:
For pesticides in properly cooled (4°C ± 2°C) aqueous samples, the maximum holding time for
extraction is seven (7) days from sample collection, and the maximum holding time for analysis is
40 days from sample extraction.
The technical holding time criteria for non-aqueous samples are as follows:
For pesticides in properly cooled (4°C ± 2°C) non-aqueous samples, the maximum holding time
for extraction is 14 days from sample collection, and the maximum holding time for analysis is 40
days from sample extraction.
D. Evaluation:
Technical holding times for sample extraction are established by comparing the sample collection dates
on the TR/COC Record with the dates of extraction on Form I PEST and the sample extraction sheets.
Information contained in the Complete SDG File (CSF) should also be considered in the determination of
holding times. To determine if the samples were analyzed within the holding time after extraction,
compare the dates of extraction on the sample extraction sheets with the dates of analysis on Form I
PEST. Verify that the analysis dates on Form I(s) and the raw data/SDG file are identical. Review the
SDG Narrative and the TR/COC Record to determine if the samples were received intact and iced. If
there is no indication in the SDG Narrative, the TR/COC Record, or the sample records that there was a
problem with the samples, assume the integrity of the samples is acceptable. If it is indicated that there
were problems with the samples, the integrity of the sample may have been compromised. Use
professional judgment to evaluate the effect of the problem on the sample results.
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E. Action:
1. Qualify aqueous sample results using preservation and technical holding time information as follows
(see Table 40):
a. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed within the technical holding times [seven (7) days from
sample collection for extraction; 40 days from sample collection for analysis], use professional
judgment to qualify the data.
b. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed outside the technical holding times [seven (7) days from
sample collection for extraction; 40 days from sample collection for analysis], use professional
judgment to qualify the data.
c. If the samples were properly preserved, and were extracted and analyzed within the technical
holding times [seven (7) days from sample collection for extraction; 40 days from sample
collection for analysis], no qualification of the data is necessary.
d. If the samples were properly preserved, and were extracted or analyzed outside the technical
holding times [seven (7) days from sample collection for extraction; 40 days from sample
collection for analysis], qualify detects with a "J" and non-detects as estimated with an
approximated "UJ" or unusable "R". Note in the Data Review Narrative that holding times were
exceeded and the effect of exceeding the holding time on the resulting data.
2. Qualify non-aqueous sample results using preservation and technical holding time information as
follows (see Table 40):
a. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed within the technical holding times [14 days from sample
collection for extraction; 40 days from sample collection for analysis], use professional judgment
to qualify the data.
b. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed outside the technical holding times [14 days from sample
collection; 40 days from sample collection for analysis], use professional judgment to qualify the
data.
c. If the samples were properly preserved, and were extracted and analyzed within the technical
holding times [14 days from sample collection; 40 days from sample collection for analysis], no
qualification of the data is necessary.
d. If the samples were properly preserved, and were extracted or analyzed outside the technical
holding times [14 days from sample collection; 40 days from sample collection for analysis],
qualify detects with a "J" and non-detects as estimated with an approximated "UJ" or unusable
"R". Note in the Data Review Narrative that holding times were exceeded and the effect of
exceeding the holding time on the resulting data.
3. Use professional judgment to qualify samples whose temperature upon receipt at the laboratory is
either below 2 degrees centigrade or above 6 degrees centigrade.
June 2008 137 Final
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4. If technical holding times are grossly exceeded, qualify all detects as estimated with a "J" and use
professional judgment to qualify sample non-detects.
5. Note in the Data Review Narrative, whenever possible, the effect of exceeding the holding time on
the resulting data.
6. Note, for Contract Laboratory Program Project Officer (CLP PO) action, when technical holding
times are grossly exceeded.
Table 40. Holding Time Actions for Pesticide Analyses
Matrix
Aqueous
Non-aqueous
Preserved
No
No
Yes
Yes
Yes/No
No
No
Yes
Yes
Yes/No
Criteria
< 7 days (for extraction) and
< 40 days (for analysis)
> 7 days (for extraction) and
> 40 days (for analysis)
< 7 days (for extraction) and
< 40 days (for analysis)
> 7 days (for extraction) and
> 40 days (for analysis)
Grossly Exceeded
< 14 days (for extraction) and
< 40 days (for analysis)
> 14 days (for extraction) and
> 40 days (for analysis)
< 14 days (for extraction) and
< 40 days (for analysis)
> 14 days (for extraction) and
> 40 days (for analysis)
Grossly Exceeded
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
Use professional judgment
Use professional judgment
No qualification
J
J
UJ
UJorR
Use professional judgment
Use professional judgment
No qualification
J
J
UJ
UJorR
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Pesticides Organic Analysis
II. Gas Chromatograph with Electron Capture Detector (GC/ECD) Instrument Performance
Check
A. Review Items:
Form VI PEST-5, Form VI PEST-6, Form VI PEST-7, Form VI PEST-8, Form VI PEST-9, Form VI
PEST-10, Form VII PEST-1, chromatograms, and data system printouts.
B. Objective:
GC/ECD instrument performance checks are performed to ensure adequate resolution and instrument
sensitivity. These criteria are not sample-specific. Conformance is determined using standard materials,
therefore, these criteria should be met in all circumstances.
C. Criteria:
1. Resolution Check Mixture
a. The Resolution Check Mixture is analyzed at the beginning of every initial calibration sequence,
on each Gas Chromatograph (GC) column and instrument used for analysis. The Resolution
Check Mixture contains the following pesticides and surrogates (see Table 41):
Table 41. Resolution Check Mixture Components
Compounds
gamma-Chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endosulfan sulfate
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC
Aldrin
Heptachlor
Endrin ketone
Methoxychlor
Endosulfan II
Heptachlor-epoxide
alpha-Chlordane
4,4'-DDD
4,4'-DDT
Endrin
Endrin aldehyde
Tetrachloro-m-xylene (surrogate)
Decachlorobiphenyl (surrogate)
b. The resolution between two adjacent peaks in the Resolution Check Mixture must be greater than
or equal to 80.0% for all analytes for the primary column and greater than or equal to 50.0% for
the confirmation column in order to use one Individual Standard Mixture (C). If two Individual
Standard Mixtures (A and B) are to be used, the resolution between two adjacent peaks in the
Resolution Check Mixture must be greater than or equal to 60.0%.
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Pesticides Organic Analysis
2. Performance Evaluation Mixture (PEM)
a. The PEM is analyzed at the beginning (following the Resolution Check Mixture) and at the end
of the initial calibration sequence. The PEM analysis must bracket one end of each 12-hour
analytical period. The PEM contains the following pesticides and surrogates (see Table 42):
Table 42. Performance Evaluation Mixture (PEM) Components
Compounds
gamma-BHC
alpha-BHC
4,4'-DDT
beta-BHC
Endrin
Methoxychlor
Tetrachloro-m-xylene (surrogate)
Decachlorobiphenyl (surrogate)
b. The resolution between any two adjacent peaks in the initial calibration and continuing
calibration verification PEMs must be greater than or equal to 90% on each GC column.
c. The Percent Breakdown is the amount of decomposition that 4,4'-DDT and Endrin undergo when
analyzed on the GC column. For Endrin, the percent breakdown is determined by the presence of
Endrin aldehyde and/or Endrin ketone in the PEM. For 4,4-DDT, the percent breakdown is
determined by the presence of 4,4'-DDD and/or 4,4'-DDE in the PEM.
i. The Percent Breakdown of 4,4'-DDT and Endrin in the PEMs must each be less than or equal
to 20.0% on each GC column.
ii. The combined Percent Breakdown for 4,4'-DDT and Endrin in PEMs must be less than or
equal to 30.0% on each GC column.
3. Mid-point Individual Standard Mixtures (A and B) or (C)
a. The resolution capabilities of the GC/ECD system used will dictate whether two Individual
Standard Mixtures (A and B) (see Table 43) or one Individual Mixture (C) (see Table 44) can be
used. This is determined by the analysis of the Resolution Check Mixture to see if the criteria in
Il.C.l.b are met. If Individual Standard Mixtures (A and B) are used, follow the procedure in 3b.
If Individual Standard Mixture (C) is used, follow the procedure in 3c.
b. Mid-point Individual Standard Mixtures (A and B)
i. The mid-point Individual Standard Mixtures (A and B; INDA/INDB) are analyzed as part of
the initial calibration. The mid-point INDA and INDB analysis must bracket one end of each
12-hour analytical period. The Individual Standard Mixtures contain the following pesticides
and surrogates:
June 2008
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Pesticides Organic Analysis
Table 43. Individual Standard Mixtures A and B Components
Individual Standard Mixture A
Individual Standard Mixture B
Compounds
alpha-BHC
Heptachlor
gamma-BHC
Endosulfan I
Dieldrin
Endrin
4,4'-DDD
4,4'-DDT
Methoxychlor
Tetrachloro-m-xylene (surrogate)
Decachlorobiphenyl (surrogate)
beta-BHC
delta-BHC
Aldrin
Heptachlor-epoxide
alpha-Chlordane
gamma-Chlordane
4,4'-DDE
Endosulfan sulfate
Endrin aldehyde
Endrin ketone
Endosulfan II
Tetrachloro-m-xylene (surrogate)
Decachlorobiphenyl (surrogate)
ii. The resolution between any two adjacent peaks in the mid-point concentration of Individual
Standard Mixtures (A and B) in the initial calibration and continuing calibration verification
must be greater than or equal to 90.0% on each column.
c. Mid-point Individual Standard Mixture (C)
i. The mid-point Individual Standard Mixture (C; INDC) is analyzed as part of the initial
calibration. The mid-point INDC analysis must bracket one end of each 12-hour analytical
period. The Individual Standard Mixture (C) contains the pesticides and surrogates listed in
Table 44.
ii. The resolution between any two adjacent peaks in the mid-point concentration of Individual
Standard Mixture (C) in the initial calibration and continuing calibration verification must be
greater than or equal to 80.0% for the primary column and greater than or equal to 50.0% for
the secondary column.
June 2008
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Pesticides Organic Analysis
Table 44. Individual Standard Mixture C Components
Compounds
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC
Aldrin
Heptachlor
Heptachlor-epoxide
alpha-Chlordane
gamma-Chlordane
Endosulfan I
Endosulfan II
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endrin
Endosulfan sulfate
Endrin ketone
Endrin aldehyde
Methoxychlor
Tetrachloro-m-xylene
Decachlorobipheny 1
D. Evaluation:
1. Resolution Check Mixture
Check the Resolution Check Mixture data and Form VI PEST-5 to verify that if two Individual
Standard Mixtures (A and B) are used, the resolution between two adjacent peaks for the required
compounds in the Resolution Check Mixture is greater than or equal to 60.0% on both GC columns.
Verify that if one Individual Standard Mixture (C) is used, the resolution between two adjacent peaks
for the required compounds in the Resolution Check Mixture is greater than or equal 80.0% on the
primary column and greater than or equal to 50.0% on the secondary column.
2. PEM
a. Check the initial calibration and continuing calibration verification PEM data and Form VI
PEST-6 to verify that the resolution between adjacent peaks is greater than or equal to 90.0% on
both GC columns.
b. Check Form VII PEST-1 to verify that the breakdown of 4,4'-DDT is less than or equal to 20.0%,
the breakdown of Endrin is less than or equal to 20.0%, and the combined breakdown of 4,4'-
DDT and Endrin is less than or equal to 30.0% in all PEMs on both GC columns.
3. Mid-point Individual Standard Mixtures (A and B)
a. Check the initial calibration and continuing calibration verification mid-point Individual Standard
Mixtures (A and B) data on Form VI PEST-7 and Form VI PEST-8 to verify that the resolution
between adjacent peaks is greater than or equal to 90.0% on both GC columns.
4. Mid-point Individual Standard Mixture (C)
a. Check the initial calibration and continuing calibration verification mid-point Individual Standard
Mixture (C) data on Form VI PEST-9 and Form VI PEST-10 to verify that the resolution between
adjacent peaks is greater than or equal to 80.0% for the primary column and 50.0% for the
secondary column.
June 2008
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Pesticides Organic Analysis
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. Resolution Check Mixture
a. If resolution criteria are not met, the quantitative results may not be accurate due to inadequate
resolution. Qualitative identifications may also be questionable if coelution exists.
i. Qualify detects for target compounds that were not adequately resolved with an "NJ" (see
Table 45).
ii. Qualify non-detected compounds as unusable "R".
2. PEM
a. If PEM analysis is not performed at the required frequency (see Pesticides Organic Analysis,
Section II.C.2.a), qualify all associated sample and blank results as unusable "R".
b. If PEM resolution criteria are not met, the quantitative results may not be accurate due to
inadequate resolution. Qualitative identifications may be questionable if coelution exists.
i. Qualify detects with an "NJ".
ii. Qualify non-detects as unusable "R".
c. If 4,4'-DDT breakdown is greater than 20.0%:
i. Qualify detects for 4,4'-DDT with a "J".
ii. Qualify detects for 4,4'-DDD and/or 4,4'-DDE with a "J".
iii. If 4,4'-DDT was not detected, but 4,4'-DDD and/or 4,4'-DDE were detected, qualify non-
detects for 4,4'-DDT as unusable "R", and qualify detects for 4,4'-DDD and/or 4,4'-DDE as
presumptively present at an approximated quantity "NJ".
d. If Endrin breakdown is greater than 20.0%:
i. Qualify detects for Endrin with a "J".
ii. Qualify detects for Endrin aldehyde and/or Endrin ketone with a "J".
iii. If Endrin was not detected, but Endrin aldehyde and/or Endrin ketone were detected, qualify
the non-detects for Endrin as unusable "R", and qualify detects for Endrin aldehyde and/or
Endrin ketone as presumptively present at an approximated quantity "NJ".
e. If the combined 4,4'-DDT and Endrin breakdown is greater than 30.0%, the reviewer should
consider the degree of individual breakdown of 4,4'-DDT and Endrin and apply qualifiers as
described in this section.
3. Mid-point Individual Standard Mixtures (A and B) or (C)
a. If mid-point Individual Standard Mixture analysis is not performed at the required frequency (see
Pesticides Organic Analysis, Sections II.C.3.b and II.C.3.c), qualify all associated sample and
blank results as unusable "R".
b. If mid-point Individual Standard Mixtures (A and B) or (C) resolution criteria are not met, the
quantitative results may not be accurate due to inadequate resolution. Qualitative identifications
may be questionable if coelution exists.
June 2008 143 Final
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Pesticides Organic Analysis
i. Qualify detected target compounds that were not adequately resolved with an "NJ".
ii. Qualify non-detects as unusable "R".
4. Note in the Data Review Narrative the potential effects on the sample data resulting from the
instrument performance check criteria. Notify the Contract Laboratory Program Project Officer (CLP
PO) if the laboratory has repeatedly failed to comply with the requirements for linearity, resolution, or
4,4'-DDT/Endrin breakdown.
Table 45. Gas Chromatograph with Electron Capture Detector (GC/ECD) Instrument Performance Check Actions
Criteria [(Individual Standard
Mixtures (A and B)]
Resolution Check Mixture
% Resolution <60.0%
Criteria (Individual Standard Mixture
C)
Resolution Check Mixture
% Resolution <80.0% (primary column)
% Resolution <50.0% (secondary column)
PEM % Resolution <90.0%
PEM: 4,4'-DDT % Breakdown >20.0% and 4,4'-DDT is detected
PEM: 4,4'-DDT % Breakdown >20.0% and 4,4'-DDT is not detected
PEM: Endrin % Breakdown >20.0% and Endrin is detected
PEM: Endrin % Breakdown >20.0% and Endrin is not detected
PEM: Combined % Breakdown >30%
Mid-point Individual Standard
Mixtures (A and B)
% Resolution <90.0%
Mid-point Individual Standard Mixture (C)
% Resolution <80.0% (primary column)
Mid-point Individual Standard Mixture (C)
% Resolution <50.0% (secondary column)
PEM analysis not performed at the required frequency (see Pesticides, Section
II.C.2.a.)
Mid-point Individual Standard Mixtures analysis not performed at the required
frequency (see Pesticides, Sections II. C.S.b.l andll.C.S.c.l)
Action
Detects: NJ
Non-detects: R
Detects: NJ
Non-detects: R
Detects for 4,4'-DDT: J
Detects for 4,4'-DDD: J
Detects for 4,4'-DDE: J
Non-detects for 4,4'- DDT: R
Detects for 4,4'-DDD: NJ
Detects for 4,4'-DDE: NJ
Detects for Endrin: J
Detects for Endrin aldehyde: J
Detects for Endrin ketone: J
Non-detects for Endrin: R
Detects for Endrin aldehyde: NJ
Detects for Endrin ketone: NJ
Apply qualifiers as described above
considering degree of individual
breakdown.
Detects: NJ
Non-detects: R
All results: R
All results: R
June 2008
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Pesticides Organic Analysis
III. Initial Calibration
A. Review Items:
Form VI PEST-1, Form VI PEST-2, Form VI PEST-3, Form VI PEST-4, chromatograms, and data
system printouts.
B. Objective:
Compliance requirements for satisfactory initial calibration are established to ensure that the instrument is
capable of producing acceptable qualitative and quantitative data for pesticide compounds on the Target
Compound List (TCL). Initial calibration demonstrates that the instrument is capable of acceptable
performance at the beginning of the analytical sequence, and capable of producing a linear calibration
curve.
C. Criteria:
1. Individual Standard Mixtures (A and B) or (C) (containing all of the pesticides and surrogates) must
be analyzed at five concentration levels during the initial calibration, on each Gas Chromatograph
(GC) column and instrument used for analysis.
a. The Mean Retention Times (RTs) of each of the Single Component Pesticides (SCPs) and
surrogates are determined from the five-point initial calibration. The Retention Time (RT) for the
surrogates is measured from each Individual Standard Mixtures (A and B).
b. An RT Window must be calculated for each single component analyte and surrogate according to
SOM01.2. Exhibit D - Pesticides, Table 1 - Retention Time Windows for Single Component
Analytes, Toxaphene, and Surrogates, available at:
http://www.epa.gov/superfund/programs/clp/soml.htm
NOTE: At least one chromatogram from each of the Individual Standard Mixtures (A and B) or (C) must
yield peaks that give recorder deflections between 50-100% of full scale.
c. The five concentration level standards containing all of the Single Component Pesticides (SCPs)
and surrogates should be prepared in either two mixtures (A and B) or one mixture (C) at the
following concentration levels listed in Table 46.
June 2008 145 Final
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Pesticides Organic Analysis
Table 46. Concentration Levels of Calibration Standards
Compound
alpha-BHC
gamma-BHC
Heptachlor
Endosulfan I
Dieldrin
Endrin
4,4'-DDD
4,4'-DDT
Methoxychlor
beta-BHC
delta-BHC
Aldrin
Heptachlor-epoxide
4,4'-DDE
Endosulfan II
Endosulfan sulfate
Endrin ketone
Endrin aldehyde
alpha-Chlordane
gamma-Chlordane
Tetrachloro-m-xylene
Decachlorobiphenyl
Toxaphene
Concentration (ng/mL)
CS1
5.0
5.0
5.0
5.0
10
10
10
10
50
5.0
5.0
5.0
5.0
10
10
10
10
10
5.0
5.0
5.0
10
500
CS2
10
10
10
10
20
20
20
20
100
10
10
10
10
20
20
20
20
20
10
10
10
20
1000
CS3
20
20
20
20
40
40
40
40
200
20
20
20
20
40
40
40
40
40
20
20
20
40
2000
CS4
40
40
40
40
80
80
80
80
400
40
40
40
40
80
80
80
80
80
40
40
40
80
4000
CSS
80
80
80
80
160
160
160
160
800
80
80
80
80
160
160
160
160
160
80
80
80
160
8000
d. Mean Calibration Factor (CF) must be calculated for each single component analyte and
surrogate over the initial calibration range.
e. The Percent Relative Standard Deviation (%RSD) of the Calibration Factors (CFs) for each of the
single component target compounds must be less than or equal to 20.0%, except for alpha-BHC
and delta-BHC. The %RSD of the CFs for alpha-BHC and delta-BHC must be less than or equal
to 25.0%. The %RSD of the CFs for the two surrogates (tetrachloro-m-xylene and
decachlorobiphenyl) must be less than or equal to 30.0%.
NOTE: Either peak area or peak height may be used to calculate the CFs that are, in turn, used to
calculate %RSD. However, the type of peak measurement used to calculate each CF for a given
compound must be consistent. For example, if peak area is used to calculate the low-point CF for
Endrin, the mid-point and high-point CFs for Endrin must also be calculated using peak area.
June 2008
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Pesticides Organic Analysis
2. Toxaphene
a. Toxaphene must be analyzed separately at a minimum of five different concentration levels
during the initial calibration sequence. The analysis of Toxaphene compounds must also contain
the pesticide surrogates.
b. For each Toxaphene, the Retention Times (RTs) are determined for three to five peaks. The
peaks chosen must not share the same RT Window as any SCP in any Individual Standard
Mixture. The RT Window is calculated as ±0.07 minutes around the Absolute RTs.
c. A CF must be determined for each peak selected for Toxaphene.
d. The %RSD of the CFs for each of the Toxaphene peaks must be less than or equal to 30.0%; the
%RSD of the CFs for the two surrogates (tetrachloro-m-xylene and decachlorobiphenyl) must be
less than or equal to 30.0%.
e. The five concentration level standards containing Toxaphene and surrogates should be prepared
at the concentration levels listed in Table 46.
3. Initial Calibration Sequence
The initial calibration must be performed following a specific sequence, depending upon whether one
Individual Standard Mixture (C) (Initial Calibration Sequence 1) (see Table 47) or two Individual
Standard Mixtures (A and B) (Initial Calibration Sequence 2) are used (see Table 48).
Table 47. Initial Calibration Sequence 1
Initial Calibration Sequence 1
1.
2.
3.
4.
5.
6.
7.
Resolution Check
Performance Evaluation Mixture (PEM)
Toxaphene CS1
Toxaphene CS2
Toxaphene CS3
Toxaphene CS4
Toxaphene CSS
8. CS1 Individual Standard Mixture C
9.
10.
11.
12.
13.
14.
CS2 Individual Standard Mixture C
CSS Individual Standard Mixture C
CS4 Individual Standard Mixture C
CSS Individual Standard Mixture C
Instrument Blank
PEM
June 2008
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Pesticides Organic Analysis
Table 48. Initial Calibration Sequence 2
Initial Calibration Sequence 2
1.
2.
3.
4.
5.
6.
7.
Resolution Check
Performance Evaluation Mixture (PEM)
Toxaphene CS1
Toxaphene CS2
Toxaphene CS3
Toxaphene CS4
Toxaphene CSS
8. CS 1 Individual Standard Mixture A
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
CS1 Individual Standard Mixture B
CS2 Individual Standard Mixture A
CS2 Individual Standard Mixture B
CSS Individual Standard Mixture A
CSS Individual Standard Mixture B
CS4 Individual Standard Mixture A
CS4 Individual Standard Mixture B
CSS Individual Standard Mixture A
CSS Individual Standard Mixture B
Instrument Blank
PEM
NOTE:
D. Evaluation:
For Initial Calibration Sequence 2, Individual Standards for Mixture B may be analyzed before
corresponding Individual Standards for Mixture A.
For SCPs, follow the procedure in D.I if either two Individual Standard Mixtures (A and B) or one
Individual Standard Mixture (C) are used. For Toxaphene, follow the procedure in Pesticides Organic
Analysis, Section III.D.2.
1. Individual Standard Mixtures (A and B) or (C)
a. Check the raw data (chromatograms and data system printouts) for each standard to verify that
each of the standards was analyzed at the required concentration levels.
b. Check the Individual Standard Mixtures (A and B) data and Form VI PEST-1 and review the
calculated RT Windows for calculation and transcription errors.
c. Check the chromatograms and verify that at least one chromatogram from each of the Individual
Standard Mixtures (A and B) or (C) yields peaks registering recorder/printer deflections between
50-100% of full scale.
June 2008
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Pesticides Organic Analysis
d. Verify that the concentrations of the five standards of Individual Standard Mixtures (A and B) or
(C) meet the criteria defined in Pesticides Organic Analysis, Section Ill.C.l.d.
e. Check the Individual Standard Mixtures (A and B) or (C) data and Form VIPEST-2 to verify that
the %RSD for the CFs are in compliance with the criteria defined in Pesticides Organic Analysis,
Section III.C.
f Check and recalculate the CFs, CFs, and %RSD for one or more pesticides in Individual
Mixtures (A and B) or (C). Verify that the recalculated values agree with the reported values. If
errors are detected, perform a more comprehensive recalculation and review.
2. Toxaphene
a. Check the raw data for the standards to verify that Toxaphene was analyzed at the required
concentration.
b. Check the data for Toxaphene and Form VI PEST-3 to verify that at least three peaks were used
for identification, and RT Windows were calculated as required. Verify that the peaks chosen do
not share the same RT Window as any SCP in any Individual Standard Mixture.
c. Check the data to verify that CFs have been determined for each selected peak.
d. Check the chromatograms and verify that at least one chromatogram from each of the Toxaphene
standards yields peaks registering recorder/printer deflections between 50-100% of full scale.
e. Verify that the concentrations of the Toxaphene standards meet the criteria defined in Pesticides
Organic Analysis, Section Ill.C.l.d.
f. Check the Toxaphene data and Form VI PEST-4 to verify that the %RSD for the CFs are in
compliance with the criteria defined in Pesticides Organic Analysis, Section III.C.
g. Check and recalculate the CFs, CFs, and %RSD for one or more Toxaphene peaks. Verify that
the recalculated values agree with the reported values. If errors are detected, perform a more
comprehensive recalculation and review.
3. Initial Calibration Sequence
a. Verify that the proper initial calibration sequence (1 or 2) is used depending on if one (C) or two
Individual Standard Mixtures (A and B) are used.
b. Verify that the steps of initial calibration is followed in the proper sequence.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If the proper initial calibration sequence is not performed, or the steps of the initial calibration are not
followed in the proper sequence, use professional judgment to evaluate the effect on the data and
notify the Contract Laboratory Program Project Officer (CLP PO) (see Table 49). This is especially
critical for the low-level standards and non-detects.
2. If RT Windows are not calculated correctly, recalculate the windows and use the corrected values for
all evaluations.
3. If the chromatogram display (recorder deflection) criteria are not met, use professional judgment to
evaluate the effect on the data.
June 2008 149 Final
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Pesticides Organic Analysis
4. If the standard concentration criteria are not met, use professional judgment to evaluate the effect on
the data and notify the CLP PO. This is especially critical for the low-level standards and non-
detects.
5. If the %RSD criteria are not met, qualify detects with a "J" and use professional judgment to qualify
non-detected target compounds.
6. If the %RSD criteria are within allowable limits, no qualification of the data is necessary.
7. At the reviewer's discretion, and based on the project-specific data quality objectives, consider a more
in-depth review using the following guidelines:
a. If any pesticide target compound has a %RSD greater than the maximum criterion, and if
eliminating either the high or the low-point of the curve does not restore the %RSD to less than or
equal to the required maximum:
i. Qualify detects for that compound(s) with a" J".
ii. Qualify non-detected pesticide target compounds using professional judgment.
b. If the high-point of the curve is outside of the linearity criteria (e.g., due to saturation):
i. No qualifiers are required for detects in the linear portion of the curve.
ii. Qualify detects outside of the linear portion of the curve with a "J".
iii. No qualifiers are required for pesticide target compounds that were not detected.
c. If the low-point of the curve is outside of the linearity criteria:
i. No qualifiers are required for detects in the linear portion of the curve.
ii. Qualify low-level detects in the area of non-linearity with a "J".
iii. For non-detected pesticide compounds, use the lowest point of the linear portion of the curve
to determine the new quantitation limit.
8. Note in the Data Review Narrative potential effects on the sample data due to problems with
calibration. Notify the CLP PO if the laboratory has repeatedly failed to comply with the
requirements for frequency, linearity, RT, or resolution.
9. Qualify data for Toxaphene sharing the same RT Window with any SCP in any Individual Standard
Mixture using professional judgment.
Table 49. Initial Calibration Action for Pesticide Analyses
Criteria
Initial calibration is not performed or not
performed in the proper sequence
%RSD exceeds allowable limits*
%RSD within allowable limits*
Action
Detected Associated
Compounds
Non-Detected Associated
Compounds
Use professional judgment
J
No
Use professional judgment
qualification
* %RSD < 20.0% for single component target compounds except alpha-BHC and delta-BHC.
%RSD < 25.0% for alpha-BHC and delta-BHC.
%RSD < 30.0% for Toxaphene peaks.
%RSD < 30.0% for surrogates (tetrachloro-m-xylene and decachlorobiphenyl).
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IV. Continuing Calibration Verification (CCV)
A. Review Items:
Form VII PEST-1, Form VII PEST-2, Form VII PEST-3, Form VII PEST-4, chromatograms, and data
system printouts.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data. CCV checks and
documents satisfactory performance of the instrument over specific time periods during sample analysis.
To confirm the calibration and evaluate instrument performance, continuing calibration verification is
performed, consisting of the analyses of instrument blanks, the Performance Evaluation Mixture (PEM),
and the mid-point concentration of Individual Standard Mixtures (A and B) or (C). A CCV must be
performed at the beginning (opening CCV) and end (closing CCV) of the analytical sequence. The
opening and closing CCVs consist of an injection of an instrument blank followed by either an injection
of an PEM or mid-point concentration of Individual Standard Mixtures (A and B) or (C) in an alternating
fashion [i.e. if the PEM is part of the opening CCV, the mid-point concentration of Individual Standard
Mixtures (A and B) or (C) must be part of the closing CCV]. A continuing calibration verification for
Toxaphene is only required if Toxaphene is detected in a sample.
C. Criteria:
1. The Absolute Retention Time (RT) for each Single Component Pesticide (SCP) and surrogate in the
PEM and the mid-point concentration of Individual Standard Mixtures (A and B) or (C) used for
continuing calibration verification must be within the RT Windows determined from the initial
calibration. If a continuing calibration verification is required for Toxaphene because of its detection
in a sample, the Absolute RT for each Toxaphene peak must be within the RT Windows determined
from the initial calibration.
2. The Percent Difference (%D) between the calculated amount and the nominal amount (amount added)
for each of the SCP and surrogates in the PEM used for continuing calibration verification must be
greater than or equal to -25.0% and less than or equal to 25.0%.
3. The Percent Difference between the Calibration Factor (CF) for each of the SCP and surrogates in the
Calibration Verification Standard (CSS) and the Mean Calibration Factor (CF) from the initial
calibration must be greater than or equal to -20.0% and less than or equal to 20.0%. If a continuing
calibration verification is required for Toxaphene because of its detection in a sample, the Percent
Difference between the CF for each of the peaks used to identify Toxaphene in the Calibration
Verification Standard (CSS) and the CF from the initial calibration must be greater than or equal to -
20.0% and less than or equal to 20.0%.
4. No more than 14 hours may elapse from the injection of the instrument blank that begins an analytical
sequence (opening CCV) and the injection of either a PEM or mid-point concentration of the
Individual Standard Mixtures (A and B) or (C) that ends an analytical sequence (closing CCV).
5. No more than 12 hours may elapse from the injection of the instrument blank that begins an analytical
sequence (opening CCV) and the injection of the last sample or blank that is part of the same
analytical sequence.
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6. No more than 72 hours may elapse from the injection of the sample with a Toxaphene detection and
the Toxaphene Calibration Verification Standard (CSS).
D. Evaluation:
1. Check the data for each of the SCPs and surrogates in the PEM, the mid-point concentration of
Individual Standard Mixtures (A and B) or (C), Form VII PEST-1, and Form VII PEST-2, Form VII
PEST-3, to verify that the Absolute RTs are within the RT Windows. If a Toxaphene Calibration
Verification is required, check the data for each Toxaphene peak and surrogates in the Toxaphene
Calibration Verification Standard (CSS) and Form VIIPEST-4 to verify that the Absolute RTs are
within the RT Windows.
2. Check the data from the PEM, Form VII PEST-1, to verify that the Percent Difference between the
calculated amount and the true amount for each of the pesticides and surrogates are within ±25.0%.
3. Check the data from the mid-point concentration of Individual Standard Mixtures (A and B) or (C),
Form VII PEST-2, and Form VII PEST-3 to verify that the Percent Difference between the CF for
each of the SCP and surrogates in the Calibration Verification Standard (CS3) and the CF from the
initial calibration are within the inclusive range of ±20.0%. If a continuing calibration verification is
required for Toxaphene because of its detection in a sample, check the data from the mid-point
concentration of Toxaphenes, Form VII PEST-4 and verify that the Percent Difference between the
CF for each of the peaks used to identify Toxaphene in the Calibration Verification Standard (CS3)
and the CF from the initial calibration are within the inclusive range of ±20.0%.
4. Check the length of time that has elapsed from the beginning injection of the opening CCV
(instrument blank) and the ending injection of the closing CCV [PEM or Individual Standard
Mixtures (A and B) or (C)] to verify that no more than 14 hours has elapsed.
5. Check the length of time that has elapsed from the beginning injection of the opening CCV
(instrument blank) and the injection of the last sample or method blank to verify that no more than 12
hours has elapsed.
6. If a continuing calibration verification is required for Toxaphene because of its detection in a sample,
check the length of time that has elapsed from the injection of the sample with a Toxaphene detection
and the Toxaphene Calibration Verification Standard (CS3) to verify that no more than 72 hours has
elapsed.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. The RT Windows are used in qualitative identification. If the standards do not fall within the RT
Windows, carefully evaluate the associated sample results (see Table 50). All samples injected after
the last in-control standard are potentially affected.
a. For non-detected target compounds in the affected samples, check to see if the sample
chromatograms contain any peaks that are close to the expected RT Window of the pesticide of
interest.
i. If no peaks are present, consider non-detected values to be valid and no qualification of the
data is necessary.
ii. If any peaks are present close to the expected RT Window of the pesticide of interest, use
professional judgment to qualify the non-detects as presumptively present "NJ".
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b. For detected compounds in the affected samples, if the peaks are within the RT Window, no
qualification of the data is necessary. However, if the peaks are close to the expected RT
Window of the pesticide of interest, the reviewer may take additional effort to determine if
sample peaks represent the compounds of interest.
For example, the reviewer can examine the data package for the presence of three or more
standards containing the pesticide of interest that were run within the analytical sequence during
which the sample was analyzed. If three or more such standards are present, the RT Window can
be re-evaluated using the Mean Retention Times (RTs) of the standards.
i. If the peaks in the affected sample fall within the revised window, qualify detects as "NJ".
ii. If the reviewer cannot do anything with the data to resolve the problem of concern, qualify all
non-detects as unusable "R".
2. For the PEM, if the Percent Difference is not within ±25.0% as defined in Pesticides Organic
Analysis, Section IV.C.2, qualify associated detects with a "J" and non-detects with an approximated
"UJ".
3. For the Calibration Verification Standard (CSS), if the Percent Difference is not within ±20.0% as
defined in Pesticides Organic Analysis, Section IV.C.3, qualify associated detects with a "J" and non-
detects with an approximated "UJ".
4. If more than 14 hours has elapsed as defined in Pesticides Organic Analysis, Section IV.C.4, qualify
all data as unusable "R".
5. If more than 12 hours has elapsed as defined in Pesticides Organic Analysis, Section IV.C.5, qualify
all data as unusable "R".
6. If more than 72 hours has elapsed as defined in Pesticides Organic Analysis, Section IV.C.6, qualify
all data as unusable "R".
7. If the Percent Difference, time elapsed, and RTs are within acceptable limits, no qualification of the
data is necessary.
8. Note in the Data Review Narrative potential effects on the sample data due to problems with
calibration.
Table 50. Continuing Calibration Verification (CCV) Action for Pesticide Analyses
Criteria
RT out of RT window
Percent Difference not within limits as defined in Pesticides Organic
Analysis, Sections IV.C.2 and C.3
Time elapsed is greater than acceptable limits, as defined in Pesticides
Organic Analysis, Sections IV.C.4, C.5, and C.6
Percent Difference, time elapsed, and RT are within acceptable limits
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
Use professional judgment (see Pesticides,
Section I V.E.I)
J
UJ
R
No qualification
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V. Blanks
A. Review Items:
Form I PEST, Form IV PEST, chromatograms, and data system printouts.
B. Objective:
The purpose of laboratory or field blank analyses is to determine the existence and magnitude of
contamination resulting from laboratory, field, or sample transport activities. The purpose of the method
blank is to determine the levels of contamination associated with the processing and analysis of samples.
The results from the instrument blank analysis indicate whether there is contamination from the analysis
of a previous sample. The criteria for evaluation of blanks apply to any blank associated with the samples
(e.g., method blanks, sulfur cleanup blanks, instrument blanks, and field blanks). If problems with any
blank exist, carefully evaluate all associated data to determine whether or not there is an inherent
variability in the data or if the problem is an isolated occurrence not affecting other data.
C. Criteria:
1. Method Blanks
A method blank must be extracted each time samples are extracted. The number of samples extracted
with each method blank shall not exceed 20 field samples [excluding Matrix Spike/Matrix Spike
Duplicate (MS/MSDs), Performance Evaluation (PE) samples, and Laboratory Control Samples
(LCSs)]. In addition, a method blank shall be extracted by the same procedure used to extract
samples and be analyzed on the same Gas Chromatograph/Electron Capture Detector (GC/ECD)
system used to analyze associated samples.
2. Instrument Blanks
An acceptable instrument blank must be run at the beginning and ending of an analytical sequence in
which samples are analyzed, immediately prior to the analysis of the Performance Evaluation Mixture
(PEM) or mid-point Individual Standard Mixtures (A and B) or (C), used for continuing calibration
verification. All groups of acceptable sample analyses are to be preceded and followed by acceptable
instrument blanks.
3. Sulfur Cleanup Blanks
A sulfur cleanup blank must be analyzed whenever part of a set of samples extracted together requires
sulfur cleanup. If the entire set of samples associated with a method blank requires sulfur cleanup,
the method blank also serves the purpose of a sulfur blank and no separate sulfur blank is required.
The concentration of each target analyte in the method, sulfur cleanup, instrument, and field blanks
must be less than its Contract Required Quantitation Limits (CRQL) listed in the method.
D. Evaluation:
1. Review the results of all associated blanks, Form I PEST, Form IV PEST, and raw data
(chromatograms and data system printouts) to evaluate the presence of target or non-target analytes in
the blanks.
2. Verify that a method blank analysis has been reported per Sample Delivery Group (SDG), per
extraction batch, and per extraction procedure. The reviewer can use Form IV PEST to identify
samples associated with each blank.
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3. Verify that the method blank analysis(es) contains less than the CRQL of any target SCP or
Toxaphene, or any interfering peak.
4. Verify that the instrument blank analysis has been performed every 12 hours as the first analysis of
the continuing calibration verification sequence. Evaluate the results from the various instrument
blanks to verify that target analyte concentrations are less than the CRQL (assuming a 1 L extraction
of a aqueous sample).
5. Verify that the sulfur cleanup blanks were analyzed at the required frequency and the sulfur blanks do
not contain any target compounds greater than or equal to the CRQL (assuming a 1 L extraction of an
aqueous sample). If a separate sulfur cleanup blank was prepared, one version of Form IV PEST
should be completed associating all the samples with the method blank, and a second version of Form
IV PEST should be completed listing only those samples associated with the separate sulfur cleanup
blank.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process. Data concerning the field
blanks are not evaluated as part of the CCS process. If field blanks are present, evaluate this data
in a similar fashion as the method blanks.
E. Action:
Action regarding unsuitable blank results depends on the circumstances and the origin of the blank. In
instances where more than one of the same type of blank is associated with a given sample, base
qualification upon a comparison with the associated blank having the highest concentration of a
contaminant. Do not correct the results by subtracting the blank value.
1. If a target SCP or Toxaphene is found in the blank but not found in the sample, no qualification is
required (see Table 51).
2. If a target SCP or Toxaphene concentration in a blank is less than the CRQL, and:
a. the sample concentration is less than the CRQL, report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL, use professional judgment to
qualify the data.
3. If a target SCP or Toxaphene concentration in a blank is greater than the CRQL, and:
a. the sample concentration is less than the CRQL, report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL, and less than the blank
concentration, report the concentration of the compound in the sample at the same concentration
found in the blank with a "U", or the reviewer may elect to qualify the data as unusable "R".
c. the sample concentration is greater than or equal to the CRQL, and greater than or equal to the
blank concentration, use professional judgment to qualify the data.
4. If a target SCP or Toxaphene concentration in a blank is equal to the CRQL, and:
a. the sample concentration is less than the CRQL, report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL, use professional judgment to
qualify the data.
5. If gross contamination exists (e.g., saturated peaks, "hump-o-grams"," junk" peaks), all affected
compounds in the associated samples should be qualified as unusable "R", due to interference. Note,
June 2008 155 Final
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for Contract Laboratory Program Project Officer (CLP PO) action, if the contamination is suspected
of having an effect on the sample results.
6. There may be instances where little or no contamination was present in the associated blanks, but
qualification of the sample is deemed necessary. If the reviewer determines that the contamination is
from a source other than the sample, they should qualify the data. Contamination introduced through
dilution is one example. Although it is not always possible to determine, instances of this occurring
can be detected when contaminants are found in the diluted sample result, but absent in the undiluted
sample result.
7. If contaminants are found in the field blanks, the following is recommended:
a. Review the associated method blank data to determine if the contaminant(s) was also present in
the method blank. If the analyte was present at a comparable level in the method blank, the
source of the contamination may be in the analytical system and the action recommended for the
method blank would apply.
If the analyte was not present in the method blank, the source of contamination may have
occurred in the field or during sample transport. Consider all associated samples for possible
cross-contamination.
b. If the field blank contains a pesticide Target Compound List (TCL) compound(s) at a
concentration greater than the CRQL, and:
i. the sample concentration is less than the CRQL, report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL, but less than the blank
concentration, report the concentration of the compound in the sample at the same
concentration found in the blank and qualify with a "U", or use professional judgment to
qualify the data as unusable "R".
iii. the sample concentration is greater than the CRQL and greater than or equal to the blank
concentration, use professional judgment to qualify the data.
c. If gross contamination (e.g., saturated, "hump-o-grams", "junk" peaks) exists in the field blank,
positive sample results may require rejection. Qualify as unusable "R". Non-detected pesticide
target compounds do not require qualification unless the contamination is so high that it interferes
with the analyses of non-detected compounds.
d. If the field blank contains a pesticide TCL compound(s) at a concentration less than the CRQL
and:
i. the sample concentration is less than the CRQL, report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL, use professional judgment to
qualify the data.
e. If the field blank contains a pesticide TCL compound(s) at a concentration equal to the CRQL
and:
i. the sample concentration is less than the CRQL, report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL, use professional judgment to
qualify the data.
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Table 51. Blank Actions for Pesticide Analyses
Blank Type
Method, Sulfur
Cleanup,
Instrument,
Field
Blank Result
Detects
< TROT
>CRQL
— pT?rvr
Gross contamination
Sample Result
Not detected
CRQL
CRQL and < blank concentration
> CRQL and > blank concentration
CRQL
Detects
Action for Samples
No qualification
Report CRQL value with a U
Use professional judgment
Report CRQL value with a U
Report the blank concentration
for the sample with a U, or
qualify the data as unusable R
Use professional judgment
Report CRQL values with a U
Use professional judgment
Qualify results as unusable R
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VI. Surrogate Spikes
A. Review Items:
Form II PEST-1, Form II PEST-2, Form VIII PEST, chromatograms, and data system printouts.
B. Objective:
Laboratory performance on individual samples is established by means of spiking activities. All samples
are spiked with surrogate compounds prior to sample extraction. The evaluation of the recovery results of
these surrogate spikes is not necessarily straightforward. The sample itself may produce effects due to
such factors as interferences. Since the effects of the sample matrix are frequently outside the control of
the laboratory and may present relatively unique problems, the evaluation and review of data based on
specific sample results is frequently subjective and requires analytical experience and professional
judgment. Accordingly, this section consists primarily of guidelines, in some cases with several optional
approaches suggested.
C. Criteria:
1. Two surrogate spikes, tetrachloro-m-xylene (TCX) and decachlorobiphenyl (DCB), are added to all
samples, including Matrix Spike/Matrix Spike Duplicates (MS/MSDs), Laboratory Control Samples
(LCSs), and blanks to measure their recovery. The surrogates are also added to all the standards to
monitor Retention Times (RTs).
2. The recovery limits for the surrogates TCX and DCB are 30-150% for all samples, including MS and
MSDs, LCSs and all blanks.
3. The RTs of the surrogates in each Performance Evaluation Mixture (PEM), mid-point Individual
Standard Mixtures (A and B) or (C) used for continuing calibration verification, all samples
(including MS and MSD, LCS), and all blanks must be within the calculated RT Windows. TCX
must be within ±0.05 minutes, and DCB must be within ±0.10 minutes of the Mean Retention Time
(RTs) determined from the initial calibration.
D. Evaluation:
1. Check the raw data (e.g., chromatograms and data system printouts) to verify the recoveries on the
Surrogate Recovery Form (Form II PEST).
2. Check for any calculation or transcription errors; verify that the surrogate recoveries were calculated
correctly using the equation in the method.
3. Check the raw data (e.g., chromatograms and data system printouts) to verify that the RTs on Form
VIII PEST are accurate and within the RT Windows determined from the initial calibration.
4. Whenever there are two or more analyses for a particular sample, the reviewer must determine which
are the most accurate data to report. Considerations include, but are not limited to:
a. Surrogate recovery (marginal versus gross deviation).
b. Technical holding times.
c. Comparison of the values of the target compounds reported in each sample analysis.
d. Other Quality Control (QC) information, such as surrogate recoveries and/or RTs in blanks and
standards.
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NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
If either surrogate spike recovery is outside the acceptance limits, the reviewer must consider the
existence of coelution and interference in the raw data and use professional judgment to qualify data, as
surrogate recovery problems may not directly apply to target analytes.
1. For any surrogate recovery greater than 200% (see Table 52):
a. Qualify detected target compounds as "J".
b. Use professional judgment to qualify non-detected target compounds.
2. For any surrogate recovery greater than 150% and less than or equal to 200%:
a. Qualify detected target compounds as a "J".
b. Do not qualify non-detected target compounds.
3. If both surrogate recoveries are greater than or equal to 30%, and less than or equal to 150%, no
qualification of the data is necessary.
4. For any surrogate recovery greater than or equal to 10%, and less than 30%:
a. Qualify detected target compounds as a "J".
b. Qualify non-detected target compounds as an approximated "UJ".
5. For any surrogate recovery less than 10%, the reviewer should examine the sample chromatogram to
assess the qualitative validity of the analysis. If low surrogate recoveries are from sample dilution,
professional judgment should be used to determine if the resulting data should be qualified. If sample
dilution is not a factor:
a. Qualify detected target compounds as a "J".
b. Qualify non-detected target compounds as unusable "R".
6. In the special case of a blank analysis with surrogates out of specification, the reviewer must give
special consideration to the validity of associated sample data. The basic concern is whether the
blank problems represent an isolated problem with the blank alone, or whether there is a fundamental
problem with the analytical process. For example, if one or more samples in the batch show
acceptable surrogate recoveries, the reviewer may choose to consider the blank problem to be an
isolated occurrence. Note, for Contract Laboratory Program Project Officer (CLP PO) action,
analytical problems even if this judgment allows some use of the affected data.
7. If surrogate RTs in PEMs, Individual Standard Mixtures, samples, and blanks are outside of the RT
Windows, the reviewer must use professional judgment to qualify data.
8. If surrogate RTs are within RT windows, no qualification of the data is necessary.
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Table 52. Surrogate Actions for Pesticide Analyses
Criteria
%R > 200%
150%<%R<200%
30%<%R<150%
10%<%R<30%
%R < 10% (sample dilution not a factor)
%R < 10% (sample dilution is a factor)
RT out of RT window
RT within RT window
Action*
Detected Target Compounds
J
J
Non-detected Target
Compounds
Use professional judgment
No qualification
No qualification
J
J
UJ
R
Use professional judgment
Use professional judgment
No qualification
Use professional judgment in qualifying data, as surrogate recovery problems may not directly apply to target analytes.
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VII. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
A. Review Items:
Form III PEST-1, Form III PEST-2, chromatograms, and data system printouts.
NOTE: Data for MS and MSDs will not be present unless requested by the Region.
B. Objective:
Data for MS and MSDs are generated to determine long-term precision and accuracy of the analytical
method on the sample matrix and to demonstrate acceptable compound recovery by the laboratory at the
time of sample analysis. These data alone cannot be used to evaluate the precision and accuracy of
individual samples. However, when exercising professional judgment, this data should be used in
conjunction with other available Quality Control (QC) information.
C. Criteria:
1. If requested, MS and MSD samples are extracted and analyzed at a frequency of one MS and MSD
per 20 or fewer field samples per sample matrix.
2. MS and MSD recoveries should be within the advisory limits provided on Form III PEST-1, Form III
PEST-2.
3. Relative Percent Differences (RPDs) between MS and MSD recoveries must be within the advisory
limits provided on Form III PEST-1 and Form III PEST-2.
D. Evaluation:
1. Verify that requested MS and MSD samples were analyzed at the requested frequency and that results
are provided for each sample.
2. Check the raw data and Form III PEST-1 and Form III PEST-2 to verify that the results for MS and
MSD recoveries were calculated and transcribed correctly.
3. Check that the RPDs were calculated correctly.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. No qualification of the data is necessary on MS and MSD data alone. Use professional judgment to
use the MS and MSD results in conjunction with other QC criteria to determine the need for some
qualification of the data. Table 54 lists the pesticide target compounds that are spiked into samples to
test for matrix effects. If any MS and MSD Percent Recovery, or RPD in the pesticides fraction is out
of specification, qualify data to include the consideration of the existence of interference in the raw
data. Considerations include, but are not limited to (see Table 53):
a. For any recovery or RPD greater than the upper acceptance limit:
i. Qualify detected spiked Single Component Pesticide (SCP) target compounds as a "J".
ii. Do not qualify non-detected spiked SCP target compounds.
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b. For any recovery greater than or equal to 20% and less than the lower acceptance limit:
i. Qualify detected spiked SCP target compounds as a "J".
ii. Qualify the sample quantitation limit for non-detected spiked SCP target compounds as
approximated "UJ".
c. For any recovery less than 20%:
i. Qualify detected spiked SCP target compounds as a "J".
ii. Use professional judgment to qualify non-detected spiked SCP target compounds.
d. If recoveries and RPD are within acceptance limits, no qualification of the data is necessary.
2. The data reviewer should first try to determine to what extent the results of the MS and MSB affect
the associated sample data. This determination should be made with regard to the MS and MSB
sample itself, as well as specific analytes for all samples associated with the MS and MSB.
3. In those instances where it can be determined that the results of the MS and MSB affect only the
sample spiked, limit qualification to this sample only. However, it may be determined through the
MS and MSB results, that a laboratory is having a systematic problem in the analysis of one or more
analytes that affects all associated samples. Use professional judgment to qualify the data from all
associated samples.
4. Use professional judgment to determine the need for qualification of detects of non-spiked
compounds.
NOTE: Notify the Contract Laboratory Program Project Officer (CLP PO) if a field blank was used for
the MS and MSB, unless designated as such by the Region.
Table 53. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Pesticide Analysis
Criteria
%R or RPD > Upper Acceptance Limit
20% < %R < Lower Acceptance Limit
%R < 20%
Lower Acceptance Limit < %R;
RPD < Upper Acceptance Limit
Action
Detected Spiked Compounds
J
J
J
Non-detected Spiked
Compounds
No qualification
UJ
Use professional judgment
No qualification
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Table 54. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD)
Compound
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4'-DDT
Percent
Recovery Water
56 - 123
40-131
40 - 120
52 - 126
56 - 121
38 - 127
RPD Water
0-15
0-20
0-22
0-18
0-21
0-27
Percent
Recovery Soil
46 - 127
35-130
34-132
31-134
42-139
23-134
RPD Soil
0-50
0-31
0-43
0-38
0-45
0-50
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VIII. Laboratory Control Samples (LCSs)
A. Review Items:
Form I PEST, Form II PEST-1, Form II PEST-2, Form III PEST-3, Form III PEST-4, LCS
chromatograms, and data system printouts.
B. Objective:
Data for LCSs are generated to provide information on the accuracy of the analytical method and
laboratory performance.
C. Criteria:
The LCS contains the pesticides target compounds and surrogates listed in Table 55.
Table 55. Pesticides Laboratory Control Sample (LCS) Spike Compounds and Recovery Limits
LCS Spike Compound
gamma-BHC
Heptachlor epoxide
Dieldrin
4,4'-DDE
Endrin
Recovery Limits
(%)
50 - 120
50 - 150
30-130
50-150
50 - 120
LCS Spike Compound
Endosulfan sulfate
gamma-Chlordane
Tetrachloro-m-xylene (surrogate)
Decachlorobiphenyl (surrogate)
Recovery
Limits (%)
50 - 120
30-130
30-150
30-150
NOTE:
D. Evaluation:
The recovery limits for any of the compounds in the LCS may be expanded at any time during the
period of performance is USEPA determines that the limits are too restrictive.
All samples prepared and analyzed with an LCS that does not meet the technical acceptance
criteria in the method will require re-extraction and re-analysis.
Check the raw data (e.g., chromatograms and data system printouts) to verify the recoveries on the
Laboratory Control Sample Recovery Forms (Form III PEST-3, Form III PEST-4). For surrogate
recoveries check the Surrogate Recovery Forms (Form II PEST-1, Form II PEST-2).
Check for any calculation or transcription errors; verify that the LCS recoveries reported on Form II
PEST-1, Form II PEST-2, Form III PEST-3, and Form III PEST-4 are within the Quality Control (QC)
limits.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
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E. Action:
If the LCS criteria are not met, laboratory performance and method accuracy are in question. Use
professional judgment to determine if the data should be qualified or rejected. The following guidance is
suggested for qualifying sample data for which the associated LCS does not meet the required criteria.
1. If the LCS recovery criteria are not met, use the LCS results to qualify sample data for the specific
compounds that are included in the LCS solution (see Table 56).
a. If the LCS recovery exceeds the upper acceptance limit, qualify detected target compounds as a
"J". Do not qualify non-detected target compounds.
b. If the LCS recovery is less than the lower acceptance limit, qualify detected target compounds as
a "J" and non-detects as unusable "R".
c. Use professional judgment to qualify data for compounds other than those compounds that are
included in the LCS.
d. Use professional judgment to qualify non-LCS compounds. Take into account the compound
class, compound recovery efficiency, analytical problems associated with each compound, and
comparability in the performance of the LCS compound to the non-LCS compound.
2. If the LCS recovery is within allowable limits, no qualification of the data is necessary.
3. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if a laboratory fails to
analyze an LCS with each Sample Delivery Group (SDG), or if the reviewer has knowledge that a
laboratory consistently fails to generate acceptable LCS recoveries.
Table 56. Laboratory Control Sample (LCS) Recovery Actions
Criteria
%R > Upper Acceptance Limit
%R < Lower Acceptance Limit
Lower Acceptance Limit < %R < Upper Acceptance Limit
Action
Detected Associated
Compounds
J
J
Non-Detected Associated
Compounds
No qualification
R
No qualification
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IX. Regional Quality Assurance (OA) and Quality Control (OC)
A. Review Items:
Form I PEST, chromatograms, data system printouts, Traffic Report/Chain of Custody Record
(TR/COC), quantitation reports and other raw data from Regional QA/QC samples.
B. Objective:
Regional QA/QC refers to any QA and/or QC samples initiated by the Region, including field duplicates,
Performance Evaluation (PE) samples, blind spikes, and blind blanks. The use of these QA/QC samples
are highly recommended (e.g., the use of field duplicates can provide information on sampling precision
and sample homogeneity).
C. Criteria:
Criteria are determined by each Region.
1. PE sample frequency may vary.
2. The analytes present in the PE sample must be correctly identified and quantified.
D. Evaluation:
1. Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data review.
Each Region will handle the evaluation of PE samples on an individual basis. Compare results for PE
samples to the acceptance criteria for the specific PE samples, if available.
2. Calculate Relative Percent Difference (RPD) between field duplicates. Provide this information in
the Data Review Narrative.
E. Action:
Any action must be in accordance with Regional specifications and the criteria for acceptable PE sample
results. Note, for Contract Laboratory Program Project Officer (CLP PO) action, unacceptable results for
PE samples.
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X. Florisil Cartridge Performance Check
A. Review Items:
Form IX PEST-1, Florisil raw data, chromatograms, and data system printouts.
B. Objective:
The Florisil cartridge cleanup procedure is used to remove matrix interferences from sample extracts prior
to analysis. The use of the Florisil cartridge cleanup procedure significantly reduces matrix interferences
caused by polar compounds. The performance of each lot of Florisil cartridges used for sample cleanup is
checked by running a spiked reagent through a cartridge, and calculating the recoveries of the spiked
compounds through the cartridge.
C. Criteria:
1. The performance of each lot of Florisil cartridges used for sample cleanup must be checked at least
once, or every six months, whichever is most frequent. The performance of the Florisil cartridges is
checked with a spiking solution contain 2,4,5 -trichlorophenol and. the mid-point concentration of
Individual Standard Mixture (A). If calibration with one standard mixture is used, the mid-point
concentration of Individual Standard Mixture (C) may also be used.
2. The limits for recovery of the target pesticide compounds and surrogates in the Individual Standard
Mixture (A) are 80-120%, and the recovery limit for 2,4,5-trichlorophenol is less than 5%. If
Individual Standard Mixture (C) is used, check the limits for recovery for the target compounds and
surrogates present in the Individual Standard Mixture (A) only.
D. Evaluation:
1. Check the raw data for the Florisil cartridge performance check analysis and the results on Form IX
PEST-1. Verify that there are no calculation or transcription errors.
2. Verify that the percent recoveries of the target pesticides and surrogates in the performance check
solution are within 80-120%, and the recovery of 2,4,5-trichlorophenol is less than 5%.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If the Florisil Cartridge Performance Check criteria are not met, examine the raw data for the
presence of polar interferences and use professional judgment in qualifying the data as follows (see
Table 57):
a. If the Percent Recovery is greater than 120% for any of the pesticide target compounds in the
Florisil Cartridge Performance Check, use professional judgment to qualify detected target
compounds. Do not qualify non-detected target compounds.
b. If the Percent Recovery is greater than or equal to 80% and less than or equal to 120% for all the
pesticide target compounds, no qualification of the data is necessary.
June 2008 167 Final
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Pesticides Organic Analysis
c. If the Percent Recovery is greater than or equal to 10% and less than 80% for any of the pesticide
target compounds in the Florisil Cartridge Performance Check, qualify detected target compounds
with a "J" and non-detected target compounds with an approximated "UJ".
d. If the Percent Recovery is less than 10% for any of the pesticide target compounds in the Florisil
Cartridge Performance Check, use professional judgment to qualify detected target compounds
and qualify non-detected target compounds as unusable "R".
e. If the Percent Recovery of 2,4,5-trichlorophenol in the Florisil Cartridge Performance Check is
greater than or equal to 5%, use professional judgment to qualify detected and non-detected target
compounds, considering interference on the sample chromatogram.
2. Note in the Data Review Narrative potential effects on the sample data resulting from the Florisil
Cartridge Performance Check analysis not yielding acceptable results.
Table 57. Florisil Cartridge Performance Check Actions
Criteria
%R > 120% (pesticide target compounds)
80%<%R<120%
10% < %R < 80% (pesticide target compounds)
%R < 10% (pesticide target compounds)
%R > 5% (2,4,5-trichlorophenol)
Action
Detected Associated
Compounds
Use professional judgment
Non-Detected Associated
Compounds
No qualification
No qualification
J
Use professional judgment
UJ
R
Use professional judgment
June 2008
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XL Gel Permeation Chromatography (GPC) Performance Check
A. Review Items:
Form IX PEST-2, GPC raw data, chromatograms, and data system printouts.
B. Objective:
GPC is used to remove high molecular weight contaminants that can interfere with the analysis of target
analytes. GPC cleanup procedures are checked by adding the GPC calibration mixture to the GPC cleanup
columns and setting the appropriate elution window, and verifying the recovery of target compounds
through the cleanup procedure by the analysis of a cleanup blank.
C. Criteria:
1. GPC is a mandatory cleanup method for non-aqueous samples and is an optional cleanup method for
aqueous samples and sample extracts that contain high molecular weight components that interfere
with the analysis of the target analytes.
2. At least once every seven (7) days, the calibration of the GPC unit must be checked by injecting with
the GPC continuing calibration verification solution.
3. The GPC calibration is acceptable if the recovery of the pesticides in the GPC continuing calibration
verification solution are within 80 to 110%.
a. Peaks must be observed and symmetrical for all compounds in the calibration solution.
b. Corn oil and the phthalate peaks exhibit greater than 85% resolution.
c. The phthalate and methoxychlor peaks exhibit greater than 85% resolution.
d. Methoxychlor and perylene peaks exhibit greater than 85% resolution.
e. Perylene and sulfur peaks must not be saturated and should exhibit greater than 90% baseline
resolution.
f The Retention Time (RT) shift is less than 5% between ultraviolet (UV) traces for bis(2-
ethylhexyl)phthalate and perylene.
4. A GPC blank must be analyzed after each GPC calibration and is acceptable if the blank does not
exceed the Contract Required Quantitation Limit (CRQL) for any target analytes listed in SOM01.2.
Exhibit C - Pesticides, Target Component List and Contract Required Quantitation Limits, available
at: http://www.epa.gov/superfund/programs/clp/soml.htm.
D. Evaluation:
1. Verify that there are two UV traces present and that the RT shift for bis(2-ethylhexyl)phthalate and
perylene is less than 5%.
2. Verify that the compounds listed in Pesticides Organic Analysis, Section XI.C.3, are present and
symmetrical in both UV traces and that the compound pairs meet the minimum resolution
requirements.
3. Verify that no target compound in the GPC blank exceeds the CRQL.
4. Check the data from the GPC calibration check analyses and the Form IX PEST-2, and recalculate
some of the percent recoveries to verify that the percent recoveries of the pesticides in the matrix
June 2008 169 Final
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Pesticides Organic Analysis
spike solution are within 80 to 110%. The Region may devise other means to compare this
information. Check to make sure that no transcription errors have occurred.
NOTE:
E. Action:
For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
1. If GPC criteria are not met, examine the raw data for the presence of high molecular weight
contaminants. Examine the subsequent sample data for unusual peaks, and use professional judgment
in qualifying the data. Notify the Contract Laboratory Program Project Officer (CLP PO) if a
laboratory chooses to analyze samples under unacceptable GPC criteria.
2. If the Percent Recovery is less than 10% for the pesticide compounds and surrogates during the GPC
calibration check, the non-detected target compounds may be suspect. Use professional judgment to
qualify the detected target compounds (see Table 58). Qualify all non-detected target compounds as
unusable "R".
3. If the Percent Recovery is greater than or equal to 10% and is less than 80% for any of the pesticide
target compounds in the GPC calibration, qualify detected target compounds with a "J" and non-
detected target compounds with an approximated "UJ".
4. If the Percent Recovery is greater than or equal to 80% and less than or equal to 110% for all the
pesticide target compounds, no qualification of the data is necessary.
5. If high recoveries (i.e., greater than 110%) were obtained for the pesticides and surrogates during the
GPC calibration check, use professional judgment to qualify detected target compounds. Do not
qualify non-detected target compounds.
6. Note in the Data Review Narrative potential effects on the sample data resulting from the GPC
cleanup analyses not yielding acceptable results.
Table 58. Gel Permeation Chromatography (GPC) Performance Check Actions
Criteria
%R < 10% (pesticide target compounds)
10%<%R<80%
80%<%R<110%
%R > 110% (pesticide target compounds)
Action
Detected Associated Compounds
Use professional judgment
J
Non-Detected Associated
Compounds
R
UJ
No qualification
Use professional judgment
No qualification
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XII. Target Compound Identification
A. Review Items:
Form I PEST, Form X PEST-1, Form X PEST-2, chromatograms, and data system printouts.
B. Objective:
Qualitative criteria for compound identification have been established to minimize the number of false
positives (reporting a compound present when it is not) and false negatives (not reporting a compound
that is present).
C. Criteria:
1. The Retention Times (RTs) of both of the surrogates and reported target compounds in each sample
must be within the calculated RT Windows on both columns. Tetrachloro-m-xylene (TCX) must be
within ±0.05 minutes of the Mean RT (RT) determined from the initial calibration and
Decachlorobiphenyl (DCB) must be within ±0.10 minutes of the RT determined from the initial
calibration.
2. The Percent Difference (%D) for the detected mean concentrations of a pesticide target compound
between the two Gas Chromatograph (GC) columns must be within the inclusive range of ±25.0.
3. When no analytes are identified in a sample, the chromatograms from the analyses of the sample
extract must use the same scaling factor as was used for the low-point standard of the initial
calibration associated with those analyses.
4. Chromatograms must display Single Component Pesticides (SCPs) detected in the sample and the
largest peak of any multi-component analyte detected in the sample at less than full scale.
5. If an extract must be diluted, chromatograms must display SCPs peaks between 10-100% of full
scale, and multi-component analytes between 25-100% of full scale.
6. For any sample, the baseline of the chromatogram must return to below 50% of full scale before the
elution time of alpha-BHC, and also return to below 25% of full scale after the elution time of alpha-
BHC and before the elution time of DCB.
7. If a chromatogram is replotted electronically to meet these requirements, the scaling factor used must
be displayed on the chromatogram, and both the initial chromatogram and the replotted
chromatogram must be submitted in the data package.
D. Evaluation:
1. Review Form I PEST, the associated raw data (chromatograms and data system printouts) and Form
X PEST-1 and Form X PEST-2. Confirm reported detected analytes by comparing the sample
chromatograms to the tabulated results and verifying peak measurements and RTs. Confirm reported
non-detected analytes by a review of the sample chromatograms. Check the associated blank data for
potential interferences (to evaluate sample data for false positives) and check the calibration data for
adequate RT Windows (to evaluate sample data for false positives and false negatives).
2. For Toxaphene, compare the RTs and relative peak height ratios of major component peaks the
appropriate standard chromatograms.
June 2008 171 Final
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Pesticides Organic Analysis
3. Compare the Toxaphene peaks identified in the sample to determine that the RTs do not overlap with
the RTs of any SCPs or with chromatographic interferences from the sample matrix.
4. Check that the Percent Difference results were calculated correctly.
E. Action:
1. If the qualitative criteria for both columns were not met, all target compounds that are reported as
detected should be considered non-detected. The reviewer should use professional judgment to
assign an appropriate quantitation limit using the following guidance:
a. If the detected target compound peak was sufficiently outside the pesticide RT Window, the
reported values may be a false positive and should be replaced with the sample Contract Required
Quantitation Limits (CRQL) value.
b. If the detected target compound peak poses an interference with potential detection of another
target peak, the reported value should be considered and qualified as unusable "R".
2. If the data reviewer identifies a peak in both GC column analyses that falls within the appropriate RT
Windows, but was reported as a non-detect, the compound may be a false negative. Use professional
judgment to decide if the compound should be included. Note in the Data Review Narrative all
conclusions made regarding target compound identification.
3. If the Toxaphene peak RT windows determined from the calibration overlap with SCPs or
chromatographic interferences, use professional judgment to qualify the data.
4. If target compounds were detected on both GC columns, and the Percent Difference between the two
results is greater than 25.0%, consider the potential for coelution and use professional judgment to
decide whether a much larger concentration obtained on one column versus the other indicates the
presence of an interfering compound. If an interfering compound is indicated, use professional
judgment to determine how best to report, and if necessary, qualify the data.
5. If Toxaphene exhibits a marginal pattern-matching quality, use professional judgment to establish
whether the differences are due to environmental "weathering" (i.e., degradation of the earlier eluting
peaks relative to the later eluting peaks). If the presence of Toxaphene is strongly suggested, report
results as presumptively present "N".
June 2008 172 Final
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Pesticides Organic Analysis
XIII. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation
A. Review Items:
Form I PEST, Form X PEST-1, Form X PEST-2, chromatograms, and data system printouts.
B. Objective:
If GC/MS confirmation is required by the Region for all detected Single Component Pesticides (SCPs)
and Toxaphene that have at least one individual peak with a sufficient on-column concentration on both
columns (greater than or equal to 5.0 ng/(iL for SCPs and 125 ng/(iL for Toxaphene), GC/MS
confirmation for purposes of qualitative identification is required. GC/MS confirmation may be
accomplished by one of three general means:
1. Examination of the semivolatile GC/MS library search results [i.e., Tentatively Identified Compound
(TIC) data]
2. A second analysis of the semivolatile extract; or
3. Analysis of the pesticide extract, following any solvent exchange and concentration steps that may be
necessary.
C. Criteria:
The on-column concentration for any individual peak must be greater than or equal to 5.0 ng/(iL for SCPs
and greater than or equal to 125 ng/(iL for Toxaphene on both GC columns.
D. Evaluation:
Review Form I PEST, the associated raw data (chromatograms and data system printouts) and Form
X PEST-1 and Form X PEST-2. Confirm that GC/MS confirmation was required by ensuring
that an individual peak has an on-column concentration greater than or equal to 5.0 ng/(iL for a
SCP and greater than or equal to 125 ng/(iL for Toxaphene on both GC columns by looking at the
quantitation reports.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If the quantitative criteria for both columns were met (>5.0 ng/(iL for SCPs and >125 ng/(iL for
Toxaphene), determine whether GC/MS confirmation was performed. If it was performed, qualify
the data using the following guidance (see Table 59):
a. If GC/MS confirmation was not required because the quantitative criteria for both columns was
not met, but it was still performed, use professional judgment when evaluating the data to decide
whether the detect should be qualified with "C".
b. If GC/MS confirmation was performed, but unsuccessful for a target compound detected by
GC/ECD analysis, qualify those detects as "X".
June 2008 173 Final
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Pesticides Organic Analysis
Table 59. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation Actions
Criteria
SCP/Toxaphene was confirmed by GC/MS
SCP/Toxaphene was not confirmed by GC/MS
Action
Detects C
Detects X
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Pesticides Organic Analysis
XIV. Compound Ouantitation and Reported Contract Required Ouantitation Limits (CRQLs)
A. Review Items:
Form I PEST, Form X PEST-1, Form X PEST-2, sample preparation log sheets, chromatograms, Sample
Delivery Group (SDG) Narrative, and data system printouts.
B. Objective:
The objective is to ensure that the reported quantitative results, CRQLs, and Percent Moisture
determination (for non-aqueous samples) are accurate.
C. Criteria:
Compound quantitation, as well as the adjustment of the CRQL, must be calculated according to the
equations provided in the method.
D. Evaluation:
1. Examine raw data to verify the correct calculation of all sample results reported by the laboratory.
Compare data system printouts, chromatograms, and sample preparation log sheets to the reported
detects and non-detects sample results. Verify that the sample values are reported correctly.
2. Verify that the CRQLs have been adjusted to reflect all sample dilutions, cleanup activities, Percent
Moisture factors (for non-aqueous samples) and other factors that are not accounted for by the
method.
E. Action:
1. Qualify non-detect results affected by large, off-scale peaks as unusable "R". If the interference is
on-scale, the reviewer can provide an approximated quantitation limit "UJ" for each affected
compound.
2. For non-aqueous samples, if the Percent Moisture is less than 70.0%, no qualification of the data is
necessary (see Table 60). If the Percent Moisture is greater than or equal to 70.0% and less than
90.0%, qualify detects as "J" and non-detects as "UJ". If the Percent Moisture is greater than or equal
to 90.0%, qualify detects as "J" and non-detects as unusable "R".
3. If there are any discrepancies found, the Region's designated representative may contact the
laboratory to obtain additional information that could resolve any differences. If a discrepancy
remains unresolved, the reviewer must decide which value is the best value. Under these
circumstances, the reviewer may determine if qualification of the data is warranted. Note in the Data
Review Narrative a description of the reasons for data qualification and the qualification that is
applied to the data.
June 2008 175 Final
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Pesticides Organic Analysis
Table 60. Percent Moisture Actions for Pesticides Analyses for Non-Aqueous Samples
Criteria
%Moisture < 70.0%
70.0% < %Moisture < 90.0%
%Moisture > 90.0%
Action
Detected Associated
Compounds
Non-Detected Associated
Compounds
No qualification
J
J
UJ
R
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Pesticides Organic Analysis
XV. Overall Assessment of Data
A. Review Items:
Entire data package, data review results, and (if available) Quality Assurance Project Plan (QAPP), and
Sampling and Analysis Plan (SAP).
B. Objective:
The overall assessment of a data package is a brief narrative in which the data reviewer expresses
concerns and comments on the quality and, if possible, the usability of the data.
C. Criteria:
Review all available materials to assess the overall quality of the data, keeping in mind the additive nature
of analytical problems.
D. Evaluation:
1. Evaluate any technical problems which have not been previously addressed.
2. If appropriate information is available, the reviewer may assess the usability of the data to help the
data user in avoiding inappropriate use of the data. Review all available information, including the
QAPP (specifically the acceptance or performance criteria), SAP, and communication with data user
that concerns the intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which were not qualified
based on the Quality Control (QC) criteria previously discussed.
2. Write a brief narrative to give the user an indication of the analytical limitations of the data. Note, for
Contract Laboratory Program Project Officer (CLP PO) action, any inconsistency of that data with the
Sample Delivery Group (SDG) Narrative. If sufficient information on the intended use and required
quality of the data are available, include an assessment of the usability of the data within the given
context. This may be used as part of a formal Data Quality Assessment (DQA).
June 2008 177 Final
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Aroclors Organic Analysis
AROCLOR DATA REVIEW
The Aroclor data requirements to be checked are:
I. Preservation
II. Initial Calibration
III. Continuing Calibration Verification (CCV)
IV. Blanks
V. Surrogate Spikes
VI. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
VII. Laboratory Control Samples (LCSs)
VIII. Regional Quality Assurance (QA) and Quality Control (QC)
IX. Gel Permeation Chromatography (GPC) Performance Check
X. Target Compound Identification
XI. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation
XII. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XIII. Overall Assessment of Data
June 2008 178 Final
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Aroclors Organic Analysis
I. Preservation
A. Review Items:
Form IARO, Traffic Report/Chain of Custody Record (TR/COC), raw data, sample extraction sheets, and
Sample Delivery Group (SDG) Narrative checking for:
1. pH
2. Sample temperature
3. Holding time
4. Other sample conditions
B. Objective:
The objective is to ascertain the validity of the analytical results based on sample condition (e.g.,
preservation and temperature) and the holding time of the sample from time of collection to time of
sample extraction and analysis.
C. Criteria:
The technical holding time criteria for aqueous samples are as follows:
For Aroclors in properly cooled (4°C ± 2°C) aqueous samples, the maximum holding time for
extraction is seven (7) days from sample collection, and the maximum holding time for analysis is
40 days from sample extraction.
The technical holding time criteria for non-aqueous samples are as follows:
For Aroclors in properly cooled (4°C ± 2°C) non-aqueous samples, the maximum holding time is
14 days from sample collection, and the maximum holding time for analysis is 40 days from
sample extraction.
D. Evaluation:
Technical holding times for sample extraction are established by comparing the sample collection dates
on the TR/COC Record with the dates of extraction on Form I ARO and the sample extraction sheets.
Information contained in the Complete SDG File (CSF) should also be considered in the determination of
holding times. To determine if the samples were analyzed within the holding time after extraction,
compare the dates of extraction on the sample extraction sheets with the dates of analysis on Form I ARO.
Verify that the analysis dates on Form I(s) and the raw data/SDG File are identical. Review the SDG
Narrative and the TR/COC Record to determine if the samples were received intact and iced. If there is
no indication in the SDG Narrative, the TR/COC Record, or the sample records that there was a problem
with the samples, assume the integrity of the samples to be acceptable. If it is indicated that there were
problems with the samples, the integrity of the sample may have been compromised; use professional
judgment to evaluate the effect of the problem on the sample results.
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Aroclors Organic Analysis
E. Action:
1. Qualify aqueous sample results using preservation and technical holding time information as follows
(see Table 61):
a. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed within the technical holding times [seven (7) days from
sample collection for extraction; 40 days from sample collection for analysis], use professional
judgment to qualify the data.
b. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed outside the technical holding times [seven (7) days from
sample collection for extraction; 40 days from sample collection for analysis], use professional
judgment to qualify the data.
c. If the samples were properly preserved, and were extracted and analyzed within the technical
holding times [seven (7) days from sample collection for extraction; 40 days from sample
collection for analysis], no qualification of the data is necessary.
d. If the samples were properly preserved, and were extracted or analyzed outside the technical
holding times [seven (7) days from sample collection for extraction; 40 days from sample
collection for analysis], qualify detects with a "J" and non-detects as estimated with an
approximated "UJ" or unusable "R". Note in the Data Review Narrative that holding times were
exceeded and the effect of exceeding the holding time on the resulting data.
2. Qualify non-aqueous sample results using preservation and technical holding time information as
follows (see Table 61):
a. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed within the technical holding times [14 days from
collection for extraction; 40 days from sample collection for analysis], use professional judgment
to qualify the data.
b. If there is no evidence that the samples were properly preserved (e.g., if the sample temperature
has exceeded the allowable limits or if the integrity of the sample has been compromised), and
the samples were extracted or analyzed outside the technical holding times [14 days from sample
collection for extraction; 40 days from sample collection for analysis], use professional judgment
to qualify the data.
c. If the samples were properly preserved, and were extracted and analyzed within the technical
holding times [14 days from sample collection for extraction; 40 days from sample collection for
analysis], no qualification of the data is necessary.
d. If the samples were properly preserved, and were extracted or analyzed outside the technical
holding times [14 days from sample collection for extraction; 40 days from sample collection for
analysis], qualify detects with a "J" and non-detects as estimated with an approximated "UJ" or
unusable "R". Note in the Data Review Narrative that holding times were exceeded and the
effect of exceeding the holding time on the resulting data.
3. Use professional judgment to qualify samples whose temperature upon receipt at the laboratory is
either below 2 degrees centigrade or above 6 degrees centigrade.
4. If technical holding times are grossly exceeded, qualify all detects as estimated with a "J" and use
professional judgment to qualify sample non-detects.
June 2008 180 Final
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Aroclors Organic Analysis
5. Note in the Data Review Narrative, whenever possible, the effect of exceeding the holding time on
the resulting data.
6. Note, for Contract Laboratory Program Project Officer (CLP PO) action, when technical holding
times are grossly exceeded.
Table 61. Holding Time Actions for Aroclor Analysis
Matrix
Aqueous
Non-aqueous
Preserved
No
No
Yes
Yes
Yes/No
No
No
Yes
Yes
Yes/No
Criteria
< 7 days (for extraction) and
< 40 days (for analysis)
> 7 days (for extraction) and
> 40 days (for analysis)
< 7 days (for extraction) and
< 40 days (for analysis)
> 7 days (for extraction) and
> 40 days (for analysis)
Grossly Exceeded
< 14 days (for extraction) and
< 40 days (for analysis)
> 14 days (for extraction) and
> 40 days (for analysis)
< 14 days (for extraction) and
< 40 days (for analysis)
> 14 days (for extraction) and
> 40 days (for analysis)
Grossly Exceeded
Action
Detected
Associated
Compounds
Non-Detected
Associated
Compounds
Use professional judgment
Use professional judgment
No qualification
J
J
UJ
UJorR
Use professional judgment
Use professional judgment
No qualification
J
J
UJ
UJorR
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II. Initial Calibration
A. Review Items:
Form VIARO-1, Form VI ARO-2, Form VI ARO-3, chromatograms, and data system printouts.
B. Objective:
Compliance requirements for satisfactory initial calibration are established to ensure that the instrument is
capable of producing acceptable qualitative and quantitative data for Aroclor compounds on the Target
Compound List (TCL). Initial calibration demonstrates that the instrument is capable of acceptable
performance at the beginning of the analytical sequence, and capable of producing a linear calibration
curve.
C. Criteria:
1. An initial five-point calibration is performed using Aroclors 1016 and 1260 to demonstrate the
linearity of the detector response. These Aroclors may be analyzed in a single standard mixture. The
other seven Aroclors, 1221, 1232, 1242, 1248, 1254, 1262 or 1268, are calibrated at a single mid-
point for pattern recognition. If Aroclors 1221, 1232, 1242, 1248, 1254, 1262 or 1268 are detected in
a sample, a five-point initial calibration is required for the detected Aroclor.
a. The Mean Retention Times (RTs) of each of the three to five major peaks of Aroclors 1016 and
1260 and the Retention Time (RT) of the surrogates are determined from the five-point initial
calibration. For the other seven Aroclors, 1221, 1232, 1242, 1248, 1254, 1262 or 1268, the RTs of
each of the three to five major peaks and the RT of the surrogates are determined from the single-
point standard initial calibration. If Aroclors 1221, 1232, 1242, 1248, 1254, 1262 or 1268, are
detected in a sample, the RTs of each of the three to five major peaks and the RT of the surrogates
are determined from the five-point initial calibration.
b. An RT Window must be calculated as ±0.07 for each of the three to five Aroclor peaks and ±0.05
and ±0.10 for the surrogates tetrachloro-m-xylene (TCX) and decachlorobiphenyl (DCB)
respectively.
c. At least one chromatogram from each of the Aroclor Standards must yield peaks that give
recorder deflections between 50-100% of full scale.
d. The concentrations of the five concentration level standards containing the Aroclors should be
prepared at the following concentrations 100; 200; 400; 800; and 1600 ng/mL and surrogates at
5.0, 10, 20, 40 and 80 ng/mL for TCX and 10, 20, 40, 80 and 160 ng/mL for DCB.
e. Mean Calibration Factor (CF) must be calculated for the three to five major peaks of each
Aroclor, as well as for the surrogates, over the initial calibration range.
f The Percent Relative Standard Deviation (%RSD) of the Calibration Factors (CFs) for the three to
five major peaks of each of the Aroclor compounds must be less than or equal to 20.0%. The
Percent RSD of the CFs for the two surrogates must be less than or equal to 20.0%.
NOTE: Either peak area or peak height may be used to calculate the CFs that are, in turn, used to
calculate %RSD. However, the type of peak measurement used to calculate each CF for a given
compound must be consistent. For example, if peak area is used to calculate the CS1 CF for a
given peak of a certain Aroclor, the remaining CFs for the same peak in the remaining standards
(CS2-CS5) for that Aroclor must also be calculated using peak area.
June 2008 182 Final
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2. Initial Calibration Sequence
The initial calibration must be performed following a specific sequence (see Table 62).
Table 62. Initial Calibration Sequence
Initial Calibration Sequence
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
Aroclor 1221 CS3
Aroclor 1232 CS3
Aroclor 1242 CS3
Aroclor 1248 CS3
Aroclor 1254 CS3
Aroclor 1262 CS3
Aroclor 1268 CS3
Aroclor 1016/1260 (100 n
Aroclor 1016/1260 (200 n
Aroclor 1016/1260 (400 n
Aroclor 1016/1260 (800 n
Aroclor 1016/1260 (1600
Instrument blank
g/mL) CS1
g/mL) CS2
g/mL) CSS
g/mL) CS4
ng/mL) CSS
D. Evaluation:
1. Check the raw data (chromatograms and data system printouts) for each standard to verify that each
of the standards was analyzed at the required concentration levels.
2. Check the Aroclor Standards data and Form VIARO-1 and Form VIARO-3 and review the
calculated RT Windows for calculation and transcription errors.
3. Check the chromatograms and verify that at least one chromatogram from each of the Aroclor
Standards yields peaks registering recorder/printer deflections between 25-100% of full scale.
4. Verify that the concentrations of the Aroclor Standards meet the criteria defined in Aroclors Organic
Analysis, Section Il.C.l.d.
5. Check the Aroclor Standards data and Form VIARO-2 to verify that the %RSD for the CFs are in
compliance with the criteria defined in Aroclors Organic Analysis, Section II.C.
6. Check and recalculate the CFs and %RSD for one or more Aroclors. Verify that the recalculated
values agree with the reported values. If errors are detected, more comprehensive recalculation and
review should be performed.
7. Verify that if Aroclors 1221, 1232, 1242, 1248, 1254, 1262, or 1268 were detected in a sample, a
valid 5-point calibration for that Aroclor using proper concentrations was performed.
8. Verify that the steps of initial calibration are followed in the proper sequence defined in Table 62.
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E. Action:
1. If the proper initial calibration sequence is not performed, or the steps of the initial calibration are not
followed in the proper sequence, use professional judgment to evaluate the effect on the data and
notify the Contract Laboratory Program Project Officer (CLP PO) (see Table 63). This is especially
critical for the low-level standards and non-detects.
2. If RT Windows are not calculated correctly, recalculate the windows and use the corrected values for
all evaluations.
3. If the chromatogram display (recorder deflection) criteria are not met, use professional judgment to
evaluate the effect on the data.
4. If the standard concentration criteria are not met, use professional judgment to evaluate the effect on
the data and notify the CLP PO. This is especially critical for the low-level standards and non-
detects.
5. If the %RSD criteria are not met, qualify detects with a "J" and non-detected target compounds with
an approximated "UJ".
6. If the %RSD criteria are within allowable limits, no qualification of the data is necessary.
7. At the reviewer's discretion, and based on the project-specific data quality objectives, consider a more
in-depth review using the following guidelines:
a. If any Aroclor peak has a %RSD greater than the maximum criterion, and if eliminating either the
high or the low-point of the curve does not restore the %RSD to less than or equal to the required
maximum:
i. Qualify detects for that Aroclor with a "J".
ii. Qualify non-detected Aroclor using professional judgment.
b. If the high-point of the curve is outside of the linearity criteria (e.g., due to saturation):
i. No qualifiers are required for detects in the linear portion of the curve.
ii. Qualify detects outside of the linear portion of the curve with a "J".
iii. No qualifiers are needed for Aroclors that were not detected.
c. If the low-point of the curve is outside of the linearity criteria:
i. No qualifiers are required for detects in the linear portion of the curve.
ii. Qualify low-level detects in the area of non-linearity with a "J".
iii. For non-detected Aroclors, use the lowest point of the valid curve to determine the new
quantitation limit.
8. Note in the Data Review Narrative potential effects on the sample data due to problems with
calibration. Notify the CLP PO if the laboratory has repeatedly failed to comply with the
requirements for frequency, linearity, RT, or resolution.
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Aroclors Organic Analysis
Table 63. Initial Calibration Action for Aroclor Analyses
Criteria
Initial calibration is not performed or not performed in the
proper sequence
%RSD exceeds allowable limits*
%RSD within allowable limits*
Action
Detected Associated
Compounds
Non-Detected Associated
Compounds
Use professional judgment
J
UJ
No qualification
%RSD < 20.0% for Aroclors.
%RSD < 20.0% for surrogates (tetrachloro-m-xylene and decachlorobiphenyl).
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III. Continuing Calibration Verification (CCV)
A. Review Items:
Form VII ARO-1, chromatograms, and data system printouts.
B. Objective:
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data. CCV checks and
documents satisfactory performance of the instrument over specific time periods during sample analysis.
To confirm the calibration and evaluate instrument performance, CCV is performed, consisting of the
analyses of instrument blanks, and the mid-point concentration (CSS) of Aroclor standards. A CCV must
be performed at the beginning (opening CCV) and end (closing CCV) of the analytical sequence. The
opening and closing CCVs consist of an injection of an instrument blank followed by an injection of mid-
point concentration (CSS) of Aroclor 1016/1260 Standard Mixture. If an Aroclor other than 1016 or 1260
is detected in any samples, that Aroclor must have a mid-point concentration (CSS) standard analyzed as
part of the opening and closing CCV.
C. Criteria:
1. The Absolute Retention Time (RT) for each Aroclor and surrogate in the mid-point concentration
(CSS) of the Aroclor Standards used for CCV must be within the RT Windows determined from the
initial calibration.
2. For the opening CCV, or closing CCV that is used as an opening CCV for the next 12-hour period,
the Percent Difference (%D) between the CF of each of the three to five peaks used to identify an
Aroclor and surrogates in the mid-point concentration (CSS) of the Aroclor Standards and the CF
from the initial calibration must be within ±15.0%.
3. For a closing CCV, the Percent Difference between the CF of each of the three to five peaks used to
identify an Aroclor and surrogates in the mid-point concentration (CSS) of the Aroclor Standards and
the CF from the initial calibration must be within ±50.0%.
4. No more than 14 hours may elapse from the injection of the instrument blank that begins an analytical
sequence (opening CCV) and the injection of the last mid-point concentration (CSS) of the Aroclor
Standards that ends an analytical sequence (closing CCV).
5. No more than 12 hours may elapse from the injection of the instrument blank that begins an analytical
sequence (opening CCV) and the injection of the last sample or blank that is part of the same
analytical sequence.
D. Evaluation:
1. Check the data for each of the Aroclors and surrogates in the mid-point concentration (CSS) of the
Aroclor Standards on Form VII ARO-1 to verify that the Absolute RTs are within the RT Windows.
2. For an opening CCV, or closing CCV that is used as an opening CCV for the next analytical
sequence, check the data for each of the Aroclors and surrogates in the mid-point concentration (CSS)
of the Aroclor Standards on Form VII ARO-1 to verify that the Percent Difference between the CF of
each of the three to five peaks used to identify an Aroclor and surrogates in the mid-point
concentration (CSS) of the Aroclor Standards and the CF from the initial calibration is within
±15.0%.
June 2008 186 Final
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Aroclors Organic Analysis
3. For a closing CCV, check the data for each of the Aroclors and surrogates in the mid-point
concentration (CSS) of the Aroclor Standards on Form VIIARO-1 to verify that the Percent
Difference between the CF of each of the three to five peaks used to identify an Aroclor and
surrogates in the mid-point concentration (CSS) of the Aroclor Standards and the CF from the initial
calibration is within ±50.0%.
4. Check the length of time that has elapsed from the beginning injection of the instrument that belongs
to the opening CCV and the ending injection of the last Aroclor Standard that is part of the closing
CCV to verify that no more than 14 hours has elapsed.
5. Check the length of time that has elapsed from the beginning injection of the instrument blank that
belongs to the opening CCV (instrument blank) and the injection of the last sample or method blank
to verify that no more than 12 hours has elapsed.
E. Action:
1. RT Windows are used in qualitative identification. If the standards do not fall within the RT
Windows, use professional judgment to evaluate the associated sample results (see Table 64). All
samples injected after the last in-control standard are potentially affected.
a. For non-detected target compounds in the affected samples, check to see if the sample
chromatograms contain any peaks that are close to the expected RT Window of the Aroclor of
interest.
i. If no peaks are present, consider the non-detected values to be valid and no qualification of
the data is necessary.
ii. If any peaks are present close to the expected RT Window of the Aroclor of interest, qualify
the non-detected values as presumptively present "N".
b. For detected compounds in the affected samples, if the peaks are within the RT Window, no
qualification of the data is necessary. If the peaks are close to the expected RT Window of the
Aroclor of interest, the reviewer may take additional effort to determine if sample peaks represent
the compounds of interest.
For example, the reviewer can examine the data package for the presence of three or more
standards containing the Aroclor of interest that were run within the analytical sequence during
which the sample was analyzed. If three or more such standards are present, the RT Window can
be re-evaluated using the Mean Retention Times (RTs) of the standards.
i. If the peaks in the affected sample fall within the revised window, qualify the detected target
compounds as "NJ".
ii. If the reviewer cannot do anything with the data to resolve the problem of concern, qualify all
non-detects as unusable "R".
2. If the Percent Difference is not within ±15% as specified in Aroclors Organic Analysis, Section
III.C.2, qualify associated detects with a "J" and non-detects with an approximated "UJ".
3. If the Percent Difference is not within ±50% as specified in Aroclors Organic Analysis, Section
III.C.3, qualify associated detects with a "J" and non-detects with an approximated "UJ".
4. If more than 14 hours has elapsed as defined in Aroclors Organic Analysis, Section III.C.4, qualify
associated as unusable "R".
5. If more than 12 hours has elapsed as defined in Aroclors Organic Analysis, Section III.C.5, qualify
associated data as unusable "R".
June 2008 187 Final
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Aroclors Organic Analysis
6. If RT, Percent Difference, and time elapsed are within acceptable limits, no qualification of the data is
necessary.
7. Note in the Data Review Narrative potential effects on the sample data due to problems with
calibration.
Table 64. Continuing Calibration Verification (CCV) Action for Aroclor Analyses
Criteria
RT out of RT window
Percent Difference not within ±15% as specified in
Aroclors, Section I V.C. 2
Percent Difference not within ±50% as specified in
Aroclors, Section I V.C. 3
Time elapsed is greater than acceptable limits as
defined in Aroclors, Sections IV.C.4, and C.5
RT, Percent Difference, time elapsed are within
acceptable limits
Action
Detected Associated
Compounds
Non-Detected Associated
Compounds
Use professional judgment (see Aroclors, Section III.E. 1 )
J
J
UJ
UJ
R
No qualification
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Aroclors Organic Analysis
IV. Blanks
A. Review Items:
Form I ARO, Form IV ARO, chromatograms, and data system printouts.
B. Objective:
The purpose of laboratory or field blank analyses is to determine the existence and magnitude of
contamination resulting from laboratory, field, or sample transport activities. The purpose of the method
blank is to determine the level of contamination associated with the processing and analysis of samples.
The results from the instrument blank indicate whether there is contamination from a previous sample.
The purpose of the sulfur cleanup blank is to determine the level of contamination associated with the
sulfur cleanup process. The criteria for evaluation of laboratory blanks apply to any blank associated with
the samples (e.g., method blanks, sulfur cleanup blanks, instrument blanks, and field blanks). If problems
with any blank exist, evaluate all associated data carefully to determine whether or not there is an inherent
variability in the data or if the problem is an isolated occurrence not affecting other data.
C. Criteria:
1. Method Blanks
A method blank must be extracted each time samples are extracted. The number of samples extracted
with each method blank shall not exceed 20 field samples [excluding Matrix Spike/Matrix Spike
Duplicate (MS/MSDs), Performance Evaluation (PE) samples, and Laboratory Control Samples
(LCSs)]. In addition, a method blank shall be extracted by the same procedure used to extract
samples and be analyzed on the same Gas Chromatograph/Electron Capture Detector (GC/ECD)
system used to analyze associated samples.
2. Instrument Blanks
An acceptable instrument blank must be run at the end of the initial calibration sequence. An
acceptable instrument blank must be run at the beginning and ending of an analytical sequence in
which samples are analyzed, immediately prior to the analysis of the mid-point concentration (CSS)
Aroclor Standard 1016/1260 Mixture, used for continuing calibration verification. All groups of
acceptable sample analyses are to be preceded and followed by acceptable instrument blanks.
3. Sulfur Cleanup Blanks
A sulfur cleanup blank must be analyzed whenever part of a set of samples extracted together requires
sulfur cleanup. If the entire set of samples associated with a method blank requires sulfur cleanup,
the method blank also serves the purpose of a sulfur blank and no separate sulfur blank is required.
The concentration of each target analyte in the method, sulfur cleanup, instrument blanks, and field
blanks must be less than its Contract Required Quantitation Limits (CRQL) listed in the method.
D. Evaluation:
1. Review the results of all associated blanks, Form I ARO, Form IV ARO, and raw data
(chromatograms and data system printouts) to evaluate the presence of target or non-target analytes in
the blanks.
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Aroclors Organic Analysis
2. Verify that a method blank analysis has been reported per Sample Delivery Group (SDG), per
extraction batch, and per extraction procedure. The reviewer can use Form IV ARO to identify
samples associated with each blank.
3. Verify that the method blank analysis(es) contains less than the CRQL of any target Aroclor or any
interfering peak.
4. Verify that the instrument blank analysis has been performed at the beginning and end of every 12-
hour period in which samples were analyzed, immediately before the analysis of the mid-point
concentration (CSS) Aroclor Standard 1016/1260 Mixture or Aroclor of interest detected in a sample.
Evaluate the results from the various instrument blanks to verify that target analyte concentrations are
less than the CRQL (assuming a 1 L extraction of an aqueous sample).
5. Verify that the sulfur cleanup blanks were analyzed at the required frequency and the sulfur blanks do
not contain any target compounds greater than or equal to the CRQL (assuming a 1 L extraction of an
aqueous sample and 30g of a non-aqueous sample). If a separate sulfur cleanup blank was prepared,
one version of Form IV ARO should be completed associating all the samples with the method blank,
and a second version of Form IV ARO should be completed listing only those samples associated
with the separate sulfur cleanup blank.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process. Data concerning the field
blanks are not evaluated as part of the CCS process. If field blanks are present, the data reviewer
should evaluate this data in a similar fashion as the method blanks.
E. Action:
Action regarding unsuitable blank results depends on the circumstances and the origin of the blank. In
instances where more than one of the same type of blank is associated with a given sample, base
qualification upon a comparison with the associated blank having the highest concentration of a
contaminant. Do not correct the results by subtracting the blank value.
1. If a target Aroclor compound is found in the blank but not found in the sample, no qualification is
required (see Table 65).
2. If a target Aroclor compound concentration in a blank is less than the CRQL, and:
a. the sample concentration is less than the CRQL, report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL, use professional judgment to
qualify the data.
3. If a target Aroclor compound concentration in a blank is greater than the CRQL, and:
a. the sample concentration is less than the CRQL, report the CRQL value with a "U".
b. the sample concentration is greater than or equal to the CRQL, and less than the blank
concentration, report the concentration of the compound in the sample at the same concentration
found in the blank with a "U", or the reviewer may elect to qualify the data as unusable "R".
c. the sample concentration is greater than or equal to the CRQL, and greater than or equal to the
blank concentration, use professional judgment to qualify the data.
4. If a target Aroclor compound concentration in a blank is equal to the CRQL, and:
a. the sample concentration is less than the CRQL, report the CRQL value with a "U".
June 2008 190 Final
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Aroclors Organic Analysis
b. the sample concentration is greater than or equal to the CRQL, use professional judgment to
qualify the data.
5. If gross contamination exists (e.g., saturated peaks, "hump-o-grams", "junk" peaks), all affected
compounds in the associated samples should be qualified as unusable "R", due to interference. Note,
for Contract Laboratory Program Project Officer (CLP PO) action, if the contamination is suspected
of having an effect on the sample results.
6. There may be instances where little or no contamination was present in the associated blanks, but
qualification of the sample is deemed necessary. If the reviewer determines that the contamination is
from a source other than the sample, they should qualify the data. Contamination introduced through
dilution is one example. Although it is not always possible to determine, instances of this occurring
can be detected when contaminants are found in the diluted sample result, but absent in the undiluted
sample result.
7. If contaminants are found in the field blanks, the following is recommended:
a. Review the associated method blank data to determine if the contaminant(s) was also present in
the method blank. If the analyte was present at a comparable level in the method blank, the
source of the contamination may be in the analytical system and the action recommended for the
method blank would apply.
If the analyte was not present in the method blank, the source of contamination may have
occurred in the field or during sample transport. Consider all associated samples for possible
cross-contamination.
b. If the field blank contains an Aroclor Target Compound List (TCL) compound(s) at a
concentration greater than the CRQL and:
i. the sample concentration is less than the CRQL, report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL, and less than the blank
concentration, report the concentration of the compound in the sample at the same
concentration found in the blank and qualify with a "U", or use professional judgment to
qualify the data as unusable "R".
iii. the sample concentration is greater than the CRQL and greater than or equal to the blank
concentration, use professional judgment to qualify the data.
c. If gross contamination (e.g., saturated peaks, "hump-o-grams", "junk" peaks) exists in the storage
or field blank, positive sample results may require rejection. Qualify as unusable "R". Non-
detected Aroclor target compounds do not require qualification unless the contamination is so
high that it interferes with the analyses of non-detected compounds.
d. If the field blank contains an Aroclor volatile TCL compound(s) at a concentration less than the
CRQL and:
i. the sample concentration is less than the CRQL, report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL, use professional judgment to
qualify the data.
e. If the field blank contains an Aroclor TCL compound(s) at a concentration equal to the CRQL
and:
i. the sample concentration is less than the CRQL, report the CRQL value with a "U".
ii. the sample concentration is greater than or equal to the CRQL, use professional judgment to
qualify the data.
June 2008 191 Final
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Aroclors Organic Analysis
Table 65. Blank Actions for Aroclor Analyses
Blank Type
Method, Sulfur
Cleanup,
Instrument,
Field
Blank Result
Detects
< TROT
>CRQL
— pT?rvr
Gross contamination
Sample Result
Not detected
CRQL
CRQL and < blank concentration
> CRQL and > blank concentration
CRQL
Detects
Action for Samples
No qualification
Report CRQL value with a U
Use professional judgment
Report CRQL value with a U
Report the blank concentration
for the sample with a U, or
qualify the data as unusable R
Use professional judgment
Report CRQL values with a U
Use professional judgment
Qualify results as unusable R
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V. Surrogate Spikes
A. Review Items:
Form II ARO-1, Form II ARO-2, Form VIII ARO, chromatograms, and data system printouts.
B. Objective:
Laboratory performance on individual samples is established by means of spiking activities. All samples
are spiked with surrogate compounds prior to sample extraction. The evaluation of the recovery results of
these surrogate spikes is not necessarily straightforward. The sample itself may produce effects due to
such factors as interferences. Since the effects of the sample matrix are frequently outside the control of
the laboratory and may present relatively unique problems, the evaluation and review of data based on
specific sample results is frequently subjective and requires analytical experience and professional
judgment. Accordingly, this section consists primarily of guidelines, in some cases with several optional
approaches suggested.
C. Criteria:
1. Two surrogate spikes, tetrachloro-m-xylene (TCX) and decachlorobiphenyl (DCB), are added to all
samples, including Matrix Spike/Matrix Spike Duplicates (MS/MSDs), Laboratory Control Samples
(LCSs) and blanks to measure their recovery. The surrogates are also added to all the standards to
monitor Retention Times (RTs).
2. The recovery limits for the surrogates TCX and DCB are 30-150% for all samples, including MS and
MSDs, LCSs and all blanks.
3. The RTs of the surrogates in each Performance Evaluation Mixture (PEM), mid-point Aroclor
standards used for continuing calibration verification, all samples [including MS and MSD, LCS, and
Performance Evaluation (PE) samples] and all blanks must be within the calculated RT Windows.
TCX must be within ±0.05 minutes, and DCB must be within ±0.10 minutes of the Mean Retention
Time (RT) determined from the initial calibration.
D. Evaluation:
1. Check the raw data (e.g., chromatograms and data system printouts) to verify the recoveries on the
Surrogate Recovery Form (Form II ARO).
2. Check for any calculation or transcription errors; verify that the surrogate recoveries were calculated
correctly using the equation in the method.
3. Check the raw data (e.g., chromatograms and data system printouts) to verify that the RTs on Form
VIII ARO are accurate and within the RT Windows determined from the initial calibration.
4. Whenever there are two or more analyses for a particular sample, the reviewer must determine which
are the most accurate data to report. Considerations include, but are not limited to:
a. Surrogate recovery (marginal versus gross deviation).
b. Technical holding times.
c. Comparison of the values of the target compounds reported in each sample analysis.
d. Other Quality Control (QC) information, such as surrogate recoveries and/or RTs in blanks and
standards.
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Aroclors Organic Analysis
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
If either surrogate spike recovery is outside the acceptance limits, consider the existence of coelution and
interference in the raw data and use professional judgment to qualify data, as surrogate recovery problems
may not directly apply to target analytes.
1. For any surrogate recovery greater than 200% (see Table 66):
a. Qualify detected target compounds are qualified as "J".
b. Use professional judgment to qualify non-detected target compounds.
2. For any surrogate recovery greater than 150%, and less than or equal to 200%:
a. Qualify detected target compounds are qualified as a " J".
b. Do not qualify non-detected target compounds.
3. If both surrogate recoveries are greater than or equal to 30% and less than or equal to 150%, no
qualification of the data is necessary.
4. For any surrogate recovery greater than or equal to 10% and less than 30%:
a. Qualify detected target compounds as a "J".
b. Qualify non-detected target compounds as an approximated "UJ".
5. For any surrogate recovery less than 10%, the reviewer should examine the sample chromatogram to
assess the qualitative validity of the analysis. If low surrogate recoveries are from sample dilution,
use professional judgment to determine if the resulting data should be qualified. If sample dilution is
not a factor:
a. Qualify detected target compounds as a "J".
b. Qualify non-detected target compounds as unusable "R".
6. In the special case of a blank analysis with surrogates out of specification, the reviewer must give
special consideration to the validity of associated sample data. The basic concern is whether the
blank problems represent an isolated problem with the blank alone, or whether there is a fundamental
problem with the analytical process. For example, if one or more samples in the batch show
acceptable surrogate recoveries, the reviewer may choose to consider the blank problem to be an
isolated occurrence. Note, for Contract Laboratory Program Project Officer (CLP PO) action,
analytical problems even if this judgment allows some use of the affected data.
7. If surrogate RTs in PEMs, mid-point Aroclor standards used for Continuing Calibration Verification
(CCV), samples, and blanks are outside of the RT Windows, use professional judgment to qualify
data.
8. If surrogate RTs are within the RT windows, no qualification is necessary.
June 2008 194 Final
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Table 66. Surrogate Actions for Aroclor Analyses
Criteria
%R > 200%
150%<%R<200%
30%<%R<150%
10%<%R<30%
%R < 10% (sample dilution not a factor)
%R < 10% (sample dilution is a factor)
RT out of RT window
RT within RT window
Action*
Detected Target Compounds
J
J
Non-detected Target
Compounds
Use professional judgment
No qualification
No qualification
J
J
UJ
R
Use professional judgment
Use professional judgment
No qualification
Use professional judgment in qualifying data, as surrogate recovery problems may not directly apply to target analytes.
June 2008
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VI. Matrix Spike/Matrix Spike Duplicates (MS/MSDs)
A. Review Items:
Form III ARO-1, Form III ARO-2, chromatograms, and data system printouts.
NOTE: Data for MS and MSDs will not be present unless requested by the Region.
B. Objective:
Data for MS and MSDs are generated to determine long-term precision and accuracy of the analytical
method on the sample matrix and to demonstrate acceptable compound recovery by the laboratory at the
time of sample analysis. These data alone cannot be used to evaluate the precision and accuracy of
individual samples. However, when exercising professional judgment, use this data in conjunction with
other available Quality Control (QC) information.
C. Criteria:
1. If requested, MS and MSD samples are extracted and analyzed at a frequency of one MS and MSD
per 20 or fewer field samples.
2. MS and MSD recoveries should be within the advisory limits provided on Form III ARO-1.
3. Relative Percent Difference (RPD) between MS and MSD recoveries should not exceed the advisory
limits provided on Form III ARO-1.
D. Evaluation:
1. Verify that requested MS and MSD samples were analyzed at the requested frequency and that results
are provided for each sample.
2. Check the raw data and Form III ARO-1 to verify that the results for MS and MSD recoveries were
calculated and transcribed correctly.
3. Check that the RPD was calculated correctly.
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with this criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. No qualification of the data is necessary on MS and MSD data alone. Use professional judgment to
use the MS and MSD results in conjunction with other QC criteria to determine the need for some
qualification of the data. Table 68 lists the Aroclor target analytes that are spiked into samples to test
for matrix effects. If any MS and MSD, Percent Recovery, or RPD in the Aroclor fraction is out of
specification, qualify data to include the consideration of the existence of interference in the raw data.
Considerations include, but are not limited to (see Table 67):
a. For any recovery or RPD greater than the upper acceptance limit:
i. Qualify detected spiked Aroclor target compounds as a "J".
ii. Do not qualify non-detected Aroclor target compounds.
June 2008 196 Final
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Aroclors Organic Analysis
b. For any recovery greater than or equal to 20% and less than the lower acceptance limit:
i. Qualify detected spiked Aroclor target compounds as a "J".
ii. Qualify the sample quantitation limit for non-detected spiked Aroclor target compounds as
approximated "UJ".
c. For any recovery less than 20%:
i. Qualify detected spiked Aroclor target compounds as a " J".
ii. Use professional judgment to qualify non-detected spiked Aroclor target compounds.
d. If recoveries are within the acceptance limits, no qualification of the data is required.
2. The data reviewer should first try to determine to what extent the results of the MS and MSB affect
the associated sample data. This determination should be made with regard to the MS and MSB
sample itself, as well as specific analytes for all samples associated with the MS and MSB.
3. In those instances where it can be determined that the results of the MS and MSB affect only the
sample spiked, limit qualification to this sample only. However, it may be determined through the
MS and MSB results, that a laboratory is having a systematic problem in the analysis of one or more
analytes that affects all associated samples. Use professional judgment to qualify the data from all
associated samples.
4. Use professional judgment to determine the need for qualification of detects of non-spiked
compounds.
NOTE: Notify the Contract Laboratory Program Project Officer (CLP PO) if a field blank was used for
the MS and MSB, unless designated as such by the Region.
Table 67. Matrix Spike/Matrix Spike Duplicate (MS/MSD) Actions for Aroclor Analysis
Criteria
%R or RPD > Upper Acceptance Limit
20% <%R < Lower Acceptance Limit
%R < 20%
Lower Acceptance Limit < %R < Upper Acceptance Limit
Action
Detected Spiked
Compounds
J
J
J
Non-detected Spiked
Compounds
No qualification
UJ
Use professional judgment
No qualification
Table 68. Matrix Spike (MS) Recovery and Relative Percent Difference (RPD) Limits
Compound
AR1016
AR1260
Percent Recovery QC
Limits
29-135
29-135
RPD
0-15
0-20
June 2008
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Aroclors Organic Analysis
VII. Laboratory Control Samples (LCSs)
A. Review Items:
Form I ARO, Form II ARO-1, Form II ARO-2, Form III ARO-3, Form III ARO-4, LCS chromatograms,
and data system printouts.
B. Objective:
Data for LCSs are generated to provide information on the accuracy of the analytical method and
laboratory performance.
C. Criteria:
1. The LCS contains the Aroclors target compounds and surrogates listed in Table 69.
Table 69. Aroclor Laboratory Control Sample (LCS) Recovery
Compound
Aroclor 1016
Aroclor 1260
Tetrachloro-m-xylene (surrogate)
decachlorobiphenyl (surrogate)
% Recovery QC Limits
50 - 150
50 - 150
30-150
30-150
2. The Percent Recoveries (%R) for the LCS compounds must be within the limits specified in Table 69.
NOTE:
D. Evaluation:
All samples prepared and analyzed with an LCS that does not meet the technical acceptance
criteria in the method will require re-extraction and re-analysis.
Check the raw data (e.g., chromatograms and data system printouts) to verify the recoveries on the
Laboratory Control Sample Recovery Form (Form III ARO-3, Form III ARO-4). Check the raw data to
verify the recoveries on the Surrogate Recovery Forms (Form II ARO-1, Form II ARO-2).
Check for any calculation or transcription errors; verify that the LCS recoveries reported on Form II
ARO-1, Form II ARO-2, Form III ARO-3, and Form III ARO-4 are within the QC limits.
NOTE:
E. Action:
For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
If the LCS criteria are not met, laboratory performance and method accuracy are in question. Use
professional judgment to determine if the data should be qualified or rejected. The following guidance is
suggested for qualifying sample data for which the associated LCS does not meet the required criteria (see
Table 70).
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Aroclors Organic Analysis
1. If the LCS recovery criteria are not met, use the LCS results to qualify sample data for the specific
compounds that are included in the LCS solution.
a. If the LCS recovery exceeds the upper acceptance limit, qualify detected target compounds as a
"J". Do not qualify non-detected target compounds.
b. If the LCS recovery is less than the lower acceptance limit, qualify detected target compounds as
a "J" and non-detects as unusable "R".
c. Use professional judgment to qualify data for compounds other than those compounds that are
included in the LCS.
d. Use professional judgment to qualify non-LCS compounds. Take into account the compound
class, compound recovery efficiency, analytical problems associated with each compound, and
comparability in the performance of the LCS compound to the non-LCS compound.
2. If the LCS recovery criteria are within the acceptance limit, no qualification of the data is necessary.
3. Note, for Contract Laboratory Program Project Officer (CLP PO) action, if a laboratory fails to
analyze an LCS with each Sample Delivery Group (SDG), or if a laboratory consistently fails to
generate acceptable LCS recoveries.
Table 70. Laboratory Control Sample (LCS) Recovery Actions
Criteria
%R > Upper Acceptance Limit
%R < Lower Acceptance Limit
Lower Acceptance Limit < %R < Upper Acceptance Limit
Action
Detected Associated
Compounds
J
J
Non-Detected Associated
Compounds
No qualification
R
No qualification
June 2008
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Aroclors Organic Analysis
VIII. Regional Quality Assurance (OA) and Quality Control (OC)
A. Review Items:
Form I ARO, chromatograms, data system printouts, Traffic Report/Chain of Custody Record (TR/COC),
quantitation reports, and other raw data from Regional QA/QC samples.
B. Objective:
Regional QA/QC refers to any QA and/or QC samples initiated by the Region, including field duplicates,
Performance Evaluation (PE) samples, blind spikes, and blind blanks. The use of these QA/QC samples
are highly recommended (e.g., the use of field duplicates can provide information on sampling precision
and sample homogeneity).
C. Criteria:
Criteria are determined by each Region.
1. PE sample frequency may vary.
2. The analytes present in the PE sample must be correctly identified and quantified.
D. Evaluation:
1. Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data review.
Each Region will handle the evaluation of PE samples on an individual basis. Compare results for PE
samples to the acceptance criteria for the specific PE samples, if available.
2. Calculate Relative Percent Difference (RPD) between field duplicates. Provide this information in
the Data Review Narrative.
E. Action:
Any action must be in accordance with Regional specifications and the criteria for acceptable PE sample
results. Note, for Contract Laboratory Program Project Officer (CLP PO) action, any unacceptable results
for PE samples.
June 2008 200 Final
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Aroclors Organic Analysis
IX. Gel Permeation Chromatography (GPC) Performance Check
A. Review Items:
Two ultraviolet (UV) traces, GPC cleanup blank quantitation reports, and chromatograms.
B. Objective:
GPC is used to remove high molecular weight contaminants that can interfere with the analysis of target
analytes. GPC cleanup procedures are checked by adding the GPC calibration mixture to the GPC
cleanup columns and setting the appropriate elution window, and verifying the recovery of target
compounds through the cleanup procedure by the analysis of a cleanup blank.
C. Criteria:
1. GPC is an optional cleanup method for both aqueous and non-aqueous samples and is used for the
cleanup of all non-aqueous and aqueous sample extracts that contain high molecular weight
components that interfere with the analysis of the target analytes.
2. At least once every seven (7) days, the calibration of the GPC unit must be checked by injecting with
the GPC calibration verification solution.
3. The GPC calibration is acceptable if the two UV traces meet the following requirements:
a. Peaks must be observed and should be symmetrical for all compounds in the calibration solution.
b. Corn oil and the phthalate peaks should exhibit greater than 85% resolution.
c. The phthalate and methoxychlor peaks should exhibit greater than 85% resolution.
d. Methoxychlor and perylene peaks should exhibit greater than 85% resolution.
e. Perylene and sulfur peaks must not be saturated and should exhibit greater than 90% baseline
resolution.
f The Retention Time (RT) shift is less than 5% between UV traces for bis(2-ethylhexyl)phthalate
and perylene.
4. A GPC blank must be analyzed after each GPC calibration and it is acceptable if the blank does not
exceed the Contract Required Quantitation Limit (CRQL) for any target analytes listed in SOM01.2.
Exhibit C - Aroclors Target Compound List and Contract Required Quantitation Limits, available at:
http://www.epa.gov/superfund/programs/clp/som 1 .htm
D. Evaluation
1. Verify that there are two UV traces present and that the RT shift for bis(2-ethylhexyl)phthalate and
perylene is less than 5%.
2. Verify that the compounds listed in IX.C.3 are present and symmetrical in both UV traces and that the
compound pairs meet the minimum resolution requirements.
3. Verify that no target compound exceeds the CRQL.
June 2008 201 Final
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Aroclors Organic Analysis
NOTE: For data obtained from the Contract Laboratory Program (CLP), the preceding criteria are
evaluated as part of the Contract Compliance Screening (CCS) process. Information regarding
the laboratory's compliance with these criteria can be obtained from the Data Assessment Tool
(DAT) reports, and may be used as part of the evaluation process.
E. Action:
1. If GPC criteria are not met, examine the raw data for the presence of high molecular weight
contaminants. Examine the subsequent sample data for unusual peaks and use professional judgment
in qualifying the data. Notify the Contract Laboratory Program Project Officer (CLP PO) if a
laboratory chooses to analyze samples under unacceptable GPC criteria.
2. Note in the Data Review Narrative potential effects on the sample data resulting from the GPC
cleanup analyses not yielding acceptable results.
June 2008 202 Final
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Aroclors Organic Analysis
X. Target Compound Identification
A. Review Items:
Form I ARO, Form X ARO, chromatograms, and data system printouts.
B. Objective:
Qualitative criteria for compound identification have been established to minimize the number of false
positives (reporting a compound present when it is not) and false negatives (not reporting a compound
that is present).
C. Criteria:
1. The Retention Times (RTs) of both of the surrogates and reported target compounds in each sample
must be within the calculated RT Windows on both columns. Tetrachloro-m-xylene (TCX) must be
within ±0.05 minutes of the Mean Retention Time (RT) determined from the initial calibration and
Decachlorobiphenyl (DCB) must be within ±0.10 minutes of the RT determined from the initial
calibration.
2. The Percent Difference (%D) for the detected mean concentrations of an Aroclor target compound
between the two Gas Chromatograph (GC) columns must be within the inclusive range of ±25.0.
3. When no analytes are identified in a sample, the chromatograms from the analyses of the sample
extract must use the same scaling factor as was used for the low-point standard of the initial
calibration associated with those analyses.
4. Chromatograms must display the largest peak of any Aroclors detected in the sample at less than full
scale.
5. If an extract must be diluted, chromatograms must display Aroclors peaks between 25 -100% of full
scale.
6. If a chromatogram is replotted electronically to meet these requirements, the scaling factor used must
be displayed on the chromatogram, and both the initial chromatogram and the replotted
chromatogram must be submitted in the data package.
D. Evaluation:
1. Review Form I ARO, the associated raw data (chromatograms and data system printouts) and Form X
ARO. Confirm reported detected analytes by comparing the sample chromatograms to the tabulated
results and verifying peak measurements and RTs. Confirm reported non-detected analytes by a
review of the sample chromatograms. Check the associated blank data for potential interferences (to
evaluate sample data for false positives) and check the calibration data for adequate RT Windows (to
evaluate sample data for false positives and false negatives).
2. Compare the Aroclor peaks identified in the sample to determine that the RTs do not overlap with the
RTs of any chromatographic interferences from the sample matrix.
3. Check that the Percent Difference results were calculated correctly.
June 2008 203 Final
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Aroclors Organic Analysis
E. Action:
1. If the qualitative criteria for both columns were not met, all target compounds that are reported as
detected should be considered non-detected. The reviewer should use professional judgment to
assign an appropriate quantitation limit using the following guidance:
a. If the detected target compound peak was sufficiently outside the Aroclor RT Window, the
reported values may be a false positive and should be replaced with the sample Contract Required
Quantitation Limits (CRQL) value.
b. If the detected target compound peak poses an interference with potential detection of another
target peak, the reported value should be considered and qualified as unusable "R".
2. If the data reviewer identifies a peak in both GC column analyses that falls within the appropriate RT
Windows, but was reported as a non-detect, the compound may be a false negative. Use professional
judgment to decide if the compound should be included. Note in the Data Review Narrative all
conclusions made regarding target compound identification.
3. If the Aroclor peak RT Windows determined from the calibration overlap with chromatographic
interferences, use professional judgment to qualify the data.
4. If Aroclors were detected on both GC columns, and the Percent Difference between the two results is
greater than 25.0%, consider the potential for coelution and use professional judgment to decide
whether a much larger concentration obtained on one column versus the other indicates the presence
of an interfering compound. If an interfering compound is indicated, use professional judgment to
determine how best to report, and if necessary, qualify the data.
5. If Aroclors exhibit marginal pattern-matching quality, use professional judgment to establish whether
the differences are due to environmental "weathering" (i.e., degradation of the earlier eluting peaks
relative to the later eluting peaks). If the presence of an Aroclor is strongly suggested, report results
as presumptively present "N".
June 2008 204 Final
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Aroclors Organic Analysis
XL Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation
A. Review Items:
Form I ARO, Form X ARO, chromatograms, and data system printouts.
B. Objective:
If GC/MS confirmation is required by the Region for all detected Aroclors that have at least one
individual peak with a sufficient on-column concentration on both columns (greater than or equal to
10 ng/(iL), GC/MS confirmation for purposes of qualitative identification is required. GC/MS
confirmation may be accomplished by one of three general means:
1. Examination of the semivolatile GC/MS library search results [i.e., Tentatively Identified Compound
(TIC) data];
2. A second analysis of the semivolatile extract; or
3. Analysis of the Aroclor extract, following any solvent exchange and concentration steps that may be
necessary.
C. Criteria:
The on-column concentration for any individual peak belonging to an Aroclor must be greater than or
equal to 10 ng/(iL on both GC columns. If the on-column concentration to run GC/MS confirmation is
adequate, the laboratory must have permission from the Region before GC/MS performing confirmation.
D. Evaluation:
1. Review Form I ARO, the associated raw data (chromatograms and data system printouts) and Form X
ARO-1 and Form X ARO-2. Confirm that GC/MS confirmation was required by ensuring that an
individual peak belonging to an Aroclor has an on-column concentration greater than or equal to 10
ng/(iL on both GC columns by looking at the quantitation reports.
E. Action:
1. If the quantitative criteria for both columns were met (>10 ng/(iL), determine whether GC/MS
confirmation was performed. If it was performed, qualify the data using the following guidance (see
Table 71):
a. If GC/MS confirmation was not required because the quantitative criteria for both columns was
not met, but it was still performed, the reviewer should use professional judgment when
evaluating the data to decide whether the detect should be qualified with "C".
b. If GC/MS confirmation was requested and performed, but not successful for a target compound
detected by GC/ECD analyses, qualify those detects as "X".
Table 71. Gas Chromatograph/Mass Spectrometer (GC/MS) Confirmation Actions
Criteria
Aroclor peak was confirmed by GC/MS
Aroclor peak was not confirmed by GC/MS
Action
Detects C
Detects X
June 2008 205 Final
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Aroclors Organic Analysis
XII. Compound Ouantitation and Reported Contract Required Ouantitation Limits (CROLs)
A. Review Items:
Form I ARO, Form X ARO-1, sample preparation log sheets, chromatograms, Sample Delivery Group
(SDG) Narrative, and data system printouts.
B. Objective:
The objective is to ensure that the reported quantitative results and CRQLs are accurate.
C. Criteria:
Compound quantitation, as well as the adjustment of the CRQL, must be calculated according to the
equations provided in the method.
D. Evaluation:
1. Examine raw data to verify the correct calculation of all sample results reported by the laboratory.
Compare data system printouts, chromatograms, and sample preparation log sheets to the reported
detects and non-detects sample results. Verify that the sample values are reported correctly.
2. Verify that the CRQLs have been adjusted to reflect all sample dilutions, cleanup activities, Percent
Moisture determination (for non-aqueous samples) and other factors that are not accounted for by the
method.
E. Action:
1. Qualify non-detect results affected by large, off-scale peaks as unusable "R". If the interference is
on-scale, provide an approximated quantitation limit "UJ" for each affected compound.
2. For non-aqueous samples, if the Percent Moisture is less than 70.0%, no qualification of the data is
necessary (see Table 72). If the Percent Moisture is greater than or equal to 70.0% and less than
90.0%, qualify detects as "J" and non-detects as "UJ". If the Percent Moisture is greater than or equal
to 90.0%, qualify detects as "J" and non-detects as unusable "R".
3. If there are any discrepancies found, the Region's designated representative may contact the
laboratory to obtain additional information that could resolve any differences. If a discrepancy
remains unresolved, the reviewer must decide which value is the best value. Under these
circumstances, determine if qualification of the data is warranted. Note in the Data Review Narrative
a description of the reasons for data qualification and the qualification that is applied to the data.
Table 72. Percent Moisture Actions for Aroclors Analyses for Non-Aqueous Samples
Criteria
%Moisture < 70.0%
70.0% < %Moisture < 90.0%
%Moisture > 90.0%
Action
Detected Associated
Compounds
Non-Detected Associated
Compounds
No qualification
J
J
UJ
R
June 2008 206 Final
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Aroclors Organic Analysis
XIII. Overall Assessment of Data
A. Review Items:
Entire data package, data review results, and (if available) Quality Assurance Project Plan (QAPP), and
Sampling and Analysis Plan (SAP).
B. Objective:
The overall assessment of a data package is a brief narrative in which the data reviewer expresses
concerns and comments on the quality and, if possible, the usability of the data.
C. Criteria:
Review all available materials to assess the overall quality of the data, keeping in mind the additive nature
of analytical problems.
D. Evaluation:
1. Evaluate any technical problems which have not been previously addressed.
2. If appropriate information is available, assess the usability of the data to help the data user avoid
inappropriate use of the data. Review all available information, including the QAPP (specifically the
acceptance or performance criteria), SAP, and communication with data user that concerns the
intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which were not qualified
based on the Quality Control (QC) criteria previously discussed.
2. Write a brief narrative to give the user an indication of the analytical limitations of the data. Note, for
Contract Laboratory Program Project Officer (CLP PO) action, any inconsistency of that data with the
Sample Delivery Group (SDG) Narrative. If sufficient information on the intended use and required
quality of the data are available, include an assessment of the usability of the data within the given
context. This may be used as part of a formal Data Quality Assessment (DQA).
June 2008 207 Final
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Appendix A
APPENDIX A: GLOSSARY
Analysis Date/Time - The date and military time (24-hour clock) of the injection of the sample, standard,
or blank into the Gas Chromatograph/Mass Spectrometer (GC/MS) or Gas Chromatograph (GC) system.
Aroclor - A trademarked name for a mixture of poly chlorinated biphenyls (PCBs) used in a variety of
applications including additives in lubricants, heat transfer dielectric fluids, adhesives, etc.
Blank - An analytical sample designed to assess specific sources of contamination. See individual
definitions for types of blanks.
Breakdown - A measure of the decomposition of certain analytes (DDT and Endrin) into by-products.
4-Bromofluorobenzene (BFB) - The compound chosen to establish mass spectrometer instrument
performance for volatile analyses.
Calibration Factor (CF) - A measure of the Gas Chromatographic response of a target analyte to the
mass injected.
Case - A finite, usually predetermined number of samples collected over a given time period from a
particular site. Case Numbers are assigned by the Sample Management Office (SMO). A Case consists
of one or more Sample Delivery Groups (SDGs).
Contract Compliance Screening (CCS) - A screening of electronic and hardcopy data deliverables for
completeness and compliance with the contract. This screening is performed under the United States
Environmental Protection Agency (USEPA) direction by the Sample Management Office (SMO)
Contractor.
Contamination - A component of a sample or an extract that is not representative of the environmental
source of the sample. Contamination may stem from other samples, sampling equipment, while in transit,
from laboratory reagents, laboratory environment, or analytical instruments.
Continuing Calibration Verification (CCV) - Analytical standard run every 12 hours to verify that the
instrument response at the concentration of the standard is within acceptable limits.
Contract Laboratory Program (CLP) - Supports the USEPA's Superfund effort by providing a range of
state-of-the-art chemical analytical services of known and documented quality. This program is directed
by the Analytical Services Branch (ASB) of the Office of Superfund Remediation and Technology
Innovation (OSRTI) of USEPA.
Contract Laboratory Program Project Officer (CLP PO) - The Regional USEPA official responsible
for monitoring laboratory performance and/or requesting analytical data or services from a Contract
Laboratory Program (CLP) laboratory.
Decafluorotriphenylphosphine (DFTPP) - Compound chosen to establish mass spectrometer
instrument performance for semivolatile analysis.
Deuterated Monitoring Compounds (DMCs) - Compounds added to every volatile and semivolatile
calibration standard, blank, and sample used to evaluate the efficiency of the extraction/purge and trap
procedures, and the performance of the Gas Chromatograph/Mass Spectrometer (GC/MS) systems.
June 2008 A-l Final
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Appendix A
DMCs are isotopically labeled (deuterated) analogs of native target compounds. DMCs are not expected
to be naturally detected in the environmental media.
Field Blank - A blank used to provide information about contaminants that may be introduced during
sample collection.
Field Sample - A portion of material to be analyzed that is contained in single or multiple containers and
identified by a unique sample number.
14-Hour Time Period - For pesticide and Aroclor analyses, the fourteen-hour time period begins at the
injection of the beginning of the sequence for an opening Continuing Calibration Verification (CCV)
(instrument blank) and must end with the injection of the closing sequence of the closing CCV
[Individual standard A, B, or C or Performance Evaluation Mixture (PEM)]. The time period ends after
14 hours have elapsed according to the system clock.
Gas Chromatograph (GC) - The instrument used to separate analytes on a stationary phase within a
chromatographic column. The analytes are volatized directly from the sample (volatile), or injected as
extracts (semivolatile, pesticides, and Aroclors). In volatile and semivolatile analyses, the compounds are
detected by a Mass Spectrometer. In pesticide and Aroclors analyses, the compounds are detected by an
Electron Capture Detector (ECD).
Gas Chromatograph/Electron Capture Detector (GC/ECD) - A Gas Chromatograph (GC) equipped
with an Electron Capture Detector (ECD). This is one of the most sensitive gas chromatographic
detectors or halon-containing compounds such as organochlorine pesticides and polychlorinated
biphenyls.
Initial Calibration - Analysis of analytical standards at different concentrations to define the linear range
of an analytical instrument [e.g., Gas Chromatograph/Mass Spectrometer (GC/MS), Gas
Chromatograph/Electron Capture Detector (GC/ECD)].
Internal Standards - Compounds added to every volatile and semivolatile standard, blank, sample, or
sample extract, including the Laboratory Control Sample (LCS), at a known concentration, prior to
analysis. Internal standards are used to monitor instrument performance and quantitation of target
compounds.
Instrument Blank - A blank designed to determine the level of contamination either associated with the
analytical instruments, or resulting from carryover.
Laboratory Control Sample (LCS) - The LCS is an internal laboratory Quality Control (QC) sample
designed to assess [on a Sample Delivery Group (SDG)-by-SDG basis] the capability of the contractor to
perform the analytical method.
m/z - Mass to charge ratio, synonymous with "m/e".
Matrix - The predominant material of which the sample to be analyzed is composed. For the purpose of
this document, the sample matrix is either aqueous or non-aqueous.
Matrix Effect - In general, the effect of a particular matrix on the constituents with which it contacts.
Matrix effects may prevent efficient purging/extraction of target analytes, and may affect DMC and
surrogate recoveries. In addition, non-target analytes may be extracted from the matrix causing
interferences.
June 2008 A-2 Final
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Appendix A
Matrix Spike (MS) - Aliquot of the sample fortified (spiked) with known quantities of specific
compounds and subjected to the entire analytical procedure in order to indicate the appropriateness of the
method for the matrix by measuring recovery.
Matrix Spike Duplicate (MSD) - A second aliquot of the same sample that is fortified (spiked) with
known quantities of specific compounds and subjected to the entire analytical procedure in order to
determine precision of the method.
Method Blank - A reagent aqueous sample spiked with internal standards, and surrogate standards (or
DMCs for volatile and semivolatile), that is carried throughout the entire analytical procedure. The
method blank is used to define the level of contamination associated with the processing and analysis of
samples.
Narrative (SDG Narrative) - Portion of the data package which includes laboratory, contract, Case and
sample number identification, and descriptive documentation of any problems encountered in processing
the samples, along with corrective action taken and problem resolution
Percent Difference (%D) - The difference between two values (usually a true value and a found value),
calculated as a percentage of the true value. The Percent Difference indicates both the direction and the
magnitude of the difference (i.e., the Percent Difference may be either negative, positive, or zero).
Percent Relative Standard Deviation (%RSD) - The Percent Relative Standard Deviation is calculated
from the standard deviation and mean measurement of either RRFs or CF from initial calibration
standards. Percent Relative Standard Deviation indicates precision of a set of measurements.
Performance Evaluation Mixture (PEM) - A calibration solution of specific analytes used to evaluate
both recovery and Percent Breakdown as measures of performance.
Poly chlorinated Biphenyls (PCBs) - A group of toxic, persistent chemicals used in electrical
transformers and capacitors for insulating purposes, and in gas pipeline systems as a lubricant. The sale
and new use of PCBs were banned by law in 1979.
Purge-and-Trap (Device) - Analytical technique (device) used to isolate volatile (purgeable) organics
by stripping the compounds from aqueous by a stream of inert gas, trapping the compounds on an
adsorbent such as a porous polymer trap, and thermally desorbing the trapped compounds onto the Gas
Chromatographic column.
Reconstructed Ion Chromatogram (RIC) - A mass spectral graphical representation of the separation
achieved by a Gas Chromatograph; a plot of total ion current versus Retention Time (RT).
Relative Percent Difference (RPD) - The difference between two values, calculated as a percent relative
to the mean of the two values.
Relative Response Factor (RRF) - A measure of the mass spectral response of an analyte relative to its
associated internal standard. RRFs are determined by analysis of standards and are used in the calculation
of concentrations of analytes in samples.
Relative Retention Time (RRT) - The ratio of the Retention Time (RT) of a compound to that of a
standard (such as an internal standard).
June 2008 A-3 Final
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Appendix A
Resolution - Also termed separation or percent resolution, the separation between peaks on a
chromatogram, calculated by dividing the depth of the valley between the peaks by the peak height of the
smaller peak being resolved, multiplied by 100.
Resolution Check Mixture - A solution of specific analytes used to determine resolution of adjacent
peaks; used to assess instrumental performance.
Retention Time (RT) - The time a target analyte is retained on a Gas Chromatograph (GC) column
before elution. The identification of a target analyte is dependent on a target compound's RT falling
within the specified RT Window established for that compound. The RT is dependent on the nature of
the column's stationary phase, column diameter, temperature, flow rate, and other parameters.
Sample Delivery Group (SDG) - A unit within a sample Case that is used to identify a group of samples
for delivery. An SDG is defined by the following, whichever is most frequent:
• Each Case of field samples received, or;
• Each twenty (20) field samples (excluding Performance Evaluation (PE) samples) within a Case, or;
• Each seven (7) calendar day period [three (3) calendar day period for seven (7) day turnaround]
during which field samples in a Case are received (said period beginning with the receipt of the first
sample in the SDG).
In addition, all samples and/or sample fractions assigned to an SDG must have been scheduled under the
same contractual turnaround time. Preliminary Results have no impact on defining the SDG.
Sample Management Office (SMO) - A contractor-operated facility operated under the Contract
Laboratory Analytical Services Support (CLASS) contract, awarded and administered by USEPA.
Sample Number (USEPA Sample Number) - A unique identification number designated by USEPA to
each sample. USEPA Sample Number appears on the Traffic Report/Chain of Custody Record
(TR/COC) which documents information on that sample.
Semivolatile Compounds - Compounds amenable to analysis by extraction of the sample with an organic
solvent. Used synonymously with Base/Neutral/Acid (BNA) compounds.
Statement of Work (SOW) - A document which specifies how laboratories analyze samples under a
particular Contract Laboratory Program (CLP) analytical program.
Storage Blank - Reagent water (two 40.0 mL aliquots) or clean sand stored with volatile samples in a
Sample Delivery Group (SDG). It is analyzed after all samples in that SDG have been analyzed; and it is
used to determine the level of contamination acquired during storage.
Sulfur Cleanup Blank - A modified method blank that is prepared only when some of the samples in a
batch are subjected to sulfur cleanup. It is used to determine the level of contamination associated with
the sulfur cleanup procedure. When all of the samples are subjected to sulfur cleanup, the method blank
serves this purpose. When none of the samples are subjected to sulfur cleanup, no sulfur cleanup blank is
required.
Surrogates (Surrogate Standard) - For pesticides and Aroclors, compounds added to every blank,
sample [including Laboratory Control Sample (LCS)], Matrix Spike/Matrix Spike Duplicate (MS/MSD),
and standard; used to evaluate analytical efficiency by measuring recovery. Surrogates are not expected
to be detected in environmental media.
June 2008 A-4 Final
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Appendix A
Target Compound List (TCL) - A list of compounds designated by the Statement of Work (SOW) for
analysis.
Technical Holding Time - The maximum length of time that a sample may be held from the collection
date until extraction and/or analysis.
Tentatively Identified Compounds (TIC) - Compounds detected in samples that are not target
compounds, internal standards, Deuterated Monitoring Compounds (DMCs), or surrogates. Up to thirty
(30) peaks, not including those identified as alkanes (those greater than 10% of the peak area or height of
the nearest internal standard), are subjected to mass spectral library searches for tentative identification.
Traffic Report/Chain of Custody Record (TR/COC) - A USEPA sample identification form filled out
by the sampler, which accompanies the sample during shipment to the laboratory and which documents
sample condition and receipt by the laboratory.
Trip Blank - A blank used to provide information about contaminants that may be introduced during
sample transport.
Twelve-hour Time Period - The twelve (12)-hour time period for Gas Chromatograph/Mass
Spectrometer (GC/MS) system instrument performance check, standards calibration [initial or Continuing
Calibration Verification (CCV)], and method blank analysis begins at the moment of injection of the
Decafluorotriphenylphosphine (DFTPP) or 4-Bromofluorobenzene (BFB) analysis that the laboratory
submits as documentation of instrument performance. The time period ends after 12 hours have elapsed
according to the system clock. For pesticide analyses performed by Gas Chromatograph/Electron Capture
Detector (GC/ECD), the 12-hour time period in the analytical sequence begins at the moment of injection
of the instrument blank that precedes sample analyses, and ends after twelve hours have elapsed
according to the system clock.
Validated Time of Sample Receipt (VTSR) - The date on which a sample is received at the Contractor's
facility, as recorded on the shipper's delivery receipt and Traffic Report/Chain of Custody Record
(TR/COC).
Volatile Compounds - Compounds amenable to analysis by the purge-and-trap technique. Used
synonymously with purgeable compounds.
June 2008 A-5 Final
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Appendix B
APPENDIX B: ORGANIC DATA REVIEW SUMMARY
CASE NO.
LABORATORY
SDGNO.
REVIEWER NAME
CLP PO: ACTION
SITE
NO. OF SAMPLES/MATRIX
SOW NO. REGION
COMPLETION DATE
FYI
Review Criteria
Preservation
GC/MS or GC/ECD Instrument
Performance Check
Initial Calibration
Continuing Calibration Verification
Blanks
Deuterated Monitoring Compound
Surrogate Spikes
Matrix Spike/Matrix Spike Duplicate
Laboratory Control Sample
Regional QA/QC
Internal Standards
GPC Performance Check
Florisil Cartridge Performance Check
Target Compound Identification
GC/MS Confirmation
Compound Quantitation and Reported
CRQLS
Tentatively Identified Compounds
System Performance
Overall Assessment of Data
Fraction
TRACE
LOW/MED
SVGA
PEST
AROCLOR
June 2008
B-l
Final
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