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X. Internal Standards 66
XI. Target Compound Identification 68
XII. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs) .. 70
XIII. Tentatively Identified Compounds (TICs) 71
XIV. System Performance 75
XV. Overall Assessment of Data 77
APPENDIX A: Contractual Requirements and Equations, Multi-media Multi-concentration .... A-l
APPENDIX B: Contractual Requirements and Equations, Low Concentration Water B-l
APPENDIX C: Contractual Requirement Comparison Tables C-l
APPENDIX D: Proposed Guidance for Tentatively Identified Compounds (VOA and SV) D-l
APPENDIX E: Glossary of Terms E-l
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INTRODUCTION
This document is designed to offer guidance on EPA Contract Laboratory Program (CLP) analytical
data evaluation and review. In some applications it may be used as a Standard Operating Procedure (SOP).
In other, more subjective areas, only general guidance is offered due to the complexities and uniqueness of
data relative to specific samples. For example, areas where the application of specific SOPs are possible are
primarily those in which definitive performance criteria are established. These criteria are concerned with
specifications that are not sample dependent; they specify performance requirements that should fully be under
a laboratory's control. These specific areas include blanks, calibration standards, performance evaluation
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 the SOW for Low
Concentration Water Organic Analysis (SOW OLC01.0). To ensure thai the data review guidelines that are unique
to the Low Concentration Water SOW are easily identified, these requirements and procedures are presented in italics and
contained within brackets ([ ]) throughout the document
This update includes changes to instrument performance checks (formerly referred to as tuning)
including changes to instrument performance checks and calibration criteria as a result of the Response Factor
Workgroup. Minor revisions 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 useability 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.
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
corresponding contractual requirements and equations from the Low Concentration Water SOW. Appropriate
equations are presented for easy reference and to allow the reviewer to verify calculations as needed.
Contractual requirements are provided to facilitate comparisons with the technical requirements. For each
analytical fraction, Appendix C contains a table comparing contractual requirements of the Multi-media, Multi-
concentration with those of the Low Concentration Water SOWs. Appendix D contains proposed guidance
for Tentatively Identified Compounds (VOA and SV), and Appendix E contains a glossary of commonly used
terms.
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The data review should include comments that clearly identify the problems associated with a Case
or Sample Delivery Group and to state the limitations of the data. Documentation should include .the sample
number, analytical method, extent of the problem, and assigned qualifiers.
A data review narrative generally accompanies the laboratory data forwarded to the intended data
recipient (client) or user to promote communication. A copy of the data review narrative should be submitted
to the CLP Quality Assurance Coordinator (QAC), the Regional CLP Technical Project Officer (TPO)
assigned oversight responsibility for the laboratory producing the data, and the Environmental Monitoring
Systems Laboratory in Las Vegas, Nevada (EMSL-LV).
It is the responsibility of the data reviewer to notify the appropriate Regional CLP TPO concerning
problems and deficiencies with regard to laboratory data. If there is an urgent requirement, the TPO may be
contacted by telephone to expedite corrective action. It is recommended that all items for TPO action be
presented at one time.
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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 (SDG) 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 SDG data package.
Sample 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 SDG Narrative is another source of general information. Notable problems with
matrices, insufficient sample volume for analysis or reanalysis, samples received in broken containers, and
unusual events should be found in the SDG Narrative.
The SDG Narrative for the sample data package must include a Laboratory Certification Statement
(exactly as stated.in the SOW), signed by the laboratory manager or his designee. This statement authorizes
the validation and release of the sample data results. In addition, the laboratory must also provide comments
in the SDG narrative describing in detail any problems encountered in processing the samples in the data
package.
For every data package, the reviewer must verify that the laboratory certification statement is present.
exactly stated as in the SOW (Le., 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
laboratory's 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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DATA QUALIFIER DEFINITIONS
The following definitions provide brief explanations of the national qualifiers assigned to results in
the data review process. If the Regions choose to use additional qualifiers, a complete explanation of those
qualifiers should accompany the data review.
U - The analyte was analyzed for, bat was not detected above the reported sample quantitation
limit
J - The analyte was positively identified; the associated numerical value is the approximate
concentration of the analyte in the sample.
N - The analysis indicates the presence of an analyte for which there is presumptive evidence to
make a "tentative identification."
NJ - The analysis indicates the presence of an analyte that has been "tentatively identified" and
the associated numerical value represents its approximate concentration.
UJ - The analyte was not detected above the reported sample quantitation limit However, the
reported quantitation limit is approximate and may or may not represent the actual limit of
quantitation necessary to accurately and precisely measure the analyte in the sample.
R The sample results are rejected due to serious deficiencies in the ability to analyze the
sample and meet quality control criteria. The presence or absence of the analyte cannot be
verified.
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VOLATILE DATA REVIEW
*** Data review guidelines that an unique to data generated throutfi the Low Concentration Water SOW are contained
within brackets ([ )) and written in italics.
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 (Surrogate Spikes) (CCS)
VII. Matrix Spikes/Matrix Spike Duplicates
VIII. Laboratory Control Samples (CCS)
IX. Regional Quality Assurance and Quality Control
X. Internal Standards (CCS)
XI. Target Compound Identification
XII. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XIII. Tentatively Identified Compounds
XIV. System Performance
XV. 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
Review Items: Form I VOA (Form ILCV], 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. 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 non-aromatic volatile compounds in cooled (@ 4°C) water samples,
the maximum holding time is 14 days from sample collection.
Maximum holding times for purgeable aromatic hydrocarbons in cooled
(@ 4°C ± 2°C), acid-preserved (pH 2 or below) water samples is 14 days
from sample collection.
Water samples that have not been maintained at 4°C (+. 2°C) and
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 circumstanes, the temperature of the samples may exceed 4°C.
It is further recommended that volatile compounds in properly preserved non-aqueous samples be
analyzed within 14 days of sample collection.
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 {Form I LCV] 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
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Technical Holding Times
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data/SDG file are identical. Examine the 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 @ 4°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.
Action
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):
a. If there is no evidence that the samples were properly preserved and the technical
holding times exceeded 7 days, qualify positive results for aromatic compounds
with "J" and sample quantitation limits with "UJ". Use professional judgement to
determine if and how non-aromatic volatile compounds should also be qualified.
b. If the samples were properly preserved but the technical holding times exceeded
14 days, qualify positive results with "J" and sample quantitation limits with "UJ".
Table 1. Qualification of Volatile Analytes Based on Technical Holding Times
MATRIX
Water
Non-aqueous
PRESERVED
No
Yes
No/Yes
> 7 DAYS
All Aroma tics'
None
Professional
Judgement
> 14 DAYS
All Compounds
All Compounds
Professional
Judgement
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 approximates and are qualified with "J".
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3. Due to limited information concerning holding times for non-aqueous samples, it is left to
the discretion of the data reviewer to apply water holding times or other information that
is available.
4. Whenever possible, the reviewer should comment on the effect of the holding time
exceedance on the resulting data in the data review narrative.
5. When contractual and/or technical holding times are grossly exceeded, this should be
noted for TPO action.
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 have occurred so that the field problem can be corrected. The
reviewer may pass this information on to the laboratory's TPO, but should explain that
contractually the laboratory met the requirements.
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II. GC/MS Instrument Performance Check
A. Review Items: Form V VOA [Form VLCVj, 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)
mjz 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 10% 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.
0. Evaluation
1. Compare the data presented for each Instrument Performance Check (Form V VOA
[Form V LCV]) with each mass listing submitted to ensure the following:
a. Form V VOA [Form V LCV] is present and completed for each 12-hour period
during which samples were analyzed.
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b. The laboratory has not made transcription errors between the data and the form.
If there are major differences between the mass listing and the Form Vs, a more
in-depth review of the data is required. This may include obtaining and reviewing
additional information from the laboratory.
c. The appropriate number of significant figures has been reported (number of
significant figures given for each ion in the ion abundance criteria column) and
that rounding is correct.
d. The laboratory has not made 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. The laboratory's TPO
should be notified.
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 , - ' VGA
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, 74/176,
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 on 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. 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.
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ffl. Initial Calibration
A. Review Items: Form VI VOA [Form VILCVJ, 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, SO, 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.
{For data generated through the Low Concentration Water SOW: Initial calibration standards containing
both volatile target compounds and surrogate are analyzed at concentrations of I, 2, 5, 10, and 25 ug/L
for non-ketones and 5, 10, 25, 50, and 125 ug/L for ketones 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 BFB tuning
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 all 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 [Appendix
BJ)
4. The Percent Relative Standard Deviation (%RSD) from the initial calibration must be
less than or equal to 30.0% for all compounds.
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).
[Verify that the correct concentration of standards were used for the initial calibration (ie.. I, 2. 5. 10,
and 25 ug/L for non-ketones and 5, 10, 25, 50, and 125 ug/L for ketones).]
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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.
[If any sample results were calculated using an initial calibration, verify that the correct standard (Le.,
the 5 ug/L for non-ketones and 25 ug/L for ketones) was used for calculating sample results and that the
samples were analyzed within 12 hours of the associated instrument performance check. /
4. Evaluate the initial calibration RRFs and RRF for all volatile target compounds and
system monitoring compounds (surrogates):
a. deck and recalculate the RRFs and RRF for at least one volatile target
compound associated with each internal standard; verify that the recalculated
value(s) agrees with the laboratory reported value(s).
b. Verify that for all volatile target compounds and system monitoring compounds
(surrogates), 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 1,2-Dichloropropane
2-Butanone 2-Hexanone
Carbon disulfide Methylene chloride
Chloroethane 4-Methyl-2-pentanone
Chloromethane Toluene-dS f
1,2-Dichloroethene (total) f U-DichIoroethane-d4t
traru-l,2-Dichloroethene t l,2-Dibromo-3-chloropropane
cis-1,2-Dichloroethene f
f Multi-media, Multi-concentration only
t Low Concentration Water onfy
5. Evaluate the %RSD for all volatile target compounds and system monitoring compounds
(surrogates):
a. Check and recalculate the %RSD for one or more volatile target compound(s);
verify that the recalculated value(s) agrees with the laboratory reported value(s).
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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 either the RRFs or the %RSD, perform a
more comprehensive recalculation.
Action
1. Ail volatile target compounds, including the 12 "poor performers" 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 T, and non-detected volatile target
compounds using professional judgement
b. If any initial calibration RRF is less than O.OS, qualify positive results that have
acceptable mass spectral identification with "J", using professional judgement, and
non-detected anaiytes 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. Qualify non-detected volatile 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.
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Initial Calibration VGA
ii. Qualify positive results outside of the linear portion of the curve with a
n f H
iii. No qualifiers are needed volatile target compounds that were not
detected.
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 volatile target compounds based on 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 due to calibration criteria exceedance
should be noted in the data review narrative.
5. If calibration criteria are grossly exceeded, this should be noted for TPO action.
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VGA
IV. Continuing Calibration
A. Review Items: Form VII VOA [Form VIILCVJ, 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 (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 the method blank and samples.
2. The continuing calibration RRF for volatile target compounds and system monitoring
compounds (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 data generated through the Low Concentration Water SOW: The percent difference (%D) between
the 'mined calibration RRF and the continuing calibration RRF must be within ±_ 30.0%.]
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 compounds 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 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 %O 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.
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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
%O 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 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 ± 25.0% criterion and the continuing calibration RRF is
greater than or equal to 0.05, qualify non-detected volatile target compounds with
UJ".
c. If the continuing calibration RRF is less than 0.05, qualify positive results that
have acceptable mass spectral identifications with "J" or use professional
judgement.
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. Whenever possible, the potential effects on the data due to calibration criteria exceedance
should be noted in the data review narrative.
4. If calibration criteria are grossly exceeded, this should be noted for TPO action.
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VGA
V. Blanks
Review Items: Form I VOA [Form ILCV], Form IV VOA [Form IVLCV], 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., method 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.
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.
[5. For data generated through the Low Concentration Water SOW: A storage blank must be prepared upon
receipt of the first samples from an SDG, and stored with samples until analysis. The storage blank must
be analyzed once per SDG.]
0. 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 IV VOA [Form IV LCV]) 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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Blanks VGA
[4. Verify that a storage blank has been analyzed and included with each SDG and that the storage blanks
are free of contamination.]
Action
If the appropriate blanks were not analyzed with the frequency described in Criteria 2, 3, and 4,
[and 5] 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.
Action regarding 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 (lOx) the amount in any blank for the common volatile
laboratory contaminants (methyiene chloride, acetone, and 2-butanone), or 5 times (5x) the
amount for other volatile target 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 not be corrected by
subtracting any blank value.
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.
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 if the sample
concentration is less than five times (5x) the blank concentration. The quantitation limit
may also be elevated. Typically, the sample CRQL is elevated to the concentration found
in the sample. The reviewer should use professional judgement to determine if further
elevation of the CRQL is required. For the common volatile laboratory contaminants, the
results are qualified by elevating the quantitation limit to the concentration found in the
sample when the sample concentration is less than 10 times (lOx) the blank concentration.
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 "lOx" 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 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. In this case, the "5x" or "10x" rules may
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Blanks VGA
not apply; the target compound should be reported as not detected, and an explanation of
the data qualification should be provided in the data review narrative.
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 numbers 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 VOA Section XII for TIC guidance.)
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(s). 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. If contaminants are found in the storage blanks, the following action is recommended.
a. The associated method blank data should be reviewed to determine if the contaminant(s) was
also present in the method blank. If the anafyte was present at a comparable level in the
method blank, then the source of the contamination may be in the analytical system and the
action recommended for the method blank would apply.
If the anafyte was not present in the method blank, then the source of contamination may be in
the storage and all associated samples should be considered for possible cross-contamination.
b. If the storage blank contains a volatile TCL compound(s) at a concentration greater than the
CRQL, then all positive results for that compounds^) should be qualified with "f. If the
concentration level in the blank is significantly high, then positive sample results may require
rejection and be Qualified with "R". Non-detected volatile target compounds should not require
qualification unless the contamination is so high that it interferes with the analysis of the non-
detect compounds.]
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Blanks
VGA
The following are examples of applying the blank qualification guidelines. Certain circumstances
may warrant deviations from these guidelines.
Example 1:
Example 2:
Sample result is greater than the Contract Required Quantitation Limit
(CRQL), but is less than the 5x or lOx multiple of the blank result.
Rule
Blank Result
CRQL
Sample Result
Final Sample Result
Ipx
7
5
60
60U
7
5
30
SOU
In the example for the "lOx* rule, sample results less than 70 (or 10 x 7)
would be qualified as not detected. In the case of the "5x* rule, sample
results less than 35 (or 5 x 7) would be qualified as not detected.
Sample result is less than the CRQL, and is also less than the 5x or lOx
multiple of the blank result.
Blank Result
CRQL
Sample Result
Final Sample Result
10x
6
5
4J
5U
Rule
6
5
4J
5U
Note that data are not reported as 4U, as this would be reported as a
detection limit below the CRQL.
Example 3: Sample result is greater than the 5x or lOx multiple of the blank result.
Rule
Blank Result
CRQL
Sample Result
Final Sample Result
lOx
10
5
120
120
10
5
60
60
For both the "lOx" and "5x" rules, sample results exceeded the adjusted
blank results of 100 (or 10x10) and SO (or 5x10), respectively.
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VGA
VI. System Monitoring Compounds
(Surrogate Spikes)
A. Review Items: Form II VOA [Form IILCVJ, 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 (l,2-dichloroethane-d4, bromofluorobenzene, and
toluene-d8) are added to all samples and blanks to measure their recovery in
environmental samples in sample and blank matrices.
[For data generated through the Low Concentration Water SOW: A single surrogate,
bromofluorobenzene, is added to all samples and blanks to measure the recovery in sample and blank
matrices./
2. Recoveries for system monitoring compounds [surrogates} in volatile samples and blanks
must be within the limits specified in Appendix A [Appendix B] and the SOW.
0. 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 [Surrogate Recovery Form
Form II LCVJ. Check for any calculation or transcription errors.
2. Check that the system monitoring compound [surrogate] recoveries were calculated
correctly. The equation can be found in Appendix A [Appendix B).
3. The following should be determined from the System Monitoring Compound [Surrogate]
Recovery form(s):
.a. If any system monitoring [surrogate] 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.
When there are unacceptable system monitoring compound [surrogate] recoveries followed
by successful re-analyses, the laboratories are required to report only the successful run.
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System Monitoring Compounds ' ' VGA
(Surrogates)
b. The laboratory failed to perform acceptably if system monitoring compounds
[surrogate/ are outside criteria with no evidence of re-analysis. Medium soils must
first be re-extractracted prior to re-analysis when this occurs.
c. . Verify that no blanks have system monitoring compounds [surrogate] outside the
criteria.
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 [surrogate/ recovery (marginal versus gross
deviation).
b. Technical holding times.
c. Comparison of the values of the target compounds reported in each sample
analysis.
d. Other QC information, such as performance of internal standards.
E. Action
Data are qualified based on system monitoring compounds [surrogate] results if the recovery of any
volatile system monitoring compound [surrogate] is out of specification. For system monitoring
compound [surrogate] 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.
1. If a system monitoring compound [surrogate] in the volatile sample has a recovery greater
than the upper acceptance limit (UL):
a. Detected volatile target compounds are qualified "J.".
b. Results for non-detected volatile target compounds should not be qualified.
2. If a system monitoring compound [surrogate] in the volatile sample has a recovery greater
than or equal to 10% but less than the lower acceptance limit (LL):
a. Detected volatile target compounds are qualified "J."
b. For non-detected volatile target compounds, the sample quantitation limit is
qualified as approximated (UJ).
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System Monitoring Compounds
(Surrogates)
VGA
3. If a system monitoring compound {surrogate/ in a volatile sample shows less than 10%
recovery:
a. Detected volatile target compounds are qualified "J".
b. . Non-detected volatile target compounds may be qualified as unusable (R).
Table 3. Qualification of Volatile Analytes Based on
System Monitoring Compound [Surrogate] Recoveries
Detected analytes
Non-detected analytes
SMC/Surrogate Recovery
> UL 10% to LL < 10%
J
No
Qualification
J
UJ
J
R
In the special case of a blank analysis with system monitoring compounds [surrogate] 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 [surrogate] 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. Also
note if there are potential contractual problems associated with the lack of reanalysis of
samples that were out of specification.
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.
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VGA
VII. Matrix Spikes/Matrix Spike Duplicates
(Not Required for Low Concentration Water Data)
A. Review Items: Form III VOA-1 and VOA-2, chromatograms, and quantiiation 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 spikes (MS) and matrix spike duplicate (MSD) samples are analyzed at 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 2.
3. Relative percent difference (RPD) between MS and MSD recoveries must be within the
advisory limits provided on Form III VOA-1 and VOA-2.
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 RPD 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
judgment the data reviewer may use the MS and MSD results in conjunction with other
QC criteria and determine the need for some qualification of the data.
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Matrix Spikes/Matrix Spike Duplicates ' , - ' VGA
2. The data reviewer should first try to determine to what extent the results of the MS/MS D
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.
NOTE: If a field blank was used for the MS/MSD, a statement to that effect must be included for
the TPO.
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VGA
Vffl. Laboratory Control Samples
(Low Concentration Water)
[A. Review Items: Form III LCV-1, LCS chromatograms and quantitation reports.
B. Objective
Data for laboratory control samples (LCS) are generated to provide information on the accuracy of the analytical
method and on the laboratory performance.
C. Criteria
1. A laboratory control sample (LCS) must be analyzed once per SDC and concurrently with the samples
inthe SDG.
2. The LCS contains the following volatile compounds, in addition to the required surrogate:
Vinyl chloride Benzene
1,2-Dichloroethane cis-l,3-Dichlaropropene
Carbon tetrachloride Bromoform
1,2-Dichloropnpane Tetrachloroethene
Trichloroethene 1,2-Dibromoethane
1,1,2-Trichloroethane 1,4-Dichlorobenzene
3. The percent recoveries for the LCS compounds must be within 60-140%. The LCS must meet this
recovery criteria for the sample data to be accepted.
4. The criteria for surrogate recovery and internal standard performance also apply.
D. Evaluation
1. Verify that LCS samples were analyzed at the required frequency and that results are provided for each
SDC.
2. Inspect results for the LCS Recovery on Form III LCV-1 and verify that the results for recovery are
within the QC limits of 60 to 140 percent.
3. Verify transcriptions from raw data and verify calculations.
4. Check that the LCS recovery was calculated correctly by using the correct equation.
E. Action
If the LCS criteria are not met, then the laboratory performance and method accuracy are in question.
Professional judgement should be used to determine if the data should be qualified or rejected. The following
guidance'is .suggested for qualifying sample data for which the associated LCS does not meet the required criteria.
1. Action on the LCS recovery should be based on both the number of compounds that are outside of the
recovery criteria and the magnitude of the exceedance of the criteria.
2. If the LCS recovery criteria are not met, then the LCS results should be used to qualify sample data for
the specific compounds that are included in the LCS solution. Professional judgement should be used to
27 DRAFT 12/90
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Laboratory Control Samples VGA
qualify data for compounds other than those compounds that an included in the LCS. Professional
judgement to qualify non-LCS compounds should take into account the compound class, compound
recovery efficiency, analytical problems associated with each compound, and comparability in
performance of the LCS compound to the non-LCS compound.
3. If the LCS recovery is greater than 140%, then positive sample results for the affected compound(s)
should be qualified with a T.
4. If the mass spectral criteria are met but the LCS recovery is less than 60%, then the associated detected
target compounds should be qualified V and the associated non-detected target compounds should be
qualified "R".
5. If more than half of the compounds in the LCS are not within the required recovery criteria, then all of
the associated detected target compounds should be qualified "/" and all associated non-detected target
compounds should be qualified "R."
6. Action on non-compliant surrogate recovery and internal standard performance should follow the
procedures provided in Vl.E and X£, respectively. Professional judgement should be used to evaluate
the impact that non-compliance for surrogate recovery and internal standard performance in the LCS has
on the associated sample data.
7. It should be noted for TPO action if a laboratory fails to analyze an LCS with each SDC, or if a
laboratory consistently fails to generate acceptable LCS recoveries.]
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VGA
IX. Regional Quality Assurance and Quality Control
A. Review Items: Form I VOA (Form ILCV], chromatograms, and quantitation reports.
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. It is highly recommended that Regions adopt the use of these.
C. Criteria
Criteria are determined by each Region.
1. Performance evaluation sample frequency may vary.
[For data generated through the Low Concentration Water SOW: A performance evaluation (PE)
sample may be required as frequently as once per SDC.J
2. The analytes present in the PE sample must be correctly identified and quantified.
D. Evaluation
Evaluation procedures must follow the Region's SOP for data review. Each Region will handle
the evaluation of PE samples on an individual basis. Results for PE samples should be compared
to the acceptance criteria for the specific PE samples, if available.
E. Action
Any action must be in accordance with Regional specifications and the criteria for acceptable PE
sample results. Unacceptable results for PE samples should be noted for TPO action.
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VGA
X. Internal Standards
A. Review Items: Form VIII VOA [Form VIIILCVJ, quantitation reports, and chromatograms.
B. Objective
Internal Standards (IS) performance criteria ensures tbat 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.
[For data generated through the Low Concentration Water SOW: Internal standard area counts must not
vary by more than a factor of t 40.0% 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.
{For data generated through the Low Concentration Water SOW: The retention time of the internal
standard must not vary more than +_ 20.0 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 (Form VIIILCVJ).
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.
e. Other QC.
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Internal Standards VGA
Action
1. If an IS area count for a sample or blank is outside -50% or +100% of the area for
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%
should not be qualified.
c. Non-detected compounds quantitated using an IS area count less than 50% are
reported as the associated sample quantitation limit and qualified with °UJ".
d. 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).
[If an IS area count for a sample or blank is outside t 40.0% of the area for associated standard:
a. Positive results for compounds quantitated using that IS should be qualified with V.
b. Non-detected compounds quantitated using an IS area count greater than 40% should not be
qualified.
c. Non-detected compounds quantitated using an IS area count less than 40% are reported as the
associated sample quantitation limit and qualified with "Uf.
d. 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).]
2. If an IS retention time varies by more than 30 seconds:
[If an IS retention time varies by more than 20.0 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 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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VGA
XI. Target Compound Identification
A. Review Items: Form I VOA [Form ILCVJ, quantitation reports, mass spectra, and chromatograms.
B. Objective
The objective of the criteria for GC/MS qualitative analysis is to minimize the number of
erroneous identifications of compounds. An erroneous identification can either be a false positive
(reporting a compound present when it is not) or a false negative (not reporting a compound that
is present).
The identification criteria can be applied more easily in detecting false positives than false
negatives. More information is available for false positives due to the requirement for submittal
of data supporting positive identifications. Negatives, or non-detected compounds, on the other
hand represent an absence of data and are, therefore, more difficult to assess. One example of
detecting false negatives is the not reporting of a Target Compound that is reported as a TIC.
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.
[For data generated through the Low Concentration Water SOW: All ions present in the
standard mass spectrum at a relative intensity greater than 25% 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.
[For data generated through the Low Concentration Water SOW: Ions present at greater than
25% in the sample mass spectrum but not present in the standard spectrum must be considered
and accounted for.]
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Target Compound Identification ' VGA
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 carryover is a possibility and should use
judgment 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.
[The reviewer should be aware of situations when sample carryover is a possibility and should use
judgment to determine if instrument emu-contamination has affected any positive compound
identification. The SOW specifies that an instrument blank must be run after samples which contain
target compounds at levels exceeding the initial calibration range (25 ug/L for non-ketones, 125 ug/L for
ketones) or non-target compounds at concentrations greater than 100 ug/L or saturated ions from a
compound (excluding the compound peaks in the solvent front).]
4. Check the chromatogram to verify that peaks are accounted for, i.e., major peaks are
either identified as target compounds, TTCs, system monitoring compounds [surrogate], 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.
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VGA
XII. Compound Quantitation and Reported CRQLs
Review Items: Form I VOA [Form ILCV], sample preparation sheets, SDG narrative, quantitation
reports, and chroma lograms.
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 [Appendix B] (also as specified in the Statement of
Work) 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 throughout, 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
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Compound Quantitation and Reported CRQLs ' VOA
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;
Numerous or significant failures to accurately quantify the target compound or to properly
evaluate and adjust CRQLs should be noted for TPO action.
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VGA
XIII. Tentatively Identified Compounds
A. Review Items: Form I VOA-TIC [Form ILCV-TIC], chroraatograms, and library search printout
and spectra for three TIC candidates.
B. Objective
Chromatographic peaks in volatile fraction analyses that are not target analytes, system monitoring
compounds [surrogate/, 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 compound, 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
reponed for each sample on the Organic Analyses Data Sheet (Form I VOA-TIC).
[For data generated through the Low Concentration Water SOW: 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 surrogate, internal standard, or TCL compounds, but which have area greater than or equal to 40
percent of the area of the nearest internal standard. Estimated concentrations for TICs are calculated similarly to
the TCL compounds, using total ion areas for the TIC and the internal standard, and assuming a relative response
factor of 1.0. TIC results are reported for each sample on the Organic Analyses Data Sheet (Form I LCV-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.
[Major ions (greater than 25% 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.
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Tentatively Identified Compounds ' , ' VGA
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 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".
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 cnromatograms 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 cnromatograms
may require looking for peaks which are less than 10 percent of the internal standard
height, but present in the blank chromatogram at similar relative retention time.
[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 40 percent of the internal standard area but present in the blank chromatogram at 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: CO2 (m/z 44), siloxanes (m/z 73), diethyl
ether, hexane, certain freons (l,l,2-trichJoro-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 preser-
vative. Related by-products include cyclohexanone, cyclohexenone, cyclohexanol.
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.
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Tentatively Identified Compounds ' , - ' VGA
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.
E. Action
1. All TIC results should be qualified "NJ", tentatively identified, with approximated
concentrations.
2. General actions related to the review of TIC results are as follows:
a. If it is determined that a tentative identification of a non-target compound is 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. TIC results which are not sufficiently above IQx 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 of common
laboratory contaminant, the result may be qualified as unusable (R).
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.,
13,5-trimethyl benzene to trimethyl benzene isomer) or to a compound class (e.g.. 2-
methyl, 3-ethyl benzene to substituted aromatic compound).
6. The reviewer may elect to report all similar compounds as a total, (e.g., All alkanes may
be summarized and reported as total hydrocarbons.)
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Tentatively Identified Compounds ' , - ' VGA
7. Other case factors may influence TIC judgements. 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.
8. Physical constants, such as boiling point, may be factored into professional judgement of
TIC results.
9. Any changes made to the reported data or any concerns regarding TIC identifications
should be indicated in the data review narrative.
10. Failure to properly evaluate and report TICs should be noted for TPO action.
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VGA
XIV. System Performance
A. Review Items: Form VIII VGA [Form VIIILCVJ, Form III VOA-1 and VOA-2 (Form III LCV-1J,
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.
D. Evaluation
1. Abrupt, discrete shifts in the reconstructed ion chromatogram (RIC) baseline may indicate
a change in the instrument's sensitivity or the zero setting. A baseline "shift" could
indicate a decrease in sensitivity in the instrument or an increase in the instrument zero,
possibly causing target compounds, at or near the detection limit, to miss detection. A
baseline "rise" could indicate problems such as a change in the instrument zero, a leak, or
degradation of the column.
2. Poor chromatographic performance affects both qualitative and quantitative results.
Indications of substandard performance include:
a. High RIC background levels or shifts in absolute retention times of internal
standards.
b. Excessive baseline rise at elevated temperature.
c. Extraneous peaks.
d. Loss of resolution.
e. Peak tailing or peak splitting that may result in inaccurate quantitation.
(3. A drift in instrument sensitivity may occur during the 12-hour time period. This could be discerned by
examination of the IS area on Form VIIILCV for trends such as a continuous or near-continuous
increase or decrease in the IS area over time.
4. The results of the LCS analysis (Form III LCSV) may also be used to assess instrument performance.]
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VGA
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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VGA
XV. 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.
O. Evaluation
1. Evaluate any technical problems which have not been previously addressed.
2. 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 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. 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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sv
SEMIVOLATILE DATA REVIEW
«" Data review guidelines thai are unique to data generated through the Low Concentration Water SOW are contained
within brackets ([ ]) and written in italics. ***
The semivolatile 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 (CCS)
VI. Surrogate Spikes (CCS)
VII. Matrix Spikes/Matrix Spike Duplicates
VIII. Laboratory Control Samples (CCS)
IX. Regional Quality Assurance and Quality Control
X. Internal Standards (CCS)
XI. Target Compound Identification
XII. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XIII. Tentatively Identified Compounds
XTV. System Performance (CCS)
XV. 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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sv
I. Technical Holding Times
A. Review Items: Form I SV-1 and SV-2 [Form ILCSV-l and LCSV-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 (@ 4°C) water samples the
maximum holding time is 7 days from sample collection to extraction and
40 days from sample extraction to analysis.
It is recommended that semivolatile compounds in non-aqueous samples be extracted within 14
days of sample collection.
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.
[For data generated through the Low Concentration SOW: The contractual delivery due date is 14 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-l and SV-2 [Form I
LCSV-l -and LCSV-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 [Form I LCSV-l and LCSV-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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Technical Holding Times SV
Action
1. If technical holding times are exceeded, flag all positive results as estimated T and sample
quantitation limits as estimated *UJ" and document that holding times were exceeded.
2. If technical holding times are grossly exceeded, 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. Due to limited information concerning holding times for soil samples, it is left to the
discretion of the data reviewer to apply water holding time criteria to soil samples.
Professional judgement is required to evaluate holding times for soil samples.
4. Whenever possible, the reviewer should comment on the effect of the holding time
exceedance on the resulting data in the data review narrative.
5. When contractual and/or technical holding times are exceeded, this should be noted as an
action item for the TPO.
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 have occurred so that the field problem can be corrected. The
reviewer may pass this information on to the laboratory's TPO, but should explain that
contractually the laboratory met the requirements.
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sv
n. GC/MS Instrument Performance Check
A. Review Items: Form V SV [Form VLCSV], 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 volatile 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: All 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.
O. Evaluation
1. Compare the data presented on each GC/MS Instrument Performance Check (Form V SV
[Form V LCSV]) with each mass listing submitted and ensure the following:
a. Form V SV [Form V LCSV] is present and completed for each 12-hour period
during which samples were analyzed.
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GC/MS Instrument Performance Check . SV
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 tn/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.
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 laboratory's TPO
should be notified.
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:
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GC/M.J Instrument Performance Check - . SV
a. Some of tbe most critical factors in the DFTPP criteria are the non-instrument
specific requirements that are also not unduly affected by the location of the
spectrum on the chromatographic profile. The m/z ratios for 198/199 and 442/443
are critical. These ratios are based on the natural abundances of carbon 12 and
carbon 13 and should always be met Similarly, the relative abundances for m/z
68, 70, 197, and 441 indicate the condition of the instrument and the suitability of
the resolution adjustment 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. 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.
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sv
III. Initial Calibration
A. Review Items: Form VI SV-1 and SV-2 [Form VILCSV-1 and LCSV-2/, quantitaiion reports, and
chromatograms.
B. Objective
Compliance requirements for satisfactory instrument calibration are established to ensure chat 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.
{For data generated through the Low Concentration SOW: Initial calibration standards containing both
semivolatile TCL compounds and surrogates are analyzed at concentrations of 5, 10, 20, 50, and 80
ug/L at the beginning of each analytical sequence or as necessary if the continuing calibration acceptance
criteria an not met. The initial calibration (and any associated samples and blanks) must be analyzed
within 12 hours of the associated DFTPP tuning check. The following nine compounds require initial
calibration at 20, 50, 80, 100, and 120 ug/L- 2,4-dinitrophenol, 2,4,5-trichlorophenol, 2-nitroaniline, 3,
nitroaniline, 4-naroaniline, 4-nitrophenol, 4,6-dinitro-2-methylphenol, pentachlorophenol, and 2,4,6-
tribromophenol (surrogate).]
2. Minimum Relative Response Factor (RRF) criteria must be greater than or equal to 0.05.
Contractual RRF criteria are listed in Appendix A [Appendix B].
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).
[Verify that the correct concentration of standards were used for the initial calibration (Le., 5, 10, 20, 50,
and 80 ug/L). For the nine compounds listed in Ill.C.l. with higher CRQLs, verify that a five point
initial calibration at 20, 50, 80, 100, and 120 ug/L was performed.]
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Initial Calibration . SV
2. If any sample results were calculated using an initial calibration, verify that the correct
standard (i.e., the SO ppb standard) was used for calculating sample results and that the
samples were analyzed within 12 hours of the associated instrument performance check.
/// any sample results were calculated using an initial calibration, verify that the correct standard (Le.,
the 20 ug/L standard or SO ug/L for the compounds listed in I I I.C.I.) was used for calculating sample
results and that the samples were analyzed within 12 hours of the associated DFTPP tuning 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 O.OS.
r
greater than or equal to O.OS.
NOTE: Because historical performance data indicate poor response and/or erratic behavior, the
semivolatile compounds in Table 4 have no contractual maximum %RSD criteria.
Contractually they must meet a minimum RRF criteria of 0.01, however, for data review
purposes, the "greater than or equal to 0.05" criterion is applied to all semivolatile
compounds.
Table 4. Semivolatile Target Compounds Exhibiting Poor Response
2^'-oxybis( 1-Chloropropane) Oiethylphthalate
4-Chloroaniline 4-Nitroaniline
Hexachlorobutadiene 4,6-Dinitro-2-methylphenol
Hexachlorocyclopentadiene N-Nitrosodiphenylamine
2-Nitroaniline Di-n-butylphthalate
Dimethylphthalate Butylbenzylphthalate
3-Nitroaniline 3-3'-Dichlorobenzidine
2,4-Dinitrophenol bis(2-Ethylhexyl)phthalate
4-Nitrophenol Di-n-ocrylphthalate
Carbazolef 2,4,6-Tribromophenol (surr)t
Nurobenzene-d, (surr)t
\ Multi-media, Multi-concentration only
tLow Concentration Water only
4. Evaluate the %RSD for all semivolatile target compounds and surrogates.
a. 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).
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Initial Calibration . SV
b. Verify that all semivolatile target compounds have a %RSD of less than 30%.
The contractual criteria for an acceptable initial calibration specifies that up to
any 4 semivolatile target compounds may foil 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.
5. If errors are detected in the calculations of either the RRF or the %RSD, perform a
more comprehensive recalculation.
Action
1. All semivolatile target compounds, including the 19 "poor performers" will be qualified
using the following criteria:
a. If the %RSD is greater than or equal to 30.0% and the RRF is greater than O.OS,
qualify positive results with "J", and non-detected semivolatile target compounds
using professional judgement.
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 semivolatile 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".
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Initial Calibration ' , SV
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 due to calibration criteria exceedance
should be noted in the data review narrative.
5. If calibration criteria are grossly exceeded, this should be noted for TPO action.
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IV. Continuing Calibration
A. Review Items: Form VII SV-1 and SV-2 [Form VII LCSV-l and LCSV-2J, 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 III.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.
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Continuing Calibration . SV
3. Evaluate the %D between initial calibration R"R~F~ 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).
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 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%. 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
"UJ".
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 due to calibration criteria exceedance
should be noted in the data review narrative.
4. If calibration criteria are grossly exceeded, this should be noted for TPO action.
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V. Blanks
A. Review Items: Form I SV-1 and SV-2 [Form ILCSV-1 and LCSV-2], Form IV SV [Form W LCSV],
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 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. The method blank must be analyzed on each GC/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.
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 (IQx) 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 not
be corrected by subtracting any blank value.
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Specific actions are as follows:
1. If a semivolatile 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.
2. Any semivolatile compound detected in the sample (other than the common phthalate
contaminants), that was also detected in any associated blank, is qualified if the sample
concentration is less than five times (5x) the blank concentration. The quantitation limit
may also be elevated. Typically, the sample CRQL is elevated to the concentration found
in the sample. The reviewer should use professional judgement to determine if further
elevation of the CRQL is required. For phthalate contaminants, the results are qualified
"U" by elevating the sample quantitation limit to the sample concentration when the
sample result is less than lOx the blank concentration.
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 "lOx" 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. In this case, the "5x" or "10x" rules may not
apply; the sample value should be reported as a non-detect. 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.)
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
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SV
identification(s). 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.
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 lOx multiple of the blank result.
Example 2;
Blank Result
CRQL
Sample Result
Qualified Sample Result
Rule
lOx 5x
7 7
5 5
60 30
60U 30U
In the example for the "lOx* rule, sample results less than 70 (or 10 x 7)
would be qualified as non-detects. In the case of the "5x" rule, sample
results less than 35 (or 5x7) would be qualified as non-detects.
Sample result is less than CRQL, and is also less than the 5x or lOx
multiple of the blank result
Rule
5x
Blank Result
CRQL
Sample Result
Qualified Sample Result
6
5
4J
5U
6
5
4J
5U
Note that data are not reported as 4U, as this would be reported as a
detection limit below the CRQL
Example 3: Sample result is greater than the 5x or lOx multiple of the blank result.
Rule
lOx 5x
Blank Result
CRQL
Sample Result
Qualified Sample Result
10
5
120
120
10
5
60
60
For both the "lOx" 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 II SV-1 and SV-2 (Form IILCSV], 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 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 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 I advisory) are added to all samples and blanks to measure
their recovery in sample and blank matrices.
[For data generated through the Low Concentration SOW: Surrogate spikes, 3 acid compounds and 3
base/neutral compounds, are added to all samples and blanks to measure their recovery in sample and
blank matrices.]
2. Surrogate spike recoveries for semivolatile samples and blanks must be within the limits
specified on in Appendix A and on Form II SV-1 and SV-2.
[For data generated through the Low Concentration SOW: Surrogate spike recoveries for semivolatile
samples and blanks must be within the limits specified in Appendix B and on Form II LCSV.]
0. 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 [Form II LCSV].
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 [Appendix B].
3. The following should be determined from the Surrogate Recovery form(s):
a. If any two base/neutral or 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 reanalvsis to confirm that the non-compliance is due to sample
matrix effects rather than laboratory deficiencies.
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Surrogate Spikes ' , SV
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 reinjection of the extract, or
reextraction and reanalysis (if reinjection fails to resolve the problem).
c. Verify that no blanks have surrogates recoveries outside the criteria.
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.
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.
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 "J."
c. Results for non-detected semivolatile target compounds should not be qualified.
2. If two or more surrogates in either semivolatile 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 semivolatile target compounds are qualified "J."
c. For non-detected semivolatile target compounds, the sample quantitation limit is
qualified as approximated (UJ).
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3. If any surrogate in either semivoiatile fraction show less than 10% recovery:
a. Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.
b. Detected semivoiatile target compounds are qualified "J".
c. Non-detected semivoiatile target compounds may be qualified as unusable (R).
Table 5. Qualification of Semivoiatile Analytes Based on
Surrogate Recoveries
Detected analytes
Non-detected analytes
Surrogate Recovery
> UL 10% to LL < 10%
J
No
Qualification
J
UJ
J
R
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.
Whenever possible, the potential effects of the data resulting from system monitoring
recoveries not meeting the advisory limits should be noted in the data review narrative.
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VII. Matrix Spikes/Matrix Spike Duplicates
(Not Required for Low Concentration Water Data)
A. Review Items: Form III 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 other available QC
information.
C. Criteria
1. Matrix spikes 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.
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.
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 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.
4. Check that the recoveries and RPD 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
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Matrix Spikes/Matrix Spike Duplicates . SV
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 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.
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Laboratory Control Samples
(Low Concentration Water)
[A. Review Items: Form HI LCSV, LCS chromatograms and quantitation reports.
B. Objective
Data for laboratory control samples (LCS) are generated to provide information on the accuracy of the analytical
method and the laboratory performance.
C. Criteria
1. Laboratory control samples are analyzed at frequency of once per 20 samples per SDG. The LCS must
be prepared and analyzed concurrently with the samples in the SDG.
Z LCS percent recoveries must be within the QC limits provided on Form III LCSV. The LCS must meet
the recovery criteria for the sample data to be accepted.
3. The LCS contains the following semivolatile target compounds, in addition to the required surrogates:
Phenol 1,2.4-Trichlarobetuene
2-Chlarophenol Naphthalene
4-Chloroaniline 2,4-Dinitrotoluene
2,4,6-Trichlorophenol Diethylphthalate
bis(2-Chloroethyl)ether N-Nttrosodiphenylamine
N-Nlsroso-di-n-propylamine Hexachloroberaene
Hexachloroethane Benzo(a)pyrene
Isophorone
4. The criteria for surrogate recovery and internal standard performance also apply.
D. Evaluation
1. Verify that LCS samples were analyzed at the required frequency.
2 Inspect the results for LCS Recovery on Form III LCSV and verify that the results for recovery are
within the advisory limits.
3. Verify transcriptions from raw data and verify calculations.
4. Check that the recoveries were calculated correctly.
E. Action
If the LCS criteria are not met, then the laboratory performance and method accuracy are in question.
Professional judgement should be used to determine if the data should be qualified or rejected. The following
guidance is suggested for qualifying sample data for which the associated LCS does not meet the required criteria.
I. Action on the LCS recovery should be based on both the number of compounds that are outside of the
recovery criteria and the magnitude of the exceedance of the criteria.
2. If the LCS recovery criteria are not met, then the LCS results should be used to qualify sample data for
the specific compounds that are included in the LCS solution. Professional judgement should be used to
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Laboratory Control Samples ' . ' SV
qualify data for compounds other than those compounds that are included in the LCS. Professional
judgement to qualify non-LCS compounds should take into account the compound class, compound
recovery efficiency, analytical problems associated with each compound, and comparability in
performance of the LCS compound to the non-LCS compound.
3. If tlte LCS recovery is greater than 140%, then positive sample results for the affected compound(s)
should be qualified with a T.
4. If the mass spectral criteria are met but the LCS recovery is less than 60%, then the associated detected
target compounds should be qualified V and the associated non-detected target compounds should be
qualified "R".
5. If more than half of the compounds in the LCS are not within the required recovery criteria, then all of
the associated detected target compounds should be qualified T and all associated non-detected target
compounds should be qualified "R."
6. Action on non-compliant surrogate recovery and internal standard performance should follow the
procedures provided in Vl.E and X.E, respectively. Professional judgement should be used to evaluate
the impact that non-compliance for surrogate recovery and internal standard performance in the LCS has
on the associated sample data.
7. It should be noted for TPO action if a laboratory fails to analyze an LCS with each SDG, or if a
laboratory consistently fails to generate acceptable LCS recoveries.]
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IX. Regional Quality Assurance and Quality Control
A. Review Items: Form I SV-1 and SV-2 [Form ILCSV-1 and LCSV-2J, chromatograms, quantitation
report, traffic report and raw data for Regional QC samples.
B. Objective
Regional Quality Assurance and Quality Control (QA/QQ refer to any QA and/or QC initiated
by the Region, including field duplicates, Regional Performance Evaluation (PE) samples, blind
spikes, and blind blanks. It is highly recommended that Regions adopt the use of these.
C. Criteria
Criteria are determined by each Region.
1. Performance evaluation sample frequency may vary.
[For data generated through the Low Concentration SOW: A performance evaluation (PE) sample may
be required as frequently as once per SDG.]
2. The analytes present in the PE sample must be correctly identified and quantified.
0. Evaluation
Evaluation procedures must follow the Region's SOP for data review. Each Region will handle
the evaluation of PE samples on an individual basis. Results for PE samples should be compared
to the acceptance criteria for the specific PE samples, if available.
E. Action
Any action must be in accordance with Regional specifications and the criteria for acceptable PE
sample results. Unacceptable results for PE samples should be noted for TPO action.
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X. Internal Standards
A. Review Items: Form VIII SV-1 and SV-2 [Form VIIILCSV-1 andLCSV-2], quantitation reports, and
chromatograms.
B. Objective
Internal Standards (IS) performance criteria ensure that GC/MS sensitivity and response are stable
during 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.
[For data generated through the Low Concentration Water SOW: Internal standard area counts must not
vary by more than a factor of ± 40.0% 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.
[For data generated through the Low Concentration SOW: The retention time of the internal standards
in samples and blanks must not vary by more than ±20.0 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-l, VIII SV-2 {Form Vltt LCSV-i and LCSV-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:
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a. Positive results for compounds quantitated using that IS should be qualified with
jr.
b. Non-detected compounds quantitated using an IS area count greater than 100%
should not be qualified.
c. Non-detected compounds quantitated using an IS area count less than 50% are
reported as the associated sample quantitation limit and qualified with "UJ".
d. 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).
[If an IS area count for a sample or blank is outside t 40.0% of the area for associated standard:
a. Positive results for compounds quantitated using that IS should be qualified with T.
b. Non-detected compounds quantitated using an IS area count greater than 40% should not be
qualified.
c. Non-detected compounds quantitated using an IS area count less than 40% are reported as the
associated sample quantitation limit and qualified with "UJ*.
d. 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).]
2. If an IS retention time varies by more than 30 seconds:
[If an IS retention time varies by more than 20.0 seconds:]
The chromatographic profile for that sample must be examined to determine if any false
positives or negatives exist For shirts 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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XI. Target Compound Identification
A. Review Items: Form I SV-1 and SV-2 (Form I LCSV-1 and LCSV-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
[For data generated through the Low Concentration SOW: All ions present in the standard
mass spectrum at a relative intensity greater than 25% must be present in the sample spectrum. J
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.
[For data generated through the Low Concentration SOW: Ions present at greater than 25% in
the sample mass spectrum but not present in the standard mass 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.
68 DRAFT 12/90
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Target Compound Identification SV
2, Check that 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.
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.
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XII. Compound Quantitation and Reported CROLS
Review Items: Form I SV-1 and SV-2 [Form ILCSV-1 and LCSV-2], sample preparation sheets, case
narrative, sample clean-up sheets, quamitation 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 (IS)
associated with that compound, as listed in Appendix A [Appendix B] (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 all
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.
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.
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 properly
evaluate and adjust CRQLs should be noted for TPO action.
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XIII. Tentatively Identified Compounds
Review Items: Form I SV-TIC [Form ILCSV-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).
[For data generated through the Low Concentration SOW: For each sample, the laboratory must conduct a mass
spectral search of the A/757* 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 an ana greater than 50 percent
of the area of the nearest interned standard. Estimated concentrations for TICs are calculated similarly to the
TCL compounds, using total ion anas for the TIC and the internal standard, and assuming a relative response
factor of 1.0. TIC results are reported for each sample on the Organic Analyses Data Sheet (Form ILCSV-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.
[Major ions (greater than 25% 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.
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Tentatively Identified Compounds - SV
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".
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.
(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 with areas greater than or equal to 50 percent of the area of
the nearest internal standard.]
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.
[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
have areas less than 50 percent of the internal standard area, 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: CO2 (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 preser-
vative. Related by-products include cyclohexanone, cyclohexenone, cyclohexanol,
cyclohexenol, chlorocyclohexene, and chlorocyclohexanol.
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Tentatively Identified Compounds SV
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 "NJ", tentatively identified, with approximated
concentrations.
2. General actions related to the review of TIC results are as follows:
a. If it is determined that a tentative identification of a non-target compound is 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. 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 of common
laboratory contamination, the result may be qualified as unusable (R).
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-
methyl, 3-ethyl benzene to substituted aromatic compound).
6. The reviewer may elect to report all similar isomers as a total. (All alkanes may be
summarized and reported as total hydrocarbons.)
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Tentatively Identified Compounds SV
7. 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.
8. Physical constants, such as boiling point, may be factored into professional judgment of
TIC results.
9. Any changes made to the reported data or any concerns regarding TIC identifications
should be indicated in the data review narrative.
10. Failure to properly evaluate and report TICs should be noted for TPO action.
74 DRAFT 12/90
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sv
XIV. System Performance
A. Review Items: Form III SV-1 and SV-2 [Form III LCSVJ, Form VIII SV-1 and SV-2 (Form Vlll
LCSV-1 and LCSV-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" 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 between by factors such as non-resolution of 2.4-
and 24- dinitrotoluene.
e. Peak tailing or peak splitting that may result in inaccurate quantitation.
[3. A drift in instrument sensitivity may occur during the 12-hour time period. This could be discerned by
examination of the IS area on Form Vlll LCSV-1 and LCSV-2for trends such as a continuous or near-
continuous increase or decrease in the IS area over time.
4. The results of the LCS analysis (Form III LCSV) may also be used to assess instrument performance, j
75 DRAFT 12/90
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System Performance SV
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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sv
XV. 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 useabiliry 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 ail 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 useabiliry 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 qualiry of the
data.
E. Action
I. 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 SDG 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 useabiliry of the data
within the given context.
77 DRAFT 12/90
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APPENDIX A
CONTRACTUAL REQUIREMENTS AND EQUATIONS
MULTI-MEDIA, MULTI-CONCENTRATION - MM/MC
(OLM01.0)
DRAFT 12/90
Revised 6/91
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APPENDIX A
MULTI-MEDIA, MULTI-CONCENTRATION
CONTRACTUAL REQUDXEMENTS AND EQUATIONS FOR VOLATILE DATA REVIEW
II. GC/MS Instrument Performance Check
Use equation II. 1 to verify that the laboratory has not made errors the calculation of the percent relative
abundance.
% Relative Abundance = <*»*»** <** x 100% (H.1)
abundance of Y
For example, the percent relative abundance of m/z % (X) relative to m/z 95 (Y) is calculated as follows:
% Relative Abundance - ^undance of mlz 96
abundance of m/z 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 0.05 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 vary 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 %RSO 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%.
Table A.1 Minimum RRF Criteria for Volatile Target Compunds
Volatile Minimum
Compound RRF
Bromomethane 0.100
Vinyl chloride 0.100
1,1-Dichloroethene 0.100
1,1-Dichloroethane 0.200
Chloroform 0.200
1,2-Dichloroethane 0.100
1,1,1-Trichloroethane 0.100
Carbon tetrachloride 0.100
Bromodichloromethane 0.200
cis-l,3-Dichloropropene 0.200
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MM/MC APPENDIX A
Table A.1 Minimum RRF Criteria for Volatile Target Compunds (continued)
Volatile Minimum
Compound RRF
Trichloroethene 0.300
Dibromochloromethane 0.100
1,1,2-Trichloroethane 0.100
Benzene 0.500
trans-l,3-Dichloropropene 0.100
Bromoform 0.100
Tetrachloroethene 0.200
1,1,2,2-Tetrachloroethane 0.500
Toluene 0.400
Chlorobenzene 0.500
Ethylbenzene 0.100
Styrene 0.300
Xylenes (total) 0.300
Bromofluorobenzene 0.200
Initial calibration RRFs and RRF are calculated using equations III.l and III.2.
RRF = ^- x -^ (IIM)
5
£ RXFi (III.2)
RRF
where:
?j = "i'th Relative Response Factor
A = Area of the characteristic ion (EICP) measured
C = Concentration
is ss Internal standard
x = Analyte of interest
The %RSD is calculated using equations III.3 and III.4.
(IIL3)
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MM/MC , APPENDIX A
%RSD= 4 x 100 (IH.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 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%.
Check the continuing calibration RRF calculations for volatile target compounds using equation III.l. The
%D between initial calibration RRF and continuing calibration RRF is calculated using equation I V.I.
% D . "~/"~c x 10Q% fly.!,
/WF,
where:
/WVj = average relative response factor from initial calibration.
RRFC = relative response factor from continuing calibration standard.
VI. System Monitoring Compounds
The volatile system monitoring compounds (surrogates) and their contractual recovery limits are listed in
Table A.2.
Table A.2 System Monitoring Compound Contractual Requirements
System Monitoring Compound %Recoverv Limits
Water Samples Soil Samples
SMC1 Toluene-
-------
MM/MC APPENDIX A
Use equation VI. 1 to check that the system monitoring compound recoveries were calculated correctly:
% Recovery * Concemration/amowa found x IQQ% ^
Concentrationlamount 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
Compound %R - Water %R Soil RPD - Water RPD - Soil
1,1-Dichloroethene 61 - 145 59 - 172 <.14 <22
Trichloroethene 71 - 120 62 - 137 <.14 <24
Benzene 76 - 127 66 - 142 <.!! £21
Toluene 76 -125 59 - 139 <.13 ^21
Chlorobenzene 75-130 60-133 <13 <21
Verify that the matrix spike recoveries and RPD were calculated correctly using equations VII. 1 and VII.2.
% Recovery = SSR ~ SR x 100% (VII.I)
where:
where:
SSR = Spiked sample result
SR = Sample result
SA = Spike added
* \MSR ~ MSDR\ x 100% (VTI.2)
1/2 (MSR + MSDR)
RPD = Relative percent difference
MSR = Matrix spike recovery
MSDR = Matrix spike duplicate recovery
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MM/MC
IX. Internal Standards
APPENDIX A
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 capillary 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-d
5
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1,1-Dichloroethene
1,1-Dichloroe thane
l,2-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
Ethylbenzene
Styrene
Total Xylenes
Bromofluorobenzene (SMC)
Toluene-d8 (SMC)
SMC = System Monitoring Compound
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
Check the reponed positive sample results and quantitation limits with the quantitation lists and
chromatograms using equations XI. 1, XI.2, or XI.3. 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 A.6.
Concentration for waters:
x RKF x V
(XI.l)
A-5
DRAFT 12/90
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MM/MC APPENDIX A
Concentration for. low level soils:
(Dry weight basis)
x RRF x W, x D
Concentration for medium level soils:
(Dry weight basis)
m ,,.
8 ^
A,, x RRF x Va x W, x D
where:
Ax = area of characteristic ion (EICP) for compound being measured
A-a = area of characteristic ion (EICP) for the internal standard
/, = amount of internal standard added (ng)
RRF = daily response factor for compound being measured
VQ = volume of water purged (mL)
Ws = weight of sample (g)
D = (100 - % moisture)/100% - conversion to dry weight
V: = volume of methanol (mL)f
fj = volume of extract added (uL) for purging
Df = dilution factor^
VA - 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 (Va) to the number of microliters of the methanol extract of the
sample contained in volume Va. 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 = Non-adjusted CRQL x Sample Dilution Factor (XI.4)
\-6 DRAFT 12/90
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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:
Dry Weight CRQL = *»"#"« CR&
* , 100 - %moisrure. (XI.5)
100
For example, the dry weight CRQL for a soil sample with a 10U non-adjusted CRQL and a 10%
moisture would be 11U, according to the following calculation:
lie;
(100-10)
100
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MM/MC
APPENDIX A
Table A.5 Characteristic Ions for Volatile Target Compounds
Analyte
Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1, 1-Dichloroethene
1,1-Dichloroethane
1,2-Dichloroethene
Chloroform
1,2-Dichloroethane
2-Butanone
1,1,1-Trichloroethane
Carbon tetrachloride
Bromodichloromethane
1,1,2,2-Tetrachloroethane
1,2-Dichloropropane
trans-13-Dichloropropene
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Benzene
cis-13-Dichloropropene
Bromoform
2-Hexanone
4-Methyl-2-pentanone
Primary Ion*
50
94
62
64
84
43
76
96
63
96
83
62
43"
97
117
83
V «
63
75
130
129
97
78
75
173
43
43
Secondary Ion(s)
52
96
64
66
49, 51, 86
58
78
61,98
65, 83, 85, 98, 100
61,98
85
64, 100, 98
57
99, 117, 119
119, 121
85
85, 131, 133, 166
65, 114
77
95, 97, 132
208, 206
83, 85, 99, 132, 134
77
171, 175, 250, 252, 254, 256
58, 57, 100
58, 100
A-8
DRAFT 12/90
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MM/MC
APPENDIX A
Table A.5 Characteristic Ions for Volatile Target Compounds (Continued)
Analyte
Tetrachloroethene
Toluene
Chlorobenzene
Ethyl benzene
Styrene
Total Xylenes
Primary Ion*
164
92
112
106
104
106
Secondary Ion(s)
129, 131, 166
92
114
91
78, 103
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-Bromofluorobenzene
l,2-Dichloroethane-d4
Toluene-dg
95
65
98
174, 176
102
70, 100
INTERNAL STANDARDS
Bromochloromethane
1 ,4-Difiuorobenzene
Chlorobenzene-d5
128
114
117
49, 130. 51
63,88
82,119
A-9
DRAFT 12/90
Revised 6/91
-------
APPENDIX A
MULTI-MEDIA, MULTI-CONCENTRATION
CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR SEMTVOLATILE DATA REVIEW
II. GC/MS Instrument Performance Check
Use equation 11.1 to verify that the laboratory has not made errors in the calculation of the percent
relative abundance.
For example, the percent relative abundance of m/z 443 (X) relative to m/z 442 (Y) is calculated as follows:
% Relative Abundance - abundance of m/z 443 x m%
abundance of m/z 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). 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%.
Table A.7 Minimum RRF Criteria for Semivolatile Target Compounds
Semivolatile Minimum
Compounds RRF
Phenol 0.800
bis(-2-Chloroethy!)ether 0.700
2-Chlorophenol 0.800
1,3-Dichlorobenzene 0.600
1,4-Dichlorobenzene 0.500
1,2-Dichlorobenzene 0.400
2-Methylphenol 0.700
4-MethyIphenol 0.600
N-Nitroso-di-propylamine 0.500
Hexachloroethane 0.300
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
Compounds RRF
2,4-Dichlorophenol 0.200
1,2,4-Trichlorobenzene 0.200
Naphthalene 0.700
4-Chloro-3-methylphenol 0.200
2-Methylnaphthalene 0.400
2,4,6-Trichlorophenol 0.200
2,4,5-TrichlorophenoI 0.200
2-Chloronaphthalene 0.800
Acenaphthylene 1.300
2,6-Dinitrotoluene 0.200
Acenaphthene 0.800
Dibenzofuran 0.800
2,4-Dinitrotoluene 0.200
4-Chlorophenyl-phenylether 0.400
Fluorene 0.900
4-Bromophenyl-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
Chrysene 0.700
Benzo(b)fluoranthene 0.700
Benzo(k)fluoranthene 0.700
Benzo(a)pyrene 0.700
Indeno(l^-cd)pyrene 0.500
Dibenz(a,h)anthracene 0.400
Benzo(g,h,i)perylene 0.500
Nitrobenzene-d5 0.200
2-Fluorobiphenyl 0.700
Terphenyl-d14 0.500
Phenol-ds 0.800
2-Fluorophenol 0.600
2-ChJorophenol-d4 0.800
l,2-Dichlorobenzene-d4 0.400
A-ll DRAFT 12/90
Revised 6/91
-------
MM/MC , APPENDIX A
Initial calibration RRF and RRF are calculated using equations III.l and III.2; %RSD is calculated
using equations III.3 and III.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 any 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
I V.I.
VI. Surrogate Spikes
The semivolatile surrogate compounds and their contractual recovery limits are listed in Table A.8.
Table AJt Semivolatile Surrogate Requirements
Surrogate %Recoverv Limits
Water Samples Soil Samples
SI Nitrobenzene-d5 35-114 23-120
S2 2-Fluorobiphenyl 43-116 30-115
S3 Terphenyl-d14 33 - 141 18 - 137
S4 Phenol-d5 10-110 24-113
S5 2-Fluorophenol 21-110 25 - 121
S6 2,4,6-Tribromophenol 10 -123 19 - 122
S7 2-Chlorophenol-d4 33.- 110* 20 - 130*
S8 l,,2-Dichlorobenzene-d4 16 - 110* 20 - 130*
* Advisory limits
Use equation VI. 1 to verify that the surrogate recoveries were calculated correctly.
vn. Matrix Spikes/Matrix Spike Duplicates
The matrix spike/matrix spike duplicate contractual requirements are listed in Table A.9.
Verify that the matrix spike recoveries and RPD were calculated correctly using equations VII. 1 and VII.2.
IX. Internal Standards
Table A. 10 contains the semivolatile internal standards and their corresponding target compounds.
A-12 DRAFT 12/90
Revised 6/91
-------
MM/MC , APPENDIX A
Table A.9 Semivoiatile MS/MSD Contractual Requirements
Compound %R Water %R - Soil RPD - Water RPD - Soil
Phenol 12-110 26-90 <.42 <. 35
2-Chlorophenol 27-123 25-102 <. 40 <. 50
1,4-Dichlorobenzene 36 - 97 28-104 <. 28 <. 27
N-Nitroso-di-n-propylamine 41-116 41-126 <. 38 <. 38
1,2,4-Trichlorobenzene 39 - 98 38 - 107 <. 28 <. 23
4-Chloro-3-methylphenol 23-97 26-103 < 42 <. 33
Acenaphthene 46-118 31-137 ^31 <. 19
4-Nitrophenol 10-80 11-114 <. 50 <. 50
2,4-Dinitrotoluene 24 - 96 28-89 <. 38 <. 47
Pentachlorophenol 9 - 103 17-109 <. 50 <. 47
P""""5 26-127 35 - 142 < 31 * ^
A'13 DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A. 10 Semivolatile Internal Standards and Their Corresponding Target Compounds
l,4-Dichlorobenzene-d4
Naphthalene-d8
Acenaphthene-d10
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
2,2'-oxybis-( 1-Chloropropane)
4-Methylphenol
N-Nitroso-Di-n-propylamine
Hexachloroethane
2-Fluorophenol (SUIT)
Phenol-d5 (SUIT)
2-Chlorobenzene-d4 (surr)
l,2-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-d, (surr)
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-DinitrophenoI
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethyl phthalate
4-Chlorophenyl-phenyl ether
Fluorene
4-Nitroaniline
2-Fluorobiphenyl (surr)
2,4,6-Tribromophenol (surr)
Phenanthrene-d10
Chrysene-d12
Perylene-djj
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-BromophenyI phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Carbazole
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butylbenzyl phthalate
33'-Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylhexyi)phthalate
Chrysene
Terphenyl-d14 (surr)
Di-n-octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno( 1.2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
SUIT = surrogate compound
A-14
DRAFT12/90
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, XI.7, or XI.8. Equation XI.4 should be used to adjust the CRQL for
a diluted sample, and equation XI.5 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. 13.
Concentration for waters:
US/L
Concentration for soils/sediments:
(Dry weight basis)
A,, x RRF
m ..,
*^ AI, x RRF x V. x Wt x D
where:
Ax = area of characteristic ion (EICP) for compound being measured
AU = area of characteristic ion (EICP) for the internal standard
/s = amount of internal standard added (ng)
RRF = daily relative response factor for compound being measured
V0 = volume of water extracted (mL)
Vt ss volume of extract injected (uL)
Vt = volume of concentrated extract (uL)
Df = dilution factor f
D = (100 - % moisture)/100% - conversion to dry weight
Ws = weight of sample (g)
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.
_, uL of the most concentated extract used + uL of clean solvent /vr a\
JJT 3 * * {J\.itOj
uL of the most concentrated extract used
A-15 DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A.11 Characteristic Ions for Semivoladle Target Compounds
Analyte
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
2,2'-oxybis( 1-Chloropropane)
4-Methylphenol
N-Nitroso-di-propylamine
Hexachloroethane
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-Methylnaph'thalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
Primary Ion
94
93
128
146
146
146
108
45
108
70
117
77
82
139
107
93
162
180
128
127
225
107
142
237
1%
1%
162
Secondary Ion(s)
65.66
63, 95
64, 130
148, 113
148, 113
148, 113
107
77,79
107
42, 101, 130
201, 199
123,65
95,138
65, 109
121, 122
95, 123
164,98
182, 145
129, 127
129
223,227
144, 142
141
235, 272
198, 200
198,200
164, 127
A-16
DRAFT 12/90
Revised 6/91
-------
MM/MC , APPENDIX A
Table A.11 Characteristic Ions for Semivolatile Target Compounds (Continued)
Parameter
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Carbazole
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3'-Dichlorobenzidine
Primary Ion
65
163
152
138
153
184
109
168
165
165
149
204
166
138
198
169
248
284
266
178
178
167
149
202
202
149
252
Secondary Ion(s)
92, 138
194, 164
151, 153
108,92
152, 154
63, 154
139, 65
139
63. 182
89. 121
177. 150
206, 141
165, 167
92, 108
182, 77
168, 167
250, 141
142, 249
264,268
179, 176
179, 176
166, 139
150, 104
101, 100
101, 100
91,206
254, 126
A-17
DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A.11 Characteristic ions for Semivolatile Target Compounds (Continued)
Analyte
Benz(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Di-n-Octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranihene
Benzo(a)pyrene
Indeno( 1^3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
Primary Ion
228
149
228
149
252
252
252
276
278
276
Secondary Ion(s)
229,226
167, 279
226, 229
253, 125
253,125
253,125
138, 227
139, 279
138, 277
A-18
DRAFT 12/90
Revised 6/91
-------
MM/MC APPENDIX A
Table A.12 Characteristic Ions for Semivolatile Surrogates and Internal Standards
Analyte
Primary Ion
Secondary Ion(s)
SURROGATES
Phenol-d5
2-Fluorophenol
2,4,6-Tribromophenol
Nitrobenzene-d5
2-Fluorobipbenyl
Terphenyl
2-Chlorophenol-d4
l,2-Dicnlorobenzene-d4
99
112
330
82
172
244
132
152
42,71
64
332, 141
128,54
171
122, 212
68, 134
115, 150
INTERNAL STANDARDS
l,4-Dichlorobenzene-d4
Naphthalene-dg
Acenaptbene-d10
Phenanthrene-d10
Chrysene-d12
Perylene-dl2
152
136
164
188
240
264
115
68
162, 160
94,80
120, 236
260, 265
A-19
DRAFT 12/90
Revised 6/91
-------
MM/MC
APPENDIX A
Table A.13 Characteristic Ions for Pesticides/Aroclors
Analyte
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
Heptachlor
AJdrin
Heptachlor epoxide
Endosulfan I
Dieldrin
4,4'-DDE
Endrin
Endrin ketone
Endrin aldehyde
Endosulfan II
4,4'-DDD
Endosulfan sulfate
4,4'-DDT
Methoxychlor
Chlordane (alpha and/or gamma)
Toxaphene
Arochlor-1016
Arochlor-1221
Arochlor-1232
Arochlor-1242
Arochlor-1248
Arochlor-1254
Arochlor-1260
Primary Ion
183
181
183
183
100
66
353
195
79
246
263
317
67
337
235
272
235
227
373
159
222
190
190
222
292
292
360
Secondary Ion(s)
181. 109
183, 109
181, 109
181, 109
272, 274
263, 220
355, 351
339, 341
263, 279'
248, 176
82,81
67, 319
250, 345
339, 341
237, 165
387, 422
237, 165
228
375, 377
231, 233
260,292
222, 260
222, 260
256, 292
362, 326
362, 326
362. 394
A-20
DRAFT 12/90
Revised 6/91
-------
APPENDIX B
CONTRACTUAL REQUIREMENTS AND EQUATIONS
LOW CONCENTRATION WATER - LCW
(OLC01.0)
DRAFT 12/90
Revised 6/91
-------
APPENDIX B
LOW CONCENTRATION WATER
CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR VOLATILE DATA REVIEW
II. GC/MS Instrument Performance Check
Use equation II. 1 to verify that the laboratory has not made errors the calculation of the percent relative
abundance.
% Relative Abundance = abundance °f X x 100* (II.l)
abundance of Y
For example, the percent relative abundance of m/z 96 (X) relative to m/z 95 (Y) is calculated as follows:
% Relative Abundance = '^dance of m/z 96 x IQQ%
abundance of m/z 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 0.05 and a percent relative standard deviation
(%RSD) of less than or equal to 30%.
Contractual Criteria: The maximum %RSD for most volatile compounds is 20.5% and the minimum
RRF criteria vary as specified in the following table (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%.
Initial calibration RRFs and RRF are calculated using equations III.l and III.2.
RRF = ^- x -^ (III.1)
5
£ RJ(Fi (III.2)
RRF =
where:
RRFj = "i'th Relative Response Factor
A = Area of the characteristic ion (EICP) measured
C = Concentration
is = Internal standard
x - Analyte of interest
B-l DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
Table B.I. Technical Acceptance Criteria for Initial
and Continuing Calibration for Volatile Organic Compounds
Target Volatile Compound
Benzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroform
Dibromochloromethane
1,2-Dibromoethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1 . 1 -Dich loroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis- 1,3-Dichloropropene
trans- 1,3-Dichloropropene
Ethylbenzene
Styrene
1.1,2.2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1 -Trichloroethane
1,1.2-Trichloroethane
Trichloroethene
Vinyl Chloride
Xylenes (total)
4-Bromofluorobenzene
Minimum RRF
0.500
0.100
0.200
0.100
0.100
0.100
0.500
0.200
0.100
0.100
0.400
0.600
0.500
0.200
0.106
0.100
0.200
0.100
0.100
0.300
0.500
0.200
0.400
0.100
0.100
0.300
0.100
0.300
0.200
Maximum
%RSD
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
%D
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0-
±30.0
±30.0
B-2
DRAFT 12/90
Revised 6/91
-------
LCW APPENDIX B
The %RSD is calculated using equations III.3 and III.4.
_^ (X[X)
£r (»-D
%ASD= -? x 100 (III.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 volatile target compounds should meet a %D criterion of +, 30%.
Contractual Criteria; The percent difference (%D) between the initial calibration RRF and the
continuing calibration RRF is +. 30% for all compounds listed in Table B.I (Page B-2). 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%.
Check the RRF calculations for volatile target compounds using equation III.1 (Page B-l). The %D
between initial calibration RRF and continuing calibration RRF is calculated using equation I V.I.
RRF.-RRFC ._.,.
' c x 100% (IV.l)
RRF,
where:
RRft = average relative response factor from initial calibration.
RRFC = relative response factor from continuing calibration standard.
VI. Surrogate Spikes
The volatile surrogate compound and the contractual recovery limits are listed below.
Surrogate Spike %Recoverv Limits
BFB Bromofluorobenzene 80 - 120
B-3 DRAFT 12/90
Revised 6/91
-------
LCW APPENDIX B
Use equation VI.2 to check that the surrogate percent recovery was calculated correctly:
% Recovery = - x 100% (VI.2)
where:
QD = Quantity determined by analysis.
QA ~ Quantity added to samples/blanks.
VII. Laboratory Control Samples (LCS)
Laboratory Control Sample compounds are listed in Table B.2. The contractual percent recovery limits
are from 60 to 140 percent However, these limits may eventually be expanded by the Agency during the
period of performance if the limits are found to be too restrictive.
Table B.2 Volatile Laboratory Control Sample Compounds
Vinyl Chloride
1,2-Dichloroethane
Carbon Tetrachloride
1,2-Dichloropropane
Trichloroethene
1,1,2-Trichloroethane
Benzene
cis-13-Dichloropropene
Bromoform
Tetrachloroethene
1,2-Dibromoethane
1,4-Dichlorobenzene
Check that the LCS recovery was calculated correctly by using equation VI.2.
IX. Internal Standards
Table B.3 contains the volatile internal standards and their corresponding target compounds.
B-4 DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
Table B J. Volatile Internal Standards
and Their Corresponding Target Compounds
1,4-Difluorobenzene
Chlorobenzene-d,
1,4-Dichlorobenzene d4
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Bromochloromethane *
Methylene Chloride
Acetone
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
cis-l^-Dichloroethene* *
trans-1,2-Dichloroethene* *
Chloroform
1,2-Dichloroethane
2-Butanone
4-Bromofluorobenzene (SUIT)
1,1,1-Trichloroethane
Carbon tetrachloride
Bromodichloromethane
1,2-Dichloropropane
cis- 1,3-Dichloropropene
Trichloroethene
Dibromochloromeihane
1,1,2-Trichloroethane
Benzene
trans-1,3-Dichloropropene
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1,1,2,2-Tetrachloroethane
1,2-Dibromoethane*
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes
Bromoform
1,2-Dibromo-3-chloropropane *
1,2-Dichlorobenzene*
1,3-Dichlorobenzene*
1,4-Dichlorobenzene*
* compounds not on Multi-media, Multi-concentration TCL
** on Multi-media, Multi-concentration TCL as total 1,2-Dichloroethene
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
Check the reponed positive sample results and quantitation limits with the quantitation lists and
chromatograms using equation XI. 1. Primary and secondary Quantitation ions are listed in Table B.4
(Page B-7).
(XI.1)
' where:
Ax = area of characteristic ion (EICP) for compound being measured
A^ = area of characteristic ion for the internal standard
7S = amount of internal standard added (ng)
RRF = relative response factor for compound being measured
V0 = volume of water purged (mL)
Df = dilution factor
B-5
DRAFT 12/90
Revised 6/91
-------
LCW APPENDIX B
The CRQL for a diluted sample should be calculated as follows:
Adjusted CRQL = Non-adjusted CRQL x Sample Dilution Factor (XI.4)
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 at 10U x 100
B-6 DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
TABLE B.4 Volatile Quantitation Ions
Volatile Target Compounds
Acetone
Benzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroe thane
Chloroform
Chloromethane
Dibromochloromethane
l,2-Dibromo-3-chloropropane
1 ,2-Dibromoethane
1 ,2-Dichlorobenzene
1,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1,1-Dichloroethane
1.2-Dichloroethane
1,1-Dichloroethene
cis- 1,2-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis- 1,3-Dichloropropene
Primary Quantitation
Ion
43
78
128
83
173
94
43
76
117
112
64
83
50
129
75
107
146
146
146
63
62
96
96
96
63
75
Secondary Ions
58
...
49, 130
85, 127
175, 254
%
72*
78
119
77, 114
66
85
52
127
155, 157
109, 188
111. 148
111, 148
111, 148
65, 83
98
61,63
61,98
61,98
112
77
Quanutation ot this analyte is based on m/z 43 but m/z 72 must be present in the spectrum.
B-7
DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
TABLE B.4 Volatile Quantitation Ions (Continued)
Volatile Target Compounds
trans- 1,3-Dichloropropene
Ethylbenzene
2-Hexanone
Methylene chloride
4-Methyl-2-pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1 -Trichloroethane
1,1,2-Trichloroe thane
Trichloroethene
Vinyl chloride
Xylenes (total)
Primary Quantitation
Ion
75
91
43
84
43
104
83
166
91
97
97
95
62
106
Secondary Ions
77
106
58, 57, 100
86,49
58, 100
78
131,85
168, 129
92
99,61
83, 85, 99. 132, 134
130, 132
64
91
SURROGATE COMPOUND AND INTERNAL STANDARDS:
4-Bromofluorobenzene
Chlorobenzene-d;
l,4-Dichlorobenzene-d4
1,4-Difluorobenzene
95
117
150
114
174, 176
82, 119
115, 152
63,88
B-8
DRAFT 12/90
Revised 6/91
-------
LCW APPENDIX B
LOW CONCENTRATION WATER
CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR SEMIVOLATILE DATA REVIEW
II. GC/MS Instrument Performance Check
Use equation II. 1 (Page B-l) to verify that the laboratory has not made errors the calculation of the
percent relative abundance.
For example, the percent relative abundance of m/z 443 (X) relative to m/z 442 (Y) is calculated as follows:
% Relative Abundance . ^undance of mfz 443 x IQQ%
abundance ofm/z 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 the following table (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). The 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 that are greater than or equal to 0.010, and %RSD of less than or equal to 40.0%.
Initial calibration RRFs and RRF are calculated using equations III.l and III.2 (Page B-l); %RSD is
calculated using equations III.3 and III.4 (Page B-3).
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 B.5. 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 RRF calculations for semivolatile target compounds using equation III.l (Page B-l), and
evaluate the %D between initial calibration RRF and continuing calibration RRF using equation I V.I
(Page B-3).
B-9 DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
Table B.5. Acceptance Criteria for Initial and Continuing
Calibration for Semivolatile Organic Compounds
Semivolatile Compounds
Phenol
bis(-2-Chloroethyl)ether
2-Chlorophenol
2-Methylphenol
4-Methylphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Diraethylphenol
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
4-Chloro-3-methylphenol
2-Methylnaphthalene
2,4,6-Trichlorophenol
2,4.5-Trichlorophenol
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Dibenzofuran
2.4-Dinitrotoluene
2.6-Dinitrotoluene
4-Chlorophenyl-phenylether
Fluorene .
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Fluoranthene
Minimum RRF
0.800
0.700
0.700
0.700
0.600
0.500
0.300
0.200
0.400
0.100
0.200
0.300
0.200
0.200
0.700
0.200
0.400
0.200
0.200
0.800
1.300
0.800
0.800
0.200
0.200
0.400
0.900
0.100
0.100
0.050
0.700
0.700
0.600
Maximum %RSD
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
30.0
30.0
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
30.0
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
%D
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±30.0
±30.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±30.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
B-10
DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
Table B.5. Acceptance Criteria for Initial and Continuing
Calibration for Semivolatile Organic Compounds (continued)
Semivolatile Compounds
Pyrene
Benz(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno( 1^3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(gju)perylene
Phenol-dj (SUIT)
2-Fluorophenol (surr)
Terphenyl-d14 (surr)
2-Fluorobiphenyl (SUIT)
Minimum RRF
0.600
0.800
0.700
0.700
0.700
0.700
0.500
0.400
0.500
0.800
0.600
0.500
0.700
Maximum %RSD
20.5
20,5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
%D
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
VI. Surrogate Spikes
Surrogate spike recoveries for Semivolatile samples and blanks must be within the limits specified in Table
B.6.
Table B.6 Semivolatile Surrogate Recovery Requirements
Surrogate Compound
Nitrobenzene-ds
2-Fluorobiphenyl
p-Terphenyl-d14
Phenol-ds
2-Fluorophenol
2,4,6-Tribromophenol
% Recovery
40- 112
42 - 110
24- 140
17 - 113
16 - 110
18 - 126
Use equation VI.2 to verity that the surrogate recoveries were calculated correctly.
B-ll
DRAFT 12/90
Revised 6/91
-------
LCW APPENDIX B
VD. Laboratory Control Samples (LCS)
The percent recovery for each of the compounds in the LCS spiking solution must be within the recovery
limits listed in Table B.7. However, these limits may eventually be expanded by the Agency during the
period of performance if the limits are found to be too restrictive.
Table B.7 Semivolatile Laboratory Control Sample Compounds and Recovery Limits
Compound %Recovery
Phenol 44 - 120
2-Chlorophenol 58-110
4-Chloroaniline 35 - 98
2,4,6-Trichlorophenol 65-110
bis(2-Chloroethyl)ether 64-110
N-Nitroso-di-n-propylamine 34 - 102
Hexachloroethane 32 - 77
Isophorone 49-110
1,2,4-Trichlorobenzene 44 - 96
Naphthalene 56 - 160
2,4-Dinitrotoluene 61 - 140
Diethylphthalate 76 - 104
N-Nitrosodiphenylamine 35 - 120
Hexachlorobenzene 30 - 95
Benzo(a)pyrene 55-92
Check that the recoveries were calculated correctly by using equation VI.2 (Page B-4).
IX. Internal Standards
Table B.8 (Page B-14) contains the semivolatile internal standards and their corresponding target
compounds.
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 equation XI.6. Equation XI.4 (Page B-6) should be used to adjust the CRQL for a
diluted sample. Table B.9 (Page B-15,16,17) contains the semivolatile primary and secondary Quantitation
ions.
A x / x V x Df .-.
ugL = = '- ' (XI.6)
A x RRF *VxV
B-12 DRAFT 12/90
Revised 6791
-------
LCW APPENDIX B
where:
Ax = area of characteristic ion (EICP) for compound being measured
A± = area of characteristic ion (EICP) for the internal standard
Ss = amount of internal standard added (ng)
RRF = daily relative response factor for compound being measured
V0 = volume of water extracted (mL)
KJ = volume of extract injected (uL)
yt = volume of concentrated extract (uL)
Df = dilution factor
B-13 DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
Table B.8. Semivolatile Internal Standards
and Their Corresponding Target Compounds
l,4-Dichlorobenzene-d4
Naphthalene-ds
Acenaphthene-d10
Phenol
bis(2-Chloroethyl)ether
2-ChIorophenol
2-Methylphenol
2,2'-oxybis-(l-Chloropropane)
4-Methylphenol
N-Nitroso-di-n-propylamine
2-Fluorophenol (SUIT)
Phenol-d5 (sun)
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-d5 (SUIT)
Hexachlorocyclopentadiene
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-Fluorobiphenyl (surr)
2,4,6-Tribromophenol (surr)
surr = surrogate compound
Phenanthrene-d10
Chrysene-d12
Pervlene-d
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bromophenyl phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butylbenzyl phthalate
33'-Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Terphenyl-d14 (surr)
Di-n-octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno( l,23-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g.h.i) perylene
SUIT = surrogate compound
B-14
DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
Table B.9 Semivolatile Quantitation Ions
Analyte
Phenol
bis(2-Chloroethyl)etheir
2-Chlorophenol
1,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
2,2'-oxybis(l-Chloropropane)
4,-Methylphenol
N-nitroso-di-n-propylamine
Hexachloroethane
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
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Primary Ion
94
93
128
146
146
146
108
45
108
70
117
77
82
139
107
93
162
180
128
127
225
107
142
237
196
196
162
65
Secondary Ion(s)
65,66
63, 95
64, 130
148, 113
148, 113
148, 113
107
77,79
107
42, 101, 130
201, 199
123, 65
95, 138
65, 109
121, 122
95, 123
164,98
182, 145
129, 127
129
223. 227
144, 142
141
235, 272
198, 200
198, 200
164, 127
92, 138
B-L5
DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
Table B.9 Semivolatile Quantitation Ions (Continued)
Analyte
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3'Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylhexyl)phthalate
Chiysene
Di-n-octyi phthalate
Primary Ion
163
152
138
153
184
109
168
165
165
149
204
166
138
198
169
248
284
266
178
178
149
202
202
149
252
228
149
228
149
Secondary Ion(s)
194, 164
151, 153
108,92
152, 154
63, 154
139, 65
139
63, 182
89, 121
177, 150
206, 141
165, 167
92, 108
182,77
168, 167
250, 141
142, 249
264, 268
179, 176
179, 176
150, 104
101, 100
101, 100
91,206
254, 126
229, 226
167, 279
226, 229
...
B-16
DRAFT 12/90
Revised 6/91
-------
LCW
APPENDIX B
Table B.9 Semivolatile Quantitation Ions (Continued)
Analyte
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno( l,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)peiylene
Primary Ion
252
252
252
276
278
276
Secondary Ion(s)
253,125
253, 125
253,125
138, 227
139, 279
138, 277
Surrogates
Phenoi-ds
2-Fluorophenol
2,4,6-Tribromophenol
d-5 Nitrobenzene
2-Fluorobiphenyl
Terphenyl
99
112
330
82
172
244
42,71
64
332, 141
128. 54
171
122, 212
Internal Standards
1 ,4-Dichlorobenzene-d4
Naphthalene-d8
Acenaphthene-d10
Phenanthrene-dj0
Chrysene-dT2
Perylene-d12
152
136
164
188
240
264
115
68
162, 160
94,80
120. 236
260, 265
B-17
DRAFT 12/90
Revised 6/91
-------
APPENDIX C
CONTRACTUAL REQUIREMENT COMPARISON TABLES
DRAFT IZ/90
-------
APPENDIX C
Table Cl. Comparison of Requirements for
Volatile Data Review
REQUIREMENT
Target Compound List
Data Turnaround
Technical Holding Time
Initial Calibration
Continuing Calibration
Blanks
SMC/Surrogates
MS/MSD
LCS
Regional QA/QC
Internal Standards
CRQL
TICs
MULTI-MEDIA, MULTI-
CONCENTRATION
33 Target Compounds
35 days
7 days if not preserved
14 days if preserved
5 levels: 10 - 200 ug/L
mid-level: 50 ug/L
Method Blanks
Instrument Blanks
SMC:
l,2-Dichloroethane-d4
Bromofluorobenzene
Toluene-dg
Frequency: 1 per 20 samples,
per matrix
N/A
PEs - variable
IS Area: - 50% to + 100%
IS RT Shift: ± 30 sec.
3 compounds:
Chlorobenzene-d5
1 ,4-Difluorobenzene
Bromochloromethane
10 ppb (water/low soil)
1200 ppb (med soil)
largest 10 M0% of nearest IS
LOW CONCENTRATION
WATERS
40 Target Compounds
14 days
7 days if not preserved
14 days if preserved
5 levels: 1 - 25 ug/L
(5 - 125 for Ketones)
mid-level: 5 ug/L
(25 for Ketones)
Method Blanks
Instrument Blanks
Storage Blanks
Surrogate: Bromofluorobenzene
N/A
1 per SDG
PEs - 1 per SDG
IS Area: + 40%
IS RT Shift: ± 20 sec.
3 compounds:
Chlorobenzene-d5
1,4-Difluorobenzene
1,4-Dichlorobenzene
1 -5 ug/L
largest 10 >40% of nearest IS
C-l
DRAFT 12/90
-------
APPENDIX C
Table C.2. Comparison of Requirements for
Semivolatile Data Review
REQUIREMENT
Target Compound List
Data Turnaround
Technical Holding Time
Initial Calibration
Continuing Calibration
Blanks
Surrogates
MS/MSD
LCS
Regional QA/QC
Internal Standards
CRQLs
TICs
MULTI-MEDIA, MULTI-
CONCENTRATION
64 Target Compounds
35 days
Extraction - 5 days
Analysis - 40 days after
extraction
5 levels: 20 - 160 ug/L
mid-level: 50 ug/L
Method Blanks
Instrument Blanks
8 compounds
Frequency: 1 per 20 samples,
per matrix
N/A
PEs - variable
IS Area: - 50% to + 100%
IS RT Shift: ± 30 sec.
10 - 50 ppb (water)
330 - 1700 ppb (low soil)
10,000 - 50.000 (med soil)
largest 20 M0% of nearest IS
LOW CONCENTRATION
WATERS
60 Target Compounds
14 days
Extraction - 5 days
Analysis - 40 days after
extraction
5 levels: varies
mid-level: varies
Method Blanks
Instrument Blanks
Storage Blanks
6 compounds
N/A
1 per SDG
PEs - 1 per SDG
IS Area: - 50% to 100%
IS RT Shift: ± 20 sec.
5 - 20 ug/L
largest 20 >50% of nearest IS
C-2
DRAFT 12/90
-------
APPENDIX D
PROPOSED GUIDANCE FOR
TENTATIVELY IDENTIFIED COMPOUNDS
(VOA AND SV)
DRAFT 6/90
-------
Proposed Guidance for Tentatively Identified Compounds (VGA)
A. Review Items: Form IVOA-TIC, chromatograms, 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 (MIST) 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
repon 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 repon
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 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 of
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
- DRAFT 6/90
-------
Tentatively Identified Compounds VGA
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+ 1)/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, Cl, 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
222
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 DRAFT 6/90
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Tentatively Identified Compounds VOA
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 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 spectrum 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-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: CO2 (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, cyclohexenone, cyclohexanol,
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 identified in more than one fraction. Verify that quantuation 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.
D.3 DRAFT 6/90
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Tentatively Identified Compounds . VGA
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 according to the evaluation
guidelines in 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 SOG.
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 design-
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-4 DRAFT 6/90
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Tentatively Identified Compounds VGA
APPENDIX
Equation 1:
RI = 100 RTunk - RTz + 100Z
RTz+1-RTz
where: RTunk is the retention time of the unknown
RTz is the retention time of the proceeding retention index standard
RTz+l is the retention time of the following retention index standard
Z s number of rings in the retention index standard
RI a Lee Retention Index
Retention Index Standards
naphthalene z=2
phenanthrene z=3
chrysene z=4
Benzo(g4u) z=5
perylene
RI=200.00
RI=300.00
RI-400.00
RI=500.00
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
222
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.
DRAFT 6/90
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Tentatively Identified Compounds . VOA
REFERENCES
1. Lee, M.L. Vassilaros, D.L., White, CM., and Novotny, M., "Retention Indices for Programmed-
Temperature Capillary-Column Gas Chromatography of Polycyclic Aromatic Hydorcarbons",
Analytical Chemistry. V. 51, no. 6, 1979, pp. 768-773.
2. Rostad, C.E., and Pereira, W.E, "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, Spectrometric 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
poiycyclic Aromatic Compounds. Critical Evaluation and Additional Indices". J. of Chromatographv.
252 (1982) pp. 1-20.
D-6 DRAFT 6/90
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sv
Proposed Guidance for Tentatively Identified Compounds CSV)
A. Review Items: Form I SV-TIC, chromatograms, library search printout and spectra 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 50 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 TICs.
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 SOG) in which the unknown
compound occurs. Calculation of retention indices (RI) and comparison of RI 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:
D.7 DRAFT 6/90
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Tentatively Identified Compounds SV
RI = 100 RTunJc - RTz + 100Z
RTz-H - RTz
where: RTunk is the retention time of the unknown
RTz b the retention time of the proceeding 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
phenanthrene
chrysene
Benzo(gji,i)
perylene
z=2
z=3
z-4
z=5
RI=200.00
RI=300.00
RI =400.00
RI=500.00
'ote: 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 S V (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 spectra and
RI data, a full .~3ss 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 MW
of the retrieved library spectra, interpreted in light ct me RI, may be helpful
if the molecular ion is not present.
o Determine the isotope ratios (M + 1)/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, Cl, and Br.
D.g DRAFT 6/90
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Tentatively Identified Compounds SV
o Calculate the total number of rings-plus-double-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 + N +1
222
where: C a 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 polycyclic
aromatic pattern at m/z 230, the MW of terphenyl. 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 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-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.
D.9 DRAFT 6/90
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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 TTCs.
Examples:
a. Common laboratory contaminants: CO2 (m/z 44), siloxanes (m/z 73), diethyl ether,
hexane, certain freons (l,l,2-trichloro-l,2,2-trifluoroethane or fluoro-
trichloromethane),
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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.U DRAFT 6/90
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APPENDIX E
GLOSSARY OF TERMS
DRAFT 12/90
Revised 6/91
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MMMINDIX I.
GLOSSARY OF TERMS
APO Administrative Project Officer
BFB Bromofluorobenzene - volatile instrument performance check compound
\
BNA Base/Neutral/Acid Compounds - compounds analyzed by semivolatile 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 Croupes).
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-l
DRAFT 11/90
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(JLOSSARV APPENDIX K
PCS Polyehlonnated biphenyl (Aiochlor is a trademark)
PE Sample Performance Evaluation Sample
QA Quality .Assurance - Total program tor 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 Meld 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 - Method 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 DRAFT 11/90
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GLOSSARY VlM'KNDI-X K
V'OA Volatile Organic Analysis - Method based on- ihe..puree and irap tecnniqui: -lor organic
compound analysis.
VTSR Validated Time of Sample Receipt - Time ol'sample receipt at ihe Moratory as recorded on
the shipper's deliver,- receipt and Sample Traffic Report.
E-3 DRAFT 11/90
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