REGION III MODIFICATIONS
TO
NATIONAL FUNCTIONAL GUIDELINES
FOR
ORGANIC DATA REVIEW
MULTI-MEDIA, MULTI-CONCENTRATION
(0LM01.0-OLMO1.6)
JUNE 1992
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FORWORD
Regional Cen.er for Environmcnta, ,nformation
us EPA Region III
1650 Arch St.
Philadelphia, PA 1910?
This document is a modification to the National Functional
Guidelines for Organic Data Review (Draft, June 1991).
This document describes those procedures that are to be used for
Region III Data Validation. It is intended for implementation
for all CLP data acquired for use within Region III
but it may be adapted for use with other similar methods.
All comments and questions pertaining to this document
should be addressed to:
U.S. Environmental Protection Agency
Region III
Central Regional Laboratory
Quality Assurance Branch
839 Bestgate Road
Annapolis, MD 21401
c/o Program Support Section
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/ Prtnmr III
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TABLE OF CONTENTS
£209
INTRODUCTION i
PRELIMINARY REVIEW ii
DATA QUALIFIER DEFINITIONS iii
VOLATILE DATA REVIEW 1
I. Technical Holding Times 2
II. GC/MS Instrument Performance Check 5
III. Initial Calibration 8
IV. Continuing Calibration 12
V. Blanks •. 14
VI. System Monitoring Compounds (Surrogate Spikes) 18
VII. Matrix Spikes/Matrix Spike Duplicates 22
VIII. Regional Quality Assurance and Quality Control 24
IX. internal Standards 26
X. Target Compound Identification 28
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs) 30
XII. Tentatively Identified Compounds (TICs) 32
XIII. System Performance 36
XIV. Overall Assessment of Data 37
SEMIVOLAHLE DATA REVIEW 38
I. Technical Holding Times 39
II. GC/MS Instrument Performance Check 41
III. Initial Calibration 44
IV. Continuing Calibration 48
U.S. EPA Region III t
Regional Center for Environmental
Information
1650 Arch Street (3PM52)
Philadelphia, PA 19103
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Rector* iti
V. Blanks ot
VI. Surrogate Spikes 57
VII. Matrix Spikes/Matrix Spike Duplicates 60
VIII. Regional Quality Assurance and Quality Control 62
IX. Internal Standards 64
X. Target Compound Identification 66
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs) 68
XII. Tentatively Identified Compounds (TICs) 70
XIII. System Performance 74
XIV. Overall Assessment of Data 75
APPENDIX A: Contractual Requirements and Equations, Multi-media Multi-concentration A-1
DRAFT APPENDIX B: Region III Standard Operating Procedure for Data Validation Reports B-1
APPENDIX C: Contractual Requirement Comparison Tables C-1
APPENDIX D: Proposed Guidance for Tentatively Identified Compounds (VOA and SV) D-1
APPENDIX E: Glossary of Terms E-1
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Region III Modifications
INTRODUCTION
This document is designed to offer guidance on EPA Contract Laboratory Program (CLP) analytical data
evaluation and review. It has been modified for use within U.S. EPA Region III. In some applications It may
be used as a Standard Operating Procedure (SOP). In other, more subjective areas, only general guidance
is offered due to the complexities and uniqueness of data relative to specific samples. For example, areas
where the application of specific SOPs are possible are primarily those in which definitive performance
criteria are established. These criteria are concerned with specifications that are not sample dependent; they
specify performance requirements that should fully be under a laboratory's control. These specific areas
include blanks, calibration standards, performance evaluation standard materials, and instrument
performance checks (tuning).
These Guidelines have been updated to include the requirements in the Statement of Work (SOW) for
Organic Analysis Multi-Media Multi-Concentration (SOW OLM01.0 and revisions).
This update includes changes to instrument performance checks (formerly referred to as tuning) and
calibration criteria as a result of the Response Factor Workgroup. Regional Modifications to the Data
Qualifier Definitions from the previous National Functional Guidelines are also included in this document.
This document is intended to assist in the technical review of analytical data generated through the CLP.
Determining contract compliance is not the intended objective of these guidelines or the regional data review
process. The data review process provides information on analytical limitations of data based on specific
quality control (QC) criteria. In order to provide more specific usability statements, the reviewer must have
a complete understanding of the intended use of the data. For this reason, it is recommended that whenever
possible the reviewer obtain usability issues from the user prior to reviewing the data. When this is not
possible, the user should be encouraged to communicate any questions to the reviewer. In order to facilitate
communication with the data users in Region III, specific reporting formats for the data validation report are
required. Each report must contain a table of the summarized data, sufficient narrative to inform the user
of significant data review issues and adequate documentation to support the decisions and actions of the
data reviewer. The Standard Operating Procedure for preparing the Region III data validation report is
presented in Appendix B.
At times, there may be an urgent need to use data which do not meet all contract requirements and
technical criteria. Use of these data does not constitute either a new requirement standard or full
acceptance of the data. Any decision to utilize data for which performance criteria have not been met is
strictly to facilitate the progress of projects requiring the availability of the data. A contract laboratory
submitting data which are out of specification may be required to rerun samples or resubmit data even if
the previously submitted data have been utilized due to urgent program needs; data which do not meet
specified requirements are never fully acceptable. The only exception to this requirement is in the area of
requirements for individual sample analysis. If the nature of the sample itself limits the attainment of
specifications, appropriate allowances must be made. The overriding concern of the Agency is to obtain
data which are technically valid and legally defensible.
Appendix A is based on the Multi-media Multi-concentration SOW and contains appropriate
contractual requirements and equations for verifying various calculations. Appendix B contains the Region
III SOP for Data Validation Reports. Appropriate equations are presented for easy reference and to allow
the reviewer to verify calculations as needed. Contractual requirements are provided in Appendix C to
facilitate comparisons with the technical requirements. Appendix D contains proposed guidance for
Tentatively Identified Compounds (VOA and SV), and Appendix E contains a glossary of commonly used
terms. /- \
Regional Center for Environmental Information
US EPA Region III
1650 Arch St.
Philadelphia, PA 19103
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PRELIMINARY REVIEW
In order to use this document effectively, the reviewer should have a general overview of the sample
delivery group (SOQ) or case at hand. The exact number of samples, their assigned numbers, their matrix,
and the number of laboratories involved in their analysis are essential information. Background information
on the site is helpful but often this information may be difficult to locate. The site manager is the best source
for answers to questions or further direction.
Contract Compliance Screening (CCS) is a source of summarized information regarding contract
compliance. If available, it can be used to alert the reviewer to problems in the SDQ data package.
Sampie cases (SDGs) routinely have unique samples which require special attention by the reviewer.
These include field blanks, field duplicates, and performance audit samples which need to be identified. The
sampling records should provide:
1. Project Officer for site.
2. Complete list of samples with information on:
a. sample matrix,
b. field blanks,
c. field duplicates,
d. field spikes,
e. QC audit samples,
f. shipping dates, and
g. laboratories involved.
The chain-of-custody record includes sample descriptions and date(s) of sampling. The reviewer must
take into account lag times between sampling and receipt for analysis when assessing technical sample
holding times.
The laboratory's SOQ narrative is another source of general information. Notable problems with
matrices, insufficient sample volume for analysis or reanalysis, samples received in broken containers, and
unusual events should be found in the SDQ narrative.
The SDG narrative for the sample data package must include a Laboratory Certification Statement
(exactly as stated in the SOW), signed by the laboratory manager or designee. This statement authorizes
the validation and release of the sample data results. In addition, the laboratory must also provide
ccm.T.onts in the SDG narrative "describing in detail any problems encountered in processing the samples
in the data package.
For every data package, the reviewer must verify that the laboratory certification statement is present,
exactly as in the SOW (i.e., verbatim to the statement in the SOW, and signed by the Laboratory Manager
or designee). The reviewer must further verify that the data package is consistent with the laboratoiys
certified narrative. Also, the reviewer should check the comments provided in the narrative to determine if
they are sufficient to describe and explain the associated problem.
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GLOSSARY OF DATA QUALIFIER CODES (ORGANIC)
CODES RELATING TO IDENTIFICATION
(CONFIDENCE CONCERNING PRESENCE OR ABSENCE OF COMPOUNDS):
U = Not detected. The associated number indicates approximate sample concentration necessary to
be detected.
(NO CODE) = Confirmed identification.
B = Not detected substantially above the level reported in laboratory or field blanks.
R = Unreliable result. Analyte may or may not be present in the sample. Supporting data necessary
to confirm result.
N = Tentative identification. Consider present. Special methods may be needed to confirm its
presence or absence in future sampling efforts.
CODES RELATED TO QUANTITATION
(can be used for both positive results and sample quantitation limits):
J = Analyte present. Reported value may not be accurate or precise.
K = Analyte present. Reported value may be biased high. Actual value is expected lower.
L = Analyte present. Reported value may be biased low. Actual value is expected to be higher.
UJ = Not detected, quantitation limit may be inaccurate or imprecise.
UL = Not detected, quantitation limit is probably higher.
OTHER CODES
Q = No analytical result.
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VOA
VOLATILE DATA REVIEW
The volatile data requirements to be checked are listed below
I. Technical Holding Times (CCS • Contractual holding times only)
II. GC/MS Instrument Performance Check (CCS)
III. Initial Calibration (CCS)
IV. Continuing Calibration (CCS)
V. Blanks
VI. System Monitoring Compounds (CCS)
VII. Matrix Spikes/Matrix Spike Duplicates
VIII. Regional Quality Assurance and Quality Control
IX Internal Standards (CCS)
X. Target Compound Identification
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XII. Tentatively Identified Compounds
XIII. System Performance
XIV. Overall Assessment of Data
Note: "CCS" indicates that the contractual requirements for these items will also be checked by CCS;
CCS requirements are not always the same as the data review criteria.
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VOA
I. Technical Holding Times
A. Review Items: Form I VOA, EPA Sample Traffic Report and/or chain-of-custody, raw data, and SDG
Narrative.
B. Objective
The objective is to ascertain the validity of results based on the holding time of the sample from time
of collection to time of analysis.
C. Criteria
Technical requirements for sample holding times have only been established for water matrices. The
holding times for soils (and other non-aqueous matrices such as sediments, oily wastes, and sludge)
are currently under investigation, in Region III, a 14 day holding time will be applied to all non-aqueous
samples. When soil holding time criteria are established and available, the procedure for qualifying soil
samples will be re-evaluated.
The holding time criteria for water samples, as stated in the current 40 CFR Part 136 (Clean Water Act)
is as follows:
For non-aromatic volatile compounds In cooled (@ C) water samples, the maximum holding time
is 14 days from sample collection.
Maximum holding times for purgeable aromatic hydrocarbons in cooled (@ C _± 2fC), acid-
preserved (pH 2 or below) water samples are 14 days from sample collection.
Water samples that have not been maintained at 4*C (± 2fC) and/or preserved to a pH of 2 or
. below should be analyzed within 7 days from sample collection. If insufficient ice is used to ship
samples, the laboratory may receive samples with no Ice left in the cooler. Under these
circumstances, the temperature of the samples may exceed C.
It r further required that volatile compounds in properly preserved non-aqueous samples be analyzed
within 14 days of sample collection for all volatile compounds.
The contractual maximum holding times which differ from the technical maximum holding times state
that water and soil samples are to be analyzed within 10 days from the validated time of sample receipt
(VTSR) at the laboratory.
D. Evaluation
Technical holding times are established by comparing the sampling dates on the EPA Sample Traffic
Report with dates of analysis on Form I VOA and the raw data. Information contained in the complete
SDG file (formerly called the purge file) should also be considered in the determination of holding times.
Verify that the analysis dates on the Form Is and the raw data/SDG file are identical. Examine the
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sample records to determine if samples were preserved. If adequate documentation on sample
preservation is not available, contact the sampler. If the sampler cannot be contacted,- then it must be
assumed that the samples are unpreserved. If there is no indication in the SDG narrative or the sample
records that there was a problem with the samples (e.g., samples not maintained @ C or containing
headspace in the samples), then the integrity of samples can be assumed to be good. If it is indicated
that there were problems with the samples, then the integrity of the sample may have been
compromised and professional judgement should be used to evaluate the effect of the problem on the
sample results.
E. Action
1. If technical holding times are exceeded, document in the data review narrative that holding times
were exceeded and qualify the sample results as follows. (Also see Table 1).
If there is no evidence that the aqueous samples were properly preserved and the technical
holding times exceeded 7 days, qualify positive results with "L" and sample quantitation limits
with "UL" for all aromatic compounds. Use professional judgement to determine if and how non-
aromatic volatile compounds should also be qualified.
If the samples were property preserved but the technical holding times exceeded 14 days, for
aqueous and non-aqueous samples, qualify all positive results with V and all sample
quantitation limits with "UL".
Table 1. Qualification of Volatile Analytes Based on Technical Holding Times
Matrix
Preserved
> 7 DAYS
> 14 DAYS
Water
No
All Aromatics*
All Compounds
Yes
None
All Compounds
Non-aqueous
No/Yes
None
All Compounds
* Reviewer should use professional judgement to determine if data for additional
compounds require qualification.
2. If technical holding times are grossly exceeded (e.g., by greater than two times the required time
for volatiles) either on the first analysis or upon re-analysis, the reviewer must use professional
judgement to determine the reliability of the data and the effects of additional storage on the sample
results. Should the reviewer determine that qualification is necessary, non-detected volatile target
compounds may be qualified unusable "R". Positive results are considered bias low and are qualified
with "L".
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3. Due to limited information concerning holding times for non-aqueous samples, it is recommended
that a comment in the data review narrative be included to state that a holding time of 14 days was
used.
4. Whenever possible, the reviewer should comment on the effect of the analysis beyond the holding
time on the resulting data in the data review narrative.
5. When contractual and/or technical holding times are exceeded, this should be noted on the Organic
Regional Data Summary (ORDAS) form.
6. The reviewer should also be aware of the scenario in which the laboratory has exceeded the
technical holding times, but met contractual holding times. In this case, the data reviewer should
notify the Regional TPO (where samples were collected) and/or RSCC that shipment delays may
have occurred so that the field and/or shipping problem can be corrected. The reviewer may pass
this information on to the Regional TPO for that laboratory, but should explain that contractually the
laboratory met the requirements.
7. When there are other quality control problems in conjunction with exceeded holding times (such as
suspected laboratory contamination), the reviewer should follow the hierarchy of qualifiers. In
particular, if for any reason the reviewer doubts the presence of a compound, the data summary
form should display only the "B" or "R" qualifier and not the "L" qualifier. This is because no net
direction of bias can be inferred under these conditions. When results are reported by the laboratory
as below the CRQL, the "L" qualifier is used over the "J" qualifier.
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II. GC/MS Instrument Performance Check
A. Review Items: Form V VOA, BFB mass spectra and mass listing.
B. Objective
Gas chromatograph/mass spectrometer (GC/MS) instrument performance checks (formerly referred to
as tuning) are performed to ensure 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
The analysis of the instrument performance check solution must be performed at the beginning of each
12-hour period during which samples or standards are analyzed. The instrument performance check,
bromofluorobenzene (BFB) for volatile analysis, must meet the ion abundance criteria given below.
Bromofluorobenzene (BFB)
m/z ION ABUNDANCE CRITERIA
50 8.0 - 40.0% of m/z 95
75 30.0 - 66.0% of m/z 95
95 Base peak, 100% relative abundance
96 5.0 - 9.0% Of m/z 95
173 Less than 2.0% of m/z 174
174 50.0 - 120.0% Of m/z 95
175 4.0 - 9.0% of mass 174
176 93.0 -101.0% of m/z 174
177 5.0-9.0% Of m/z 176
NOTE: All ion abundances must be normalized to m/z 95, the nominal base peak, even though the ion
abundance of m/z 174 may be up to 120 percent that of m/z 95.
D. Evaluation
1. Compare the data presented for each I nstrument Performance Check (Form V VOA) with each mass
listing submitted to ensure the following:
Form V VOA is present and completed for each 12-hour period during which samples were
analyzed.
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GC/MS Instrument Performance Check
The laboratory has not made transcription errors between the raw 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.
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. (See SOW
for requirements).
The laboratory has not made calculation errors.
2. 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.
3. Verify that the ion abundance criteria was met. The criteria for m/z 173,176, and 177 are calculated
by normalizing to the specified m/z.
4. 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.
Three scans (the peak apex scan and the scans immediately preceding and following the apex) are
acquired and averaged and background subtraction must be accomplished using a single scan prior
to the elution of BFB.
NOTE: All instrument conditions must be identical to those used in 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 objectives and are therefore unacceptable.
E. Action
1. 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.
2. 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 then the reviewer must use professional judgement
to assess the data. This should be noted on the ORDAS form.
3. If mass assignment is in error (such as m/z 96 is indicated as the base peak rather than m/z 95),
classify all associated data as unusable (R).
4. If ion abundance criteria are not met, professional judgement may be applied to determine to what
extent the data may be utilized. Guidelines to aid in the application of professional judgement to
this topic are discussed as follows:
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GC/MS Instrument Performance Check
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.
5. Decisions to use analytical data associated with BFB instrument performance checks not meeting
contract requirements should be clearly noted in the data review narrative.
6. If the reviewer has reason to believe that instrument performance check criteria were achieved using
techniques other than those described in II.D.4, then additional information on the instrument
performance checks should be obtained. If the techniques employed are found to be at variance
with the contract requirements, the performance and procedures of the laboratory may merit
evaluation. Concerns or questions regarding laboratory performance should be noted for TPO
action in the ORDAS form. 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 the BFB peak), then this
should be noted for TPO action in the ORDAS form.
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III. Initial Calibration
A. Review Items: Form VI VOA, 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.
C. Criteria
1. Initial calibration standards containing both volatile target compounds and system monitoring
compounds are analyzed at concentrations of 10, 20, 50, 100, and 200 ug/L at the beginning of
each analytical sequence or as necessary if the continuing calibration 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.
2. Separate initial calibrations must be performed for water samples (or medium level soil samples) and
for low level soil samples. The calibration for water samples and medium level soil samples is
performed with an unheated purge and the calibration for low level soil samples is performed with
a heated purge.
3. initial calibration standard Relative Response Factors (RRFs) for volatile target compounds and
system monitoring compounds (surrogates) must be greater than or equal to 0.05. (Contractual
initial calibration RRF criteria are listed in Appendix A).
4. The Percent Relative Standard Deviation (%RSD) from the initial calibration must be less than or
equal to 30.0% for all compounds. (Contractual calibration %RSD criteria are listed in Appendix A).
D. Evaluation
1. Verify that the correct concentration of standards were used for the initial calibration (i.e., 10, 20,
50, 100, and 200 ug/L for water).
2. Verify that the correct initial calibration was used for water and medium level soil samples (i.e.,
unheated purge) and for low level soil samples (i.e., heated purge).
3. If any sample results were calculated using an initial calibration, verify that the correct standard (i.e.,
the 50 ug/L standard) was used for calculating sample results and that the samples were analyzed
within 12 hours of the associated instrument performance check.
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4. Evaluate the initial calibration RRFs and RRF for all volatile target compounds and system monitoring
compounds (surrogates):
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 ail volatile target compounds and system monitoring compounds, the initial
calibration RRFs are greater than or equal to 0.05.
NOTE: Because historical performance data Indicate poor response and/or erratic behavior, the volatile
compounds In Table 2 have no contractual maximum %RSD criteria. Contractually they must
meet a minimum RRF criterion of 0.01; however, for data review purposes, the "greater than
or equal to 0.05" criterion is applied to all volatile compounds.
Table 2. Volatile Target Compounds Exhibiting Poor Response
Acetone
2-Butanone
Carbon disulfide
Chloroethane
Chloromethane
1,2-Dichloroethene (total)
1,2-Dichloropropane
2-Hexanone
Methylene chloride
4-Methyl-2-pentanone
Toluene-d8
1,2-Dichloroethane-d4
NOTE: Compounds in bold are system monitoring compounds.
5. Evaluate the %RSD for all volatile target compounds and system monitoring compounds:
a. Check and recalculate the %RSD for one or more volatile target compound(s) associated with
each internal standard; verify that the recalculated value(s) agrees with the laboratory reported
value(s).
b. Verify that all volatile target compounds have a %RSD of less than or equal to 30.0%. The
contractual criteria for an acceptable initial calibration specifies that up to any 2 volatile target
compounds may fail to meet minimum RRF or maximum %RSD as long as they have RRFs that
are greater than or equal to 0.010, and %RSD of less than or equal to 40.0%. For data review
purposes, however, all compounds must be considered for qualification when the %RSD
exceeds the ± 30.0% criterion.
c. If the %RSD is greater than 30.0%, then the reviewer should use professional judgement 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.
6. If errors are detected in the calculations of the initial calibration for either RRF or %RSD, perform
a more comprehensive evaluation.
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initial Calibration
E. Action
1. All volatile target compounds, including the 9 "poor performers" (see Table 2, system monitoring
compounds are excluded) will be qualified using the following criteria:
a. If the %RSD is greater than 30.0% and all initial calibration RRFs greater than or equal to 0.05,
qualify positive results with "J". Non-detects are not qualified. When the %RSD is grossly
exceeded (i.e., > 50%) use professional judgement for qualifying non-detects as "UJ".
b. If any initial calibration RRF is less than 0.05, qualify positive results that have acceptable mass
spectral identification with "L", and non-detected analytes as unusable, "R".
2. At the reviewer's discretion, a more in-depth review to minimize the qualification of data can be
accomplished by considering the following:
a. If any of the required volatile compounds have a %RSD greater than 30.0%, and if eliminating
either the high or the low point of the curve does not restore the %RSD to less than or equal
to 30.0%:
i. Qualify positive results for that compound (s) with "J".
ii. No qualifiers are needed for volatile target compounds that were not detected. If the %RSD
is grossly exceeded (i.e., >50%), professional judgement is used to qualify non-detects with
"UJ".
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 positive results in the linear portion of the curve.
ii. Qualify positive results outside of the linear portion of the curve with a "J".
iii. No qualifiers are needed for volatile target compounds that were not detected. If the %RSD
is grossly exceeded (i.e., >50%, professional judgement is used to qualify non-detects with
"UJ".
c. If the low end of the curve is outside of the linearity criteria:
i. No qualifiers are required for positive results in the linear portion of the curve.
Ii. Qualify low level positive results in the area of non-linearity with "J".
iii. No qualifiers are needed for volatile target compounds that were not detected. If the %RSD
is grossly exceeded (i.e., >50%), professional judgement is used to qualify non-detects with
"UJ".
NOTE: if a, b, or c options are used, a description of the process must be clearly stated in the data
review narrative.
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3. If the laboratory has failed to provide adequate calibration information, the designated representative
should contact the laboratory and request the necessary information. If the information is not
available, the reviewer must use professional judgement to assess the data.
4. The potential effects on the data due to unacceptable calibration criteria should be noted in the data
review narrative.
5. If calibration criteria are exceeded, this should be noted on the OROAS.
6. When there are other quality control problems in conjunction with exceeding initial calibration
criteria, the reviewer should follow the hierarchy of qualifiers. In particular, if for any reason the
reviewer doubts the presence of a compound, the data summary form should display only the "B"
or "R" qualifier and not the "L" or °J" qualifier.
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IV. Continuing Calibration
A. Review Items: Form VII VOA, 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. Continuing calibration
establishes the 12-hour relative response factors on which the quantitations are based and checks
satisfactory performance of the instrument on a day-to-day basis.
C. Criteria
1. Continuing calibration standards containing both target compounds and system monitoring
compounds are analyzed at the beginning 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. The
continuing calibration may either be a part of the initial calibration or run independently on another
12-hour analysis period.
2. The continuing calibration RRF for volatile target compounds and system monitoring compounds
must be greater than or equal to 0.05.
3. The percent difference (%D) between the initial calibration RRF and the continuing calibration RRF
must be within + 25.0%.
D. Evaluation
1. Verify that the continuing calibration was run at the required frequency and that the continuing
calibration was compared to the correct initial calibration.
2. Evaluate the continuing calibration RRF for all volatile target compounds and system monitoring
compounds:
a. Check and recalculate the continuing calibration 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 all volatile compounds and system monitoring compounds meet the RRF
specifications.
NOTE: Because historical performance data indicate poor response and/or erratic behavior, the
compounds listed in Table 2 (Section III.D.4) have no contractual maximum %D criteria.
Contractually they must meet a minimum RRF criterion of 0.01, however, (or data review
purposes, the "greater than or equal to 0.05* criterion is applied to ail volatile compounds.
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VOA
Continuing Calibration
3. Evaluate the %D between initial calibration RRF and continuing calibration RRF for one or more
compound(s).
a. Check and recalculate the %D for one or more volatile target compound(s) associated with each
internal standard; verify that the recalculated value(s) agrees with the laboratory reported
value(s).
b. Verify that the %D is within _+ 25.0% for all volatile target compounds and system monitoring
compounds. Note those compounds which have a %D outside the ± 25.0% criterion. The
contractual criteria for an acceptable continuing calibration specifies that up to any 2 volatile
target compounds may fail to meet minimum RRF or maximum %D as long as they have RRFs
that are greater than or equal to 0.010, and %D of less than or equal to 40.0%. For data review
purposes, however, all compounds must be considered for qualification when the %D exceeds
the J: 25.0% criterion.
4. If errors are detected in the calculations of either the continuing calibration RRF or the %D, perform
a more comprehensive recalculation.
E. Action
1. The reviewer should use professional judgement to determine if it is necessary to qualify the data
for any volatile target compound. If qualification of data is required, it should be performed using
the following guidelines:
a. if the %D is outside the .+ 25.0% criterion and the continuing calibration RRF is greater than or
equal to 0.05, qualify positive results with "J".
b. If the %D is outside the jf 25.0% criterion and the continuing calibration RRF Is greater than or
equal to 0.05, no qualification of non-detected volatile target compounds is necessary. If the
%D is grossly exceeded (>50%), professional judgement may be used to qualify non-detects
with "UJ".
c. If the continuing calibration RRF is less than 0.05, qualify positive results that have acceptable
mass spectral identifications with "L".
d. If the continuing calibration RRF is less than 0.05, qualify non-detected volatile target compounds
as unusable, "R".
2. If the laboratory has failed to provide adequate calibration information, the designated representative
should contact the laboratory and request the necessary information. If the information is not
available, the reviewer must use professional judgement to assess the data.
3. The potential effects on the data due to unacceptable calibration criteria should be noted In the data
review narrative.
4. If calibration criteria are exceeded, this should be noted in the ORDAS.
5. When there are other quality control problems in conjunction with exceeding continuing calibration
criteria, the reviewer should follow the hierarchy of qualifiers. In particular, if for any reason the
reviewer doubts the presence of a compound, the data summary form should display only the "B"
cr "R" qualifier and not the "L" or "J" qualifier.
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Region III Modifications
VOA
V. Blanks
A. Review Items: Form I VOA, Form IV VOA, chromatograms, and quantitation reports.
B. Objective
The purpose of laboratory (or field) blank analysis is to determine the existence and magnitude of
contamination resulting from laboratory (or field) activities. The criteria for evaluation of blanks apply
to any blank associated with the samples (e.g., methods blanks, Instrument blanks, trip blanks, and
equipment 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. No contaminants should be found in the blanks.
2. A method blank analysis must be performed after the calibration standards and once for every 12-
hour time period beginning with the injection of BFB.
3. The method blank must be analyzed on each GC/MS system used to analyze samples for each type
of analysis, i.e., unheated purge (water and medium level soil) and heated purge (low level soil).
4. An instrument blank should 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.
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.
2. Verify that a method blank analysis has been reported per matrix, per concentration level 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 l V VOA) to identify the samples associated with each method
blank.
3. Verify that the instrument blank analysis has been performed following any sample analysis where
a target analyte(s) is reported at high concentration(s).
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Region III Modifications
Blanks VOA
E. Action
If the appropriate blanks were not analyzed with the frequency described in Criteria 2,3, and 4, then the
data reviewer should use professional judgement to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the laboratory. The situation
should be noted for TPO action on the ORDAS form.
Action regarding unsuitable blank results depends on the circumstances and origin of the blank. Positive
sample results should be reported and qualified "B", If the concentration of the compound in the sample
is less than or equal to 10 times (10x) the amount in any blank for the common volatile laboratory
contaminants (methylene chloride, acetone, and 2-butanone), or 5 times (5x) the amount for other
volatile target compounds. In situations where more than one blank Is associated with a given sample,
qualification should be based upon a comparison with the blank having the highest concentration of a
contaminant The results must not be corrected by subtracting any blank value.
For qualification purposes, consider all blanks in a case associated with all samples.
Field blanks measure contamination introduced not only in the field but also from the laboratory. In
general, evaluation of the impact on specific sample results is handled the same as with laboratory
blanks. The reviewer should use caution in attributing contamination to the field as opposed to
laboratory sources. However, when field-introduced contamination is suspected, it is helpful for the
reviewer to consult the sampling group to identify possible sources and prevent future reoccurrences.
Verified field sources of contamination should be noted in the data review narrative. If a field blank has
the highest concentration of a contaminant, then all samples in the associated case are qualified "B",
using the 5x and 10x rule. Other field blanks associated with the case are not qualified.
Specific actions are as follows:
1. If a volatile compound is found in a blank but not found in the sample, no action is taken. If the
contaminants found are volatile target compounds (or interfering non-target compounds) at
significant concentrations above the CRQL, then this should be noted for TPO action in the ORDAS.
2. Any volatile compound detected in the sample (other than the common volatile laboratory
contaminants), that was also detected in any associated blank, is qualified *B", when the sample
concentration is less than five times (5x) the blank concentration. For common volatile laboratory
contaminants, the results are qualified "B", when the sample concentration is less than 10 times (10x)
the blank concentration.
3. The reviewer should note that blanks may not involve the same weights, volumes, or dilution factors
as the associated samples. These factors must be taken into consideration when applying the "5x°
and "10x" criteria, such that a comparison of the total amount of contamination is actually made.
Additionally, 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, he/she should qualify the data.
Contamination introduced through dilution water is one example. Although it is not always possible
to determine, instances of this occurring it can be detected when contaminants are found in the
diluted sample result but are absent in the undiluted sample result. Since both results are not
routinely reported, it may be impossible to verify this source of contamination.
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Region III Modifications
Blanks VOA
4. If gross contamination exists (i.e., saturated peaks by GC/MS), all affected compounds in the
associated samples should be qualified as unusable "R" due to interference. This should be noted
for TPO action in the ORDAS if the contamination is suspected of having an effect on the sample
results.
5. If inordinate numbers of other target compounds are found at low levels in the b!ank(s), it may be
indicative of a problem and should be noted for TPO action in the ORDAS form.
6. The same consideration given to the target compounds should also be given to Tentatively Identified
Compounds (TICs), which are found in both the sample and associated blank(s). (See VOA Section
X!!l for TIC guidance.)
7. If an instrument blank was not analyzed following a sample analysis which contained an analyte(s)
at high concentration®, sample analysis results after the high concentration sample must be
evaluated for carryover. Professional judgement should be used to determine if instrument cross-
contamination has affected any positive compound identification®. If instrument cross-
contamination is suggested, then this should be noted for TPO action if the cross-contamination is
suspected of having an effect on the sample results. Sample results which are possible artifacts of
carry-over should be flagged as unusable "R".
8. When there is convincing evidence that contamination is restricted to a particular instrument, matrix,
or concentration level, the 5x/10x rule will only be applied to compare contaminated blanks to
certain associated samples (as opposed to all samples in the case). Some examples are as follows:
Column bleed (siloxanes) may be localized to a particular instrument.
Methanol extractions in the medium soil volatile analysis protocol can give rise to contaminants that
are not seen in the low-level aqueous analyses.
Common laboratory contaminants, such as methylene chloride, are generally too unpredictable to
safely assume contamination is restricted to a particular instrument, matrix, or concentration level.
9. For benzene and/or toluene, the reviewer may identify that the observed laboratory contamination
is attributable to a specific, regular, and predictable process (such as trap bleed), which results in
a constant 1 or 2 ppb instrument level concentration in all runs (both samples and blanks). In this
situation, the reviewer may want to consider and flag certain results as tentatively identified, "N", as
opposed to "B", if the sample instrument level is clearly greater than the consistent level of
contamination detected in blanks and other samples. (This particular situation supercedes the
5x/10x rule.)
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Region III Modifications
Blanks VOA
10. The following are examples of applying the blank qualification guidelines. Certain circumstances
may warrant deviations from these guidelines. Any deviations must be clearly stated in the data
review narrative.
Example 1: Sample result is greater than the Contract Required Quantitation Limit (CRQL), but is
less than the 5x or 10x multiple of the blank result.
Rule
10x
5x
Blank Result
7
7
CRQL
5
5
Sample Result
60
30
Final Sample Result
60B
30B
In the example for the "10x" rule, sample results less than 70 (or 10 x 7) would be qualified
"8". In the case of the "5x" rule, sample results less than 35 (or 5x7) would be qualified
"B".
Example 2: Sample result is less than the CRQL, and is also less than the 5x or 10x multiple of the
blank result.
Rule
10x jjx
Blank Result 6 6
CRQL 5 5
Sample Result 4J 4J
Final Sample Result 4B 4B
Note that data are reported as 4B, indicating that the qualitative presence is not confirmed.
Example 3: Sample result is greater than the 5x or 10x multiple of the blank result.
Rule
1Qx
5x
Blank Result
10
10
CRQL
5
5
Sample Result
120
60
Final Sample Result
120
60
For both the "10x* and "5x" rules, sample results exceeded the adjusted blank result of 100
(or 10 x 10) and 50 (or 5 x 10), respectively.
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VI. System Monitoring Compounds
(Surrogate Spikes)
A: Review Items: Form II VOA quantitation reports and chromatograms.
B: Objective
Laboratory performance on Individual samples is established by means of spiking activities. All samples
are spiked with system monitoring compounds (formerly referred to as surrogates) prior to sample
purging. The evaluation of the results of these system monitoring compounds is not necessarily
straightforward. The sample itself may produce effects due to such factors as interferences and high
concentrations of analytes. 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 demands analytical experience and professional
judgement. Accordingly, this section consists primarily of guidelines, in some cases with several optional
approaches suggested.
C. Criteria
1. Three system monitoring compounds (1,2-dichioroethane-d4, bromofiuorobenzene, and toluene-
d8) are added to ail samples and blanks to measure their recovery in environmental samples and
blank matrices.
2. Recoveries for system monitoring compounds in volatile samples and blanks must be within the
limits specified in Appendix A and the SOW.
D. Evaluation
1. Check raw data (e.g., chromatograms and quantitation reports) to verify the recoveries on the
System Monitoring Compound Recovery Form - Form II VOA. Check for any calculation or
transcription errors.
2. Check that the system monitoring compound recoveries were calculated correctly. The equation
can be found in Appendix A.
3. The following should be determined from the System Monitoring Compound Recovery form(s):
?. If any system monitoring compound (s) in the volatile fraction is out of specification, there should
be a reanalysis to confirm that the non-compliance is due to sample matrix effects rather than
laboratory deficiencies.
NOTE: When there are unacceptable system monitoring compound recoveries followed by successful
analyses, the laboratories are required to report only the successful run.
b. The laboratory failed to perform acceptably if system monitoring compounds are outside criteria
with no evidence of re-analysis. Medium soils must first be re-extracted prior to re-analysis when
this occurs.
c. Verify that no blanks have system monitoring compounds outside the criteria.
VOA
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Region III Modifications
System Monitoring Compounds
4. Any time there are two or more analyses for a particular sample, the reviewer must determine which
are the best data to report. Considerations should include but are not limited to:
a. System monitoring compound 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 QC information, such as performance of internal standards.
E. Action
Data are qualified based on system monitoring compounds results if the recovery of any volatile system
monitoring compound is out of specification. For system monitoring compound recoveries out of
specification, the following approaches are suggested based on a review of all data from the package,
especially considering the apparent complexity of the sample matrix. (Also, see Table 3.)
1. If a system monitoring compound in the volatile sample has a recovery greater than the upper
acceptance limit:
a. Detected volatile target compounds are qualified "J".
b. Results for non-detected volatile target compounds should be qualified "UJ".
2. If a system monitoring compound in the volatile sample has a recovery greater than or equal to 10%
but less than the lower acceptance limit:
a. Detected volatile target compounds are qualified "J".
b. For non-detected volatile target compounds, the sample quantitation limit is qualified as
approximated, *UJ".
3. If a system monitoring compound in a volatile sample shows less than 10% recovery:
a. Detected volatile compounds are qualified "L".
b. Non-detected volatile target compounds are qualified as unusable, "R".
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Region III Modifications
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System Monitoring Compounds
4. I? two or three system monitoring compounds in the volatile sample have recoveries outside
acceptance limits, refer to Table 3.
Table 3. Qualification of Volatile Anatytes Based on
System Monitoring Compound Recoveries
1 or more
< 10%
1
High/
Low
2 or 3
High/
Low
2 or 3
All Low
2 or 3
All High
Detected
Analytes
L
J
J
L
K
Non-Detected
Analytes
R
UJ
UJ
UL
None
5. In the special case of a blank analysis with system monitoring compounds 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 system monitoring compound 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, analytical problems should be noted for TPO action on the
ORDAS. Also note if there are potential contractual problems associated with the lack of reanalysis
of samples that were out of specification.
6. Whenever possible, , potential effects of the data resulting from system monitoring recoveries not
meeting the advisory limits should be noted in the data review narrative.
7. - Positive results for compounds already flagged for blank contamination, "B", will not need a separate
flag for system monitoring compound recoveries. However, these situations should be addressed
in the data review narrative and the support documentation.
8. When dilutions are performed'which prevent detection of system monitoring compounds, the data
review narrative and support documentation should indicate that extraction efficiency/method
accuracy cannot be verified.
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System Monitoring Compounds
9. When both the initial analysis and the reanalysis have system monitoring compound recoveries
outside of criteria, the data summary form should normally contain the highest concentration
obtained for each compound detected, provided that system monitoring compound recoveries in
the analysis being reported do not suggest a high bias. However, if a demonstrated laboratory
contaminant is detected in one anaiysis but not in the other, the negative result may be more
appropriate to report.
When the reanalysis of a sample is within the system monitoring compound recovery criteria, the
laboratory is required to provide only data for the acceptable analysis. If both sets of data are
provided, and if a compound was detected in the initial analysis but not in the reanalysis, then the
positive result should be reported (provided the compound is not a demonstrated laboratory
contaminant). The reported result should be flagged as estimated 'J*, due to possible sample
inhomogeneity.
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VII. Matrix Spike/Matrix Spike Duplicate
A. Review Items: Form III VOA-I and VOA-2, chromatograms, and quantitation reports.
B. Objective
Data for matrix spike/matrix spike duplicates (MS/MSD) are generated to determine long-term precision
and accuracy of the analytical method on various matrices 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 judgement,
this data should be used in conjunction with other available QC information.
C. Criteria
1. Matrix spike (MS) and matrix spike duplicate (MSD) samples are analyzed at a frequency of one MS
and MSD per 20 samples of similar matrix.
2. Spike recoveries should be within the advisory limits provided on Form III VOA-1 and VOA-2 and
SOW.
3. Relative percent difference (RPD) between MS and MSD recoveries must be within the advisory limits
provided on Form ill VOA-1 and VOA-2 and SOW.
D. Evaluation
1. Verify that MS and MSD samples were analyzed at the required frequency and that results are
provided for each sample matrix.
2. Inspect results for the MS/MSD Recovery on Form III VOA-1 and VOA-2 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 matrix spike recoveries and RPDs were calculated correctly.
5. Compare %RSD results of non-spiked compounds between the original result, MS, and MSD.
E. Action
1. No action is taken on MS/MSD data alone. However, using informed professional judgement, 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.
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Region III Modifications
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Matrix Spike/Matrix Spike Duplicate
2. The data reviewer should first try to determine to what extent the results of the MS/MSD affect the
associated data. This determination should be made with regard to the MS/MSD sample itself as
well as specific analytes for all samples associated with the MS/MSD.
3. In those instances where it can be determined that the results of the MS/MSD affect only the sample
spiked, then qualification should be limited to this sample alone. However, it may be determined
through the MS/MSD results that a laboratory is having a systematic problem in the analysis of one
or more analytes, which affects all associated samples.
4. The reviewer must use professional judgement to determine the need for qualification of positive
results of non-spiked compounds.
5. When non-spiked compounds are present in either the MS or MSD results, a table in the data review
narrative is constructed showing original (unspiked) sample results for non-spiked compounds, non-
spiked compounds present in the MS and MSD and the calculated %RSD.
NOTE: If a field blank was used for the MS/MSD, a statement to that effect must be included on the
ORDAS and noted for the TPO.
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VOA
VIII. Regional Quality Assurance and Quality Control
A. Review Items: Form I VOA, chromatograms, and quantitation reports, and QAPjP.
B. Objective
Regional Quality Assurance and Quality Control (QA/QC) refer to any QA and/or QC samples initiated
by the Region, including field duplicates, Performance Evaluation (PE) samples, blind spikes, and blind
blanks.
C. Criteria
Criteria are dependent on the type of QC sample. Frequency may vary.
1. The analytes present in the PE sample must be correctly identified and quantitated.
D. Evaluation
1. Evaluation of Performance Evaluation (PE) Samples are not to be presented as part of the data
review. All Form is associated with the Performance Evaluation Samples are to be sent (with a
cover memo stating the case number and laboratory information) directly to the Quality Assurance
Branch in Region III.
U.S. Environmental Protection Agency
Region III, Central Regional Laboratory
Quality Assurance Branch
839 Bestgate Road
Annapolis, MD 21401
. Attn: Program Support Section
2. Percent difference between target compounds present in the field duplicate samples shall be
determined. Evaluation of the percent difference compared to those specified in the site QAPjP may
be presented in the data review narrative.
E. Action
1. Field duplicate results are to be presented in a table format in the data review narrative. If target
compounds were not present in either of the field duplicate samples, then a table is not required.
The percent difference is to be calculated and presented in the table. (If one of the field duplicates
was also used as a matrix spike/matrix spike duplicate sample, then the table should include any
non-spiked compounds detected, along with the relative standard deviation.)
No action is taken based on percent difference of field duplicate sample data alone. However using
informed professional judgement the data reviewer may use the field duplicate results in conjunction
with other QC criteria to determine the need for some qualification of the data.
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Regional Quality Assurance and Quality Control
2 Other types of Regional QC Samples
Region 111 Modifications
VOA
Professional judgement is needed for evaluating other types of QC samples that may be associated
with a particular case of samples. This information may be used in conjunction with other QC
criteria to determine the need for qualification of data.
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Region ill Modifications
VOA
IX. Internal Standards
A. Review Items: Form VII VOA. quantitation reports, and chromatograms.
B. Objective
Internal Standards (IS) performance criteria ensures that GC/MS sensitivity and response are stable
during each analysis.
C. Criteria
1. Internal standard area counts must not vary by more than a factor of two (-50% to +100%) from the
associated calibration standard.
2. The retention time of the internal standard must not vary more than_+30 seconds from the retention
time of the associated calibration standard.
D. Evaluation
1. Check raw data (e.g., chromatograms and quantitation lists) to verify the internal standard retention
times and areas reported on the Internal Standard Area Summary (Form VIII VOA).
2. Verify that all retention times and IS areas are within criteria.
3. If there are two analyses for a particular fraction, the reviewer must determine which are the best
data to report. Considerations should include:
a. Magnitude and direction of the IS area shift.
b. Magnitude and direction of the IS retention time shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each fraction.
"c. Other QC.
E. Action
1. If an IS area count for a sample or blank is outside -50% or +100% of the area for associated
standard, then:
a. Positive results for compounds quantitated using that IS should be qualified as estimated, "J".
b. Non-detected compounds quantitated using an IS area count greater than +100% or less that
50% should be qualified "UJ".
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Region III Modifications
VOA
internal Standards
c. if extremely low area counts are reported, or if performance exhibits a major abrupt drop-off then
a severe loss of sensitivity is indicated. Non-detected target compounds jshould then be
qualified as unusable, "R".
2. if an IS retention time varies by more than 30 seconds:
The chromatographic profile for that sample must be examined 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. Positive results should not need to be qualified as "R",
if tha mass spectral criteria are met.
3. If the internal standards performance criteria are grossly exceeded, then this should be noted for
TPO action in the ORDAS. Potential affects on the data resulting from unacceptable internal
standard performance should be noted in the data review narrative.
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Region III Modifications
VOA
X. Target Compound Identification
A. Review Items: Form I VOA, quantitation reports, mass spectra, and chromatograms.
B. Objective
The objective of the criteria for QC/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).
C. Criteria
1. The relative retention times (RRTs) must be within.* 0.06 RRT units of the standard RRT.
2. Mass spectra of the sample compound and a current laboratory-generated standard (i.e., the mass
spectrum from the associated calibration standard) 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. (Example: For an ion with an abundance of 50% in the standard spectrum, the
corresponding sample ion abundance must be between 30% and 70%.)
c. Ions present at greater than 10% in the sample mass spectrum but not present in the standard
spectrum must be considered and accounted for.
D. Evaluation
1. Check that the RRT of reported compounds is within _+ 0.06 RRT units of the standard RRT.
2. Check the sample compound spectra against the laboratory standard spectra to see that it meets
the specified criteria.
3. The reviewer should be aware of situations (e.g., high concentration samples preceding low
concentration samples ) when sample carry-over is a possibility and should use professional
judgement to determine if instrument cross-contamination has affected any positive compound
identification. The SOW specifies that an instrument blank must be run after samples in which a
target analyte ion(s) saturates the detector.
4. Check the chromatogram to verify that peaks are accounted for; i.e., major peaks are either
identified as target compounds, TICs, system monitoring compounds, or internal standards.
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Region III Modifications
VOA
Target Compound Identification
E. Action
1. The application of qualitative criteria for GC/MS analysis of target compounds requires professional
judgement. It is up to the reviewer's discretion to obtain additional information from the laboratory.
If it is determined that incorrect identifications were made, all such data should be qualified as not
detected "IT. The data review narrative and support documentation would verify that the
misidentified peak was library searched as a TIC, if appropriate.
2. Professional judgement must be used to qualify the data if it is determined that cross-contamination
has occurred.
3. If the presence of a target compound is strongly suggested by raw data, but its mass spectrum
contains minor inadequacies, the compound may be added to the data summary form and qualified
as a tentative identification, "N". The reviewer should address corroborating evidence in the
narrative, such as the presence of the compound in closely related compounds in the same sample.
4. If the laboratory did not report a compound of acceptable matching quality, the reviewer should add
this compound to the sample data summary form. The narrative and the support documentation
should indicate this action, as well as on the ORDAS. The reviewer should request the laboratory
to reexamine and resubmit the result, particularly if the value is greater than the CRQL
5. Any changes made to the reported compounds or concerns regarding target compound
identifications should be clearly indicated in the data review narrative. The necessity for numerous
or significant changes should be noted for TPO action on the ORDAS.
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Region ill Modifications
VOA
XI. Compound Quantitation and Reported CRQLs
A. Review Items: Form I VOA, sample preparation sheets, SDG narrative, quantitation reports, and
chromatograms.
B. Objective
The objective is to ensure that the reported quantitation results and Contract Required Quantitation
Limits (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 RRFs must be calculated based on the internal standard (IS) associated with that
compound, as listed in Appendix A (also as specified in the SOW) for packed column analyses. For
analyses performed by capillary column method (EPA Method 524.2),the target compounds will not
necessarily be associated with the same internal standard as in the packed column, depending on
the compound elution order. Quantitation must be based on the quantitation ion (m/z) specified
in the SOW for both the IS and target analytes. The compound quantitation must be based on the
RRF from the appropriate daily standard.
D. Evaluation
1. For all fractions, raw data should be examined to verify the correct calculation of all sample results
reported by the laboratory. Quantitation lists and chromatograms should be compared to the
reported positive sample results and quantitation limits. Check the reported values.
2. Verify that the correct internal standard, quantitation ion, and RRF were used to quantitate the
compound. Verify that the same internal standard, quantitation ion, and RRF are used consistently
through out, in both the calibration as well as the quantitation process. For analyses performed by
capillary column, the reviewer should use professional judgement to determine that the laboratory
has selected the appropriate internal standard.
3. Verify that the CRQLs have been adjusted to reflect all sample dilutions and dry weight factors that
are not accounted for by the method.
E. Action
1. If any discrepancies are found, the laboratory may be contacted by the designated representative
to obtain additional information that could resolve any differences. If a discrepancy remains
unresolved, the reviewer must use professional judgement to decide which value is the best value.
Under these circumstances, the reviewer may determine qualification of data is warranted. A
description of the reasons for data qualification and the qualification that is applied to the data
should be documented in the data review narrative and in the document support.
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Region III Modifications
VOA
Compound Quantitation and Reported CRQLs
2. Calculation errors can sometimes be revealed by abnormally high system monitoring compound
recoveries, matrix spike recoveries, or inappropriately high results for certain compounds.
3. The reviewer must assure that any results in error by more than 10 percent are identified and
corrected on the sample data summary. If laboratory resubmission is not performed, the reviewer
should document his/her changes to the data In the narrative and support documentation.
Calculation errors should also be noted on the ORDAS.
4. If a sample concentration is above the highest standard and contract required dilutions were not
performed, the TPO should be informed on the ORDAS. The chromatogram and mass spectrum
should be examined for signs of a saturated signal. If the ion used for quantitation was saturated,
then the result should be flagged as biased low, "L". If the ion used for quantitation was not
saturated, the result should be flagged as estimated, "J*.
5. Numerous or significant failures to accurately quantify the target compound or to properly evaluate
and adjust CRQLs should be noted for TPO action on the ORDAS.
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XII. Tentatively Identified Compounds
A. Review Items: Form I VOA-TIC chromatograms, and library search printout and spectra for
three tentatively identified compounds (TIC) candidates.
B. Objective
Chromatographic peaks in volatile fraction analyses that are not target analytes, system monitoring
compounds or internal standards are potential Tentatively Identified Compounds (TICs). TICs must be
qualitatively identified by a National Institute of Standards and Technology (NIST) mass spectral library
search and the identifications assessed by the data reviewer.
C. Criteria
For each sample, the laboratory must conduct a mass spectral search of the NIST library and report the
possible identity for the 10 largest volatile fraction peaks which are not system monitoring compounds,
internal standards, or target compounds, but which have an area or height greater than 10 percent of
the area or height of the nearest internal standard. TIC results are reported for each sample on the
Organic Analyses Data Sheet (Form I VOA-TIC).
NOTE: Since the SOW revision of October 1986, the CLP does not allow the laboratory to report as
Tentatively Identified Compounds any target compound which is properly reported in another
fraction. For example, late eluting volatile target compounds should not be reported as
semivolatile TICs.
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. Ions present in the sample spectrum but not in the reference spectrum should be reviewed for
possible background contamination, interference or coeiution of additional TIC or target
compounds.
e. When the above criteria are not met, but in the technical judgement of the data reviewer or mass
spectral interpretation specialist the identification is correct, the data reviewer may report the
identification.
f. If in the data reviewer's judgement the identification is uncertain or there are extenuating factors
affecting compound identifications, the TIC result may be reported as "unknown".
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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. Blank chromatograms should be examined 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 percent of the internal standard height, but present in the blank
chromatogram at a similar relative retention time.
4. All mass spectra for every sample and blank must be examined.
5. Since TIC library searches often yield several candidate compounds having a close matching score,
all reasonable choices must be considered.
6. The reviewer should 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:
a. Common laboratory contaminants: CO, (m/z 44), siloxanes (m/z 73), diethyl ether, hexane,
certain freons (1,1,2-trichloro-1,2,2-trifiuoroethane or fiuorotrichloromethane), and phthalatesat
levels less than 100 ug/L or 4000 ug/Kg.
b. Solvent preservatives such as cyclohexene which is a methylene chloride preservative. Related
by-products include cyclohexanone, cyclohexenone, cyclohexanol, cyclohexenol,
chlorocyclohexene, and chlorocyclohexanol.
c. Aidol 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.
7. Occasionally, 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. If the total area
quantitation method was used, the reviewer should request that the laboratory recalculate the result
using the proper quantitation ion. In addition, the reviewer should evaluate other sample
chromatograms and check library reference retention times on quantitation lists to determine whether
the false negative result is an isolated occurrence or whether additional data may be affected.
8. Target compounds could be Identified in more than one fraction. Verify that quantitation is made
from the proper fraction.
9. Library searches should not be performed on internal standards or system monitoring compounds.
10. TIC concentration should be estimated assuming a RRF of 1.0.
11. See Appendix B for additional guidance.
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Tentatively Identified Compounds
E. Action
1. Al! TIC results should be qualified "J", estimated concentration, on the laboratory Form l-TICs.
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 not acceptable, the
tentative identification should be changed to "unknown" or an appropriate identification.
b. If all contractually required peaks were not library searched and quantitated, the designated
representative could request these data from the laboratory.
3. Blank Results
Form l-TIC which contain sample results that are questioned by laboratory results, should be flagged
"B" and a line drawn through these data for emphasis (initialed and dated), on the Form l-TIC that
is included in the validation report.
To be considered questionable, a sample TIC concentration must be within 10 times the
concentration of one of the blank results. If different volumes/weights are used, the total amount
of compound in the extract must be compared for sample versus blank. For VOA data, an
instrument level comparison is used unless the contamination is proven to originate during sample
storage (before preparation/analysis). In general, blanks analyzed within the same case, by the
same lab, may be cross-applied to either soil or water samples extracted or analyzed on other days.
To question a sample result, only presumptive evidence for the presence of the compound in the
blank is necessary. The presence of the TIC in the blank is suggested in any of the following
situations:
a. Relative retention times (RRTs) match for sample versus blank, and the sample library search
result matches the same compounder compound class as the library search result for the blank.
b. RRTs match, but library search results do not list the same compound or class for sample versus
blank. However, some of the largest ions in the sample are also in the blank, and a direct
comparison of sample versus blank spectra suggests that the TIC in the sample is quite possibly
the same compound as that in the blank.
c. A peak at the same RRT as the sample TIC is present in the chromatogram of the blank, but no
library search was performed or included in the data. (The labs do not have to library search
peaks less than 10% of the height of the nearest internal standard, although these peaks may
still be important to identify low-level blank contaminants that can question sample results at
levels above 10% of the nearest internal standard height.)
All blank results must be attached in the support documentation section of the data review.
4. When a compound is not found in any blanks, but is a suspected artifact of common laboratory
contaminant, the result may be qualified as unusable, "R", and a line drawn through the result
(initialed and dated) on a copy of the Form l-TIC that is included in the validation report.
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5. In deciding whether a library search result for a TIC represents a reasonable Identification,
professional judgment must be exercised, If there is more than one possible match, the result may
be reported as "either compound X or compound Y". If there is a lack of isomer specificity, the TIC
result may be changed 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-methyi,3-ethyl benzene to substituted aromatic
compound). These changes may be made directly on a copy of the Form l-TIC, as long as changes
are initialed and dated.
C. 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 relative retention time, and the same ions, identification
information may be inferred from the other sample TIC result
7. Physical constants, such as boiling point, may be factored into professional judgment of TIC results.
8. Any changes made to the reported data or any concerns regarding TIC identifications should be
indicated in the data review narrative. Any changes made regarding TIC identifications or
qualifications are to be made on copies of the laboratory generated Form l-TIC and not the originals.
9. Failure to properly evaluate and report TICs should be noted for TPO action on the ORDAS form.
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XIII. System Performance
A. Review Items: Form VIII VOA, Form III VOA-1 and VOA-2, and chromatograms.
B. Objective
During the period following instrument Performance 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 judgement should be applied to
assess the system performance.
O. 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 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.
E. Action
Professional judgement must be used to qualify the data if It is determined that system performance has
degraded during sample analyses. Any degradation of system performance which significantly affected
the data should be documented for TPO action on the ORDAs form.
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XIV. Overall Assessment of Data
A. Review Kerns: Entire data package, data review results, and (if available) Quality Assurance Project
Plan (QAPjP), 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 where necessary, the useabiiity of the data.
C. Criteria
Assess the overall quality of the data.
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 aaaressed.
2. If appropriate information is available, the reviewer may assess the useabiiity of the data to assist
the data user in avoiding inappropriate use of the data. Review all available information, including
the QAPjP (specifically the Data Quality Objectives), SAP, and communication.with data user that
concerns the intended use and desired quality of these data.
E. Action
1. Use professional judgement to determine if there is any need to qualify data which were not qualified
based on the QC criteria previously discussed.
2. Write a brief narrative to give the user an indication of the analytical limitations of the data. Any
inconsistency of the data with the SDG narrative should be noted for TPO action On the ORDAS
form, if sufficient information on the intended use and required quality of the data are available, the
reviewer should include his/her assessment of the useabiiity of the data within the given context.
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sv
SEMIVOLATILE DATA REVIEW
The semivolatile data requirements to be checked are listed below:
1.
Technical Holding Times (CCS - Contractual holding times only)
11.
GC/MS Instrument Performance Check (CCS)
III.
Initial Calibration (CCS)
IV.
Continuing Calibration (CCS)
V.
Blanks (CCS)
VI.
Surrogate Spikes (CCS)
VII.
Matrix Spikes/Matrix Spike Duplicates
VIII.
Regional Quality Assurance and Quality Control
IX.
Internal Standards (CCS)
X.
Target Compound Identification
XI.
Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XII.
Tentatively Identified Compounds
XIII.
System Performance (CCS)
XIV.
Overall Assessment of Data
NOTE: "CCS" indicates that the contractual requirements for these items will also be checked by CCS; CCS
requirements are not always the same as the data review criteria.
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I. Technical Holding Times
A. Review Items: Form I SV-1 and SV-2, EPA Sample Traffic Report and/or chain-of-custody, raw
data, and sample extraction sheets.
B. Objective
The objective is to ascertain the validity of results based on the holding time of the sample from time
of collection to time of sample extraction and analysis.
C. Criteria
Technical requirements for sample holding times have only been established for water matrices.
The holding times for soils (and other non-aqueous matrices such as sediments, oily wastes, and
sludge) are currently under investigation. When the results are available they will be incorporated
into the data evaluation process. Additionally, results of holding time studies will be incorporated
into the data review criteria as the studies are conducted and approved.
The holding time criteria for water samples, as stated in the current 40 CFR Part 136 (Clean Water
Act) is as follows:
For semivolatile compounds in cooled (@ fC) water samples the
maximum holding time is 7 days from sample collection to extraction and
40 days from sample extraction to analysis.
It is further required that semivolatile compounds in properly preserved non-aqueous samples be
extracted within 7 days from sample collection and the extracts analyzed within 40 days from
sample extraction.
The contractual holding times, which differ from the technical holding times, state that water
samples are to be extracted within 5 days from the validated time of sample receipt (VTSR) at the
laboratory, and soil samples are to be extracted within 10 days from the VTSR. Also, contractually
both water and soil sample extracts must be analyzed within 40 days of sample extraction.
However, the contractual delivery due date is 35 days from the VTSR.
D. Evaluation
Technical holding times for sample extraction are established by comparing the sampling date on
the EPA Sample Traffic Report with the dates of extraction on Form I SV-1 and SV-2 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 and SV-2.
Verify that the traffic report indicates that the samples were received intact and iced. If the samples
were not iced or there were any problems with the samples upon receipt, then discrepancies in the
sample condition could effect the data.
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E. Action
1. a. If technical holding times are exceeded, flag all positive results as estimated 'J" and
sample quantitation limits as estimated "UJ" and document that holding times were
exceeded. However, please note that some extractabie compounds are extremely
persistent in the environment (e.g., PAHs) in non-aqueous matrices and would not
be expected to degrade significantly during sample storage. The reviewer must use
professional judgement in the application of data qualifiers to those compounds in
non-aqueous matrices.
b. If in the professional judgement of the data reviewer a loss of semivolatile
compound(s) is evident due to exceeding the holding time criteria, the affected
positive results or the associated quantitation limits may be qualified as biased low,
"L" or "UL" respectively. The narrative must contain the reviewer's justification for
qualification of the compound results as biased low.
2. If technical holding times are grossly exceeded (greater than 2 times the required technical
holding time), either on the first analysis or upon re-analysis, the reviewer must use
professional judgement to determine the reliability of the data and the effects of additional
storage on the sample results. The reviewer may determine that positive results or the
associated quantitation limits are approximates and should be qualified with "J" or "UJ",
respectively. The reviewer may determine that non-detect data are unusable (R).
3. Because of limited information concerning holding times for non-aqueous samples, it is
recommended that a comment in the data review narrative be included to state that
aqueous holding times were applied.
4. Whenever possible, the reviewer should comment on the effect of exceeding the holding
time on the resulting data in the data review narrative.
5. When contractual and/or technical holding times are exceeded, this should be noted on the
ORDAS form.
6. The reviewer should also be aware of the scenario in which the laboratory has exceeded
the technical holding times, but met contractual holding times. In this case, the data
reviewer should notify the Regional TPO (where samples were collected) and/or RSCC that
shipment delays may have occurred so that the field problem can be corrected. The
reviewer may pass this information on to the Regional TPO on the ORDAs, but should
explain that contractually the laboratory met the requirements.
7. When there are other quality control problems in conjunction with exceeded holding times
(such as suspected laboratory contamination), the reviewer should follow the hierarchy of
qualifiers. In particular, if for any reason the reviewer doubts the presence of a compound,
the data summary should display only the "B" or "R" qualifier, and not the 'L' qualifier. This
is because no net direction of bias can be inferred under these conditions.
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II. GC/MS Instrument Performance Check
A. Review Items: Form V SV, and DFTPP mass spectra and mass listing.
B. Objective
Gas chromatograph/mass spectrometer (GC/MS) instrument performance checks (formerly referred
to as tuning) are performed to ensure 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
The analysis of the instrument performance check solution must be performed at the beginning of
each 12-hour period during which samples or standards are analyzed. The instrument performance
check, decafluorotriphenylphosphine (DFTPP) for semivolatile analysis, must meet the ion
abundance criteria given below.
Decafluorotriphenylphosphine (DFTPP)
m/z
ION ABUNDANCE CRITERIA
51
30.0 • 80.0% of m/z 198
68
Less than 2.0% of m/z 69
69
Present
70
Less than 2.0% of m/z 69
127
25.0 - 75.0% of m/z 198
197
Less than 1.0% of m/z 198
198
Base peak, 100% relative abundance
199
5.0 - 9.0% of m/z 198
275
10.0 - 30.0% Of m/z 198
365
Greater than 0.75% of m/z 198
441
Present, but less than m/z 443
442
40.0 -110.0% of m/z 198
443
15.0 - 24.0% Of m/z 442
NOTE: Ail ion abundances must be normalized to m/z 198, the nominal base peak, even though
the ion abundances of m/z 442 may be up to 110 percent that of m/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.
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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 from the raw data (mass spectral listing) that the mass assignment is correct and that
the mass is normalized to m/z 198.
3. Verify that the ion abundance criteria was met. The criteria for m/z 68, 70, 441, and 443
are calculated by normalizing to the specified m/z.
4. 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. Three scans (the peak apex scan and the scans
immediately preceding and following the apex) are acquired and averaged and background
subtraction must be accomplished using a single scan prior to the elution of DFTPP.
NOTE: All instrument conditions must be identical to those used in 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 objectives and are
therefore unacceptable.
E. Action
1. 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.
2. 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, then the reviewer must use
professional judgement to assess the data. The Regional TPO should be notified by noting
the problem(s) on the ORDAS.
3. If mass assignment is in error (such as m/z 199 is indicated as the base peak rather than
m/z 198), classify all associated data as unusable, "R".
4. If ion abundance criteria are not met, professional judgement may be applied to determine
to what extent the data may be utilized. Guidelines to aid in the application of professional
judgement 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
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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 and are very important 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.
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 40% relative abundance (criteria: 10.0-30.0%)
and other criteria are met, then 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.
5. Decisions to use analytical data associated with DFTPP instrument performance checks not
meeting contract requirements should be clearly noted in the data review narrative.
6. if the reviewer has reason to believe that instrument performance check criteria were
achieved using techniques other than those specified in the SOW and II.D.4 above,
additional information on the DFTPP instrument performance checks should be obtained.
If the techniques employed are found to be at variance with contract requirements, the
procedures of the laboratory may merit evaluation. Concerns or questions regarding
laboratory performance should be noted for TPO action on the OBDAS. 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 the DFTPP peak), then this should be
noted for TPO action on the ORDAS.
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SV
III. Initial Calibration
A. Review Hems: Form VI SV-1 and SV-2, 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.
C. Criteria
1. Initial calibration standards containing both semivolatile target compounds and surrogates
are analyzed at concentrations of 20, 50, 80, 120, and 160 ug/L at the beginning of each
analytical sequence or as necessary if the continuing calibration 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.
2. Minimum Relative Response Factor (RRF) criteria must be greater than or equal to 0.05.
Contractual RRF criteria are listed in Appendix A.
3. The Percent Relative Standard Deviations (%RSD) for the RRFs in the initial calibration must
be less than or equal to 30%.
D. Evaluation
1. Verify that the correct concentration of standards were used for the initial calibration (i.e.,
20, 50,80,120, and 160 ug/L). For the eight compounds with higher CRQLs, only a four-
point initial calibration is required (i.e., 50,80,120, and 160 ug/L). (See Appendix A for list).
2. If any sample results were calculated using an initial calibration, verify that the correct
standard (i.e", the 50 ppb standard) was used for calculating sample results and that the
samples were analyzed within 12 hours of the associated instrument performance check.
3. Evaluate the RRFs for all semivolatile target compounds and surrogates:
a. Check and recalculate the RRF and RRF 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 all semivolatile target compounds and surrogates have RRFs that are
greater than or equal to 0.05. If problems are suspected with low response factor
or compound identification, also check elution order.
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NOTE: Because historical performance data indicate poor response and/or erratic behavior, the
semivotatile compounds in Table 4 have no contractual maximum -%RSD criteria.
Contractually they must meet a minimum RRF criteria of 0.01, however, (or data review
purposes, the "greater than or equal to 0.05" criterion is applied to all semivotatile
compounds.
Table 4. Semivolatile Target Compounds Exhibiting Poor Response
2,2'-oxybis(l -Chloropropane) Diethylphthalate
4-Chloroaniline 4-Nitroaniline
Hexachlorobutadiene 4,6-Dinitro-2-methyiphenoi
Hexachlorocyclopentadiene N-Nitrosodiphenylamine
2-N'itroaniline Di-n-butytphthalate
Dimethylphthalate Butylbenzylphthalate
3-Nitroaniline 3-3'-Dichlorobenzidine
2,4-Dinitrophenol bis(2-Ethylhexyl)phthalate
4-Nitrophenol Di-n-octylphthalate
Carbazole
4. Evaluate the %RSD for all semivolatile target compounds and surrogates.
Check and recalculate the %RSD for one or more semivolatile target compound(s);
verify that the recalculated value(s) agrees with the laboratory reported value(s).
Verify that ail semivolatile target compounds have a %RSD of less than or equal to
30%. The contractual criteria for an acceptable initial calibration specifies that up
to any 4 semivolatile target compounds may fail to meet minimum RRF or maximum
%RSD as long as they have RRFs that are greater than or equal to 0.010, and
%RSD of less than or equal to 40.0%. For data review purposes, however, all
compounds must be considered for qualification when the %RSD exceeds the_+
30.0% criterion.
If the %RSD is greater than 30.0%, then the reviewer should use professional
judgement 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.
5. If errors are detected in the calculations of either the RRF or the %RSD, perform a more
comprehensive recalculation.
E. Action
1. All semivolatile target compounds, including the 19 "poor performers" (see Table 4) will be
qualified using the following criteria:
a. If the %RSD is greater than 30.0% and the RRF is greater than or equal to 0.05,
qualify positive results with "J", and non-detected semivolatile target compounds
using professional judgement.
a.
b.
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b. If the RRF Is less than 0.05, qualify positive results that have acceptable mass
spectral identification with "J" using professional judgement, and non-detects as
unusable "R*.
2. At the reviewer's discretion, a more in-depth review to minimize the qualification of data can
be accomplished by considering the following:
a. If any of the required semlvolatile compounds have a %RSD greater than 30.0%,
and if eliminating either the high or the low point of the curve does not restore the
%RSD to less than or equal to 30.0%:
i. Qualify positive results for that compound (s) with "J".
ii. Qualify non-detected semivolatile target compounds based on professional
judgement.
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 positive results in the linear portion of the
curve.
ii. Qualify positive results outside of the linear portion of the curve with "J".
iii. No qualifiers are needed for non-detected target compounds.
c. If the low end of the curve is outside of the linearity criteria:
i. No qualifiers are required for positive results in the linear portion of the
curve.
ii. Qualify low level positive results in the area of non-linearity with "J".
iii. Qualify non-detected semivolatile target compounds using professional
judgement.
3. If the laboratory has failed to provide adequate calibration information, the designated
representative should contact the laboratory and request the necessary information. If the
information is not available, the reviewer must use professional judgement to assess the
data.
4. Whenever possible, the potential effects on the data resulting from a failure to meet
calibration criteria should be noted in the data review narrative.
5. If calibration criteria are grossly exceeded, this should be noted for TPO action on the
ORDAS.
6. When it is suspected that relative response factors were incorrectly generated from
misidentified peaks or incorrect area measurements, the laboratory should be contacted to
requantitate these RRFs and associated sample results. The ORDAS should identify
affected results and document the cause of the reviewer's suspicions. In addition, a CLP
telephone log must be completed.
SV
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Initial Calibration
7. Positive results for compounds flagged for blank contamination "B" will not need a separate
flag "J" in the data summary form for minimum RRF, %RSD, or %D -outside criteria.
However, these situations should be addressed in the data review narrative and issues
pertaining to noncompliance should be documented on the ORDAS.
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IV. Continuing Calibration
A. Review Items: Form VII SV-1 and SV-2, 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 semivolatile
target compounds. Continuing calibration establishes the 12-hour relative response factors on
which the quantitations are based and checks satisfactory performance of the instrument on a
day-to-day basis.
C. Criteria
1. Continuing calibration standards containing both target compounds and surrogates are
analyzed at the beginning of each 12-hour analysis period following the analysis of the
instrument performance check and prior to the analysis of blanks and samples.
2. The minimum Relative Response Factors (RRF) for semivolatile target compounds and
surrogates must be greater than or equal to 0.05.
3. The percent difference (%D) between the initial calibration RRF and the continuing
calibration RRF must be within ± 25.0% for all target compounds.
D. Evaluation
1. Verify that the continuing calibration was run at the required frequency and that the
continuing calibration was compared to the correct initial calibration.
2. Evaluate the continuing calibration RRF for all semivolatile target compounds and
surrogates.'
a. Check and recalculate the continuing calibration RRF for at least one semivolatile
target compound for each internal standard; verify that the recalculated value(s)
agrees with the laboratory reported value(s).
b. Verify that all semivolatile target compounds and surrogates have RRFs within
specifications.
NOTE: Because historical performance data indicate poor response and/or erratic behavior, the
compounds in Table 4 (Section lli.D.3) have no contractual maximum %D criteria.
Contractually they must meet a minimum RRF criterion of 0.01, however, for data review
purposes, the "greater than or equal to 0.05" criterion is applied to all semivolatile
compounds.
3. Evaluate the %D between initial calibration RRF and continuing calibration RRF for one or
more semivolatile compounds.
a. Check and recalculate the %D for at least one semivolatile target compound for
each internal standard; verify that the recalculated value agrees with the laboratory
reported value(s).
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Region III Modifications
SV
Continuing Calibration
b. Verify that the %D is within the _+ 25.0% criterion, for all semivolatile target
compounds and surrogates. Note those compounds which have a %D outside the
_+ 25.0% criterion. The contractual criteria for an acceptable continuing calibration
specifies that up to any 4 semh/olatiJe target compounds may fail to meet minimum
RRF or maximum %D as long as they have RRFs that are greater than or equal to
0.010, and %D of less than or equal to 40.0%. For data review purposes, however,
all compounds must be considered for qualification when the %D exceeds the _+
25.0% criterion.
4. If errors are detected in the calculations of either the continuing calibration RRF or the %D,
perform a more comprehensive recalculation.
E. Action
1. The reviewer should use professional judgement to determine if it is necessary to qualify the
data for any semivolatile target compound, if qualification of data is required, it should be
performed using the following guidelines:
a. If the %D is outside the _± 25.0% criterion and the continuing calibration RRF is
greater than or equal to 0.05, qualify positive results "J".
b. If the %D is outside the.+ 25.0% criterion and the continuing calibration RRF is
greater than or equal to 0.05, qualify non-detected semivolatile target compounds
based on professional judgement.
c. If the continuing calibration RRF is less than 0.05, qualify positive results that have
acceptable mass spectral identification with "J" or use professional judgement.
d. If the continuing calibration RRF is less than 0.05, qualify non-detected semivolatile
target compounds as unusable "R".
2. If the laboratory has failed to provide adequate calibration information, the designated
representative should contact the laboratory and request the necessary information. If the
information is not available, the reviewer must use professional judgement to assess the
data.
3. Whenever possible, the potential effects on the data resulting from a failure to meet
calibration criteria should be noted in the data review narrative.
4. If calibration criteria are grossly exceeded, this should be noted for TPO action on the
ORDAS.
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Continuing Calibration
S V
5. When it is suspected that relative response factors were incorrectly generated from
misidentified peaks or incorrect area measurements, the laboratory should be contacted to
requantitate these RRFs and associated sample results. The ORDAS should identify
affected results and document the cause of the reviewer's suspicions. In addition, a CLP
telephone log must be completed.
6. Positive results for compounds flagged for blank contamination "B" will not need a separate
flag "J* in the data summary form for mininium RRF, %RSD, or %D outside criteria.
However, these situations should be addressed in the data review narrative and issues
pertaining to noncompliance should be documented on the ORDAS.
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V. Blanks
A. Review Items: Form I SV-1 and SV-2, Form IV SV, chromatograms, and quantitation reports.
B. Objective
The purpose of laboratory (or field) blank analyses is to determine the existence and magnitude of
contamination problems resulting from laboratory (or field) activities. The criteria for evaluation of
blanks apply to any blank associated with the samples (e.g., method blanks, instrument blanks, trip
blanks, and equipment blanks). If problems with jny 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. No contaminants should be found in the blanks.
2. The method blank must be analyzed on each QC/MS system used to analyze that specific
group or set of samples.
D. Evaluation
1. Review the results of all associated blank, Form I SV-1 and SV-2, 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 per matrix, per concentration level,
for each extraction batch and for each GC/MS system used to analyze semivolatile
samples. The reviewer can use the Method Blank Summary (Form IV SV) to assist in
identifying samples associated with each method blank.
E. Action
If the appropriate blanks were not analyzed with the frequency described above, then the data
reviewer should use professional judgement to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the laboratory. The situation
should be noted for TPO action on the ORDAS.
Action in the case of unsuitable blank results depends on the circumstances and origin of the blank.
Positive sample results should be reported unless the concentration of the compound in the sample
is less than or equal to 10 times (10x) the amount in any blank for the common phthalate
contaminants, or 5 times the amount for other compounds. In instances where more than one
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. The results must nQt be
corrected by subtracting any blank value.
* For qualification purposes, to determine the highest concentration of a contaminant, consider all
blanks in a case associated with all samples.
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Blanks
Field blanks measure contamination introduced not only In the field but also from the laboratory.
In general, evaluation of the impact on specific sample results is handled as with laboratory blanks.
The reviewer should use caution in attributing contamination to the field as opposed to laboratory
sources. However, when field-introduced contamination is suspected, it is helpful for the reviewer
to consult the sampling group to identify possible sources and prevent future reoccurrences.
Verified field sources of contamination should be noted in the data review narrative. If a field blank
has a highest concentration of a contaminant, then all samples in the associated case are qualified
"3", using the 5x and 10x rule. Other field blanks associated with the case are not qualified.
Specific actions are as follows:
1. If a semivolatile compound is found in a blank but ngt found in the sample, no action is
taken. If the contaminants found are volatile target compounds (or interfering non-target
compounds) at significant concentrations above the CRQL, then this should be noted for
TPO action on the ORDAS.
2. Any semivolatile compound detected in the sample (other than the common phthalate
contaminants), that was also detected in any associated blank, is qualified "B" if the sample
concentration is less than five times (5x) the blank concentration. For phthalate
contaminants, the results are qualified "B" when the sample result is less than 10x the blank
concentration.
In using the 5x/10x rule to compare blank results to sample results which were calculated
using different weights, volumes, or dilution factors, the reviewer must choose between
comparing the levels detected with the instrument, the total amount of compound (ug of
contamination) present in the extracts, or the final concentration of the contaminant in the
sample aliquots. Often, more than one approach will be acceptable and will yield the
equivalent flagging of sample results.
a. Comparisons involving sample dry weight correction factors, but with all other
calculation factors the same for sample versus blank:
o In this case, the reviewer can compare the wet weight concentrations,
instrument levels, or the total amount of compound (ug of contaminant) in
the extracts. All of these approaches will be acceptable and will yield
equivalent flagging of sample results.
b. When the sample has a smaller initial aliquot size than the blank (purge or
extraction weight/volume), but all other calculation factors beyond this analytical
step are identical (i.e., same final extract volumes, injection volumes, and extract
dilution factors for sample versus blank):
o In this case, it is acceptable and equivalent to compare either instrument
levels, the total amount of compound (ug of contaminant) in the extracts,
or the concentration of contaminant in the extracts.
o Final concentrations of sample versus blank should not be compared.
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c. When the sample has a larger final extract volume or a greater dilution factor than
the blank:
o If the laboratory contaminant may have been introduced after or during the
sample dOution step, then a direct comparison of Instrument levels is
appropriate. For example, comparing the instrument level result for a water
sample that was diluted 1:100 prior to injection would take into account
possible laboratory contamination of the syringe, instrument, or dilution
solvent.
o On the other hand, if it is highly probable that the contamination originated
before the dilution step, then it is more appropriate to calculate and
compare the total amount of compound (ug of contaminant) present in the
undiluted extract of the sample versus the blank. For example, a BNA
extract diluted 1:100 prior to injection may only be subject to phthalate
contamination prior to the dilution step (i.e., during
extraction/concentration).
o If the results of a dilution run are to be flagged "B" because of blank
contamination, the reviewer should attempt to determine whether an
undiluted run was also performed. If so, the undiluted run may be used to
verify the presence of a compound detected at levels too high to be
questioned or, conversely, to prove that a compound was actually not
present at levels multiplied by a dilution factor.
The reviewer should note that blanks may not involve the same weights, volumes, or dilution
factors as the associated samples. These factors must be taken into consideration when
applying the "5x* and "10x" criteria, such that a comparison of the total amount of
contamination is actually made.
Additionally, there may be instances where little or no contamination was present in the
associated blanks, but qualification of the sample was deemed necessary. 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 are absent in the undiluted sample result. Since both results are not
routinely reported, it may be impossible to verify this source of contamination. However,
if the reviewer determines that the contamination is from a source other than the sample,
he/she should qualify the data. An explanation of the rationale used for this determination
should be provided in the narrative accompanying the Regional Data Assessment Summary.
3. If gross contamination exists (i.e., saturated peaks by GC/MS), all affected compounds in
the associated samples should be qualified as unusable "R", due to interference. This
should be noted for TPO action if the contamination is suspected of having an effect on the
sample results.
4. If inordinate amounts of other target compounds are found at low levels in the blank(s), it
may be indicative of a problem and should be noted for TPO action.
5. The same consideration given to the target compounds should also be given to Tentatively
Identified Compounds (TICs) which are found in both the sample and associated blank(s).
(See SV Section XII for TIC guidance.)
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Blanks
6. If an instrument blank was not analyzed following a sample analysis which contained an
analyte(s) at high concentration(s), sample analysis results after the high concentration
sample must be evaluated for carryover. Professional judgement should be used to
determine if instrument cross-contamination has affected any positive compound
identification^). if instrument cross-contamination is suggested, then this should be noted
for TPO action If the cross-contamination is suspected of having an effect on the sample
results.
7. Blanks or samples run after a matrix spike or standard should be carefully examined to
determine the occurrence of instrument or syringe carry-over. Since the efficiency of
sample transfer can vary dramatically according to apparatus and operator techniques,
professional judgment should be used in each case to determine whether sample or blank
results are attributable to carry-over. Some common examples are as follows:
o Zero to one percent syringe carry-over occasionally in BNA runs.
o Higher percentages of carry-over following BNA runs that are saturated.
Sample results which are possible artifacts of carry-over should be flagged as unusable,"R".
8. When there is convincing evidence that contamination is restricted to a particular
instrument, matrix, or concentration level, the 5X/10X rule will only be applied to compare
contaminated blanks to certain associated samples (as opposed to all siamples in the case).
Some examples are as follows:
o Column bleed (siloxanes) may be localized to a particular instrument.
o Common laboratory contaminants, such as methylene chloride and phthalates, are
generally too unpredictable to safely assume contamination is restricted to a
particular instrument, matrix, or concentration level.
The following are examples of applying the blank qualification guidelines. Certain circumstances
may warrant deviations from these guidelines.
Example 1: Sample result is greater than the Contract Required Quantitation Limit
(CRQL), but is less than the 5x or 10x multiple of the blank result.
Rule
10x 5x
Blank Result 7 7
CRQL 5 5
Sample Result 60 30
Qualified Sample Result 60B 30B
In the example for the "10x" rule, sample results less than 70 (or 10 x 7)
would be qualified "B". In the case of the "5x" rule, sample results less than
35 (or 5x7) would be qualified "B".
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Blanks
SV
Example 2: Sample result is less than CRQL, and is also less than the 5x or 10x
multiple of the blank result.
Rule
ifix £x
Blank Result
CRQL
Sample Result
Qualified Sample Result
6
5
4J
4B
6
5
4J
4B
Note that data are reported as 4B, indicating that the qualitative presence
is not confirmed.
Example 3: Sample result is greater than the 5x or 10x multiple of the blank result.
Rule
10x jjx
Blank Result
CRQL
Sample Result
Qualified Sample Result
10
5
120
120
10
5
60
60
For both the "10x" and "5x" rules, sample results exceeded the adjusted
blank results of 100 (or 10x10) and 50 (or 5x10), respectively.
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VI. Surrogate Spikes
A. Review Items: Form il SV-1 and SV-2, chromatograms, and quantitation reports.
B. Objective
Laboratory performance on individual samples is established by means of spiking activities. All
samples are spiked with surrogate compounds prior to sample preparation. The evaluation of the
results of these surrogate spikes is not necessarily straightforward. The sample itself may produce
effects because of such factors as interferences and high concentrations of analytes. 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 demands analytical experience and professional judgment. Accordingly,
this section consists primarily of guidelines, in some cases with several optional approaches
suggested.
C. Criteria
1. Surrogate spikes, 4 acid compounds (3 required and 1 advisory) and 4 base/neutral
compounds (3 required and 1 advisory) are added to all samples and blanks to measure
their recovery in sample and blank matrices.
2. Surrogate spike recoveries for semivolatiie samples and blanks must be within the limits
specified in Appendix A and on Form II SV-1 and SV-2 or SOW.
D. Evaluation
1. Check raw data (e.g., chromatograms and quantitation reports) to verify the surrogate spike
recoveries on the Surrogate Recovery Form II SV-1 and SV-2. Check for any transcription
or calculation errors.
2. Check that the surrogate spike recoveries were calculated correctly. The equation can be
found in Appendix A.
3. The following should be determined from the Surrogate Recovery form(s):
a. If any two base/neutral sr acid surrogates are out of specification, or if any one
base/neutral or acid extractable surrogate has a recovery of less than 10%, then
there should be a reanalysis to confirm that the non-compliance is because of
sample matrix effects rather than laboratory deficiencies.
NOTE: When there are unacceptable surrogate recoveries followed by successful re-analyses, the
laboratories are required to report only the successful run.
b. The laboratory has failed to perform satisfactorily if surrogate recoveries are out of
specification and there is no evidence of re-injection of the extract, or re-extraction
and reanalysis (if re-injection fails to resolve the problem).
c. Verify that no blanks have surrogates recoveries outside the criteria.
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Surrogate Spikes SV
4. Any time there are two or more analyses for a particular fraction the reviewer must
determine which are the best data to report. Considerations should 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 fraction.
d. Other QC information, such as performance of internal standards.
5. When both the initial analysis and the reanalysis have surrogate recoveries outside of
criteria, the data summary should normally contain the highest concentration obtained for
each compound detected, provided that surrogate recoveries in the analysis being reported
do not suggest a high bias. However, if a demonstrated laboratory contaminant is detected
in one analysis but not the other, the negative result may be more appropriate to report.
When the reanalysis of a fraction is within surrogate recovery criteria, the laboratory is
required to provide only data for the acceptable analysis. If both sets of data are provided,
and if a compound was detected in the initial analysis but not the reanalysis, then the
positive result should be reported (provided the compound is not a demonstrated laboratory
contaminant). The reported result should be flagged as estimated "J", due to possible
sample inhomogeneity.
6 If advisory surrogates are outside established criteria, professional judgement will be used
in qualifying the sample results. If the results are outside the criteria, then qualification
would only affect similar target compounds.
E. Action
Data are not qualified with respect to surrogate recovery unless two or more semivolatile surrogates,
within the same fraction (base/neutral or acid fraction), are out of specification. For surrogate spike
recoveries out of specification, the following approaches are suggested based on a review of all
data from the case, especially considering the apparent complexity of the sample matrix.
Note: These actions apply to alt surrogates, except for "advisory" surrogates. Professional
judgement should be used in qualifying sample results based on advisory surrogate
recoveries. Qualification based on advisory surrogate recoveries should be applied to
similar compounds in the sample only. Specify in the narrative any actions taken based on
advisory surrogate recovery.
1. If two or more surrogates in either semivolatile fraction (base/neutral or acid fraction) have
a recovery greater than the upper acceptance limit (UL):
a Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.
b. Detected semivolatile target compounds are qualified biased high, "K*.
c. Results for non-detected semivolatile target compounds should not be qualified.
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Surrogate Spikes
2 If two or more surrogates in either semivolatiie fraction have a recovery greater than or
equal to 10% but less than the lower acceptance limit (LL):
a. Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.
b. Detected semivolatiie target compounds are qualified biased low, "L\
c. For non-detected semivolatiie target compounds, the sample quantitation limit is
qualified as biased low, "UL".
3. If any surrogate in either semivolatiie fraction show less than 10% recovery:
a. Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.
b. Detected semivolatiie target compounds are qualified biased low, "L".
c. Non-detected semivolatiie target compounds may be qualified as unusable "R". (If
advisory surrogate limits are not met, use professional judgement to qualify non-
detected compounds).
Table 5. Qualification of Semivolatiie Analytes Based on
Surrogate Recoveries
SURROGATE RECOVERY
2 or 3
2 or 3
2 or 3
1 or more
all high
all low
mixed high/low
<10% rec.
Detected analytes
K
L
J
L
Non-detected analytes
none
UL
UJ
R
4. If two or more surrogate recoveries in either semivolatiie fraction (base/neutral or acid
fraction) are outside surrogate recovery limits, and one of the recoveries is below the lower
limit (but >10%) and the other recovery is above the upper limit:
a. Specify the fraction that is being qualified, i.e., acid, base/neutral, or both.
b. Detected semivolatiie target compounds are qualified as estimated, "J".
c. Non-detected semivolatiie target compounds are qualified as estimated, "UJ".
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Surrogate Spikes
5. 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. However, even if this
judgement allows some use of the affected data, analytical problems should be noted for
TPO action. Also note if there are potential contractual problems associated with the lack
of re-analysis of samples that were out of specification.
6. Whenever possible, the potential effects of the data resulting from surrogate recoveries not
meeting the advisory limits should be noted in the data review narrative.
7. Positive results for compounds already flagged for blank contamination will not need a
separate flag for surrogate recoveries. However, these situations should be addressed in
the narrative or the support documentation.
8. When dilutions are performed which prevent detection of BNA surrogate compounds, the
narrative or support documentation should indicate that extraction efficiency/method
accuracy cannot be verified.
9. Although semivolatile surrogate recoveries cannot usually be correlated with specific
analytes, in the following cases specific action will be allowed based upon a particular
surrogate:
a. When a semivolatile surrogate is the deuterated analog of a TCL analyte (for
example, <4-phenol and phenol), a low recovery for the surrogate can be used to
flag positive results and quantitation limits as biased low for the undeuterated
analog. (This applies even if no other surrogates are outside criteria or if other
surrogates are biased high instead of low.)
b. When d,2-terphenyl is biased low, positive results and quantitation limits for the
heavier poiyaromatic hydrocarbons (those which elute starting with fluorathene) can
be considered as biased low. (This applies even if no other surrogates are outside
criteria or if other surrogates are biased high instead of low.)
c. When 2,4,6-tribromophenol is biased low,positive results and quantitation limits for
trichlorophenols and pentachlorophenoi can be considered as biased low. (this
applies even if no other surrogates are outside criteria or if other surrogates are
biased high instead of low.)
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VII. Matrix Spikes/Matrix Spike Duplicates
A. Review Items: Form 111 SV-1 and SV-2, chromatograms, and quantitation reports.
B. Objective
Data for matrix spikes/matrix spike duplicates (MS/MSD) are generated to determine long-term
precision and accuracy of the analytical method on various matrices 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 judgement, this data should be used in conjunction with otheravailable QC information.
C. Criteria
1. Matrix spike and matrix spike duplicate samples are analyzed at frequency of one MS and
MSD per 20 samples of similar matrix.
2. Matrix spike and matrix spike duplicate recoveries should be within the advisory limits
established on Form III SV-1 and SV-2 and in the SOW.
3. The Relative Percent Differences (RPDs) between matrix spike and matrix spike duplicate
recoveries should be within the advisory limits listed on Form III SV-1 and SV-2 and in the
SOW.
D. Evaluation
1. Verify that MS and MSD samples were analyzed at the required frequency and that results
are provided for each sample matrix.
2. Inspect results for the MS/MSD Recovery on Form ill SV-1 and SV-2 and verify that the
results for recovery and RPD are within the advisory limits.
3. Verify transcriptions from raw data and verify calculations.
* Check that the recoveries and RPDs were calculated correctly.
5. Compare results (%RSD) of non-spiked compounds between the original result, MS, and
MSD.
E. Action
1. No action is taken on MS/MSD data alone. However, using informed professional judgment
the data reviewer may use the matrix spike and matrix spike duplicate results in conjunction
with other QC criteria and determine the need for some qualification of the data.
2. The data reviewer should first try to determine to what extent the results of the MS/MSD
effect the associated data. This determination should be made with regard to the MS/MSD
sample itself as well as specific analytes for all samples associated with the MS/MSD.
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Mai* ix Spikes/Matrix Spike Duplicates
3. In those instances where it can be determined that the results of the MS/MSD effect only
the sample spiked, then qualification should be limited to this sample alone. However, it
may be determined through the MS/MSD results that a laboratory is having a systematic
problem in the analysis of one or more anaiytes, which affects all associated samples.
4. The reviewer must use professional judgement to determine the need for qualification of
positive results of non-spiked compounds.
NOTE: If a field blank was used for the MS/MSD, a statement to that effect must be included for
TPO action on the ORDAS.
5. When extremely low % recoveries are noted, qualify data for all affected compounds using
professional judgement.
6. When non-spiked compounds are present in either the MS or MSD results, a table in the
data review narrative is constructed showing original (unspiked) sample results for non-
spiked compounds, non-spiked compounds present in the MS and MSD and the calculated
%RSD.
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VIII. Regional Quality Assurance and Quality Control
A. Review items: Form ISV, Chromatograms, and Quantitation reports.
B. Objective
Regional Quality Assurance and Quality Conlrol (QA/QC) refer to any QA and/or QC samples
initiated by the Region, including field duplicates, Performance Evaluation (PE) samples, blind
spikes, and blind blanks.
C. Criteria
Criteria are dependent on the type of QC sample. Frequency may vary.
1. The analytes present in the PE sample must be correctly identified and quantitated.
D. Evaluation
1. Evaluation of Performance Evaluation (PE) Samples are not to be presented as part of the
data review. Ail forms associated with the Performance Evaluation Samples are to be sent
(with a cover memo stating the case number and laboratory information) directly to the
Quality Assurance Branch in Region ill.
U.S. Environmental Protection Agency
Region III, Central Regional Laboratory
Quality Assurance Branch
839 Bestgate Road
Annapolis, MO 21401
Attn: Program Support Section
2. Percent difference between target compounds present in the field duplicate samples shall
be determined. Evaluation of the percent difference compared to those specified in the site
Quality Assurance Project Plan may be presented in the data review narrative.
E. Action
1. Field duplicate results are to be presented in a table form in the data review narrative. If
target compounds were not present in either of the field duplicate samples, then a table is
not required. The percent difference is to be calculated and presented in the table, (if one
of the field duplicates was aiso used as a matrix spike/matrix spike duplicate sample, then
the table should include any non-spiked compounds detected, along with the % relative
standard deviation.)
No action is taken based on percent difference of field duplicate sample data alone.
However, using informed professional judgement, the data reviewer may use the field
duplicate results in conjunction with other QC criteria and determine the need for some
qualification of the data.
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2. Other types of Regional QC Samples
Professional judgement is needed for evaluating other types of QC samples that may be
associated with a particular case of samples. This information may be used in conjunction
with other QC criteria to determine the need for qualification of data.
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IX. Internal Standards
A. Review Items: Form VIII SV-1 and SV-2 , quantitation reports, and chromatograms.
B. Objective
Internal Standards (IS) performance criteria ensure that GC/MS sensitivity and response are stable
durir.g every analytical run.
C. Criteria
1. Internal standard area counts for samples and blanks must not vary by more than a factor
of two (- 50% to + 100%) from the associated calibration standard.
2. The retention time of the internal standards in samples and blanks must not vary by more
than _+ 30 seconds from the retention time of the associated calibration standard.
D. Evaluation
1. Check raw data (e.g., chromatograms and quantitation lists) for samples and blanks to
verify the internal standard retention times and areas reported on the Internal Standard
Area Summary (Forms VIII SV-1, VIII SV-2).
2. Verify that all retention times and IS areas are within the required criteria.
3. If there are two analyses for a particular fraction, the reviewer must determine which are
the best data to report. Considerations should include:
a. Magnitude and direction of the IS area shift.
b. Magnitude and direction of the IS retention time shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each'fraction.
E. Action
1. If an IS area count for a sample or blank is outside - 50% or + 100% of the area for the
associated standard*.
a. Positive results for compounds quantitated using that IS should be qualified with
"J".
b. Non-detected compounds quantitated using an IS area count greater than +100%
or less than 50% should be qualified with "UJ".
c. If extremely low area counts are reported, or if performance exhibits a major abrupt
drop-off, then a severe loss of sensitivity is indicated. Non-detected target
compounds should then be qualified as unusable "R".
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Internal Standards
2. If an IS retention time varies by more than 30 seconds:
The chromatographic profile for that sample must be examined to determine if any false
positives or negatives exist. For shifts of a large magnitude, the reviewer may consider
partial or total rejection (R) of the data for that sample fraction. Positive results should not
need to be qualified with "R" if the mass spectral criteria are met.
3. If the internal standards performance criteria are grossly exceeded, then this should be
noted for TPO action. Potential effects on the data resulting from unacceptable internal
standard performance should be noted in the data review narrative.
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X. Target Compound Identification
A. Review Items: Form I SV-1 and SV-2 quantitation reports, mass spectra, and chromatograms.
B. Objective
Qualitative criteria for compound identification have been established 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 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, much more difficult to assess. One example of detecting false
negatives is the reporting of a Target Compound as a TIC.
C. Criteria
1. Compound must be within _+ 0.06 relative retention time (RRT) units of the standard RRT.
2. Mass spectra of the sample compound and a current laboratory-generated standard 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. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be between
30% and 70%.)
c. Ions present at greater than 10% In the sample mass spectrum but not present in
the standard spectrum must be considered and accounted for.
D. Evaluation
1. Check that the RRT of reported compounds is within _+ 0.06 RRT units of the standard
relative retention time.
2. Check the sample compound spectra against the laboratory standard spectra to verify that
its meets the specified criteria.
3. The reviewer should be aware of situations (e.g., high concentration samples preceding
low concentration samples) when sample carryover is a possibility and should use judgment
to determine if instrument cross-contamination has affected any positive compound
identification.
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Target Compound Identification
4. Check the chromatogram to verify that peaks are accounted for, i.e., major peaks are either
identified as target compounds, TICs, surrogates, or internal standards.
E. Action
1. The application of qualitative criteria for GC/MS analysis of target compounds requires
professional judgement, it is up to the reviewer's discretion to obtain additional information
from the laboratory. If it is determined that incorrect identifications were made, all such
data should be qualified as not detected "U" or unusable "R".
2. Professional judgement must be used to qualify the data if it is determined that cross-
contamination has occurred.
3. Any changes made to the reported compounds or concerns regarding target compound
identifications should be clearly indicated in the data review narrative. The necessity for
numerous or significant changes should be noted for TPO action.
4. If it is determined that incorrect identifications were made, all such data should be reported
as not-detected, and the narrative and the support documentation should indicate this
action. In addition, the reviewer should verify that the misidentified peak was library
searched as a TIC, if appropriate.
5. If the presence of a target compound is strongly suggested by raw data, but its mass
spectrum contains minor inadequacies, the compound may be added to the data summary
and qualified as a tentative identification "N". The reviewer should address corroborating
evidence in the narrative, such as the presence of the compound in closely related
compounds in the same sample.
6. If the laboratory did not report a compound of acceptable matching quality, the reviewer
should add this compound to the sample data summary. The narrative and the support
documentation should indicate this action, as well as the ORDA. The reviewer should
request the laboratory to re-examine and resubmit the result, particularly if the value is
greater than the CRQL
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XI. Compound Quantitation and Reported CRQLS
A. Review Items: Form I SV-1 and SV-2, sample preparation sheets, case narrative, sample clean-
up sheets, quantitation reports, and chromatograms.
B. Objective
The objective is to ensure that the reported quantitation results and Contract Required Quantitation
Limits (CRQLs) for semivolatile target compounds are accurate.
C. Criteria
1. Compound quantitation, as well as the adjustment of the CRQL, must be calculated
according to the correct equation.
2. Compound area responses must be calculated based on the internal standard OS)
associated with that compound, as listed in Appendix (also as specified In the Statement
of Work). Quantitation must be based on the quantitation ion (m/z) specified In the SOW
for both the IS and target analytes. The compound quantitation must be based on the RRF
from the appropriate daily calibration standard.
D. Evaluation
1. For all fractions, raw data should be examined to verify the correct calculation of ail sample
results reported by the laboratory. Quantitation lists, chromatograms, and sample
preparation log sheets should be compared to the reported positive sample results and
quantitation limits. Check the reported values. Calculation errors can sometimes be
revealed by abnormally high surrogate recoveries, matrix spike recoveries, or
inappropriately high results for certain compounds.
2. Verify that the correct internal standard, quantitation ion, and RRF were used to quantitate
the compound. Verify that the same internal standard, quantitation ion, and RRF are used
consistently throughout the calibration and quantitation processes.
3. Verify that the CRQLs have been adjusted to reflect all sample dilutions, concentrations,
splits, clean-up activities, and dry weight factors that are not accounted for by the method.
E. Action
1. If there are any discrepancies found, the laboratory may be contacted by the designated
representative to obtain additional information that could resolve any differences. If a
discrepancy remains unresolved, the reviewer must use professional judgement to decide
which value is the best value. Under these circumstances, the reviewer may determine
qualification of data is warranted. Decisions made on data quality should be included in the
data review narrative. A description of the reasons for data qualification and the
qualification that is applied to the data should be documented in the data review narrative.
2. Numerous or significant failures to accurately quantify the target compound or to property
evaluate and adjust CRQLs should be noted for TPO action.
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Compound Quantitation and Reported CRQLS
3. The reviewer must assure that any results in error by more than 10 percent are Identified
and corrected on the sample data summary. If laboratory resubmission is not performed,
the reviewer should document his/her changes to the data in the narrative or support
documentation. Calculation errors should also be noted on the ORDA.
4. If a sample concentration is above the highest standard and contract required dilutions were
not performed, the TPO should be informed on the ORDA. The chromatogram and mass
spectrum should be examined for signs of a saturated signal. If the ion used for
quantitation was saturated, then the result should be flagged as biased low, "L'. If the ion
used for quantitation was not saturated, the result should be flagged as estimated. "J".
5. When sample results were quantitated using RRFs from the wrong calibration standard, the
laboratory should resubmit these results. The ORDA should Identify affected results and
document the error. In addition, a CLP telephone log must be completed.
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XII. Tentatively Identified Compounds
A. Review Items: Form I SV-TIC, chromatograms, and library search printout with spectra for three
TiC candidates.
B. Objective
Chromatographic peaks in semivolatile fraction analyses that are not target analytes, surrogates,
or internal standards are potential tentatively identified compounds (TICs). TICs must be
qualitatively identified by a National Institute of Standards and Technology (NIST) mass spectral
library search and the identifications assessed by the data reviewer.
C. Criteria
For each sample, the laboratory must conduct a mass spectral search of the NIST library and
report the possible identity for the 20 largest semivolatile fraction peaks which are not surrogate,
internal standard, or target compounds, but which have area or height greater than 10 percent of
the area or height of the nearest internal standard. TIC results are reported for each sample on
the Organic Analyses Data Sheet (Form I SV-TIC).
NOTE: Since the SOW revision of October 1986, the CLP does not allow the laboratory to report
as tentatively identified compounds any target compound which is properly reported in
another fraction. For example, late eluting volatile target compounds should not be
reported as semivolatile TICs.
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. Ions present in the sample spectrum but not in the reference spectrum should be
reviewed for possible background contamination, interference, or coelution of
additional TIC or target compounds.
e. When the above criteria are not met. but in the technical judgment of the data
reviewer or mass spectral interpretation specialist the identification is correct, the
data reviewer may report the identification.
f. If in the data reviewer's judgment the identification is uncertain or there are
extenuating factors affecting compound identifications, the TIC result may be
reported as "unknown".
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Tentatively Identified Compounds
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. Blank chromatograms should be examined to verify that TIC peaks present in samples are
not found in blanks. When a low-Jevei 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 percent of the internal standard height,
but present in the blank chromatogram at a similar relative retention time.
4. All mass spectra for each sample and blank must be examined.
5. Since TIC library searches often yield several candidate compounds having a close
matching score, all reasonable choices should be considered.
6. The reviewer should 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:
a. Common laboratory contaminants: CO, (m/z 44), siloxanes (m/z 73), diethyl
ether, hexane, certain freons (l,1,2-trichloro-1,2,2-trifluoroethane or fluoro-
trichloromethane), and phthalates at levels less than 100 ug/L or 4000 ug/Kg.
b. Solvent preservatives, such as cyciohexene which is a methylene chloride preser-
vative. Related by-products include cyclohexanone, cyclohexenone, cyclohexanol,
cyclohexenol, chlorocyclohexene, and chlorocyciohexanol.
c. Aldol reaction products of acetone include: 4-hydroxy-4-methyl-2-pentanone, 4-
methyl-2-penten-2-one, and 5,5-dimethyl-2(5H)-furanone.
7. Occasionally, a target compound may be identified as a TIC in the proper analytical fraction
by non-target library search procedures, even though it was not found on the quantitation
list. If the total area quantitation method was used, the reviewer should request that the
laboratory recalculate the result using the proper quantitation ion. In addition, the reviewer
should evaluate other sample chromatograms and check library reference retention times
on quantitation lists to determine whether the false negative result is an isolated occurrence
or whether additional data may be affected.
8. Target compounds may be identified in more than one fraction. Verify that quantitation is
made from the proper fraction.
9. Library searches should not be performed on internal standards or surrogates.
10. TIC concentration should be estimated assuming a RRF of 1.0.
E. Action
1. All TIC results should be qualified "J", estimated concentration on the Laboratory
Form l-TICs.
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Tentatively identified Compounds
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 not
acceptable, the tentative identification should be changed to "unknown" or an
appropriate identification.
b. If aB contractually required peaks were not library searched and quantitated, the
designated representative could request these data from the laboratory.
3. Blank Results
Form l-TIC which contain sample results that are questioned by blank results, should be
flagged "B" and a line drawn through these data for emphasis (initialed and dated).
To be considered questionable, a sample TIC concentration must be within 10 times the
concentration of one of the blank results. If different volumes/weights are used, the total
amount of compound in the extract must be compared for sample versus blank. In general,
blanks analyzed within the same case, by the same lab, may be cross-applied to either soil
or water samples extracted or analyzed on other days.
To question a sample result, only presumptive evidence for the presence of the compound
in the blank is necessary. The presence of the TIC in the blank is suggested in any of the
following situations:
a. Relative retention times (RRTs) match for sample versus blank, and the sample
library search result matches the same compound jar compound class as the library
search result for the blank.
b. RRTs match, but library search results do not list the same compound or class for
sample versus blank. However, some of the largest ions in the sample are also in
the blank, and a direct comparison of sample versus blank spectra suggests that
the TIC in the sample is quite possibly the same compound as that in the blank.
c. A peak at the same RRT as the sample TIC is present in the chromatogram of the
blank, but no library search was performed or included in the data. (The labs do
not have to library search peaks less than 10% of the height of the nearest internal
standard, although these peaks may still be important to identify low-level blank
contaminants that can question sample results at levels above 10% of the nearest
internal standard height.)
All blank results must be attached in the support documentation section of the data review.
4. When a compound is not found in any blanks, but is a suspected artifact of common
laboratory contamination, the reviewer should cross off the reported TIC result on the copy
of the Form l-TIC and note the reason(s) in the narrative.
5. In deciding whether a library search result for a TIC represents a reasonable identification,
professional judgment must be exercised. If there is more than one possible match, the
result may be reported as "either compound X or compound Y". If there is a lack of isomer
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Tentatively Identified Compounds
specificity, the TIC result may be changed 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 substituted aromatic compound). These changes may be made directly
on a copy of the Form l-TIC, as long as changes are initialed and dated.
6. 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 relative retention time, and the same
ions, identification information may be inferred from the other sample TIC results.
7. Physical constants, such as boiling point, may be factored into professional judgment of
TIC results.
8. Any changes made to the reported data or any concerns regarding TIC identifications
should be indicated in the data review narrative. Any changes made regarding TIC
identifications or qualifications are to be made on copies of the laboratory generated Form
l-TIC and not the originals.
9. Failure to properly evaluate and report TICs should be noted for TPO action.
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XIII. System Performance
A. Review Items: Form III SV-1 and SV-2, Form VIII SV-1 and SV-2, and chromatograms.
B. Objective
During the period following Instrument Performance 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
through review of the ongoing data acquisition can yield Indicators of instrument performance.
C. Criteria
There are no specific criteria for system performance. Professional judgement should be used 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 be non-detects. A baseline "rise'1
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 of internal
standards.
b. Excessive baseline rise at elevated temperature.
c. Extraneous peaks.
d. Loss of resolution as suggested by factors such as non-resolution of 2,4- and 2,5-
dinitrotoluene.
e. Peak tailing or peak splitting that may result in inaccurate quantitation.
E. Action
Professional judgement must be used to qualify the data if it is determined that system performance
has degraded during sample analyses. Any degradation of system performance which significantly
affected the data should be documented for TPO action.
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XIV. Overall Assessment of Data
A. Review Items: Entire data package, data review results, and (if available) Quality Assurance Project
Plan (QAPjP), 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 useability of the data.
C. Criteria
Assess the overall quality of the data.
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. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
3. If appropriate information is available, the reviewer may assess the useability of the data
to assist the data user in avoiding inappropriate use of the data. Review all available
information, including the QAPjP (specifically the Data Quality Objectives), SAP, and
communication with data user that concerns the intended use and desired quality of the
data.
E. Action
1. Use professional judgement to determine if there is any need to qualify data which were
not qualified based on the QC criteria previously discussed.
2. Write a brief narrative to give the user an indication of the analytical limitations of the data.
Any inconsistency of that data with the SDQ Narrative should be noted for TPO action. If
sufficient information on the intended use and required quality of the data are available, the
reviewer should include his/her assessment of the useability of the data within the given
context.
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APPENDIX A
CONTRACTUAL REQUIREMENTS AND EQUATIONS
MULTI-MEDIA, MULTI-CONCENTRATION • MM/MC
(OLMOl.O)
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APPENDIX A
MULTI-MEDIA, MULTI-CONCENTRATION
CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR VOLATILE DATA REVIEW
II. GC/MS Instrument Performance Check
Use equation II. I to verify that the laboratoiy has not made errors the calculation of the percent relative
abundance.
% Relative Abundance • aoun^nee °f * x 100% (ILl)
abundance of Y
For example, the percent relative abundance of m/z 96 (AT) relative to m/z 95 (Y) is calculated as follows:
X Relative «/"ft * x s00%
abundance cf mil 95
III. Initial Calibration
Data Review Criteria: All volatile target compounds and system monitoring compounds must have a
Relative Response Factor (RRF) of greater than or equal to 0.0S and a percent relative standard deviation
(*£RSD) of less than or equal to 30%.
Contractual Criteria: The maximum %RSD.for volatile compounds is 20.5% and the minimum RRF
criteria van- as specified in the Table A.1 (The volatile compounds listed separately in Table 2 on page 13
are not contractually required to meet a maximum %RSD but do have to meet a contractual minimum
RRF of 0.010). The contractual criteria for an acceptable initial calibration specifies that up to anv 2
volatile target compounds may fail to meet minimum RRF or maximum %RSD as long as they have RRFs
that are greater than or equal to 0.010, and %RSD of less than or equal to 40.0%.
Tabie A.1 Minimum RRF Criteria for Volatile Target Compunds
Volatile Minimum
Compound RRF
Bromomethane 0.100
Vinyl chloride 0.100
1,1-Dichloroeihene 0.100
1,1-Dichloroethane 0.200
Chloroform 0.200
1,2-Dichloroethane 0.100
1,1,1-Trichloroe thane 0.100
Carbon tetrachloride 0.100
Bromodichloromethane 0.200
cis-13-DichIoropropene 0.200
A-l
DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A.1 Minimum RRF Criteria for Volatile Target Compunds (continued)
Volatile
Minimum
Comoound
-BEE.
Trichloroethene
0.300
Dibromochloromethane
0.100
1,1,2-Trichloroethane
0.100
Benzene
0.500
trans- 1.3-Dichloropropene
0.100
Bromoform
0.100
Tetrachloroethene
0.200
1,1.2,2 -Teirachloroe thane
0300
Toluene
0.400
Chlorobenzene
0.500
Ethvlbenzene
0.100
Styrene
0.300
Xylenes (total)
0.300
Bromofluorobenzene
0.200
Initial calibration RRFs and RRF are calculated using equations III.1 and II1.2.
RRF - x (IIM)
A*
E *^1 (III.2)
bsc
where:
RRFj s *i"th Relative Response Factor
A - Area of the characteristic ion (EICP) measured
C «= Concentration
is ¦ Internal standard
x « Analyte of interest
"Pie %RSD is calculated using equations 1113 and III.4.
h (»-1)
(III.3)
A-2
DRAFT 12/90
Revised 6/91
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MM/MC
APPENDIX A
%RSD- £ x 100
an.4)
x
where:
a » Standard deviation of 5 relative response factors
x =' Mean of 5 relative response factors
IV. Continuing Calibration
Data Review Criteria: All compounds must be considered for qualification when the %D exceeds the ±
25.0% criterion.
Contratual Criteria: The percent difference (%D) between the initial calibration RRF and the
continuing calibration RRF is + 25% for all compounds listed in Table A.1. The contractual criteria for
an acceptable continuing calibration specifies that up to arjv 2 volatile target compounds may fail to meet
minimum RRF or maximum %D as long as they have RRFs that are greater than or equal to 0.010, and
%D of less than or equal to 40.0%.
Check the continuing calibration RRF calculations for volatile target compounds using equation III.1. The
%D between initial calibration RRF and continuing calibration RRF is calculated using equation IV. 1.
VI. System Monitoring Compounds
The volatile system monitoring compounds (surrogates) and their contractual recovery limits are listed in
Tabte A.2.
(IV.l)
where:
RRFl ¦ average relative response factor from initial calibration.
RRFC » relative response factor from continuing calibration standard.
Table A2, System Monitoring Compound Contractual Requirements
System Monitoring Compound
%Rccovetv Limits
Water Samples
Soil Samples
SMC1 Toluene-dg
SMC2 Bromofluorobenzene
SMC3 l,2-Dichloroeihane-d4
88-110
86-115
76 -114
84-138
59 -113
70 -121
A-3
DRAFT 12/90
Revised 6/91
-------
MM/MC APPENDIX A
Use equation VI. l to check that the system monitoring compound recoveries were calculated correctly:
* feWK? - Co™*"**""™'ft** x I00% (VLD
Concettirationjamowu spiked
VII. Matrix Spikes/Matrix Spike Duplicates
The matrix spike/matrix spike duplicate contractual requirements are listed in Table A.3.
Table A J MS/MSD Contractual Requirements
Comoound
- Water
RPD - Water
RPP-i
1,1-Dichloroethene
61 -
145
59-
172
<14
<22
Trichloroethene
71 -
120
62.
137
<14
<24
Benzene
76-
127
66-
142
<11
<21
Toluene
76-
125
59-
139
<13
<21
Chlorobenzene
75-
130
60-
133
<13
<21
Veriiy thai the matrix spike recoveries and RPD were calculated correctly using equations VII. 1 and VII.2.
% Recovery • SSR " SR x 100% (VUl)
SA
where:
SSR — Spiked sample result
SR s Sample result
£4 « Spike added
RPD- I**5* " igP*l x 100% (VII.2)
1/2 (MSR * MSDK)
where:
RPD ¦ Relative percent difference
MSR ¦ Matrix spike recovery
MSDR m Matrix spike duplicate recovery
A-4
DRAFT 12/90
Revised 6/91
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MM/MC
APPENDIX A
IX Internal Standards
Table A.4 contains the volatile internal standards and their corresponding target compounds. These
criteria have been established for packed columns only. Specific criteria for capillaiy columns have not
been included in the SOW at this time.
Table A.4 Internal Standards and Their Corresponding Target Compounds
Bromochloromethane 1,4-Difluorobenzene Chlorobenzene-d5
Chloromethane
Bromomethane
Vinyl Chloride
Chloroeihane
Methylene Chloride
Acetone
Carbon Disulfide
1.1-Dichloroethene
1.1-Dichloroethane
1 ^-Dichloroethene(total)
Chloroform
1.2-Dichloroethane
2-Butanone
l,2-Dichloroethane-d4 (SMC)
1.1.1-Trichloroethane
Carbon Tetrachloride
Bromodichloromethane
Bromoform
1,2-Dichloropropane
trans-13-Dichloropropene
Trichloroethene
Dibromochloromethane
1.1.2-Trichloroethane
Benzene
cis-13*Dichloropropene
Bromoform
2-Hexanone
4-Methyl-2-Pentanone
Tetrachloroethene
1.1^2-Tetrachloroethane
Toluene
Chlorobenzene
Ethvlbenzene
Styrene
Total Xylenes
Bromofluorobenzene (SMC)
Toluene-dg (SMC)
SMC s System Monitoring Compound
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
Check the reported positive sample results and quantitation limits with the quantitation lists and
chromatograms using equations XI.l, XL2, or XL3. Characteristic ions for the volatile target compounds
are contained in Table A.5. Characteristic ions for System Monitoring Compounds and Internal Standards
are contained in Table A6.
Concentration for waters:
A. X / X Df yV| | i
ugjL - — — (XI-D
Ak x XRF x Vt
A-5 DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Concentration for low level soils:
(Dry weight basis)
uglKg . — (XI.2)
* ^ A„ * JOT x W$ x D
Concentration for medium level soils:
(Diy weight basis)
A. x I x V. x 1000 x Df
uglKg - ' ' ' j- (XI.3)
A„ x JOT x Va x W, x D
where:
Ax b area of characteristic ion (EICP) for compound being measured
Aa b area of characteristic ion (EICP) for the internal standard
/, = amount of internal standard added (ng)
RRF a daily response faaor for compound being measured
Va s volume of water purged (mL)
Ws m weight of sample (g)
D s (100 - % moisture)/100% • conversion to dry weight
Vt « volume of methanol (mL)t
Vi s volume of extract added (uLj for purging
Df b dilution factor}
Va s volume of the aliquot of the methanol extract (uL) added to reagent water
for purging
This volume is typically 10.0 mL, even though only 1.0 mL is transferred to the vial. See
the SOW for more details.
The dilution factor for analysis of soil/sediment samples for volatiles by the medium level
method is defined as the ratio of the number of microliters (uL) of methanol added to the
reagent water for purging (VJ to the number of microliters of the methanol extract of the
sample contained in volume Vr If no dilution is performed, then the dilution factor
equals 1.0.
The CRQL for a diluted sample should be calculated as follows:
Adjusted CRQL b Non-adjusted CRQL x Sample Dilution Faaor (X1.4)
A-6 DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
For example, the adjusted CRQL for a water sample with a 10U non-diluted CRQL and a 1 to
100 dilution (100.0 dilution factor) would be 1000U, according to the following calculation:
1000U » 10U x 100
The CRQL adjustment for dry weight for a soil sample should be calculated as follows:
n n^:_L. NOfl ~G$USttd CRQL
Dry W
-------
MM/MC APPENDIX A
Table AS Characteristic loos for Volatile Target Compounds
Analyte
Primary Ion*
Secondary Ion(s) f
Chloromethane
SO
52
Bromomethane
94
96
Vinyl chloride
62
64
Chloroethane
64
66
Methylene chloride
84
49. 51. 86
Acetone
43
58
Carbon disulfide
76
78
| 1.1-Dichloroethene
96
61,98
j 1,1-Dichloroethane
63
65. 83.85. 98. 100
1,2-Dichloroethene
96
61.98
Chloroform
S3
85
1.2-Dichloroethane
62
64,100,98
2-Butanone
43"
57
1.1.1-Trichloroethane
97
99,117, 119
Carbon tetrachloride
117
119,121
Bromodichloromethane
83
85
1,1.2 2-TetrachIorbethane
83
85,131. 133, 166
1.2-Dichloropropane
63
65,114
trans- 1,3-Dichloropropene
75
77
Trichloroethene
130
95. 97, 132
Dibromochloromethane
129
208, 206
1,1,2-Trichloroethane
97
83, 85,99, 132, 134
Benzene
78
—
cis-13- Dichloropropene
75
77 Z
Bromoform
173
171,175.250, 252,254, 256
''.Uflvsifi.-inp
43
58,57. 100 I
| 4-Methyl-2-pentanone
43
58. 100 |
DRAFT 12/90
Revised 4/91
-------
MM/MC APPENDIX A
Tabic AJ Characteristic Ions for Volatile Target Compounds (Continued)
Analvte
Primary Ion*
Secondary Ion(s)
Tetrachloroethene
164
129.131.166
Toluene
91
92
Chlorobenzene
112
114
Ethyl benzene
106
91
Styrene
104
78,103
Total Xylenes
106
91
While m/z 43 is used for quantitation of 2*Butanone, m/z 72 must be present for positive
identification.
The primary ion should be used unless interferences are present, in which case, a secondary ion
may be used.
Table A.6 Characteristic Ions for System Monitoring Compounds and Internal Standards
for Volatile Organic Compounds
Compound
Primary Ion
Secondary Ion(s)
SYSTEM MONITORING COMPOUNDS
4-3rumofluorobenzene
95
174, 176
1.2-Dichloroethane-d4
65
102
Toluene-da
98
70,100
INTERNAL STANDARDS
Bromochloromethane
128
49. 130. 51
1,4-Dtfluorobenzene
114
63,88
Chiorobenzene-dj
117
82,119
A-9 DRAFT 12/90
Revised 6/91
-------
APPENDIX A
MULTI-MEDIA, MULTI-CONCENTRATION
CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR SEMIVOLATILE DATA REVIEW
II. GC/MS Instrument Performance Check
Use equation II.l to verify that the laboratory has not made errors in the calculation of the percent
relative abundance.
For example, the percent relative abundance of mtz 443 (X) relative to m/Z 442 (V) is calculated as follows:
% fetox At**** . •*'*•*' „ too,
abundance of mjz 442
III. Initial Calibration
Data Review Criteria: All semivolatile target compounds and surrogates must have a Relative Response
Factor (RRF) of greater than or equal to 0.05 and a percent relative standard deviation (%RSD) of less
than or equal to 30%.
Contractual Criteria: The maximum %RSD for most semivolatile compounds is 20.5% and the minimum
RRF criteria vary as specified in Table A.7 (The semivolatile compounds listed separately in Table 4 on
page 52 are not contractually required to meet a maximum %RSD but do have to meet a contractual
minimum RRF of 0.010). llie contractual criteria for an acceptable initial calibration specifies that up to
anv 4 semivolatile target compounds may fail to meet minimum RRF or maximum %RSD as long as they
have RRFs thai are greater than or equal to 0.010, and %RSD of less than or equal to 40.0%.
Table A.7 Minimum RRF Criteria for Semivolatile Target Compounds
Semivolatile
Minimum
Comnounds
RRF
Phenol
0.800
bis(-2-Chloroethyl)ether
0.700
2-Chlorophenol
0.800
13*Dichlorobenzene
0.600
1,4-Dichlorobenzene
0.500
1,2-Dichlorobenzene
0.400
2-Methylphenol
0.700
4-Methylphenol
0.600
N-Nitroso-di-propylamine
0.500
Hexachioroethane
0300
Nitrobenzene
0.200
Isophorone
0.400
2-Nitrophenol
0.100
2,4-Dimethylphenol
0.200
bis(-2-Chloroethoxy)methane
0.300
A-10
DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A.7 Minimum RRF Criteria for Semivolatile Target Compounds (Continued)
Semivolatile
Minimum
Comoounds
RRF
2,4-Dichlorophenol
0.200
1,2,4-Trichlorobenzene
0200
Naphthalene
0.700
4-Chloro-3*methylphenoi
0.200
2-Methylnaphthalene
0.400
2,4,6-Trichlorophenol
0.200
2,4,5-TrichIorophenol
0200
2-ChIoronaphthalene
0.800
Acenaphthylene
1300
2,6-Dinitrotoluene
0200
Acenaphthene
0.800
Dibenzofuran
0.800
2,4-DinitrotoIuene
0.200
4-Chlorophenyl-phenylether
0.400
Fluorene
0.900
4-Bromophenyi-phenylether
0.100
Hexachlorobenzene
0.100
Pentachlorophenol
0.050
Phenanthrene
0.700
Anthracene
0.700
Fluoranthene
0.600
Pyrene
0.600
Benzo(a)anthracene
0.800
Chiysene
0.700
Benzo(b)fluoranthene
0.700
Benzo(k)fluoranthene
0.700
Beozo(a)pyrene
0.700
Indeno(1^3
-------
mm/mc appendix a
Initial calibration RRF and RRF are calculated using equations 111.1 and III.2; %RSD is calculated
using equations I1L3 and I1I.4.
IV. Continuing Calibration
Data Review Criteria: All semivolatile target compounds should meet a %D criterion of ± 25%.
Contractual Criteria: The percent difference (%D) between the initial calibration RRF and the
continuing calibration RRF is + 25.0% for the compounds listed in Table A.4. The contractual criteria
for an acceptable continuing calibration specifies that up to anv 4 semivolatile target compounds may fail
to meet minimum RRF or maximum %D as long as they have RRFs that are greater than or equal to
0.010, and %D of less than or equal to 40.0%.
Check the continuing calibration RRF calculations for semivolatile target compounds using equation III.l.
and evaluate the %D between initial calibration RRF and continuing calibration RRF using equation
IV.l.
VI. Surrogate Spikes
The semivolatile surrogate compounds and their contractual recoveiy limits are listed in Table A.8.
Table A4 Semivolatile Surrogate Requirements
Surrogate % Recovery Limits
51 Nitrobenzene-ds
52 2-Fluorobiphenyl
53 Terphenyl-d14
54 Phenol-d<
55 2-Fluorophenol
56 2,4.6-Tribromophenol
57 2-Chlorophenol-d4
58 1,2-Dichlorobenzene-d4
* Advisory limits
Use equation VL1 to verify that the surrogate recoveries were calculated correctly.
VII. Matrix Spikes/Matrix Spike Duplicates
The matrix spike/matrix spike duplicate contractual requirements are listed in Table A.9.
Verily that the matrix spike recoveries and RPD were calculated correctly using equations VII. 1 and VII.2.
IX. Internal Standards
T^hv a in mntain* the semivolatile internal standards and their corresponding target compounds.
Water Samples
Soil Samples
35 -114
23-120
43 • 116
30- 115
33 -141
18 - 137
10 -110
24 -113
21 -110
25 -121
10-123
19-122
33 -110'
20 - 130*
16 -110*
20 - 130*
A-12
DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A.9 SenlvoUtlle MS/MSD Contractual Requirements
Compound %R - Water %R • Soil
Phenol
2-Chiorophenol
1.4-Dichlorobenzene
N-Nitroso-di-n-propyiamine
U,4-Trichlorobenzene
4-Chloro-3-methylphenol
Acenaphthexte
4-Nitrophenol
2,4-Dinitrotoluene
Pentachlorophenol
Pyrene
12-110
26-90
27-123
25-102
36-97
28-104
41 -116
41-126
39-98
38-107
23-97
26-103
46-118
31 - 137
10-80
11• 114
24-96
28-89
9- 103
17-109
26-127
35 -142
RPD. Water RPD • Soil
<42
<35
< 40
<50
<28
<27
<38
<38
<28
<23
<42
<33
<31
< 19
<50
< 50
<38
<47
<50
< 47
<31
<36
A-13
. DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A.IO Semivolatile Internal Standards and Their Corresponding Target Compounds
l,4-Dichlorobenzene-da Naphthalene-dg Aoenaphthene-d10
Phenol
bis(2-ChIoroethyl)ether
2-Chlorophenol
13-Dichlorobenzene
1,4-Dicblorobenzene
1,2-Dichlorobenzene
2-Methylphenol
2.2'-oxybis-( 1-Chloropropane)
4-Methylphenol
N-Nitroso-Di-n-propylamine
Hexachloroethane
2-Fluorophenol (sun)
Phenol-dj (surr)
2-Chlorobenzene-d4 (surr)
lt2-Dichlorobenzene-d4 (surr)
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3>methylphenol
2-Methylnaphthalene
Nitrobenzene-dj (surr)
Hexachlorocyclopentad iene
2,4,6-Trichlorophenol
2.4.5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethyl phthalate
4-Chlorophenyl-phenyl ether
Fluorene
4-Nitroaniline
2-Fluorobiphenvl (surr)
2.4.6-Tribromophenol (surr)
Phenanthrene-d
10
Chrysene-d12
Perylene-d,-
4,£Dinitro-2-methylphenol
N-N ltrosodiphenylamine
4-BrornophenyI phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Carbazole
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butylbenzyl phthalate
33'-Dichiorobenzidine
Benzo(a)anthracene
bis (2-Ethylhexyl)phthalate
Chrysene
Terphenyl-d14 (surr)
Di-n-octyl phthalate
Benzo(b)fluoranihene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1^3-cd)pyrene
Dibenz(a,h )anthracene
Benzo(gJij)perylene
surr s surrogate compound
A-14
DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
Check the reported positive sample re ilts and quantitation limits with the quantitation lists and
chromatograms using equations XI.6, X1.7, or XI.8. Equation X1.4 should be used to adjust the CRQL for
a diluted sample, and equation XL5 should be used to adjust the CRQL for a soil sample. Characteristic
ions for semivolatile target compounds are contained in Table A.11. Characteristic ions for semivolatile
surrogates and internal standards are contained in Table A. 12. Characteristic ions for pesticides and
Aroclors are contained in Table A. 1&
Concentration for waters:
A. x /, x V. x Df
uglL - — 2 '¦ — (XI.6
* x RRF x K, x Vi
Concentration for soils/sediments:
(Dry weight basis)
¦*.»» v (JD.7)
x RRF x Vi x Wt x D
where:
Ax = area of characteristic ion (EICP) for compound being measured
y4jj = area of charaaeristic ion (EICP) for the internal standard
/s s amount of internal standard added (ng)
RRF m daily relative response factor for compound being measured
V0 a volume of water extracted (mL)
Vx b volume of extract injected (uL)
Vx b volume of concentrated extract (uL)
Df s dilution Cactorf
D = (100 - % moisture)/100% • conversion to dry weight
W% m weight of sample (g)
t The dilution factor for analysis of water samples for semivolatiles by the method specified
in SOW OLM01.0 is calculated using equation XI.8. If no dilution is performed, then the
dilution factor equals 1.0.
jjt m vL of the most coticentated extract used + uL of clean solvent (XI.8)
uL of the most concentrated extract used
A-15
DRAFT 12/90
Revised 6/91
-------
MM/MC APPENDIX A
Table A.1L Characteristic Ions for SemivolatUe Target Compounds
- Anaivte
Primary Ion
Secondary lon(s)
Phenol
94
65.66
bis(2-Chloroet hvl)ether
93
63,95
2-Chlorophenol
128
64. 130
1,3-Dichlorobenzene
146
148.113
1,4-Dichlorobenzene
146
148.113
1,2-DichIorobenzene
146
148. 113
2-Methylphenol
108
107
2^'-oxybis( 1 -Chloropropane)
45
77,79
4-Methylphenol
108
107
N-Nitroso-di-propylamine
70
42,101.130
Hexachloroethane
117
201,199
Nitrobenzene
77
123,65
Isophorone
82
95,138
2-Nitrophenol
139
65,109
2.4-Dimethylphenol
107
121,122
bi5(2-Chloroethoxy)methane
93
95,123
2.4-DichloTophenol
162
164,98
! .2.4-Trich!orobenzene
180
182. 145
Naphthalene
128
129, 127
4-Chloroaniline
127
129
Hexachlorobutadiene
225
223,227
4-Chloro-3-methylphenol
107
144, 142
1 2-Methvlnaphthalene
142
141
| Hezachlorocyclopentadiene
237
235,272
| 2,4,6-Trichlorophenol
196
198,200
jj ncnicopnenoi
196
198,200
j| 2-Chloronaphthalene
162
164.127
A-16
DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A.11 Characteristic loos for Semivolatile Target Compounds (Continued)
| Parameter
Primary Ion
Secondary Ion(s)
| 2-Nitroaniline
65
92.138
Dimethyl phthalate
163
194,164
Acenaphthylene
152
151,153
3-Nitroaniline
138
108,92
Acenaphthene
153
152, 154
2,4-DinitrophenoI
184
63,154
4-Nitrophenol
109
139, 65
Dibenzofuran
168
139
2,4-Dinitrotoluene
165
63.182
2.6-Dinitrotoluene
165
89. 121
Diethylphthalate
149
177, 150
4-Chlorophenyl-phenylether
204
206, 141
Fluorene
166
165, 167
4-Ni;roaniline
138
92. 108
{ 4.6-Dinitro-2-methy!phenol
198
182,77
N-Nitrosodiphenylamine
169
168. 167
4-Bromophenvl-phenylether
248
250. 141
Hexachlorobenzene
284
142, 249
Pentachlorophenol
266
264,268
Phenanthrene
178
179. 176
Anthracene
178
179,176
Carbazole
167
166, 139
Di -n-butylphthalate
149
150, 104
| Fluoranthene
202
101.100
1 Pyrene
202
101,100
| Butylbenzylphihalate
149
91,206
S 3.3'-D!Ch'orobenridine
252
254. 126
A-17
DRAFT 12/90
Revised 6/9L
-------
MM/MC
APPENDIX A
Table A.11 Characteristic k>os for Semi volatile Target Compounds (Continued)
——«———-
Analyte
Primary Ion
Secondary Ion(s)
Benz(a)anthracene
228
229,226
bis(2«Ethylhexyl)phthalate
149
167, 279
Chrysene
228
226,229
1 Di-n-Ociyi phihalate
149
—
Benzo(b)fluoranthene
252
253,125
Benzo(k)fluoranthene
252
253,125
Benzo(a)pyrene
252
253,125
Indeno( 1 ,2.3-cd)pyrene
276
138.227
Dibenz(a.h)anthracene
278
139, 279
Benzo(g.h.i)perylene
276
138,277
A-18
1 DRAFT 12/90
Revised 6/91
-------
MM/MC APPENDIX A
Table A.12 Characteristic Ions for Semivolatile Surrogates and Internal Standards
Analvte
Primary Ion
Secondary Ion(s) {
SURROGATES
|
Phenol-d5
99
42,71
2-Fluorophenol
112
64
2,4,6-Tribromophenol
330
332, 141
Nitrobenzene-d5
82
128, 54
2-Fluorobiphenyl
172
171
Terphenyl
244
122, 212
2-ChlorophenoI-d4
132
68, 134
l,2-Dichlorobenzene-d4
152
115, 150
INTERNAL STANDARDS
1.4-Dichlorobenzene-d4
152
115
Naphthalene-dg
136
68
Acenapthene-d10
164
162. 160
Phen2Rth:ene-d,0
188
94,80
Chrvsene-d,-,
240
120. 236
Perylenc-d12
264
260.265
A-19
DRAFT 12/90
Revised 6/91
-------
MM/MC
Table A.L3 Characteristic Ions for PestJddes/Arodors
APPENDIX A
| Analvte
Primary Ion
Secondary Ion(s)
alpha-BHC
183
181,109
beta-BHC
181
183.109
delta-BHC
183
181,109
gamma-BHC (Lindane)
183
181.109
Heptachlor
100
272. 274
Aldrin
66
263. 220
Heptachlor epoxide
353
355, 351
Endosulfan I
195
339, 341
Dieldrin
79
263,279-
4,4'-DDE
246
248,176
Endrin
263
82,81
Endrin ketone
317
67, 319
Endrin aldehyde
67
250.345
Endosulfan II
337
339. 341
4.4'-DDD
235
237.165
Endosulfan sulfate
272
387, 422
4.4--DDT
235
237,165
Methoxychlor
227
228
Chlordanc (alpha and/or gamma)
373
375. 377
Toxaphene
159
231.233
Arochlor-1016
222
260.292
Arochlor-1221
190
222,260
Arochlor-1232
190
222,260
| Arochlor-1242
222
256,292
J Aiochlor-J24S
292
362,326
II Aiotniov-1254
292
362,326
| Arochlor-1260
360
362,394
A-20
DRAFT 12/90
Revised 6/91
-------
A-21
-------
APPENDIX A
Calibration standards are prepared at a minimum of five concentration
levels (20, 50, 80, 120 and 160 total ng). Eight compounds listed below require
only a four-point initial calibration at 50, 80, 120 and 160 total ng.
2,4 - Dinitro phenol 4 - Nitroaniline
2,3,4 - Trichlorophenol 4 - Nitrophenol
2 - Nitroaniline 4,6 - Dinitro-2-methylphenol
3 - Nitroaniline Pentachlorophenol
A-22
-------
APPENDIX B
ORGANIC DATA VALIDATION REPORT PREPARATION
-------
ORGANIC DATA VALIDATION REPORT PREPARATION
1.0 Purpose
The purpose of this procedure is to establish a standard procedure for
organic data validation report preparation following USEPA Region III
approved protocol.
2.0 Discussion
Following completion of data review and validation, the data reviewer is
responsible for compiling review notes into a standardized report format.
The procedure outlined in the following pages presents guidelines to follow
when preparing the data validation report.
3.0 Procedure
3.1 Organic Data Validation Narrative
3.1.1 Header Information - The beginning of the organic data validation
narrative has an established format, which closely follows a standard
memo format. The following information must be included in the
header:
DATE: (The date the report is submitted)
SUBJECT: Organic Data Validation for Case No.
FROM: Name
Organic Data Reviewer
TO: Name
EPA Remedial Project Manager
THRU: Name
Manager or Supervisor (if applicable)
3.1.2 Overview - The first text portion of the narrative report is an
overview of the data summary package, which includes the following
information:
A) The case number;
B) The number and matrix of samples analyzed;
C) The analytes for which the samples were analyzed;
D) The laboratory code or laboratory name (if code is not
available) of the analytical laboratory;
E) A summary of blanks, field duplicate, and any other QC samples
collected during sampling; and,
-------
F)
A statement indicating whether the samples were analyzed as a
Routine Analytical Service (RAS) or Special Analytical Service
(SAS) case.
This information is to be presented in paragraph form rather than a
tabulated list.
3.1.3 Summary - The second section of the data validation narrative is a
brief summary of the acceptability of the data presented in the data
summary package. The only concerns noted here are for data which have
been invalidated (qualified "R") due to calibration outliers (the most
common problem), or other extreme QC outliers.
3.1.4 Major Problems - Following the summary information presented in the
beginning of the narrative report, any problems associated with the
case are explained in detail, in order of importance. The first of
these three sections is Major Problems, which deals with data that
have been Invalidated (qualified "R"). This portion of the report
is the detailed explanation of the summary section of the narrative
report. All data which have been invalidated must be mentioned in
this section, with specific mention as to which samples have been
affected by the problem, and any remedial action performed by the
laboratory.
3.1.5 Minor Problems - The next section of the narrative report, following
the summary information, is the Minor Problems section. This portion
of the report explains in detail the data which have been qualified
as biased (L, UL, or K) or estimated (J or UJ). All data which have
been qualified must be mentioned in this section with specific
discussion pertaining as to which samples have been affected by the
problem, and any remedial action performed by the laboratory. One
exception to this rule is the listing of blank contaminants in the
Notes section rather than the Minor Problems section of the report.
3.1.6 Notes - The next section of the narrative report following the summary
information, is the Notes section. This portion of the report is a
detailed explanation of any QC criteria or analytical problems that
did not cause data to be qualified. Some examples of information to
be included in this section are maximum concentrations of blank
contaminants, spectra that were not confirmable, tentatively
identified compounds (TIC's) that have been identified as blank
contaminants or target compounds from another fraction, MS/MSD non-
spiked compounds reported for the various fractions and precision
estimates (table format), field duplicate analysis results and
precision estimates (table format), and QC outliers that have not
caused any data to be qualified (particularly for the pesticide/PCB
target compounds).
3.1.7 At the end of the narrative report, a paragraph must be included
stating the criteria by which the data were reviewed (most commonly
the Functional Guidelines for Evaluating Organic Analyses with
..-edifications for use within USEPA Region III). This paragraph must
also state that the text of the report addresses only those problems
affecting usability.
-------
3.2 Appendices
3.2.1 The final section of the report is a listing of the appendices attached
to the data validation report.
Following is the standard format for a RAS full organic data validation
report:
Appendix A - Glossary of Data Qualifiers (see note A)
Appendix B - Data Summary Forms (see Note B). These include:
(a)All positive results for target compounds with qualifier codes
where applicable.
(b)All unusable detection limits (qualified "R").
Appendix C - Results as Reported by the Laboratory for All Target
Compounds (see note C)
Appendix D - Reviewed and Corrected Tentatively Identified Compounds
(see note D)
Appendix E - Organic Regional Data Assessment Summary (see Note G)
Appendix F - Support Documentation (see note F)
NOTES:
(A) This glossary lists the qualifiers applied to data presented
on the data summary forms. This is a stock form, and must not
be changed from report to report. An example is included as
Attachment D.
(B) Examples of the data summary forms have been included as
Attachments E. Refer to Section 3.4 for instructions.
(C) Appendix C contains a copy of all laboratory generated Form
I's upon which the results of target compound analyses have
been reported. If any corrections are to be made to these
forms, both a copy of the un-corrected and the corrected form
must be included.
(D) Appendix D contains a copy of all laboratory generated Form
I's upon which the results of the library search for
tentatively identified compounds (TIC's) have been reported.
Corrections can be made directly on these forms and only the
corrected form must be included in the report.
(E) An example of the ORDAS has been included as Attachment A -
Refer to Section 3.5 for instructions.
(F) The support documentation for the data validation report
includes, but is not limited to: tables, shipping logs,
chain-of-custody forms, analytical laboratory narratives, QC
summary forms such as Form II (surrogate recoveries), or Form
III (MS/MSD) results) upon which QC outliers have been
-------
reported, calibration summary forms (including Table I; see
Attachment B and C), telephone logs, and Form I's for blank
and MS/MSD analyses. The documentation included in Appendix
F must support all concerns addressed in the data v&liiacisri
narrative and on the ORDAS.
3.3 Report Information Forma
3.3.1 Data Validation Evaluation Checklist (for CLP data only) - This form
(Attachment F) consists of one page, and is included at the front of
the data validation report package submitted to EPA. The header
information is filled out by the data reviewer. The EPA Task Monitor
fills out the remainder of the form during oversight. The following
information is required for the header:
A)
Case or SAS Number
B)
Site Name
*C)
Assignment (TID) Number
*D)
Task Number
E)
Revision Number
F)
Analysis Type
G)
Reviewer
H)
Contractor
I)
SOW Number
J)
Analytical Lab
K)
Phone Log Information
L)
Date of Report
Request and Receipt
Submission
Dates
*M)
EPA DPO
N)
EPA RPti
0)
Number of hours consumed
P)
Number of Samples
Q) Other Persons to Whom the Data Validation Report is to be Sent
*If applicable
As with the previous form, most of this information can be found on
the assignment sheet for the case, or is specific for the report being
generated. The revision number must be supplied by the data
validator. This form is not included in the package distributed to
the various data users.
3.3.2 Data Validation Report Transmittal Memo - This form (Attachment G)
is the cover memo and is included as a cover page for the data
validation report distributed to the various data users. In the
data validation package sent to EPA for oversight, it should be
included following the Data Validation Evaluation Checklist, and
preceding the data validation narrative. The following information
is required for this form:
A) The contract under which the data validation was performed
B) Case Number C) Site Name
D) Analytical Laboratory E) Reviewer
F) Regional TPO and Region Number
Again, most of this information can be found on the assignment sheet
for the case, or is specific for the report being generated. The name
and Region of the TPO can be determined from the location of th*
analytical laboratory.
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3.4 Organic fi«tmnafy vprms
3.4.1 Obtain the appropriate copy of the Organic Data Summary Forms
(Attachment E) for the data set being reported.
3.4.2 Complete the header information for each Data Summary Form, noting
the following information:
A) Site Name - enter entire Site Name.
B) Case # - enter Case Number (or other identification of data
set).
C) Sampling Date(s) - enter the sampling dates for all samples
listed on the form.
D) Sample No. - enter the sample number.
E) Dilution Factor - enter the multiplier value that when
multiplied by the CRQL listed on the data summary form (and %
moisture for soils) will equal those CRQL values listed on the
Form 1 for that sample. If necessary, report to one decimal
place.
F) Location • enter the sample location number or station number
from chain*of-custody form; also include any QC identification,
such as filed blank, field duplicate, etc.
G) Sample Results - in the first column for each sample list the
reported result across from the associated compound; in the
second column enter the appropriate data qualifier, if
applicable.
H) Page of - enter the page number along with the total
number of data summary forms submitted in the report.
3.4.3 ' Enter each sample in a separate block. In the case of re-analysis
or dilutions, only one set of results are entered on the data summary
forms. For re-analysis results, the reviewer should take into account
all QC related problems and report the best results. For samples that
have values that exceed the calibration range and were subsequently
diluted, results from the tin-diluted sample are entered for those
compounds that were within the calibration range. For those analytes
that were outside the calibration range, results from the diluted
analysis are to be entered. Professional judgement by the reviewer
is need to determine which results should be reported on the data
summary and will vary depending on the data set.
3.5 Organic Regional Data Assessment Siiirnnarv (For CLP Data Only)
3. b. i Obtain a copy of the Organic Regional Data Assessment Summary (ORDAS)
data validation summary form (Attachment A) in either hard-copy or
electronic format for each matrix of samples that have been reported.
-------
3.5.2 Complete the header information for each ORDAS form, noting the
following information:
A)
B)
C)
D)
E)
F)
G)
H)
I)
J)
Case Number¦
Laboratory
SDG Number
Data User
SOW
Review
Completion
Date
No. of
Samples
Matrix
Reviewer
Region
from the data summary form.
use the laboratory code from the Form 1's.
from the Form I's.
the Regional Technical Project Officer (TPO),
determined by the location of the laboratory.
For a laboratory located in Region IV, the Region
IV TPO should be entered here, despite the data
package being reported for Region III.
the date of the Statement of Work (SOU) by which
the samples were analyzed. The SOW is often
identified in the analytical narrative, or on the
CLP summary forms included with the data package.
For Special Analytical Services (SAS) cases, the
SOU used is often referred ta in the SAS request.
the last calendar day that any review was performed
on the data package.
the number of samples of a specific matrix included
in the case. One ORDAS page can be used to report
results from more than one sample deliver group
(SDG), but only one matrix per page is allowed.
the matrix of the samples reported on this ORDAS
page. As noted above, only one matrix per page
is allowed, regardless of the number of samples
reported.
name of reviewer who performed the data validation
and name of affiliated company.
name of Region in which laboratory analysis
occurred.
3.5.3 Enter the appropriate code for each of the Quality Control (QC)
concerns listed on the ORDAS for each group of analytes (volatiles,
semivolatiles, pesticide/PCB's, or other). These codes must be taken
from the following list, and are used to indicate how much data has
been affected by each QC concern. If an action item exists for one
or more of the QC concerns, the "A" code should be used in conjunction
with one of the other codes as noted below:
0 - No problems or minor problems that do not affect data usability.
X - No more than about 5% of the data points are qualified as either
estimated or usable.
-------
M - More than about 5% of the data points are qualified as estimated.
Z - More than about 5% of the data points are qualified as unusable.
A - TPO action requested; use in conjunction with one of the above
codes.
The number of data points affected for each of the QC concerns can
be determined from the various notes and summary tables prepared
during the course of data review and validation.
3.5.4 Vhile determining how many data points have been affected for each
of the QC concerns, a short descriptive comment for each group of QC
outliers Is written. These comments will be included on pages
following the ORDAS, and address outliers for both technical quality
and contractual compliance. The following QC concerns are examined
during data validation, and should be addressed by notes taken during
the data review:
A) Holding Times - Holding times for the extraction and/or
analysis of the various analytes must meet the limits
established by the SOW or SAS. If the initial extraction or
analysis for a sample is not within the established limit, it
must be noted as an action item on the ORDAS. If a sample has
been re-extracted or re-analyzed outside of the holding time
limits due to QC problems or required dilutions, it is not
noted as an action item. All holding time outliers should be
mentioned in an FYI comment, even if the criteria excepting
them from TPO action or data qualification have been met.
B) GC/MS Tune - For the volatile and semivolatile analyte groups,
confirm that the GC/MS tuning analysis has been run
successfully at the beginning of each analytical sequence, and
that all samples and QC analyses associated with each
analytical sequence have been performed within twelve (12)
hours of the tuning analysis. If these criteria have not been
met, and the associated samples have not been successfully re-
analyzed, the problem should be noted as an action item on the
ORDAS. All GC/MS timing outliers should be mentioned in an
FYI comment, even if the criteria excepting them from TPO
action or data qualification have been met.
GC Performance - For the pesticide/PCB analyte group, several
QC concerns must be examined, as follows:
1. Confirm that the retention time for 4,4'-DDT is greater
than twelve minutes (>12 minutes) for packed columns,
with the exception of OV-1 or OV-101 columns. This
retention time limitation helps to insure that acceptable
peak separation is achieved.
2. Confirm that the retention times of the calibration
standard compounds are within the windows established
by the laboratory, as noted on the Form IX's.
-------
3. Confirm that endrin and/or 4,4'-DDT breakdown are less
than or equal to twenty percent (£ 20%).
4. Confirm that the dibutylchlorendate (DBC) retention time
shift for each sample is within the acceptable range for
the type of column used. The criteria currently accepted
are 2.0% for packed columns, 0.3% for narrow-bore
capillary columns (I.D. < 0.32 mm), and 1.5% for wide-
bore capillary columns (I.D. £ 0.32 mm).
If these criteria have not been met, and the associated samples
have not been successfully re-analyzed, the problem should be
noted as an action item on the 0RDAS. All GC/MS tuning
outliers should be mentioned in an FYI comment, even if the
criteria excepting them from TPO action or data qualification
have been met.
Initial Calibration -
1. For the volatile and semivolatile compound groups, the
average response factors for the SPCC's (System
Performance Check Compounds) must be greater than or
equal to the criteria noted on the initial calibration
summary forms (Form VI). Also, the percent relative
standard deviation (%RSD) values for the CCC's
(Calibration Check Compounds) must be less than or equal
to thirty percent (£ 30%) as noted on the initial
calibration summary forms (Form VI). If these criteria
have not been met, and the associated samples have not
been successfully re-analyzed, the problem should be
noted as an action item on the ORDAS. Any non SPCC or
CCC calibration outliers (average response factor less
than five hundredths (< 0.05) or % RSD value greater than
thirty percent (> 30%) should be mentioned in an FYI
comment. A summary of all outliers is included in the
support documentation in tabular format as "Table I".
(Examples of the Table I forms have been included with
this SOP as Attachments B through C.) Also, included
in the support documentation should be all Form VI 's
included as part of the data summary package, with the
samples and/or QC analyses (if any) quantitated from the
particular initial calibration noted on the form by the
reviewer. The associated samples for each calibration
are listed on the associated Form V for each calibration.
If a continuing calibration has been run between the
initial calibration and sample analysis, no sample ID's
need to be included on the Form VI's.
2. For the pesticide/PCB compound group, the %RSD values
for aldrin, endrin, 4,4'-DDT, and dibutylchlorendate
(DBC) must not exceed ten (10%) percent. If the 10%
limit is exceeded, a three point calibration curve must
be used to quantitate these compounds if detected in the
samples. Also, if toxaphene is to be quantitated in the
-------
samples, a three point calibration is required. If the
%RSD for 4,4'-DDT is greater than the 10% limit, three
point calibration curves must be used for the
quantitation of 4,4'-DDT and 4,4'-DDE as well as 4,4'-
DDT, as mentioned above. If these criteria have not been
met, and the associated samples have not been
successfully re-analyzed, the problem should be noted
as an action item on the ORDAS. All calibration outliers
should be mentioned in an FYI comment, even if the
criteria excepting them from TFO action or data
qualification have been met.
Continuing Calibration -
1. For the volatile and semivolatile compound groups, the
relative response factors for the SPCC's (System
Performance Check Compounds) must be greater than or
equal to the criteria noted on the continuing calibration
summary forms (Form VII). Also, the percent difference
(%D) values for the CCC's (Calibration Check Compounds)
must be less than or equal to twenty-five percent (< 25%)
as noted on the continuing calibration summary forms
(Form VII). If these criteria have not been met, and
the associated samples have not been successfully re-
analyzed, the problem should be noted as an action item
on the ORDAS. Any non SPCC or CCC calibration outliers
(average response factor less than five hundredths (<
0.05) or %D value greater than twenty-five percent (>
25%) should be mentioned in an FYI comment. A summary
of all outliers is included in the support documentation
in tabular format as "Table I". Also included in the
support documentation should be all Form VII 's included
as part of the data summary package, with the samples
ahd/or QC analyses (if any) quantitated from the
particular continuing calibration noted on the form by
the reviewer. The associated samples for each
calibration are listed on the associated Form V for each
calibration.
2. For the pesticide/PCB compound group, the %RSD values
for aldrin, endrin, 4, 4'-DDT, and dibutylchlorendate
(DBC) must not exceed ten (10%) percent. If the 10%
limit is exceeded, a three point calibration curve must
be used to quantitate these compounds if detected in the
samples. Also, if toxaphene is to be quantitated in the
samples, a three point calibration is required. If the
%RSD for a 4,4'-DDT is greater than the 10% limit, three
point calibration curves must be used for the
quantitation of 4,4'-DDD and 4,4'-DDE as well as 4,4'-
DDT, as mentioned above. If these criteria have not been
met, and the associated samples have not been
successfully re-analyzed, the problem should'be noted
as an action item on the ORDAS. All calibration outliers
should be mentioned in an FYI comment, even if the
-------
criteria excepting them from TPO action or data
qualification have been met.
E) Field Blanks - Field blanks are not required by the SOW, but
are often run as an additional QC requirement. If no field
blank has been collected for a group of samples, it should be
noted on the ORDAS with the "F" flag. Trip blanks are often
collected for volatile analysis only, and do not apply for the
semivolatile or pesticide/PCB analyses. As noted above, any
fraction for which a field blank has not been collected is to
be flagged "F" on the ORDAS. If any blank contaminants are
present in the field blanks, they should be mentioned in an
FYE comment, even if the criteria excepting them from data
qualification have been met.
F) Lab Blanks - Any laboratory (method) blanks associated with
a group of samples must meet the following criteria:
1. The volatile and semivolatile blanks must not have any'
"common laboratory contaminants" (methylene chloride,
acetone, toluene, 2-butanone, or commonphthalate esters)
present at concentrations greater than five time (>5X)
the contract required quantitation limit (CRQL), or any
other target compounds present at concentrations greater
than the CRQL.
2. The pesticide/PCB blanks must not have any target
compounds present at concentrations greater than the
CRQL.
If these criteria have not been met, and the associated samples
have not been successfully re-extracted and/or re-analyzed,
the problem should be noted as an action item on the ORDAS.
All blank contaminants should be mentioned in an FYI comment,
even if the criteria excepting them from TPO action or data
qualification have been met.
G) Surrogate recoveries for each sample and QC analysis must be
within the limits established by the SOW or SAS, or must be
re-extracted and/or re-analyzed in order to confirm matrix
effect as the reason for non-compliance. If a sample or QC
analysis with surrogate outliers has not been re-extracted
and/or re-analyzed it must be noted as an action item on the
ORDAS. If a sample has been analyzed as a matrix spike and
matrix spike duplicate (MS/MSD) in addition to the initial
analysis, then no re-analysis is required for surrogate
outliers. All surrogate outliers should be mentioned in an
FYI comment, even if the criteria excepting them from TPO
action or data qualification have been met.
K) Matrix Spike/Duplicates - Matrix spikes and matrix spike
duplicates (MS/MSD's) must be analyzed at a frequency following
one or more of the following criteria, whichever is more
frequent:
-------
1.
One set (MS and MSD) per each case of field samples, per
matrix.
2. One set per each twenty (20) field samples in a case,
per matrix.
3. One set per each group of samples of a similar
concentration level (soils only).
4. One set per each fourteen (14) days period during which
samples were received for a sample delivery group (DSG),
beginning with the verified time of sample receipt (VTSR)
of the first sample received for that SDG, per matrix.
If MS/MSD analyses have not been performed at the required
frequency, it should be noted on the ORDAS as an action item.
Also, if a blank sample was used for the MS/MSD analyses, an
FYI comment should be made. In addition, all MS/MSD spike
recovery and RPD value outliers should be mentioned in an FYI
comment.
I) Regional QC - Regional QC samples are sometimes included in
regular analytical services (RAS), and special analytical
services (SAS) cases as a check on alnalytical performance.
If no regional QC sample has been included for a case, it must
be noted by the "F" flag on the ORDAS. If a regional QC sample
is required for the case, but has not been analyzed, it must
be noted as an action item on the ORDAS. All regional QC
outliers should be mentioned in an FYI comment, even if the
criteria excepting them from TPO action or data qualification
have been met.
J) Internal Standards - Internal standard (IS) recoveries and
retention times must be within the QC limits for all volatile
and semivolatile sample and QC analyses. If the QC criteria
are not met, a re-analysis must be performed to confirm matrix
effect. The current QC criteria for volatile and semivolatile
internal standards are IS recoveries greater than or equal to
one half, and less than or equal to twice (>1/2X and <2X) the
reference IS recoveries; and retention times less than or equal
to thirty seconds (<30 seconds) difference as compared with
the reference IS retention times. If one or more of the
internal standards for a sample or QC analysis do not meet the
QC criteria, and have not been re-analyzed, it must be noted
as an action item on the ORDAS. All internal standard recovery
or retention time outliers should be mentioned in an FYI
comment, even if the criteria excepting them from TPO action
or data qualification have been met.
K) Compound Identification -
1) Volatile and semivolatile target compound list (TCL)
compounds must have retention times within ±0.06 units
of the relative retention time established during
-------
instrument calibration. Also, the mass spectra for the
volatile and semivolatile target compounds must closely
natch the library reference spectra, as outlined in the
National Functional Guidelines for Organic Data
Validation, as modified for use in Region III. In cases
where these criteria have not been met, an FYI comment
must be included in the notes associated with the ORDAS.
If the samples have been re-extracted or re-analyzed with
acceptable results, the first set of data can be
disregarded, but all compound identification outliers
should be mentioned in an FYI comment.
2) Single response pesticide TCL compounds must have
retention times for both the quantitation and
confirmation columns within retention time windows
established following the SOW analytical method. These
retention time windows cannot be validated from the data
summary package, so any questions about the validity of
the retention time window must be referred to the
analytical laboratory, or the IPO. If a reported result
for a pesticide/PCB target compound does not meet the
retention time criteria, or if the retention time window
is in doubt, it should be mentioned in an FYI comment.
3) Multi-response pesticide/PCB TCL compounds (toxaphene,
and the various Aroclors) also have an established
retention time window for a single peak on both the
quantitation and confirmation columns, but are better
identified by pattern identification (fingerprint)
techniques. If the reference peak is not within the
retention time window on the quantitation or reference
column, or if the pattern identification is in doubt,
it should be mentioned in an FYI comment.
4) Tentatively Identified Compounds (TIC's) - For each
sample analysis, a mass spectral search of the NBS
library must be made for the ten (10) largest volatile
and twenty (20) largest semivolatile fraction peaks which
are not surrogate, internal standard, or TCL compounds,
and which have an area or height value greater than ten
percent (>10%) of the nearest internal standard area or
height value. TCL compounds from another fraction, such
as volatile compounds identified as semivolatile TIC's
are not to be reported as TIC's. Also, if a TIC is
identified in one of the blanks associated with the case,
it should be crossed off the TIC Form I's, and noted as
a blank contaminant. If these criteria have not been
met, or if there is a suspect identification of a TIC,
it should be noted on the ORDAS in an FYI comment.
Coicpound Quantitation -
1)
Each volatile and semivolatile TCL compound RRF must be
calculated based on the internal standard (IS) and
-------
quantitation ion (m/z) specified in the SOW for that
compound. The volatile and semivolatile TCL compound
quantitation must be based on the -RRF from the
appropriate daily standard. If these criteria have not
been met it should be noted on the ORDAS. All compound
quantitation outliers should be mentioned in an FYE
comment, even if the criteria excepting them from data
qualification have been met.
2) Each pesticide/PCB TCL compound must be quantitated based
on guidelines established in the SOW. If these
guidelines have not been met it should be noted on the
ORDAS. All compound quantitation outliers should be
mentioned in an FYI comment, even if the criteria
excepting them from data qualification have been met.
3) The contract required quantitation limit (CRQL)
established for each organic analyte in the SOW must be
adjusted to reflect all sample dilutions or
concentrations, splits, cleanup techniques performed
(notably GPC) , and dry weight factors (for soil samples) .
If the CRQL values have not been properly calculated,
it should be noted on the ORDAS in an FYI comment, even
if the criteria excepting them from data qualification
have been met.
M) System Performance - In addition to the QC checks required
during sample analysis, several other indicators of system
performance should be monitored, as follows:
1) Abrupt, discrete shifts in the reconstructed ion
chromatogram (RIC) baseline.
2) High RIC background levels.
3) Absolute retention time shifts of internal standards.
4) Excessive baseline rise at elevated temperature.
5) Extraneous Peaks.
6) Loss of resolution of compounds eluting at nearly the
same time, such as 2, 4- and 2,5-dinitrotoluene.
7) Peak tailing or splitting.
If one of these Indicators appears to be outside of the
acceptable limits, based on the reviewers professional
judgement, it should be mentioned on the ORDAS, as an FYI
comment.
N) Overall Assessment - Overall assessment of the case must be
based on the amount of data qualified by the QC concerns listed
previously, as outlined in the USEPA Region III quality
assurance directive "Implementation of New Regional Data
-------
Assessment Summary Forms", bulletin No. QAD014. Also, any
comments that do not apply directly to one of the subjects
listed above should be presented here.
3.5.5 TPO Action Items - Any action items identified on the ORDAS must be
summarized briefly here. A more detailed explanation is to be
presented in the comments attached to the ORDAS.
3.5.6 Areas of Concern - If the reviewer has some particular overall concern
about the data package, it should be summarized here briefly. This
concern may be explained in more detail in one or more of the comments
attached to the ORDAS.
3.5.7 If one or more action items have been Identified on the ORDAS during
the course of report preparation, it must be noted at the top right
corner of the page by placing an "X" in the box beside the word
"ACTION". If no action items have been identified, an "X" must be
placed in the box beside the letters "FYI", indicating that the
information is "For Your Information", and does not require action.
4.0 Report Organisation
The final organization of the data validation report must be as follows:
A) Report Information Forms (Section 3.5)
fi) Data Validation Narrative (Section 3.2)
C) Appendices (Section 3.3)
D) Document Control Number (Section 3.4)
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ATTACHMENTS TO APPENDIX B
ORGANIC REGIONAL DATA ASSESSMENT SUMMARY FORM
CALIBRATION OUTLIERS FORM FOR VOLATILE COMPOUNDS
CALIBRATION OUTLIERS FORM FOR SEMI-VOLATILE COMPOUNDS
GLOSSARY OF DATA QUALIFIERS CODES (ORGANIC)
DATA SUMMARY FORMS
DATA VALIDATION CHECKLIST
TRANSMITTAL MEMO
-------
PO;* IJACnON 11™ Region.
ORGANIC KE&nVAL DATA ASSESSMENT SUMMARY
ASE NO. I-AttOBATQgY
50 NO. ' DATA USER
vk REVIEW COMPLETION DATE,
*
O.OF SAMPLES MATRIX
EVIEWER fJESD ( ] ESAT [ ] OTHER, CONTRACT/CONTRACTOR,
VOA BNA PEST OTHER
1. HOLDING TIMES
2. OC-MS TUNE/ OC PERFORMANCE ' __
3. INITIAL CALIBRATIONS _ ¦
4. CONTINUING CALIBRATIONS _ _
5. FIELD BLANKS fP ¦ aot applicable) _______ _
6. LABORATORY BLANKS ,
7. SURROGATES
8. MATRIX SPIKE/DUPLICATES _ __
9. REGIONAL QC ("F" » aot applicable) _____
10. INTERNAL STANDARDS
11. COMPOUND IDENTIFICATION _
12. COMPOUND QUANTITATION '
13. SYSTEM PERFORMANCE"
14 OVERALL ASSESSMENT
O * No problems or minor problems that do not affect data nubility.
X ¦ No more than about 5% of the data points are qualified as either estimated or unusable.
M ¦ More than about 5% of the data pouts are qualified as estimated.
Z « More than about 5% of the data points are qualified as unusable.
A ¦ DPO action requested; use In conjunction with one of the above codes.
DPO ACTION ITEMS:
AREAS OF CONCERN:
Reg.Ill Rev.8/89 4/89
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TABLE I
page of
ENVIRONMENTAL PROTECTION AGENCY REGION III
CALIBRATION OUTLIERS
VOLATILE HSL COMPOUNDS
CASE/SAS Ufa- CONTRACTOR
Instrument*
PATE/TIME;
Tnlt. Cal. iCont. Cal
Cont. Cal.lCont. Cal
IConti Cal
BP URSPf
RF HP
BF IIP 1«
*p HP »*
»» '•
Chlopomethane
Broinoaethane
Vlnvl Chloride
Cnloroetnane
Methylene Chloride
Aeetone
Carbon Plsulflde
1.1-Dlehloroethene
1.1-Dlehloroethane
Total-1.2-Bichloroethene
Chloroform
1.2-Dlehloroethane
-2,-Bu^anone
1.1.1-Triehloroethane
Carbon Tetrachloride
.Ytnvl Aspm?.
Bromodlchioromethane
1.2-Dlehloropronane
Qj-8-1 ..B-PlOMQrOgrQPW?
Trlqhloroethene
Pllvroaoohloroiaethane
1.1.2-Trlohloroethane
I
t trans-"M-Dlchlorgprgrea?
Bromoform
I 4-Methvl»2-Pentanone
1 2-FIeyanone
I Tetraehloroethene
1 1.1.2.2-Tetraehloroethane
Toluene
t Chlorobenzene
1 Ethvlbenzene
1. Styrgne
Total Xylenes
•AFFECTED
SAMPLES:
Reviewer
Initials/Date:
* See last page of this table for DEFINITION OF CODES.
-------
TABLE I
page of
CASE/SAS Ho..
ENVIRONMENTAL PROTECTION AGEHCT REGION HI
CALIBRATION OUTLIERS
SEMIYOLATILE HSL COMPOUNDS (Part 1 of 2)
CONTRACTOR , ,
T IngtrvgBsafel,.
PAIE/TIME;
Inlt. Cal
Cont. Cal.lCont. Cal.
Cont. Cal
'Cont. CalJ
nr mm*
w »»
nr tip i*
up »«
'«P '»
Phenol
blaf 2-Chloroethvl)ether
2-Chloropbenol
1.3-Dichlorobenzene
1iVPAoMor9b?M9ne
Benzyl alcphol
1.2-Dlehlorobenzene
2-Metbv1phenol
bisf 2~Chlopolaoppopvl)ether
*hM9thYlPh?nQl
K-Nltroao-di-p-propvlamlne
Hexachloroethane
Nitrobenzene
Iaophorone
2-Nitrgphengl
2.a»Plfflcthvlphenol
Bsnzgite acid
blaf 2-Chloroethorv)methane
2.fr-Dlehlorophenol
1.2, q-Trlchlgrgfrgnzgaa
h>gntpalsr.e
H-Chloroanlllne
Hexachlorobutadiene
^-Chlorg-VMetfrYlphenol
2-Methvlnaohthalene
Hexaohlorocvelopentadlene
2.».6-Trieblorophenol
2.1.5-TrAohlgrgphengl
2-Chloroaaphthalene
2-Httrganiltn9
Dimethvlphthalate
Aaenaphthvlane
2.b-Dinltrotoluene
3-Nltroaniline
Aeenaphthene
.Sifr-DAnltrgphTOPl
il-Kltropbenol
AFFECTED
SAMPLES:
Rsviewer
Initials/Date
« See last page nf *h* *ahla for PEPTWTTTOW flF MT>FS.
-------
TABLE Z
naac ef
CASE/SAS Ho..
ENVIRONMENTAL PROTECTION AGENCT REQION III
CALIBRATION OUTLIERS
SEMI7QLATILE ESL COMPOUNDS (Part 2 of 2)
CONTRACTOR
Instrument#
iBlt. Cal
Cont. Cal.iCont. Cal.
Cont. Cal
ICont. Cal,
PATE/TIME:
i-
bp hp i« »bf >
-------
GLOSSARY OF DATA QUALIFIER COOES (ORGANIC)
CODES RELATING TO IDENTIFICATION
(confidence concerning presence or absence of compounds):
U - Not detected. The associated number Indicates approximate sample
concentration necessary to be detected.
(NO CODE) - Confirmed Identification.
B - Not detected substantially above the level reported In laboratory
or field blanks.
r - Unreliable result. Analyte may or may not be present 1n the
sample. Supporting data necessary to confirm result.
N - Tentative Identification. Consider present. Special methods
may be needed to confirm its presence or absence 1n future
sampling efforts.
CODES RELATED TO QUANTITATION
(can be used for both positive results and sample quantitation limits):
J - Analyte present. Reported value may notlie accurate or precise.
K - Analyte present. Reported value may be biased high. Actual
value 1s expected to be lower.
L - Analyte present. Reported value may be biased low. Actual ~
value 1s expected to be higher.
UJ - Not detected. Quantitation limit may be inaccurate or Imprecise.
UL - Not detected. Quantitation 11m1t is probably higher.
OTHER CODES
Q - No analytical result.
-------
- of ¦ ¦ ¦
DATA SUMMARY FORM I OftOARXCS
Site Naac : HATER SAMPLES
(W/*«)
Case #» Saapling Dat«(*)i ________
To calculate sample quantitation lisItt
(flL * Dilution Factor)
Sanplt No.
Dilution Factor
Location
QL CCMPdUNO
1
1 1 III
II II
1 ""
1
-
1
1
1 1
II
•
1
II II
U • H
H II
II H
-
H
II II i
H y
II II
QL - Quantitation Liait SEE NARRATIVE FOR CODE DEFINITIONS
revised 07/92
-------
*49*
of
Site R Ml
Case #
Sampling Date(s)t
DATA SUMMARY FORM: OROAM1C8
SOIL SAMPLES
(M9/K9)
To calculate aaaplo quantitation ].laii
(QL * Dilution Factor) / ((100 - % noisturo)/lot
Sapl« No.
Dilution Factor
X Moisture
Location
i
in ¦ hi
II
||
•
||
||
||
A
i
H
||
1
H
I
H
|
H
II
||
1
1
||
¦ II
||
1
: 0
H
||
U
¦
|
1
||
H
1
||
|
1
||
1
II
II
II
QL a Quantitation Liait
-------
Sitn It me* _
Caso # Mapling Date(s) »
son. BRmss
To calculate sample quantitation liai
(CRQL * Dilution Factor) / ((100 - H Boiature)/lc
Swple Mo.
Dl1utIon Factor
X Moisture
Location
CMC COMPOUND
ii'
i
¦
10 || Chloronethane
10 || Brcmomethane
II
10 || vinyl Chloride
H
10 || Chloroethane
10 || Methylene Chloride
||
I
io || Acetone
|
I
10 || Carbon Disulfide
II
II
10 | 1,1-Dlchloroethene
10 U 1,1-Dtchloroethane
I
10 || Total 1,2-Dichloroethene
n
10 || Chloroform
I
10 || 1.Z-D1chloroethane
1
10 || 2-Butanone
I
10 U 1,1,1-Trichloroethane
.
10 || Carbon Tetrachloride
||
10 || Vinyl Acetate
I
H
n
10 || Broaodlchloromthane ||
|
1
1
1 H
|
0
fl
H II
n
H
•
1
II
1 u
1
n
B II
|
I
II
II
B
|
1
0
U
|
I
1
II
II
II
I
CRQXi ¦ Contract Required Quantitation Liait SEE NARRATIVE FOR CODS 0EFXWIT3
-------
site Ham s . SOIL SAMPLES
(fig/Kg)
Case gt Baapling D>te(>)i
To cnlcnlat* lupla quantitation lia itt
(CRQL * Dilation Factor) / ((100 - « noistura)/100)
Saaple No.
01(utfan Factor
X Moisture
Location
CRQL COMPOUND
II
1111
II 1 111
H
1
H
1
H
H
10 II 1.2-Dlchtorooroosne
10 II Cls-1.3-0lehloropropeno
10 || Trichloroethene
10 || Dlbromoctiloromethane
10 I 1.1.2-Trlchloroethane
10 || Benzene
10 || Trans-1.3-Dlchloropropene
10 || Broaofora
10 | 4-Methyl-2-pentanone
10 || 2-Hexartone
10 || Tetrachloroethene
10 1,1,2,2,-Tetrachloroethene
10 || Toluene
10 || Chlorobenzene
• \
10 || Ethylbenzene
10 || Stvrene
10 || Total Xylenes
||..
II
II II
1
-
II H
!
H
i
CRQL ¦ Contract Required Quantitation Liait SEE NARRATIVE FOR CODE DEFINITION
-------
Pug* ==_=> of _
DATA SUMMARY FOKMt VOLATILES 1
Sit* Name WATER SAMPLES
<«/!•>
Case it _ Sampling Date(a) i
To calculate oaaple quantitation liaitt
(CRQL * Dilution Pactc>r)
revised 07/92
-------
sit* Ka* «i mam samples
Case ft Sampling l>ate(c)s
To calculate Maple quantitation lltiit
(CRQL * Dilution rad.ox
Sample No.
D(tutfan Factor
Location
t
1
1
am.
COMPOUND
•
10
*1.2-Dfch loroorooane
10
Cf»-1,3-Dlchloropropene
10
THchloroethene
10
D < bromochIoromethane
i
10
1,1,2-Trichlorethane
10
•Benzene
10
Trans-1.3-DlchlorooroDena
10
Bromofona
I
10
4-Nethy(-2-pentanone
H
10
2-Hexanone
10
•Tetrachloroethene
10
1,1,2,2-Tetrachloroethane
10
*Toliwm
•CMoroberaene
10
•Ethylbenzene
10
•Stvrene
i
10
•Total Xvlenea
•«
¦
II
CRQL a Contract Required Quantitation Lialt 6Action Level Exists SEE KARRATXVE FOR CODE DEPXNITIO
-------
Site Kb
-------
f»«9« el
DATA SUMMARY FORM I B II A 8 2
Site Men I WATER SAMPLES
Case #« Sanpling Date(s) i
To calculate saaple quantitation llailtt
(CRQL * Dilation fadnr)
Sample No.
Dilution Factor
Location
L
1
"ll "
l
CML
COMPOUND
Uexacruorotxitadiene
10
4-Chtoro-3-«ethy(phenol
"TO"
Z-Nethylnaphthalene
"10
Hexacn i orocyc i opemecn eo»
¦
10
z,«,o-Trtciiioropnenoi
8
Z,«,5-Trlcniorophenol
10
Z-Chloronaphthalene
X
Z-NitroanHtne
1
10
Dlmethylphtftatate
10
Acenaphthylene
i
10
2,6-Dtnttrotoiuene
f
8
3-NltroanlUne
id
Acenaphtltene
8
2,4-Dtnltrophenol
25
^•Nitrophenol
10
Olbenzofuran
10
2,4-Oinitrotoluene
H
10
. Dlethylphthatate
|
10
4-Chlorophenyl •phenylether
|
10
Fluorene
•
-•
25
4-Nitroanllfne
25
4.6-Dinltro-2-eethylphenol
I
I
«
=J
CRQL - Contract Required Quantitation Liait SEE KARRATIVB FOR CODE DEFIWTIOW?
revised 07/9;
-------
frage . of ..
DATA SX1MMARV FORMS B M A 8 3
Site Van* t HATER SAMPLES
(pg/M
Cits* #i _ ___ Sampling Data(*) t
To calculate sanpla quantitation lisitt
(CRQIj * Dilution Pact ar)
SSBBBB= III II ,B 1 1 '1
Sample No.
Dilution Factor
Location
CMl COMPOUND
1
1
10 II N-Nftrosodiphenylanfne II
10 II 4-Braaophenyl -phenylether ||
10 || •Hexachlorobenzene ||
25 || •Pentachlorophenol ||
10 || Phenanthrene ||
10 || Anthracene ||
10 || Carbezole
10 II Dl-n-butylphthalate
10 || Fluoranthene
10 || Pyrene
10 | Butylbenzylphthalate
10 | 3.3'-0iclitorobenzid1m
n
10 || Benzo(a)anthracerw
10 || Chrvsene
II
10 || bla(2-Ethvlhexvl)Dhthalate
1
1
%
u
10 || • - BMisorklfluroantfiem
1
II
1
*
II
111 II ImoIh !¦
1
II
II
II
CRQL ¦ Contract Required Quantitation Limit 'Action Level Exists SEE HARRAT1VE FOR CODE DBFIHIXIOf
reviaed 07/-
-------
Of . ¦
DATA SUMMARY FORM I BRAS 1
Site Ha i«! . SOIL SAMPLES
(pg/Kg)
Case #: Sampling Datei
To calculate lupla quantitation lijait
(CRQL * Dilution Factor) / <(1 - * »ointure) /' 100
Sample No.
Dilution Factor
X Moisture
Location
CRQL COMPOUND
T ^"1
11
|
II
II
330 | Phenol
330 H bfs(2-Chloroethyl)ether *
330 H 2-Chlorophenol
330 I 1(3*Dlchlorobenzene
330 II 1,4-Dlchlorobenzene
330 || 1,2-Dlchlorobenzene
H
330
2-Methylphenol
330
bls(2-Chloro
330
2,4-Dfchlorophenol
330
1,2,4-Trlchlorobenzene
330
Naphthalene
330
4-ChloroanlIine
II
CRQh » Contract Required Quantitation Limit SEE NARRATIVE FOR CODE DEFIlflTI'
revised 07
-------
*•9* __ °* ——
OATH SUMMARY FORMS BRAS
Sit* Ka wi
Case #»
Saapling Date(s)i
SOIL SAMPLES
(pg/Kg)
To calculate saaple quantitation lJaii
(CRQL * Dilution Factor) / ((100 - % Mixture)/ 10i
Sample No.
Dilution Factor
X Moisture
Location
—, - "n i1 • ¦ i -
CROL
COMPOUND
330
4-Chloro-3-inethvlohenol *
330
2-Nethylnsphthalene
330
Hexechtorocvclooentadfene
330
2.4.6-THchloroohenol
II
800
2.4.5-Trlehloroohenol
330
2-Chloronaohthalene
800
2-Nftroanlline
'
330
Dlnethylphthalate
H
330
Acenaohthvlene
|
330
2.6-Dlnl trotoluene
|
800
3-NitroaniUne
330
Acenaohthene
i
|
800
2.4-Dinftroohenol
fl
800
4-Nftropfienol
|
330
Dlbenzofuran
|
% II
330
2.4-Dlnttrotoluene
|
1
330
Dtethvlphthalate
|
H
|
t
1
330
Fluorens
|
H
800
4-Mltroanlllne
II
800
4.A-Dinftro-2metfivlnhenol
H
|
1
1
|
II
II
CRQL « Contract Required Quantitation Liait
8KB NARRAXZVB FOR CODS OSFIMISI
revised 07
-------
ftgt _ of .
DATA SUMMARY FORMS B M A 8
Site Mas «t
Case #»
SOIL SAMPLES
(W/KflT)
Saapling Data(*)>
To calculate sMpla quantltat.ion lliiltt
(CRQL * Dilution Factor) / ((100 - % aoiitute) / \00)
Sample No.
Dilution Factor
X Nolatura
Location
CRQL COMPOUND
j
i
V
330 II N-Ni trosodfuhenvlanine
330 II 4-Brcawphenyl-phenylether •
330 || Hexachlorobenzene
800 || Pentaehlorophenol
•
330 || Phenenthreno
330 | Anthracene
330 A Carbazote
0
330 | Df-n-butytphthalate
|
II
A
330 || Fluor ant hene
|
|
330 || Pyrene
|
|
330 H Butylbenzylphthalate
|
|
330 II 3f3,-Dlchlorobenztdlne
II
|
330 || 8enzo(a)anthracene
330 || Chrysene
n
330 || bis(2-Ethylhexyl )phthalate
|
330 H Dl-n-octylphthalate
•
|
330 (J Benzo(b)fluoranthene
|
930 0 a Benzo(k)fluorantttene
||
||
330 | Benzo(a)pyrene
H
|
330 P lndeno(1,Z,3-ed)pyrene
1
-
||
330 || Dibenz(a,h)anthracene
|
II
330 || Benzo(s,h)pery(ene
|
|
|
|
|
II
II
¦
II
CRQL a contract Required Quantitation Liait
SEE NARRATIVE f6r CODE DEFIHITIOl
revised 07/'
-------
• DATA SUMMARY FOftMt PESTICIDES AMD PCI 1 8
Sit* Manes
Cua #«
Stapling Dita(t)t
MATER 8MCPUS8
(fig/L)
To calculate aupla qnan^itation liaict
(CRQL * Dilution Factor)
Saaple No.
Dilution Factor
Location
CRQL COMPOUND
1 1 II
1 II
0.05 ]| alDha-BHC
0.05 beta-BHC
0.05 delta-BHC
0.05 | *gamna-BHC (Lindane)
0.05 | *Heptachlor
0.05 Aldrln
0.05 II Heotachlor Emxfde
0.05 || Endosulfan !
0.10 A Dleldrln
0.10 4.4'-00E
0.10 | *Endrln
0.10 I Endosulfan 11
0.10 4.4'-00D
0.10 | Endosulfan Sulfate
0.10 | 4.4*-DDT
0.50 | *Methoxvchlor
,
I
0.10 H Endrin Ketone
n
0.10 | Endrin Aldehyde
|
0.05 | 'aloha-Chlordane
I
»
0.05 | *ganm-Chtordane
II
5.0 H *Toxaohene
I
1.0 | *Aroclor-1016
I
2.0 | *Aroclor-1221
I
1.0 | °Aroclor-1232
||
1
1.0 I *Aroclor-1242
H '
|
1.0 || *Aroclor-1248
|
1.0 || *Aroclor-1254
II
||
1.0 || *Aroclor-1260
II
II
CRQL ¦ Contract Raqulrad Quantitation Limit
Action Level Exist*
SEE NARRATIVE FOR CODE DEFINITIONS
revised 07/92
-------
data summary forms ristiettn hhb >cb 1 fi
Site Mane ; ' SOIL SAMPLES
(M9/K9)
Case #i Soipliag Date(s) >
To calculate tupl* quantitation limit
(CRQL * Dilution Factor) / ((100 - % Boiature)/100)
Sample No.
Dilution Factor
X Moisture
Location
CRQL COMPOUND
a II III 1 llll 1
,
/
1.7 || alpha-BHC
1.7 beta-BHC
1.7 II del ta-BHC
1.7 gama-BNC (Lindane)
1.7 || Heptachlor
,
1.7 | Aldrln
1.7 || Heptachlor Epoxide
1.7 | Endosulfan I
3.3 | Dieldrin
3.3 4,4*'DOE
l
!
3.3 | Endrin
3.3 II Endosulfan It
3.3 0 4.4'-DOO
3.3 | Endosulfan Sulfate
3.3 4,4* -HOT
II
17 fl Methoxvchlor
3.3 tt Endrin Ketone
3.3 | Endrin Aldehyde
1.7 || alpha-Chlordane
•
1.7 || ganaa-Chtordane
||
170 H 'Toxaphene
1
33 Q Aroclor-1016
67 | Aroctor-1221
33 II Aroclor-1232
33 H Aroclor-1242
||
|
« II IrarlwIM
i
II
CRQL ¦ Contract Required Quantitation Liait 8KB NARRATIVE FOR CODB DBPIMITXOl
revised 07/'
-------
MX* VALXMXXOK SVALOAXXO* CHECKLIST
C«**/SAS guabari Site Sanei
Aeeigrment #i Revision Munbcri Analysis
fjerimreri Contractor i SON
Analytical Laboratory*,
Information Information
vequest dates _ received d»fi
Sat* tobiaitttd to »a»
SPA pfoi Murtber of hours spant
jpk mmi on mitwi
eei Mumber of
^Moplaat ______
CRITERIA
Tonnat according to
Slegion XXX protocol
Clarity of raport
Qualifiers applied
correctly
Consistency between
narrative, data a usury
£orm{e), end DPO report
Zrror-frea transcription
TBS ffO COMMENTS
Tf'FICIKNCY OF XE£ Efi gPHMBWTg
gPNTTOCTPP
Approval recooaended
ior current suboission __ __ ______
Sine spent en review
in reasonable
«SP OVERSIGHT
MONITOR/
DATES ATC/DPO SVALVATOR ______ ISAT
Jteceived at SPA
Oversight assigned
Oversight ree'd by TK
Oversight complete
feedback given
Mailed to RPM
XVALUATOR SIGNATURE t
revised 01/90
-------
W"\ UNITED STATES ENVIRONMENTAL PROTEL1 iON
• J REGION m
5 CENTRAL REGIONAL LABORATORY
839 BESTGATE ROAD
ANNAPOLIS, MARYLAND 21401* 3013
(410)573-2799
DATE:
SUBJECT: Region ZZZ CLP Data Quality Assurance Review
FROM: Cynthia C. Metzger, Chief
Program Support Section (3ES23)
Remedial Project Manager (3HW )
Z have attached for your information and use the data validation
report for RAS/SAS Number
The attached report was prepared in accordance with the Region
111 modified Functional Guidelines by __________
and its subcontractors under
Contract Number My staff has
reviewed this report and approved it for distribution.
The specfic details for the report are listed below:
RAS/SAS Number:
Site Name:
Laboratory:
Reviewer:
if you have any questions regarding this report, please call
of my staff. He/she can be reached at
FTs or at EMail box number .
Attachment
cc: Edward Kantor, EMSL-LV
Regional CLP TPO: • Region: _____
Revised March 1991
Priired or. Reryclti faptr
-------
APPENDIX C
CONTRACTUAL REQUIREMENT COMPARISON TABLES
-------
APPENDIX C
Table CI. Comparison of Requirements for
Volatile Data Review
REQUIREMENT
MULTI-MEDIA. MULTI-
CONCENTRATION
LOW CONCENTRATION
WATERS
Target Compound list
33 Target Compounds
40 Target Compounds
Data Turnaround -
35 days
14 days
Technical Holding Tine
7 days if not preserved
14 days if preserved
7 days if not preserved
14 days if preserved
Initial Calibration
5 levels: 10 - 200 ug/L
S levels: 1 - 25 ug/L
(5 « 125 for Ketones)
Continuing Calibration
mid-level: 50 ug/L
mid-level: 5 ug/L
(25 for Ketones)
Blanks
Method Blanks
Instrument Blanks
Method Blanks
Instrument Blanks
Storage Blanks
SMOSurrogates
SMC:
l^-Dichloroethane-d4
Bromofluorobenzene
Toluene-dg
Surrogate: Bromofluorobenzene
j MS.MSD
Frequency: 1 per 20 samples,
per matrix
N/A
| LCS
N/A
1 per SDG
| Regional QA-'QC
PEs - variable
PEs • 1 per SDG
Internal Standards
IS Area: - 50% to + 100%
IS RT Shift: ± 30 sec
3 compounds:
Chtoroben2ene-ds
1,4-Difluorobenzene
Bromochloromethane
IS Area: ± 40%
IS RT Shift: ± 20 sec.
3 compounds:
Chlorobenzene-d5
1,4-Difluorobenzene
1,4-Dichlorobenzene
1 CRQL
10 ppb (water/low soil)
1200 ppb (med soil)
1 • 5 ug/L
1 "ncs
largest 10 >10% of nearest IS
largest 10 >40% of nearest IS
C-l
. DRAFT 12/90
-------
APPENDIX C
Table G2. Comparison of Requirements for
Semivolatile Data Review
REQUIREMENT 1 MULTI-MEDIA. MULTI-
J CONCENTRATION
LOW CONCENTRATION
WATERS
Target Compound List
64 Target Compounds
60 Target Compounds •
Data Turnaround
35 days
14 days
Technical Holding Time
Extraction - 5 days
Analysis • 40 days after
extraction
Extraction • 5 days
Analysis • 40 days after
extraction
| Initial Calibration
5 levels: 20 • 160 ug/L
5 levels: varies
Continuing Calibration
mid-level: SO ug/L
mid-level: varies
Blanks
Method Blanks
Instrument Blanks
Method Blanks
Instrument Blanks
Storage Blanks
| Surrogates
8 compounds
6 compounds
MS/MSD
1
Frequency: 1 per 20 samples,
per matrix
N/A
| LCS
N/A
1 per SDC
| Regional QA/QC
PEs • variable
PEs -1 per SDC
Internal Standards _
IS Area: • 50% to + 100%
IS RT Shift: ±30 sec
IS Area: - 50% to 100%
IS RT Shift: + 20 sec.
| CRQLs
| TICs
10 • 50 ppb (water)
330 - 1700 ppb (low soil)
10,000 • 50.000 (med soil)
5.20 ug/L
largest 20 >.10% of nearest IS
largest 20 ,>50% of nearest IS
C-2
DRAFT 12/90
-------
APPENDIX D
PROPOSED GUIDANCE FOR
TENTATIVELY IDENTIFIED COMPOUNDS
(VOA AND SV)
-------
Proposed Guidance for Tentatively Identified Compounds (VOA)
A. Review Items: Form IVOA-TIC, chromatograras, library search printout and spectra for three TIC
candidates, and GC retention time data.
B. Objective
Chromatographic peaks in volatile analyses that are not TCL compounds, system monitoring
compounds, or internal standards are potential tentatively identified compounds (TICs) or library
search compounds (LSCs). TICs must be qualitatively identified by a library search of the National
Institute of Standards and Technology (NIST) mass spectral library, and the identifications assessed
by the data reviewer.
C. Criteria
For each sample, the laboratory must conduct a library search of the NIST mass spectral library and
report the possible identity for the 10 largest volatile fraction peaks which are not surrogates, internal
standards, or TCL compounds, but which have a peak area greater than 40 percent of the peak area
of the nearest internal standard. TIC results are reported for each sample on the Organic Analysis
Data Sheet (Form I VOA-TIC).
Note: Since the SOW revision of October 1986, the CLP does not allow the laboratory to report
as tentatively identified compounds any TCL compound which is properly reported in another
fraction. (For example, late eluting volatile TCL compounds must not be reported as
semivoiatile TICs.)
D. Evaluation
1. Guidelines for Tentative Identification are as follows:
The interpretation of library search compounds (LSCs) is one of the aspects of data review
which calls for the fullest exercise of professional judgement. The reviewer must be
thoroughly familiar with the principles and practice of mass spectral interpretation and of gas
chromatography. Because the interpretation process is labor-intensive, it is important to
document the process involved in arriving at a tentative identification.
Worksheets for "Tentative Identification of Library Search Compounds" are provided in
Appendix B for the volatile GC/MS fractions to assist in generating the information needed
to make a reasonable tentative identification of the LSCs.
The process involved in tentatively identifying a library search compound may be summarized
as follows:
a. Identify all samples in the related group (Case, SAS or SDG) in which the unknown
compound occurs. Calculation of relative retention times (RRT) and comparison ot
RRT and mass spectral data across samples is extremely helpful in identifying
unknowns that occur repeatedly in related samples. Use one worksheet per unknown
for all samples in which it occurs.
b. Inspect the library search spectrum retrieved for each unknown, to determine if
detailed mass spectral interpretation is necessary. Often, it is obvious that the
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Identified Compounds
VOA
correct match is among the spectra retrieved for the unknown from the several
samples in which it is found. It may only be necessary to check the unknown's RRT
versus a reference list of VOA (generated under similar conditions and after
accounting for bias in the sample) to arrive at a satisfactory tentative identification.
Some references are provided. If a reference RRT is not available, then a
comparison of the unknown's RRT or boiling point to the RRT or boiling point of
a closely related compound may also provide a satisfactory tentative identification.
Within a compound class, retention time increases with increasing boiling point.
c. In the event that serious ambiguity still exists after examining the library spectra and
RRT data, a full mass spectral interpretation can narrow down the possibilities.
While a full discussion of manual mass spectral interpretation is beyond the scope
of this document, several key points may be mentioned as important objects:
o Determine a likely molecular weight Depending on the unknown, the MW
may or may not be apparent due to the extent of fragmentation. The MW
of the retrieved library spectra, interpreted in light of the RRT. may be
helpful if the molecular ion is not present
o Determine the isotope ratios (M+l)/M, (M+2)/M (M+4)/M, etc (where
M is the molecular ion) and determine a short list of possible molecular
formulas. Isotope ratios will also reveal the presence of S, CI, and Br.
o Calculate the total number of rings-plus-double-bonds in the unknown by
applying the following equation to the likely molecular formulas, to
determine the degree of unsaturation.
Number of rings-plus-double bonds (r+db):
(r+db) = C-H-X + N +1
2 2 2
where: C = no. of carbons
H = no. of hydrogens
X = no. of halogens
N = no. of nitrogens
Note: oxygen and sulfur do not need to be accounted for.
An aromatic ring counts as four rings and double
bonds.
o Calculate the mass losses represented by major peaks in the unknown
spectrum, and relate these to the fragmentation of neutral moieties from the
molecular ion or other daughter ions.
o Using the information gathered on molecular weight, molecular formula,
degree of unsaturation, and mass losses in the unknown spectrum, combined
with the RRT data, give as precise a description of the unknown as possible,
including an exact identification if it is justified.
D-2
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Tentatively Identified Conponnds
VOA
d. In the event that the unknown spectrum is not that of a pore compound, mass
spectral interpretation may not be possible. However, in some instances, a mixed
spectrum may be recognised as two compounds having very similar relative retention
times. Target compounds, surrogates and internal standards may also be responsible
for extra ions in an unknown spectrum.
2. Check the raw data to verify that the laboratory has generated a library search s pea rum for
all required peaks in the chromatograms for samples and blanks.
3. Blank chroma tograms should be examined to verify that TIC peaks present in samples are not
found in blanks. When a low-level non-TCL 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 40 percent of the internal standard peak
area or height, but present in the blank chromatogram at similar relative retention time.
4. All mass spectra for every sample and blank must be examined.
5. The reviewer should 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:
a. Common laboratory contaminants: CO? (m/z 44), siloxanes (m/z 73), diethyl ether,
hexane, certain "reons (1,1,2-trichloro* 1,2^2-trifluoroethane or fluoro-
trichloromethane), and phthalates at levels less than 100 ug/L or 4000 ug/Kg.
b. Solvent preservatives such as cydohexene which is a methylene chloride preservative.
Related by-products include cyclohexanone, cyclohexenone. cyclohexanoi.
cyclohexenol, chlorocyclohexene, and chlorocyclohexanol.
c. 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.
6. Occasionally, a TCL 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. If the
total area quantitation method was used, the reviewer should request that the laboratory
recalculate the result using the proper quantitation ion. In addition, the reviewer should
evaluate other sample chromatograms and check library reference retention times on
quantitation lists to determine whether the false negative result is an isolated occurrence or
whether additional data may be affected.
7. TCL compounds may be ..emitted in more than one fraction. Verify that quantitation is
made from the proper fraction.
8. Library searches should not be performed on internal standards or surrogates.
9. TIC concentration should be estimated assuming a RRF of 1.0.
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Tentatively Identified Compounds
VOA
E. Action
1. Ail TIC results should be qualified as tentatively identified (N) with estimated concentrations
(J) or (NJ).
2. General actions related to the review of TIC results are as follows:
a. A non-TCL compound is not considered to be "tentatively identified" until the mass
spectrum and retention time data have been reviewed according to the evaluation
guidelines in XI1LD. The review should be documented on the Tentative
Identification of Library Search Compound worksheet Hie worksheet will be useful
if a better library match for the unknown is retrieved in another Case, SAS, or SDG.
It may also be used in writing a Special Analytical Service Statement of Work to
identify the unknown, or if the sample is sent to an EPA research laboratc LSC
identification by multiple spectral techniques.
b. If all contractually required peaks were not library searched, the desig...
representative could request these data from the laboratory.
3. TIC results which are not sufficiently above the level in the blank should not be reported.
(Dilutions and sample size must be taken into account when comparing the amounts present
in blanks and samples.)
4. When a compound is not found in any blanks, but is a suspected artifact or common
laboratory contaminant, the result may be qualified as unusable (R).
5. The reviewer may elect to report all similar isomers as a total. (All alkanes may be
summarized and reported as total hydrocarbons.)
6. The data reviewer should state the degree of confidence (high, medium, low) in the tentative
identification after completing the review process.
7. The complete "Tentative Identification of Library Search Compound" worksheet should be
attached to the final data review report.
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Tentatively Identified Compounds
APPENDIX
VOA
Equation 1:
R1 « 100 RTnnk ¦ RTz + IOOZ
RTz+l-RTz
where: RTunk is the retention time of the unknown
RTz is the retention time of the proceeding retention inda standard
RTz+1 is the retention time of the following retention index standard
Z ¦ number of rings in the retention index standard
RI « Lee Retention Index
Retention Index Standards
naphthalene
z-2
RI«200.00
phenanthrene
z«3
RI«=300.00
chrysene
Z=4
RI=400.00
Benzo(g,h,i)
z=5
RIs500.00
peiyiene
Note: when these compounds are not dound in the sample of interest, Rt data for the deuterated internal
standards or most recent calibration may be used. Retention time shifts and bias must be accounted
for.
Equation 2
Number of rings-plus-double bonds (r+db):
(r+db) = C -H - X + N +1
2 2 2
where: C = no. of carbons
H = no. of hydrogens
X * no. of halogens
N b no. of nitrogens
Note: ¦ oxygen and sulfur do not need to be accounted for. An aromatic ring counts as four rings and double
bonds.
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Tentatively Identified Compounds
REFERENCES
VOA
1. Lee. M.L. Vassilaros. D.L., White. C.M.. and Novotny, M., 'Retention Indices for Programmed-
Temperature Capillary-Column Gas Chromatography of Polvcyclic Aromatic Hydorcarbons".
Analytical Chemistry. V. 51, no. 6.1979, pp. 768-773.
2. Rostad, C.E., and Pereira, W.R, "Kovats and Lee Retention Indices Determined by Gas
Chromatography/Mass Spectrometry fo Organic Compounds of Environmental Interest." J. High
Resolution Chrom. and Chrom. Commun.. vol. 9,1986, pp. 328-334.
3. Silverstein. R.M., Bassler. G.C. and Morrill, T.C. Spectrometry Identification of Organic Compounds
^ 4th ed., Wiley, New York, 1981.
4. Vassilaros, D.M.. Kong, R.C, Later. D.W. and Lee. M.L., "Linear Retention Index System for
polvcyclic Aromatic Compounds. Critical Evaluation and Additional Indices". J. of Chromatography.
252 (1982) pp. 1-20.
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sv
Proposed Guidance for Tentative!? Identified Compoonds fSY)
A. Review items: Form I SV-TIC, chromatograms, library searcb printout and spcara for three TIC
candidates, and GC retention time data.
B. Objective
Chromatographic peaks in semivolatile analyses that are not TCL compounds, surrogates, or internal
standards are potential tentatively identified compounds (TICs) or library search compounds (LSCs).
TICs must be qualitatively identified by a library search of the National Institute of Standards and
Technology (NIST) mass spectral library, and the identifications assessed by the data reviewer.
C. Criteria
For each sample, the laboratory must conduct a library search of the NIST mass spectral library and
report the possible identity for the 20 largest semivolatile fraction peaks which are not surrogates,
internal standards, or TCL compounds, but which have a peak area greater than SO percent of the
peak area of the nearest internal standard. TIC results are reported for each sample on the Organic
Analysis Data Sheet (Form I SV-TIC).
Note: Since the SOW revision of October 1986, the CLP does not allow the laboratory to report
as tentatively identified compounds any TCL compound which is properly reported in another
fraction. (For example, late eluting volatile TCL compounds must not be reported as
semivolatile TICs.)
D. Evaluation
1. Guidelines for Tentative Identification are as follows:
The interpretation of library search compounds (LSCs) is one of the aspects of data review
which calls for the fullest exercise of professional judgement. The reviewer must be
thoroughly familiar with the principles and practice of mass spectral interpretation and of gas
chromatography. Because the interpretation process is labor-intensive, it is important to
document the process involved in arriving at a tentative identification.
Worksheets for Tentative Identification of Library Search Compounds" are provided in
Appendix B for the semivolatile GC/MS fractions to assist in generating the information
needed to make.a reasonable identification of the HQ.
The process involved in tentatively identifying a library search compound may be summarized
as follows:
a) Identify all samples in the related group (Case, SAS or SDG) in which the unknown
compound occurs. Calculation of retention indices (RI) and comparison of R1 and
mass spectra across samples is extremely helpful in identifying unknowns that occur
repeatedly in related samples. Use one worksheet per unknown for all samples in
which it occurs. Retention indices are calculated according to the following example:
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Tentatively Identified Compourds
SV
RI ¦ 100 RTunk ¦ RTz + 100Z
RTz+1 - RTz
where: RTunk is the retention time of the unknown
RTz the retention time of the preceeding retention index standard
RTz+1 is the retention time of the following retention index standard
Z = number of rings in the retention index standard
RI = Lee Retention Index
Retention Index Standards
naphthalene
z=2
RI=200.00
phenanthrene
z=3
RI=300.00
chrysene
z=4
RI=400.00
Benzo(gJi.i)
z=5
RI=500.00
perylene
Note: when these compounds are not dound in the sample of interest. RT data for
the deuterated internal standards or most recent calibration may be used.
Retention time shifts and bias must be accounted for.
b) Inspect the library search spectrum retrieved for each unknown, to determine if
detailed mass spectral interpretation is necessary. Often, it is obvious that the
correct match is among the spectra retrieved for the unknown from the several
samples in which it is found. It may only be necessary to check the unknown's RI
versus a reference list of SV (generated under similar conditions and after accounting
for bias in the sample) to arrive at a satisfactory tentative identification. Some
references are provided. If a reference RI is not available, then a comparison of the
unknown's RI or boiling point to the RI or boiling point of a closely related
compound may also provide a satisfactory tentative identification. Within a
compound class, retention time increases with increasing boiling point.
c) In the event that serious ambiguity still exists after examining the library spectrs and
RI data, a full r*3« spectral interpretation can narrow down the possibilities. While
a full discussion manual mass spectral interpretation is beyond the scope of this
document, several key points may be mentioned as important objects:
o Determine a likely molecular weight. Depending on the unknown, the MW
may or may not be apparent due to the extent of fragmentation. The
of the retrieved library spectra, interpreted in light of me RI, may be helpful
if the molecular ion is not present.
o Determine the isotope ratios (M+l)/M. (M+2)/M. (M+4)/M. etc. (where
M is the molecular ion) and determine a short list of possible molecular
formulas. Isotope ratios will also reveal the presence of S, CI, and Br.
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Tentatively Identified Compounds
SV
o Calculate the total number of rings-plus-doable-bonds in the unknown by
applying the follwing equation to the likely molecular formulas, to determine
the degree of unsaturation.
Number of rings-plus-double bonds (r+db):
(r+db) -C-H-X + Ii+1
2 2 2
where: C « no. of carbons
H » no. of hydrogens
X « no. of halogens
N » no. of nitrogens
Note: oxygen and sulfur do not need to be accounted for.
An aromatic ring counts as four rings and double
bonds.
o Calculate the mass losses represented by major peaks in the unknown
spectrum, and relate these to the fragmentation of neutral moieties from the
molecular ion or other daughter ions.
o Using the information gathered on molecular weight, molecular formula,
degree of unsaturation, and mass losses in the unknown spectrum, combined
with the RI data, give as precise a description of the unknown as possible,
including an exact identification if it is justified.
d) In the event that the unknown spectrum is not that of a pure compound, mass
spectral interpretation may not be possible. However, in some instances, a mixed
spectrum may be recognized as two compounds having very similar retention indices
(for example, ortho-terphenyl, RI**317.43 and nonadecane, RI=317.20). This
particular coelution would result in an unknown spectrum having a polvcyclic
aromatic pattern at m/z 230, the MW of terphenvl, with an hydrocarbon type pattern
at m/z 43,57,71, etc Target compounds, surrogates and internal standards may also
be responsible for extra ions in an unknown spectrum, and may be treated similarly.
2. Check the raw data to verify that the laboratory has generated a library search spectrum tor
all required peaks in the chromatograms for samples and blanks.
3. Blank chromatograms should be examined to verify that TIC peaks present in samples are not
found in blanks. When a low-level non-TCL 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 percent of the internal standard peak
area or height, but present in the blank chromatogram at similar relative retention time.
4. All mass spectra for every sample and blank must be examined.
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Tentatively Identified Compounds
SV
5. The reviewer should 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:
a. Common laboratory contaminants: C02 (m/z 44), siloxanes (m/z 73), diethyl ether,
hexane, certain freons (l,l,2-trichloro-l,2,2-trifluoroethane or fluoro-
trichloromethane),-and phthalates at levels less than 100 ug/L or 4000 ug/Kg.
b. Solvent preservatives such as cyclohexene which is a methylene chloride preservative.
Related by-products include cyclohexanone, cydohexenone, cyclohexanol,
cvclohexenol, chlorocyclohexene, and chlorocyclohexanol.
c. Aldol condensation reaction products of acetone include: 4-hvdroxy-4-methyl-2-
pentanone, 4-methyl-2-penten-2-one, and 5,5-dimethyl-2(5H)-furanone.
6. Occasionally, a TCL 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. If the
total area quantitation method was used, the reviewer should request that the laboratory
recalculate the result using the proper quantitation ion. In addition, the reviewer should
evaluate other sample chromatograms and check library reference retention times on
quantitation lists to determine whether the false negative result is an isolated occurrence or
whether additional data may be affected.
7. TCL compounds may be identified in more than one fraction. Verify that quantitation is
made from the proper fraction.
8. Library searches should not be performed on internal standards or surrogates.
9. TIC concentration should be estimated assuming a RRF of 1.0.
E. Action
1. All TIC results should be qualified as tentatively identified (N) with estimated concentrations
(J) or (NJ).
2. General actions related to the review of TIC results are as follows:
a. A non-TCL compound is not considered to be "tentatively identified" until the mass
spectrum and retention time data have been reviewed as per section XIII D. The
review should be documented on the Tentative Identification of Library Search
Compound worksheet. The worksheet will be useful if a better library match for the
unknown is retrieved in another Case, SAS, or SDG. It may also be used in writing
a Special Analytical Service Statement of Work to identify the unknown, or if the
sample is sent to an EPA research laboratory for LSC identification by multiple
spectral techniques.
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Tentatively Identified Compounds
SV
b. If all contractually required peaks were not library searched, the designated
representative could request these data from the laboratory.
3. TIC results which are not sufficiently above the level in the blank should not be reported.
(Dilutions and sample size must be taken into account when comparing the amounts present
in blanks and samples.)
4. When a compound is not found in any blanks, but is a suspected artifact or common
laboratory contaminant, the result may be qualified as unusable (R).
5. The reviewer may elect to report all similar isomers as a total. (All alkanes may be
summarized and reported as total hydrocarbons.)
6. The data reviewer should state the degree of confidence (high, medium, low) in the tentative
identification after completing the review process.
7. The complete Tentative Identification of Library Search Compound* worksheet should be
attached to the final data review report.
D-ll
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GLOSSARY OF TERMS
APPENDIX E
APO Administrative Project Officer
BFB Bromofluorobenzene - volatile instrument performance check compound
BNA Base/Neutral/Acid Compounds - compounds analyzed by semivotatile technique
Case A finite, usually predetermined number of samples collected over a given time period for a
particular site. A Case consists of one or more Sample Delivery Group(s).
CCS Contract Compliance Screening • process in which SMO inspects analytical data for
contractual compliance and provides results to the Regions, laboratories and EMSL/LV.
CF Calibration Factor
CRQL Contract Required Quantitation Limit
CSF Complete SDG File
DFTPP Decafluorotriphenylphosphine - semivolatile instrument performance check compound
DPO Deputy Project Officer
EICP Extracted Ion Current Profile
GC/EC Gas Chromatography/Electron Capture Detector
GC/MS Gas Chromatograph/Mass Spectrometer
GPC Gel Permeation Chromatography - A sample clean-up technique that separates compounds
by size and molecular weight Generally used to remove oily materials from sample extracts.
IS Internal Standards • Compounds added to every VOA and BNA standard, blank, matrix spike
duplicate, and sample extract at a known concentration, prior to instrumental analysis.
Internal standards are used as the basis for quantitation of the target compounds.
LCS Laboratory Control Sample
MS/MSD Matrix Spike/Matrix Spike Duplicate
m/z The ratio of mass (m) to charge (z) of ions measured by GC/MS
OADS Organic Analysis Data Sheet (Form I)
ORDA Organic Regional Data Assessment • from earlier version of the Functional Guielines
NIST National Institute of Standards and Technology
E-i
DRAFT 11/90
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GLOSSARY APPENDIX E
PCB Polychlorinated biphenyl (Arochlor is a trademark)
PE Sample Performance Evaluation Sample
QA Quality Assurance • Total program for assuring the reliability of data.
QC Quality Control - Routine application of procedures for controlling the monitoring process.
RIC Reconstructed Ion Chromatogram
RPD Relative Percent Difference (between matrix spike and matrix spike duplicate)
RRF Relative Response Factor
RRF Average Relative Response Factor
RRT Relative Retention Time (with relation to internal standard)
RSD Relative Standard Deviation
RT Retention Time
SDG Sample Delivery Group - Defined by one of the following, whichever occurs first:
Case of field samples
Each 20 field samples within a Case
Each 14-day calendar period during which field samples in a Case are received,
beginning with receipt of the first sample in the SDG. (For VOA contracts, the
calendar period is 7-day.)
SMC System Monitoring Compound • formerly surrogates for volatile analysis.
SMO Sample Management Office
SOP Standard Operating Procedure
SOW Statement of Work
SV Semivolatile analysis - l^ethod based on analysis by GC/MS for BNA organic compounds.
TCL Target Compound List
TIC Tentatively Identified Compound - A compound tentatively identified from search of the
NIST mass spectral library that is not on the TCL.
TPO Technical Project Officer
E-2
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GLOSSARY APPENDIX E
VOA Volatile Orpnlc Analysis - Method based on the purge and trap technique for organic
compound analysis.
VT5K Validated Time of Sample Receipt * Time of sample receipt at the laboratoiy as recorded on
the shipper^ deliveiy receipt and Sample Traffic Report.
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