Ul
REGION m MODIFICATIONS
TO
NATIONAL FUNCTIONAL GUIDELINES
FOR
ORGANIC DATA REVIEW
MULTI-MEDIA, MULTI-CONCENTRATION
(OLMO1.0-OLMO1.9)
SEPTEMBER 1994
i
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Region III Modifications
FOREWORD
This document is a modification to the National Functional
Guidelines for Organic Data Review (Draft, February, 1994).
This document describes those procedures that are to be used for
Region in Data Validation. It is intended for implementation
for all CLP data acquired for use within Region ffl
but it may be adapted for use with other similar methods.
. All comments and questions pertaining to this document
" should be addressed to:
U.S. Environmental Protection Agency
Region ffl
Central Regional Laboratory
Quality Assurance Branch
201 Defense Highway
Suite 200
Annapolis, MD 21401
c/o Program Support Section
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Region HI Modification*
TABLE OF CONTENTS
Page
INTRODUCTION •, . . i
PRELIMINARY REVIEW , ii
DATA QUALIFIER DEFINITIONS Hi
VOLATILE DATA REVIEW . / 1
I. Technical Holding Times , 2
H. GC/MS Instrument Performance Check 5
m. Initial Calibration g
IV. Continuing Calibration 12
V. Blanks 15
VI. System Monitoring Compounds (Surrogate Spikes) 19
Vfl. Matrix Spikes/Matrix Spike Duplicates 23
VBd. Regional Quality Assurance and Quality Control 25
IX. Internal Standards 27
X. , Target Compound Identification , 29
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs) . . 31
XH. Tentatively Identified Compounds (TICs} . 33 -
Xffl. System Performance 37
XTV. Overall Assessment of Data 38
SEMTVOLATILE DATA REVIEW 39
I. Technical Holding Times 40
H. GC/MS Instrument Performance Check 42
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Region m Modifications
m. Initial Calibration 45
*.
IV. Continuing Calibration 49
V. Blanks 52
VI. Surrogate Spikes 57
VH, Matrix Spikes/Matrix Spike Duplicates % 61
Vm. Regional Quality Assurance and Quality Control 63
DL Internal Standards 65
X. Target Compound Identification' 67
X. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs) . . 69
Xfl. Tentatively Identified Compounds (TICs) 71
Xm. System Performance . 1 75
XIV. Overall Assessment of Data 76
PESTICIDE DATA REVIEW 77
I. Technical Holding Times 78
n. GC/ECD Instrument Performance . 80
m. Initial Calibration 85
IV. Continuing Calibration ,-.... 88
V. Blanks , 90
VI. Surrogate Spikes . 94
VI. Matrix Spike/Matrix Spike Duplicates 97
VIII. Regional Quality Assurance and Quality Control 99
DC. Pesticide Cleanup Checks 100
X. Target Compound Identification 102
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Region HI Modifications
XI. Compound Quantitation and Reported CRQLs , 105
*i
XD. Overall Assessment ...,....,...,, 107
APPENDIX A: Contractual Requirements and Equations, Multi-media Multi-concentration . . A-l
DRAFT APPENDIX B: Region ffl Standard Operating Procedure for Data Validation Reports . 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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Region Dl Modification*
INTRODUCTION
This document is designed to offer guidance on EPA Contract Laboratory Program (CLP)
analytical data evaluation and review. It has been modified for use within U.S. EPA Region HI. 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
mat 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).
t
These Guidelines have been updated to include the requirements in the Statement of Work (SOW)
for Organic Analysis Multi-Media Multi-Concentration (SOW OLM01.0 and revisions through
OLM01.9).
This update includes changes to instrument performance checks (formerly referred to as tuning)
and calibration criteria as a result of the Response Factor Workgroup. Regional Modifications to the Data
Qualifier Definitions from the previous National Functional Guidelines are also included in this document.
This document is intended to assist in the technical review of analytical data generated through
the CLP. Determining contract compliance is not the intended objective of these guidelines or the
regional data review process. The data review process provides information on analytical limitations of
data based on specific quality control (QC) criteria. In order to provide more specific usability
statements, the reviewer must have a complete understanding of the intended use of the data. For this
reason, it is recommended that whenever possible the reviewer obtain usability issues from the user prior
to reviewing the data. When mis is not possible, the user should be encouraged to communicate any
questions to the reviewer. In order to facilitate communication with the data users in Region ffl, specific
reporting formats for the data validation report are required. Each report must contain a table of the
summarized data, sufficient narrative to inform the user of significant data review issues and adequate
documentation to support the decisions and actions of the data reviewer. The Standard Operating
Procedure for preparing the Region in data validation report is presented in Appendix B.
At tunes, there may be an urgent need to use data which do not meet all contract requirements
and technical criteria. Use of these data does not constitute either a new requirement standard or full
acceptance of the data. Any decision to utilize data for which performance criteria have not been met
is strictly to facilitate the progress of projects requiring the availability of the data. A contract laboratory
submitting data which are out of specification may be required to rerun samples or resubmit data even
if the previously submitted data have been utilized due to urgent program needs; data which do not meet
specified requirements are never fully acceptable. The only exception to this requirement is in the area
of requirements for individual sample analysis. If the nature of the sample itself limits the attainment of
specifications, appropriate allowances must be made. The overriding concern of the Agency is to obtain
data which are technically valid and legally defensible.
Appendix A is based on the Multi-media Multi-concentration SOW and contains appropriate
contractual requirements and equations for verifying various calculations. Appendix B contains the
Region ID SOP for Data Validation Reports. Appropriate equations are presented for easy reference and
to allow the reviewer to verify calculations as needed. Contractual requirements are provided in
Appendix C to facilitate comparisons with the technical requirements. Appendix D contains proposed
guidance for Tentatively Identified Compounds (VOA and SV), and Appendix E contains a glossary of
commonly used terms.
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Region III Modifications
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 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 as in the SOW (i.e., verbatim to the statement in the SOW, and signed by the Laboratory
Manager or designee). The reviewer must further verify that the data package is consistent with the
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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Region 111 Modifications
GLOSSARY OF DATA QUALIFIER CODES (ORGANIC)
CODES RELATING TO IDENTIFICATION
(CONFIDENCE CONCERNING PRESENCE OR ABSENCE OF COMPOUNDS):
U = Not detected. The associated number indicates approximate sample concentration necessary
to be detected.
(NO CODE) = Confirmed identification.
B = Not detected substantially above the level reported in laboratory or field blanks.
R = Unreliable result. Analyte may or may not be present in the sample. Supporting data
necessary to confirm result.
N = Tentative identification. Consider present. Special methods may be needed to confirm its
presence or absence in future sampling efforts.
CODES RELATED TO OUANTTTATION
(can be used for both positive results and sample quantitation limits):
J = Analyte present. Reported value may not be accurate or precise.
K = Analyte present. Reported value may be biased high. Actual value is expected lower.
L = Analyte present. Reported value may be biased low.. Actual value is expected to be higher.
UJ = Not detected, quantitation limit may be inaccurate or imprecise.
UL = Not detected, quantitation limit is probably higher.
O_THEJI CODES.
Q = No analytical result.
NJ = Qualitative identification questionable due to poor resolution. Presumptively present at
approximate quantity.
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Region ID Modification!
VGA
VOLATILE DATA REVIEW
The volatile data requirements to be checked are listed below
I. Technical Holding Times (CCS - Contractual holding times only)
n. GC/MS Instrument Performance Check (CCS)
ffl. Initial Calibration (CCS)
IV. Continuing Calibration (CCS)
V. Blanks
VI. System Monitoring Compounds (CCS)
VII. Matrix Spikes/Matrix Spike Duplicates
Vin. Regional Quality Assurance and Quality Control
DC. Internal Standards (CCS)
X. Target Compound Identification
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XII. Tentatively Identified Compounds
XIII. System Performance
XIV. Overall Assessment of Data
Note: "CCS" indicates that the contractual requirements for these items will also be checked by CCS;
CCS requirements are not always the same as the data review criteria.
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Ragion III Modification*
VGA
I. Technical Holding Times
A. Review Items: Form I VOA, EPA Sample Traffic Report and/or chain-of-custody, raw data, and
SDG Narrative.
B. Objective
The objective is to ascertain the validity of results based on the holding time of the sample from
time of collection to time of analysis.
C. Criteria
Technical requirements for sample holding times have only been established for water matrices.
The holding times for soils (and other non-aqueous matrices such as sediments, oily wastes, and
sludge) are currently under investigation. In Region HI, a 14 day holding time will be applied to
all non-aqueous samples. When soil holding time criteria are established and available, the
procedure for qualifying soil samples will be re-evaluated.
The holding time criteria for water samples, as stated in the current 40 CFR Part 136 (Clean Water
Act) is as follows:
For non-aromatic volatile compounds in cooled (@ 4°Q 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 are 14 days from sample collection.
Water samples mat have not been maintained at 4°C (± 2°C) and/or preserved to a pH of
2 or below should be analyzed within 7 days from sample collection. If insufficient ice is
used to ship samples, the laboratory may receive samples with no ice left in the cooler.
Under these circumstances, the temperature of the samples may exceed 4°C.
It is further required mat volatile compounds in properly preserved non-aqueous samples be
analyzed within 14 days of sample collection for all volatile compounds.
The contractual maximum holding times which differ from the technical maximum holding times
state mat water and soil samples are to be analyzed within 10 days from the validated time of
sample receipt (VTSR) at the laboratory.
D. Evaluation
Technical holding times are established by comparing the sampling dates on the EPA Sample
Traffic Report with dates of analysis on Form I VOA and the raw data. Information contained in
the complete SDG file (formerly called the purge file) should also be considered in the
determination of holding times. Verify that the analysis dates on the Form Is and the raw
data/SDG file are identical. Examine me sample records to determine if samples were preserved.
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Technical Holding Times
Region III Modifications
VOA
If adequate documentation on sample preservation is not available, contact the sampler. If the
sampler cannot be contacted, then it must be assumed mat the samples are unpreserved. If there
is no indication in the SDG narrative or the sample records that mere was a problem with the
samples (e.g., samples aot maintained @ 4°C or containing headspace in the samples), then the
integrity of samples can be assumed to be good. If it is indicated mat there were problems with
the samples, men the integrity of the sample may have been compromised and professional
judgement should be used to evaluate die effect of the problem on the sample results.
E. Action
1. If technical holding tunes are exceeded, document in the data review narrative that holding times
were exceeded and qualify the sample results as follows. (Also see Table 1).
If there is no evidence mat the aqueous samples were properly preserved and the technical
holding times exceeded 7 days, qualify positive results with "L" and sample quantitation
limits with "UL" for all aromatic compounds. Use professional judgement to determine if
and how non-aromatic volatile compounds should also be qualified.
If the samples were properly preserved but the technical holding times exceeded 14 days, for
aqueous and non-aqueous samples, qualify all positive results with "L" and all sample
quantitation limits with "UL*.
Table L Qualification of Volatile Analytes Based on Technical Holding Times
Matrix
Water
Non-aqueous
Preserved
No
Yes
No/Yes
> 7 Days
All Aromatics*
None
None
> 14 Days
All Compounds
All Compounds
All Compounds
* Reviewer should use professional judgement to determine if data for additional
compounds require qualification.
2. If technical holding times are grossly exceeded (e.g., by greater than two tunes 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 mat qualification is necessary, non-detected
volatile target compounds may be qualified unusable "R". Positive results are considered bias
low and are qualified with "L".
3. Due to limited information concerning holding times for non-aqueous samples, it is
recommended that a comment in the data review narrative be included to state mat a holding
time of 14 days was used.
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• Region III Modifications
Technical Holding Times
4. Whenever possible, the reviewer should comment on the effect of the analysis beyond the
holding time on the resulting data in the data review narrative.
5. He reviewer should also be aware of the scenario in which the laboratory has exceeded the
technical holding times, but met contractual holding times. In this case, the data reviewer
should notify the Regional TPO (where samples were collected) and/or RSCC that shipment
delays may have occurred so that the field and/or shipping problem can be corrected. The
reviewer may pass mis information on to the Regional TPO for that laboratory, but should
explain mat contractually the laboratory met the requirements,
6. When there are other quality control problems to conjunction with exceeded holding times (such
as suspected laboratory contamination), the reviewer should follow the hierarchy of qualifiers.
In particular, if for any reason the reviewer doubts the presence of a compound, the data
summary form should display only the "B" or "R" qualifier and not the "L" qualifier. This is
because no net direction of bias can be inferred under these conditions. When results are
reported by the laboratory as below the CRQL, the "L" qualifier is used over die "J" qualifier.
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Region III Modifications
VGA
D- GC/MS Instrument Performance Check
A. Review Items: Form V VOA, BFB mass spectra and mass listing.
B. Objective
Gas chromatograph/mass spectrometer (GC/MS) instrument performance checks (formerly referred
to as tuning) are performed to ensure mass resolution, identification, and to some degree, sensitivity.
These criteria are not sample specific. Conformance is determined using standard materials,
therefore, these criteria should be met in all circumstances.
C. Criteria
Hie analysis of the instrument performance check solution must be performed at the beginning of
each 12-hour period during which samples or standards are analyzed. The instrument performance
check, bromofluorobenzene (BFB) for volatile analysis, must meet the ion abundance criteria given
below. '
Bromofluorobenzene (BFB)
m/z ION ABUNDANCE CRITERIA
50 8.0-40.0% of m/z 95
75 30.0-66.0% of m/z 95
95 Base peak, 100% relative abundance
96 5.0-9.0% of m/z 95
173 Less man 2.096 of m/z 174
174 50.0-120.0% of m/z 95
175 4.0-9.0% of mass 174
176 93,0 - MM .0% of m/z 174
177 5.0-9.0% of m/z 176
NOTE: All ion abundances must be normalized to m/z 95, the nominal base peak, even
though the ion abundance of m/z 174 may be up to 120 percent that of m/z 95.
D. Evaluation
1. Compare the data presented for each Instrument Performance Check (Form V VOA) with each
mass listing submitted to ensure the following:
Form V VOA is present and completed for each 12-hour period during which samples were
analyzed.
The laboratory has not made transcription errors between the raw data and the form. If there
are major differences between the mass listing and the Form Vs, a more in-depth review of
die data is required. This may include obtaining and reviewing additional information from
the laboratory.
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Region 111 Modifications
GC/MS Instrument Performance Check VGA
Hie appropriate number of significant figures has been reported (number of significant
figures given for each ion in the ion abundance criteria column) and mat rounding is correct.
(See SOW for requirements).
The laboratory has not made calculation errors.
2. Verify from the raw data (mass spectral listing) that the mass assignment is correct and that the
mass listing is normalized to m/z 95.
3. Verify mat 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.
HQTjg; 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.
3. If mass assignment is in error (such as m/z 96 is indicated as the base peak rather man 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 mis topic are discussed as follows:
The most important factors to consider are die empirical results mat are relatively insensitive
to location on the chromatographic profile and the type of instrumentation. Therefore, the
critical ion abundance criteria for BFB are the m/z 95/96, 174/175, 174/176, and 176/177
ratios. The relative abundances of m/z 50 and 75 are of lower importance.
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Raoion 111 Modifications
GC/MS Instrument Performance Check VOA
5. Decisions to use analytical data associated with BFB instrument performance checks not meeting
contract requirements should be clearly noted in the data review narrative.
6. If the reviewer has reason to believe that instrument performance check criteria were achieved
using techniques otter than those described in n.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.
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Region 01 Modifications
VGA
III. Initial Calibration
A. Review Items: Form VI VOA, quantitation reports, and chromatograms.
B. Objective
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data for compounds on the
volatile target compound list (TCL). Initial calibration demonstrates mat 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.
2. Separate initial calibrations must be performed for water samples (or medium level soil samples)
and for low level soil samples. The calibration for water samples and medium level soil samples
is performed with an unheated purge and the calibration for low level soil samples is performed
with a heated purge.
3. Initial calibration standard Relative Response Factors (RRFs) for volatile target compounds and
system monitoring compounds (surrogates) must be greater than or equal to 0.05. (Contractual
initial calibration RRF criteria are listed in Appendix A).
4. The Percent Relative Standard Deviation (%RSD) from the initial calibration must be less than
or equal to 30.0% for all compounds. (Contractual calibration %RSD criteria are listed hi
Appendix A).
D. Evaluation
1. Verify that the correct concentration of standards were used for the initial calibration (i.e., 10,
20, SO, 100, and 200 ug/L for water).
2. Verify that the correct initial calibration was used for water and medium level soil samples (i.e.,
unheated purge) and for low level soil samples (i.e., heated purge).
3. If any sample results were calculated using an initial calibration, verify that the correct standard
(i.e., the SO ug/L standard) was used for calculating sample results and that the samples were
analyzed within 12 hours of the associated instrument performance check.
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Region III Modification*
Initial Calibration VOA
4. Evaluate the initial calibration RRFs and RRF for all volatile target compounds and system
monitoring compounds (surrogates):
a. Check and recalculate the RRFs and RRF for at least one volatile target compound
associated with each internal standard, verity that the recalculated value(s) agrees with the
laboratory reported value(s).
b. Verify that for all volatile target compounds and system monitoring compounds, the initial
calibration RRFs are greater than or equal to 0.05.
NOTE: Because historical performance data indicate poor response and/or erratic behavior, the
volatile compounds in Table 2 have no contractual maximum %RSD criteria. Contractually
they must meet a minimum RRF criterion of 0.01; however, for data review purposes, the
"greater than or equal to 0.05" criterion is applied to all volatile compounds.
Table 2. Volatile Target Compounds Exhibiting Poor Response
Acetone 1,2-Dichloropropane
2-Butanone 2-Hexanone
Carbon disulfide Methylene chloride
Chloroethane 4-Methyl-2-pentanone
Chloromethane Toluene-d8
1,2-Dichloroethene (total) l,2-Dichloroethane-d4
NOTE: Compounds in bold are system monitoring compounds.
5. Evaluate the %RSD for all volatile target compounds and system monitoring compounds:
a. Check and recalculate the %RSD for one or more volatile target compound(s) associated
with each internal standard; verity that the recalculated value(s) agrees with the laboratory
reported value(s).
b. Verity that all volatile target compounds have a % RSD of less man or equal to 30.0%. The
contractual criteria for an acceptable initial calibration specifies mat 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 man or equal to 40.0%.
For data review purposes, however, alt compounds must be considered for qualification
when the %RSD exceeds the ± 30.0% criterion.
c. If the %RSD is greater than 30.0%, then the reviewer should use professional judgement
to determine the need to check the points on the curve for the cause of the non-linearity.
This is checked by eliminating either the high point or the low point and recalculating the
%RSD.
6. If errors are detected in the calculations of the initial calibration for either RRF or %RSD,
perform a more comprehensive evaluation.
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Region 111 Modifications
Initial Calibration VOA
E. Action
1. All volatile target compounds, including the 9 "poor performers" (see Table 2, system
monitoring compounds are excluded) will be qualified using the following criteria:
a. If the %RSD is greater than 30.0% and all initial calibration RRFs greater than or equal to
0.05, quality positive results with "I". Non-detects are not qualified. When the %RSD is
grossly exceeded (i.e., > 50%) use professional judgement for qualifying non-detects as
"UJ".
b. If any initial calibration RRF is less than 0.05, qualify positive results that have acceptable
* mass spectral identification with "L", and non-detected analytes as unusable, "R".
2. At the reviewer's discretion, a more in-depth review to minimize the qualification of data can
be accomplished by considering the following:
a. If any of the required volatile compounds have a %RSD greater man 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 mat compound(s) with "J".
ii. No qualifiers are needed for volatile target compounds mat were not detected. If the
%RSD is grossly exceeded (i.e., >50%), professional judgement is used to qualify
iron-detects with "UJ".
b. If the high point of the curve is outside of the linearity criteria (e.g., due to saturation):
i. No qualifiers are required for positive results in the linear portion of the curve.
ii. Qualify positive results outside of the linear portion of the curve with a "J".
iii. No qualifiers are needed for volatile target compounds that were not detected. If the
%RSD is grossly exceeded (i.e., > 50%), professional judgement is used to qualify
non-detects with "UJ".
c. If the low end of the curve is outside of the linearity criteria:
i. No qualifiers are required for positive results hi the linear portion of the curve.
ii. Qualify low level positive results in the area of non-linearity with "J".
iii. No qualifiers are needed for volatile target compounds that were not detected. If the
%RSD is grossly exceeded (i.e., >50%), professional judgement is used to qualify
non-detects with "UJ").
NOTE: If a, b, or c options are used, a description of the process must be dearly stated in
the data review narrative.
10
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Region 111 Modifications
Initial Calibration VOA
3. If the laboratory has failed to provide adequate calibration information, the designated
representative should contact the laboratory and request the necessary Information. If the
information is not available, the reviewer must use professional judgement to assess the data.
4, The potential effects on the data due to unacceptable calibration criteria should be noted in the
data review narrative.
5, When there are other quality control problems in conjunction with exceeding initial calibration
criteria, the reviewer should follow die hierarchy of qualifiers. In particular, if for any reason
the reviewer doubts the presence of a compound, die data summary form should display only
the *B" or "R" qualifier and not the "L" or "J" qualifier.
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Roflion HI Modifications
VOA
IV. Continuing Calibration
A. Review Items: Form VII VOA, quantitation reports, and chromatograms
B. Objective
Compliance requirements for satisfactory instrument calibration are established to ensure mat 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 bom target compounds and system monitoring
compounds are analyzed at the beginning of each 12-hour analysis period following the analysis
of the instrument performance check and prior to the analysis of the method blank and samples.
The continuing calibration may either be a part of the initial calibration or run independently on
another 12-hour analysis period.
2. The continuing calibration ERF for volatile target compounds and system monitoring compounds
must be greater man or equal to 0.05.
3. The percent difference (%D) between the initial calibration RRF and die continuing calibration
RRF must be within ±. 25.0%.
D. Evaluation
1. Verify that the continuing calibration was run at die 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 die continuing calibration RRF for at least one volatile target
compound associated with each internal standard; verify oat the recalculated value(s) agrees
with the laboratory reported value(s),
b. Verify mat all volatile compounds and system monitoring compounds meet die RRF
specifications.
Because historical performance data indicate poor response and/or erratic behavior, die
compounds listed in Table 2 (Section HLD.4) 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 volatile
compounds.
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Region ill Modifications
Continuing Calibration VOA
3. Evaluate the %D between initial calibration RRF and continuing calibration RRF for one or
more compounds).
a. Check and recalculate the %D for one or more volatile target compound(s) associated with
each internal standard; verify that die recalculated value(s) agrees with the laboratory
reported value(s).
b. Verify that the %D is within ± 25.0% for all volatile target compounds and system
monitoring compounds. Note those compounds which have a %D outside the +. 25.0%
criterion. The contractual criteria for an acceptable continuing calibration specifies that up
to any 2 volatile target compounds may fail to meet minimum RRF or maximum %D as
long as they have RRFs that are greater than or equal to 0.010, and %D of less than or
equal to 40.0%. For data review purposes, however, all compounds must be considered for
qualification when the %D exceeds the ±_ 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
man or equal to 0.05, qualify positive results with "1".
b. If the %D is outside the +, 25.0% criterion and the continuing calibration RRF is greater
man or equal to 0.05, no qualification of non-detected volatile target compounds is
necessary. If the %D is grossly exceeded (>50%), professional judgement may be used
to qualify non-detects with *UJ".
c. If the continuing calibration RRF is less man 0.05, qualify positive results that have
acceptable mass spectral identifications with "L".
d. If the continuing calibration RRF is less than 0.05, qualify non-detected volatile target
compounds as unusable, "R".
2. If the laboratory has failed to provide adequate calibration information, the designated
representative should contact the laboratory and request the necessary information. If the
information is not available, the reviewer must use professional judgement to assess the data.
3. The potential effects on the data due to unacceptable calibration criteria should be noted in the
data review narrative.
13
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Region 111 Modifications
Continiuing Calibration VGA
4. When there are otter quality control problems in conjunction with exceeding continuing
calibration criteria, the reviewer should follow the hierarchy of qualifiers. In particular, if for
any reason the reviewer doubts the presence of a compound, the data summary form should
display only the "B* or "R* qualifier and not the "L" or "I" qualifier.
14
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Region III Modifications
VOA
v.
A, Review Items: Form I VOA, Form IV VOA, chromatograms, and quantitation reports.
B. Objective
The purpose of laboratory (or field) blank analysis is to determine the existence and magnitude of
contamination resulting from laboratory (or field) activities. The criteria for evaluation of blanks
apply to any blank associated with the samples (e.g., methods blanks, instrument blanks, trip blanks,
and equipment blanks). If problems with any blank exist, all associated data must be carefully
evaluated to determine whether or not there is an inherent variability in the data, or if the problem
is an isolated occurrence not affecting other data.
C. Criteria
1. No contaminants should be found in the blanks.
2. A method blank analysis must be performed after the calibration standards and once for every
12-hour time period beginning with the injection of BFB.
3. Hie 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 mat the blank is free of interference and the system is not contaminated.
D. Evaluation
1. Review the results of all associated blanks on the forms and raw data (chromatograms and
quantitation reports) to evaluate the presence of target and non-target compounds in the blanks.
2. Verify that a method blank analysis has been reported per matrix, per concentration level for
each 12-hour time period on each GC/MS system used to analyze volatile samples. The
reviewer can use the Method Blank Summary (Form IV VOA) to identify the samples associated
with each method blank.
3. Verify mat the instrument blank analysis has been performed following any sample analysis
where a target analyte(s) is reported at high concentration^).
E. Action
If the appropriate blanks were not analyzed with the frequency described in Criteria 2,3, and 4, then
die 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.
15
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Region III Modifications
Blanks VGA
Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
Positive sample results should be reported and qualified "B", if the concentration of the compound
in the sample is less than or equal to 10 times (lOx) the amount in any blank for the common volatile
laboratory contaminants (methylene chloride, acetone, and 2-butanone), or 5 times (5x) the amount
for other volatile target compounds. In situations where more than one blank is associated with a
given sample, qualification should be based upon a comparison with the blank having the highest
concentration of a contaminant. The results must not be corrected by subtracting any blank value.
For qualification purposes, consider all blanks in a case associated with all samples.
Field blanks measure contamination introduced not only in the field but also from the laboratory.
In general, evaluation of the impact on specific sample results is handled the same as with laboratory
blanks. The reviewer should use caution in attributing contamination to the field as opposed to
laboratory sources. However, when field-introduced contamination is suspected, it is helpful for the
reviewer to consult the sampling group to identify possible sources and prevent future reoccurrences.
Verified field sources of contamination should be noted in the data review narrative. If a field blank
has the highest concentration of a contaminant, then all samples in the associated case are qualified
"B", using the 5x and lOx rule. Other field blanks associated with the case are not qualified.
Specific actions are as follows:
1. If a volatile compound is found in a blank but not found in the sample, no action is taken.
2. Any volatile compound detected in the sample (other than the common volatile laboratory
contaminants), mat was also detected in any associated blank, is qualified "B", when the sample
concentration is less than five times (5x) the blank concentration. For common volatile
laboratory contaminants, the results are qualified "B*, when the sample concentration is less man
10 times (lOx) the blank concentration.
3. The reviewer should note mat 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 "Sx" and "10x" criteria, such that a comparison of the total amount of contamination is
actually made.
Additionally, mere 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 man the sample, he/she should qualify
the data. Contamination introduced through dilution water is one example. Although it is not
always possible to determine, instances of this occurring it can be detected when contaminants
are found in the diluted sample result but are absent in the undiluted sample result. Since both
results are not routinely reported, it may be impossible to verify mis source of contamination.
16
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Region 111 Modifications
VOA
¥1. System Monitoring Compounds
(Surrogate Spikes)
A: Review Items: Form II VOA quantitation reports and chromatograms.
B: Objective
Laboratory performance on individual samples is established by means of spiking activities. All
samples are spiked with system monitoring compounds (formerly referred to as surrogates) prior to
sample purging. Hie evaluation of the results of these system monitoring compounds is not
necessarily straightforward. Hie 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
I. Three system monitoring compounds (1,2-dichloroethane-d4, bromofluorobenzene, and toluene-
d8) are added to all samples and blanks to measure their recovery hi environmental samples and
blank matrices.
m
2. Recoveries for system monitoring compounds in volatile samples and blanks must be within the
limits specified in Appendix A and the SOW.
D. Evaluation
1. Check raw data (e.g., chromatograms and quantitation reports) to verify the recoveries on the
System Monitoring Compound Recovery Form ~ Form n VOA. Check for any calculation or
transcription errors.
2. Check that the system monitoring compound recoveries were calculated correctly. The equation
can be found in Appendix A.
3. The following should be determined from the System Monitoring Compound Recovery form(s):
a. If any system monitoring compound(s) in the volatile fraction is out of specification, there
should be a reanalysis to confirm that the non-compliance is due to sample matrix effects
rather than laboratory deficiencies.
NOTE: When there are unacceptable system monitoring compound recoveries followed by successful
analyses, the laboratories are required to report only the successful run.
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Region III Modifications
System Monitoring Compounds VOA
b. Hie laboratory failed to perform acceptably if system monitoring compounds are outside
criteria with DO evidence of re-analysis. Medium soils must first be re-extracted prior to re-
analysis when this occurs.
c. Verify that no blanks have system monitoring compounds outside the criteria,
4. Any time there are two or more analyses for a particular sample, the reviewer must determine
which are the best data to report. Considerations should include but are not limited to:
a. System monitoring compound recovery (marginal versus gross deviation).
b. Technical holding times.
c. Comparison of the values of the target compounds reported in each sample analysis.
d. Other QC information, such as performance of internal standards.
E. Action
Data are qualified based on system monitoring compounds results if the recovery of any volatile
system monitoring compound is out of specification. For system monitoring compound recoveries
out of specification, the following approaches are suggested based on a review of all data from the
package, especially considering the apparent complexity of the sample matrix. (Also, see Table 3.)
1. If a system monitoring compound in the volatile sample has a recovery greater man the upper
acceptance limit:
a. Detected volatile target compounds are qualified "J".
b. Results for non-detected volatile target compounds should be qualified "UJ".
2. If a system monitoring compound in the volatile sample has a recovery greater than or equal to
10% but less than the lower acceptance limit:
a. Detected volatile target compounds are qualified "J".
b. For non-detected volatile target compounds, the sample quantitation limit is qualified as
approximated, "UJ".
3. If a system monitoring compound in a volatile sample shows less than 10% recovery:
a. Detected volatile compounds are qualified "L".
b. Non-detected volatile target compounds are qualified as unusable, "R".
20
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Region 111 Modifications
Blanks VGA
4. If gross contamination exists (i.e., saturated peaks by GC/MS), all affected compounds in the
. associated samples should be qualified as unusable "R" due to interference.
5. 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 in the report narrative.
6. The same consideration given to the target compounds should also be given to Tentatively
Identified Compounds (TlCs), which are found in both the sample and associated blank(s). (See
VGA Section Xffl for TIC guidance.)
7. If an instrument blank was not analyzed following a sample analysis which contained an
analyte(s) at high concentration^), sample analysis results after the high concentration sample
must be evaluated for carryover. Professional judgement should be used to determine if
instrument cross-contamination has affected any positive compound identifications). If
instrument cross-contamination is suggested, then this should be noted for TPO action if the
cross-contamination is suspected of having an effect on the sample results. Sample results which
are possible artifacts of carry-over should be flagged as unusable "R".
8. When there is convincing evidence that contamination is restricted to a particular instrument,
matrix, or concentration level, the Sx/lOx rule will only be applied to compare contaminated
blanks to certain associated samples (as opposed to all samples in the case). Some examples are
as follows:
Column bleed (siloxanes) may be localized to a particular instrument.
Methanol extractions in the medium soil volatile analysis protocol can give rise to contaminants
that are not seen in the low-level aqueous analyses.
Common laboratory contaminants, such as methylene chloride, are generally too unpredictable
to safely assume contamination is restricted to a particular instrument, matrix, or concentration
level.
9. For benzene and/or toluene, the reviewer may identify that the observed laboratory
contamination is attributable to a specific, regular, and predictable process (such as trap bleed),
which results in a constant 1 or 2 ppb instrument level concentration in all runs (bom samples
and blanks). In this situation, the reviewer may want to consider flaging certain results as
tentatively identified, "N", as opposed to "B", if the sample instrument level is clearly greater
man the consistent level of contamination detected in blanks and other samples. (This particular
situation supercedes the 5x/10x rule.)
Blanks VOA
17
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Rogion HI Modifications
10. The following are examples of applying the blank qualification guidelines. Certain
circumstances may warrant deviations from these guidelines. Any deviations must be clearly
stated in the data review narrative.
3gx ample ....... |; Sample result is greater than the Contract Required Quantitation Limit (CRQL),
but is less man the 5x or lOx multiple of the blank result.
Rule
10* 5%
Blank Result 7 7
CRQL 5 5
Sample Result 60 30
Final Sample Result 60B 30B
In the example for the "lOx" rule, sample results less man 70 (or 10 x 7) would be qualified
"B". In the case of the "5x" rule, sample results less than 35 (or 5x7) would be qualified
Example 2: Sample result is less than the CRQL, and is also less man the 5x or lOx multiple
of the blank result.
Rule
lOx 5x
Blank Result 6 6
CRQL 5 5
Sample Result 4J 4J
Final Sample Result 4B 4B
Note that data are reported as 4B, indicating that the qualitative presence is not confirmed.
fa ample j: Sample result is greater man the 5x or lOx multiple of the blank result.
Bills
10% 5%
Blank Result 10 10
CRQL 5 5
Sample Result 12O 60
Final Sample Result 12O 60
For both the "lOx" and "5x* rules, sample results exceeded the adjusted blank result of 100
(or 10 x 10) and 50 (or 5 x 10), respectively.
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System Monitoring Compounds
Region III Modifications
VGA
4. If two or three system monitoring compounds in the volatile sample have recoveries outside
acceptance limits, refer to Table 3.
Table 3. Qualification of Volatile Analytes Based on
System Monitoring Compound Recoveries
Detected
Analytes
Non-
Detected
Analytes
1 or more
< 10%
L
R
1
High/Low
J
UJ
2 or 3
High/Low
J
UJ
2 or 3
All Low
L
UL
2 or 3
All
High
K
None
"
5. In the special case of a blank analysis with system monitoring compounds out of specification,
the reviewer must give special consideration to the validity of associated sample data. The basic
concern is whether the blank problems represent an isolated problem with the blank alone, or
whether there is a fundamental problem with the analytical process. For example, if one or
more samples in the batch show acceptable system monitoring compound recoveries, the
reviewer may choose to consider the blank problem to be an isolated occurrence.
6. Whenever possible, potential effects of the data resulting from system monitoring recoveries not
meeting the advisory limits should be noted in the data review narrative.
7. Positive results for compounds already flagged for blank contamination, "B", will not need a
separate flag for system monitoring compound recoveries. However, these situations should be
addressed hi the data review narrative and the support documentation.
8. When dilutions are performed which prevent detection of system monitoring compounds, the
data review narrative and support documentation should indicate that extraction
efficiency/method accuracy cannot be verified.
9. When both the initial analysis and the reanalysis have system monitoring compound recoveries
outside of criteria, the data summary form should normally contain the highest concentration
obtained for each compound detected, provided mat system monitoring compound recoveries in
the analysis being reported do not suggest a high bias. However, if a demonstrated laboratory
contaminant is detected in one analysis but not in the other, the negative result may be more
appropriate to report.
21
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Region III Modifications
System Monitoring Compounds VOA
When the reanalysis of a sample is within the system monitoring compound recovery criteria,
the laboratory is required to provide only data far the acceptable analysis. If both sets of data
are provided, and if a compound was detected in die initial analysis but not in the reanalysis,
then the positive result should be reported (provided the compound is not a demonstrated
laboratory contaminant). He reported result should be flagged as estimated "J", due to possible
sample inhomogeneity.
22
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Rayon til Modifications
VOA
VH. Matrix Spike/Matrix Spike Duplicate
A. Review Items: Form in VOA-I and VOA-2, chromatograms, and quantitation reports.
B. Objective
Data for matrix spike/matrix spike duplicates (MS/MSD) are generated to determine long-term
precision and accuracy of the analytical method on various matrices and to demonstrate acceptable
compound recovery by the laboratory at the time of sample analysis. These data alone cannot be
used to evaluate the precision and accuracy of individual samples. However, when exercising
professional judgement, this data should be used in conjunction with other available QC information.
C. Criteria
1. Matrix spike (MS) and matrix spike duplicate (MSD) samples are analyzed at a frequency of one
MS and MSD per 20 samples of similar matrix.
2. Spike recoveries should be within the advisory limits provided on Form m VOA-1 and VOA-2
and SOW.
3. Relative percent difference (RPD) between MS and MSD recoveries must be within the advisory
limits provided on Form ffl VOA-1 and VOA-2 and SOW.
D. Evaluation
1. Verify that MS and MSD samples were*analyzed at the required frequency and that results are
provided for each sample matrix.
2. Inspect results for the MS/MSD Recovery on Form in VOA-1 and VOA-2 and verify that the
results for recovery and RPD are within the advisory limits.
3. Verify transcriptions from raw data and verify calculations.
4. Check that the matrix spike recoveries and RPDs were calculated correctly.
5. Compare %RSD results of non-spiked compounds between the original result, MS, and MSD.
E. Action
1. No action is taken on MS/MSD data alone. However, using informed professional judgement,
the data reviewer may use the MS and MSD results in conjunction with other QC criteria to
determine the need for some qualification of the data.
2. The data reviewer should first try to determine to what extent the results of the MS/MSD affect
the associated data. This determination should be made with regard to the MS/MSD sample
itself as well as specific analytes for all samples associated with the MS/MSD.
23
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Region HI Modifications
Matrix Spike/Matrix Spike Duplicate VOA
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 die MS/MSD results that a laboratory is having a systematic problem in the
analysis of one or more analytes, which affects all associated samples.
4. The reviewer must use professional judgement to determine the need for qualification of positive
results of non-spiked compounds.
5. When non-spiked compounds are present in either the MS or MSD results, a table in the data
review narrative is constructed showing original (unspiked) sample results for non-spiked
compounds, non-spiked compounds present in the MS and MSD and the calculated %RSD.
24
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Region IK Modification*
VOA
Vin. Regional Quality Assurance and Quality Control
A. Review Items: Form I VOA, cbromatograms, and quantitation reports, and QAPjP,
B. Objective
Regional Quality Assurance and Quality Control (QA/QC) refer to any QA and/or QC samples
initiated by die Region, including field duplicates, Performance Evaluation (PE) samples, blind
spikes, and blind blanks.
C. Criteria
Criteria are dependent on the type of QC sample. Frequency may vary,
1. The analytes present in the PE sample must be correctly identified and quant Stated.
D. Evaluation
1. Evaluation of Performance Evaluation (PE) Samples are not to be presented as part of the data
review. All Form Is associated with the Performance Evaluation Samples are to be sent (with
a cover memo stating the case number and laboratory information) directly to the Quality
Assurance Branch in Region EQ.
U.S. Environmental Protection Agency
Region M, Central Regional Laboratory
Quality Assurance Branch
201 Defense Highway, Suite 200
Annapolis, MD 21401
Attn: Program Support Section
2. Percent difference between target compounds present in the field duplicate samples shall be
determined. Evaluation of the percent difference compared to those specified in the site QAPjP
may be presented in the data review narrative.
£. Action
1. Field duplicate results are to be presented in a table format in the data review narrative. If
target compounds were not present in either of the field duplicate samples, then a table is not
required. The percent difference is to be calculated and presented in the table. (If one of the
field duplicates was also used as a matrix spike/matrix spike duplicate sample, men the table
should include any non-spiked compounds detected, along with the relative standard deviation.)
No action is taken based on percent difference of field duplicate sample data alone. However
using informed professional judgement the data reviewer may use the field duplicate results in
conjunction with other QC criteria to determine the need for some qualification of the data.
25
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. Region III Modifications
Regional Quality Assurance and Quality Control • VOA
2. Other types of Regional QC Samples
Professional judgement is needed for evaluating other types of QC samples that may be
associated with a particular case of samples. This information may be used in conjunction with
other QC criteria to determine the need for qualification of data,
26
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Region 111 Modifications
VGA
IX. Internal Standards
A. Review Items: Form VH VOA, quantitation reports, and chromatograms.
B. Objective
Internal Standards (IS) performance criteria ensures that GC/MS sensitivity and response are stable
during each analysis.
C. Criteria
1. Internal standard area counts must not vary by more than a factor of two (-50% to +100%)
from the associated calibration standard.
2. The retention time of the internal standard must not vary more than .±.30 seconds from the
retention time of the associated calibration standard.
D. Evaluation
1. Check raw data (e.g., chromatograms and quantitation lists) to verify the internal standard
retention times and areas reported on the Internal Standard Area Summary (Form Vm VOA).
2. Verify that all retention times and IS areas are within criteria.
3. If there are two analyses for a particular fraction, the reviewer must determine which are the
best data to report. Considerations should include:
a. Magnitude and direction of the IS area shift.
b. Magnitude and direction of the IS retention time shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each fraction,
c. Other QC,
E. Action
1. If an IS area count for a sample or blank is outside -50% or +100% of the area for associated
standard, then:
a. Positive results for compounds quantitated using mat IS should be qualified as estimated, "J".
b. Non-detected compounds quantitated using an IS area count greater man +100% or less that
50% should be qualified "UF.
27
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Region 111 Modifications
Internal Standards VOA
c. If extremely low area counts are reported, or if performance exhibits a major abrupt drop-off
then a severe loss of sensitivity is indicated. Non-detected target compounds should then be
qualified as unusable, "R".
2. If an IS retention time varies by more than 30 seconds:
The chromatographic profile for mat 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 lor mat sample fraction. Positive results should not need to be
qualified as "R", if the mass spectral criteria are met
28
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Region ill Modifications
VGA
X. Target Compound Identification
A. Review Items: Form I VOA, quantitation reports, mass spectra, and chromatograms.
B. Objective
The objective of die 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 mat is present),
C. Criteria
1. The relative retention times (RRTs) must be within ± 0.06 RRT units of the standard RRT.
2. Mass spectra of the sample compound and a current laboratory-generated standard (i.e., the mass
spectrum from the associated calibration standard) must match according to the following
criteria:
a. All ions present in the standard mass spectrum at a relative intensity greater man 10% must
be present in the sample spectrum.
b. The relative intensities of these ions must agree within _+ 20% between the standard and
sample spectra. (Example: For an ion with an abundance of 50% in the standard spectrum,
the corresponding sample ion abundance must be between 30% and 70%.)
c. Ions present at greater wan 10% in the sample mass spectrum but not present in the standard
spectrum must be considered and accounted for.
D. Evaluation
1. Check that the RRT of reported compounds is within ± 0.06 RRT units of the standard RRT.
2. Check the sample compound spectra against the laboratory standard spectra to see mat it meets
the specified criteria.
3. The reviewer should be aware of situations (e.g., high concentration samples preceding low
concentration samples ) when sample carry-over is a possibility and should use professional
judgement to determine if instrument cross-contamination has affected any positive compound
identification. The SOW specifies that an instrument blank must be run after samples in which
a target analyte ion(s) saturates the detector.
4. Check the chromatogram to verify that peaks are accounted for; i.e., major peaks are either
identified as target compounds, TICs, system monitoring compounds, or internal standards.
29
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Region III Modifications
Target Compound Identification VOA
E. Action
1, Hie 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
tram the laboratory. If it is determined that incorrect identifications were made, all such data
should be qualified as not detected "U". Hie data review narrative and support documentation
would verify that the misidentified peak was library searched as a TIC, if appropriate.
2, Professional judgement must be used to qualify the data if it is determined that cross-
contamination has occurred,
3. If the presence of a target compound is strongly suggested by raw data, but its mass spectrum
contains minor inadequacies, the compound may be added to the data summary form and
qualified as a tentative identification, "N". The reviewer should address corroborating evidence
in the narrative, such as the presence of the compound in closely related compounds in the same
sample.
4. If the laboratory did not report a compound of acceptable matching quality, the reviewer should
add this compound to the sample data summary form. The narrative and the support
documentation should indicate this action. The reviewer should request the laboratory to
reexamine and resubmit the result, particularly if the value is greater man the CRQL.
5. Any changes made to the reported compounds or concerns regarding target compound
identifications should be clearly indicated in the data review narrative. .
30
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Region 111 Modifications
VGA
XI. Compound Ouantitation and Reported CROLs
A. Review Items: Form 1 VOA, sample preparation sheets, SDG narrative, quantitation reports, and
chromatograms.
B. Objective
The objective is to ensure that the reported quantitation results and Contract Required Quantitation
Limits (CRQLs) are accurate.
C. Criteria
1. Compound quantitation, as well as the adjustment of the CRQLs, must be calculated according
to the correct equation.
2. Compound RRFs must be calculated based oa the internal standard (IS) associated with mat
compound, as listed in Appendix A (also as specified in the SOW) for packed column analyses.
For analyses performed by capillary column method (EPA Method 524.2),the target compounds
will not necessarily be associated with the same internal standard as in the packed column,
depending on the compound elution order. Quantitation must be based on the quantitation ton
(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 ail 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 ton, and RRF were used to quantitate the
compound. Verify that the same internal standard, quantitation ion, and RRF are used
consistently through out, in bom the calibration as well as the quantitation process. For analyses
performed by capillary column, the reviewer should use professional judgement to determine mat
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 mat could resolve any differences. If a discrepancy remains
unresolved, the reviewer must use professional judgement to decide which value is the best
value. Under these circumstances, the reviewer may determine qualification of data is
warranted. A description of the reasons for data qualification and the qualification mat is
applied to the data should be documented in the data review narrative and in the document
support.
31
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• Region III Modifications
Compound Quantitation and Reported CRQLs VOA
2. Calculation errors can sometimes be revealed by abnormally high system monitoring compound
recoveries, matrix spike recoveries, or inappropriately high results for certain compounds.
3. The reviewer must assure mat any results in error by more man 10 percent are identified and
corrected on the sample data summary. If laboratory resubmission is not performed, the
reviewer should document his/her changes to the data in the narrative and support
documentation.
4. If a sample concentration is above the highest standard and contract required dilutions were not
performed, the chromatogram and mass spectrum should be examined for signs of a saturated
signal. If the ion used for quantitation was saturated, then the result should be flagged as biased
low, "L". If the ion used for quantitation was not saturated, the result should be flagged as
estimated, "J".
32
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Region til Modifications
VGA
XD. Tentatively Identified Compounds
A. Review Items: Form I VOA-TIC chromatograms, and library search printout and spectra for
three tentatively identified compounds (TIC) candidates.
B. Objective
Chromatographic peaks in volatile fraction analyses that are not target analytes, system monitoring
compounds or internal standards are potential Tentatively Identified Compounds (TICs). TICs must
be qualitatively identified by a National Institute of Standards and Technology (NIST) mass spectral
library search and the identifications assessed by the data reviewer.
C. Criteria
For each sample, the laboratory must conduct a mass spectral search of the NIST library and report
the possible identity for the 10 largest volatile fraction peaks which are not system monitoring
compounds, internal standards, or target compounds, but which have an area or height greater than
10 percent of the area or height of the nearest internal standard. TIC results are reported for each
sample on the Organic Analyses Data Sheet (Form I VOA-TIC).
NOTE: Since the SOW revision of October 1986, the CLP does not allow the laboratory to
report as Tentatively Identified Compounds any target compound which is properly
reported in another fraction. For example, late eluting volatile target compounds should
not be reported as semivolatile TICs.
D. Evaluation
1. Guidelines for tentative identification are as follows:
a. Major ions (greater than 10% relative intensity) in the reference spectrum should be present
in the sample spectrum.
b. The relative intensities of the major ions should agree within ±_ 20% between the sample and
the reference spectra.
c. Molecular ions present in the reference spectrum should be present in the sample spectrum.
d. Ions present in the sample spectrum but not in the reference spectrum should be reviewed
for possible background contamination, interference or 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.
33
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Region 111 Modifications
Tentatively Identified Compounds VGA
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 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 man 10 percent of the internal standard height, but present in
the blank chromatogram at a similar relative retention time.
4. All mass spectra for every sample and blank must be examined.
5. Since TIC library searches often yield several candidate compounds having a dose matching
score, all reasonable choices must be considered.
6. Hie 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: COj (m/z 44), siloxanes (m/z 73), diethyl ether, hexane,
certain freons (1, l,2-trichloro-l ,2,2-trifluoroethaneorfluorotrichJorometbane), andphthalates
at levels less man 100 ug/L or 4000 ug/Kg.
b. Solvent preservatives such as cyclohexene which is a methylene chloride preservative.
Related by-products include cydohexanone, cydohexenone, cydohexanol, 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.
7. Occasionally, a target compound may be identified in the proper analytical fraction by non-target
library search procedures, even {hough 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 man one fraction. Verify mat quantitation is
made from the proper fraction.
34
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Region 111 Modifications
Tentatively Identified Compounds VOA
9. Library searches should not be performed on internal standards or system monitoring
compounds.
10. TIC concentration should be estimated assuming a RRF of 1.0.
11. See Appendix B for additional guidance.
E. Action
1. All TIC results should be qualified "J", estimated concentration, on the laboratory Form I-TICs.
2. General actions related to the review of TIC results are as follows:
a. If it is determined that a tentative identification of a non-target compound is not acceptable,
the tentative identification should be changed to "unknown" or an appropriate identification.
b. If all contractually required peaks were not library searched and quantitated, the designated
representative could request these data from the laboratory.
3. Blank Results
Form I-TIC which contain sample results that are questioned by laboratory results, should be
flagged "B" and a line drawn through these data for emphasis (initialed and dated), on the Form
I-TIC that is included in the validation report.
To be considered questionable, a sample TIC concentration must be within 10 times the
concentration of one of the blank results. If different volumes/weights are used, the total
amount of compound in the extract must be compared for sample versus blank. For VOA data,
an instrument level comparison is used unless the contamination is proven to originate during
sample storage (before preparation/analysis). In general, blanks analyzed within the same case,
by the same lab, may be cross-applied to either soil or water samples extracted or analyzed on
other days.
To question a sample result, only presumptive evidence for the presence of the compound in the
blank is necessary. The presence of the TIC in the blank is suggested in any of the following
situations:
a. Relative retention times (RRTs) match for sample versus blank, and the sample library search
result matches the same compound 01 compound class as the library search result for the
blank.
b. RRTs match, but library search results do not list the same compound or class for sample
versus blank. However, some of the largest ions in the sample are also in the blank, and a
direct comparison of sample versus blank spectra suggests that the TIC in the sample is quite
possibly the same compound as that in the blank.
35
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Region III Modifications
Tentatively Identified Compounds VOA
c. A peak at the same RRT as the sample TIC is present in the chromatogram of die blank, but
no library search was performed or included in the data. (The labs do not have to library
search peaks less than 10% of the height of the nearest internal standard, although these
peaks may still be important to identify low-level blank contaminants that can question
sample results at levels above 10% of the nearest internal standard height.)
All blank results must be attached in the support documentation section of the data review.
4. When a compound is not found in any blanks, but is a suspected artifact of common laboratory
contaminant, the result may be qualified as unusable, "R", and a line drawn through the result
(initialed and dated) on a copy of the Form I-TIC that is included in the validation report.
5. In deciding whether a library search result for a TIC represents a reasonable identification,
professional judgment must be exercised. If mere 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). These changes may be made directly on a copy of the Form
I-TIC, as long as changes are initialed and dated.
6. Other case factors may influence TIC judgments. If a sample TIC match is poor but other
samples have a TIC with a good library match., similar relative retention time, and the same
ions, identification information may be inferred from the other sample TIC result.
7. Physical constants, such as boiling point, may be factored into professional judgment of TIC
results.
8. Any changes made to the reported data or any concerns regarding TIC identifications should be
indicated in the data review narrative. Any changes made regarding TIC identifications or
qualifications are to be made on copies of the laboratory generated Form I-TIC and not the
originals.
36
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Region 111 Modifications
VGA
. System Performance
A. Review Items: Form Vm VOA, Form IH VOA-1 and VOA-2, and chromatogfams.
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 (R1C) baseline may indicate a
change in the instrument's sensitivity or the zero setting. A baseline "shift" could indicate a
decrease in sensitivity in the instrument or an increase in the instrument zero, possibly causing
target compounds, at or near the detection limit, to miss detection. A baseline "rise" could
indicate problems such as a change in the instrument zero, a leak, or degradation of the column.
2. Poor chromatographic performance affects both qualitative and quantitative results, indications
of substandard performance include:
a. High RIC background levels or shifts in absolute retention times of internal standards.
b. Excessive baseline rise at elevated temperature.
c. Extraneous peaks.
d. Loss of resolution.
e. Peak tailing or peak splitting that may result in inaccurate quantitation.
E. Action
Professional judgement must be used to qualify the data if it is determined that system performance
has degraded during sample analyses.
VOA
37
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Region HI Modification*
XIV. Overall Assessment of Data
A. Review items: Entire data package, data review results, and (if available) Quality Assurance Project
Plan (QAPjP), and Sampling and Analysis Plan (SAP),
B. Objective
The overall assessment of a data package is a brief narrative in which the data reviewer expresses
concerns and comments on the quality and where necessary, the useability of die 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. 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.
£. Action
1. Use professional judgement to determine if mere 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.
* 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.
-------
sv
SEMTVOLATILE DATA REVIEW
The semivoiatile data requirements to be checked are listed below:
I. Technical Holding Times (CCS - Contractual holding times only)
D. GC/MS Instrument Performance Check (CCS)
ni. Initial Calibration (CCS)
IV. Continuing Calibration (CCS)
V. Blanks (CCS)
VI. Surrogate Spikes (CCS)
VH. Matrix Spikes/Matrix Spike Duplicates
VDL Regional Quality Assurance and Quality Control
DC. Internal Standards (CCS)
X. Target Compound Identification
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
Xn. Tentatively Identified Compounds
XIH. System Performance (CCS)
XTV. 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.
39
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Region Ht Modifications
sv
I. Technical Holding Times
A. Review Items: Form I SV-1 and SV-2, EPA Sample Traffic Report ami/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 tune 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 further required that semivolatile compounds in properly preserved non-aqueous samples be
extracted within 7 days from sample collection and the extracts analyzed within 40 days from
sample extraction.
The contractual holding times, which differ from the technical holding times, state that water
samples are to be extracted within 5 days from the validated time of sample receipt (VTSR) at the
laboratory, and soil samples are to be extracted within 10 days from the VTSR. Also,
contractually both water and soil sample extracts must be analyzed within 40 days of sample
extraction. However, the contractual delivery due date is 35 days from the VTSR.
D. Evaluation
Technical holding times for sample extraction are established by comparing the sampling date on
the EPA Sample Traffic Report with the dates of extraction on Form I SV-1 and SV-2 and the
sample extraction sheets. To determine if the samples were analyzed within the holding time after
extraction, compare the dates of extraction on the sample extraction sheets with the dates of
analysis on Form I SV-1 and SV-2.
40
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Region ffl Modification!
Technical Holding Times SV
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 die data.
E. Action
1. a. If technical holding times are exceeded, flag all positive results as estimated "I* and
sample quantitation limits as estimated "UJ" and document that holding times were
exceeded. However, please note that some extractable compounds are extremely
persistent in the environment (e.g., PAHs) in non-aqueous matrices and would not be
expected to degrade significantly during sample storage. The reviewer must use
professional judgement in the application of data qualifiers to those compounds in non-
aqueous matrices.
b. If in the professional judgement of the data reviewer a loss of semivolatile compound(s)
is evident due to exceeding the holding time criteria, the affected positive results or the
associated quantitation limits may be qualified as biased low, "L" or "UL" respectively.
The narrative must contain the reviewer's justification for qualification of the compound
results as biased low.
2. If technical holding times are grossly exceeded (greater than 2 times the required technical
holding time), either on the first analysis or upon re-analysis, the reviewer must use
professional judgement to determine the reliability of the data and the effects of additional
storage on the sample results. The reviewer may determine that positive results or the
associated quantitation limits are approximates and should be qualified with "J" or "UJ",
respectively. The reviewer may determine mat non-detect data are unusable (R).
3. Because of limited information concerning holding times for non-aqueous samples, it is
recommended that a comment in the data review narrative be included to state that aqueous
holding times were applied.
4. Whenever possible, the reviewer should comment on the effect of exceeding the holding time
on the resulting data in die data review narrative.
5. The reviewer should also be aware of die scenario in which the laboratory has exceeded the
technical holding times, but met contractual holding tunes. In mis case, the date reviewer
should notify the Regional TPO (where samples were collected) and/or RSCC that shipment
delays may have occurred so that the field problem can be corrected.
6. When there are other quality control problems in conjunction with exceeded holding times
(such as suspected laboratory contamination), the reviewer should follow the hierarchy of
qualifiers. In particular, if for any reason the reviewer doubts the presence of a compound,
the data summary should display only the "B" or "R" qualifier, and not the "L" qualifier.
This is because no net direction of bias can be inferred under these conditions.
41
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Region 01 ModiGcatkm*
sv
n. GC/MS Instrument Performance Cheek
A. Review Items: Form V SV, and DFTPP mass spectra and mass listing.
B. Objective
Gas chromatograph/mass spectrometer (GC/MS) instrument performance checks (formerly referred
to as tuning) are performed to ensure mass resolution, identification and, to some degree,
sensitivity. These criteria are not sample specific. Conformance is determined using standard
materials, therefore, these criteria should be met in all circumstances.
C. Criteria
The analysis of the instrument performance check solution must be performed at the beginning of
each 12-hour period during which samples or standards are analyzed. The instrument performance
check, decafluorotriphenylphosphine (DFTPP) for semivolatile analysis, must meet the ion
abundance criteria given below.
Decafluorotriphenylphosphine (DFTPP)
m/z ION ABUNDANCE CRITERIA
51 30.0-80.0% of m/z 198
68 Less than 2.0% of m/z 69
69 Present
70 Less than 2.0% of m/z 69
127 25.0-75.0% of m/z 198
197 Less than 1.0% of m/z 198
198 Base peak, 100% relative abundance
199 5.0-9.0% of m/z 198
275 10.0-30.0% of m/z 198
365 Greater man 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 mat of m/z 198.
D. Evaluation
1. Compare the data presented on each GC/MS Instrument Performance Check (Form V SV)
with each mass listing submitted and ensure the following:
a. Form V 5V is present and completed for each 12-hour period during which samples
were analyzed.
42
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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 mere are major differences between the mass listing and the Form Vs, a more in-
depth review of the data is required. This may include obtaining and reviewing
additional information from the laboratory.
c. The appropriate number of significant figures has been reported (number of significant
figures given for each ion in the ion abundance criteria column) and that rounding is
correct.
d. The laboratory has not made any calculation errors.
2. Verify from the raw data (mass spectral listing) that the mass assignment is correct and that
the mass is normalized to m/z 198.
3. Verify mat 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 mat spectra were generated using appropriate background subtraction
techniques. Since the DFTPP spectrum is obtained from chromatographic peaks that should
be free from coelution problems, background subtraction should be done in accordance with
the following procedure. Three scans (the peak apex scan and the scans immediately
preceding and following the apex) are acquired and averaged and background subtraction
must be accomplished using a single scan prior to the elution of DFTPP.
Note: All instrument conditions must be identical to those used in the sample analysis.
Background subtraction actions resulting in spectral distortions for the sole purpose of
meeting the contract specifications are contrary to the quality assurance objectives and
are therefore unacceptable.
E. Action
1. If the laboratory has made minor transcription errors which do not significantly affect the
data, the data reviewer should make the necessary corrections on a copy of the form.
2. If the laboratory has failed to provide the correct forms or has made significant transcription
or calculation errors, the Region's designated representative should contact the laboratory
and request corrected data. If the information is not available, men the reviewer must use
professional judgement to assess the data.
3. If mass assignment is in error (such as m/z 199 is indicated as the base peak rather man 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:
43
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Region m Modifications
GC/MS Instrument Performance Check SV
a. Some of the most critical factors in the DFTPP criteria are the non-instrument specific
requirements that are also not unduly affected by the location of the spectrum on the
chromatographic profile. The m/z ratios for 198/199 and 442/443 are critical. These
ratios are based on the natural abundances of carbon 12 and carbon 13 and should
always be met. Similarly, the relative abundances for m/z 68, 70, 197, and 441
indicate the condition of the instrument and the suitability of the resolution adjustment
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 man 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 n.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. 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 man the DFTPP peak), men this should be noted in the report
narrative.
44
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Region ffl Modification*
sv
Initial Calibration
A. Review Items: Form VI SV-1 and SV-2, quantitation reports, and chromatograms.
B. Objective
Compliance requirements for satisfactory instrument calibration are established to ensure that die
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, SO, 80, 120, and 160 ug/L at the beginning of each
analytical sequence or as necessary if the continuing calibration acceptance criteria are not
met. The initial calibration (and any associated samples and blanks) must be analyzed within
12 hours of the associated instrument performance check.
2. Minimum Relative Response Factor (RRF) criteria must be greater than or equal to 0.05.
Contractual RRF criteria are listed in Appendix A.
3. The Percent Relative Standard Deviations (%RSD) for the RRFs in the initial calibration
must be less than or equal to 30%.
D. Evaluation
1. Verify that the correct concentration of standards were used for the initial calibration (i.e.,
20, 50, 80,120, and 160 ug/L). For the eight compounds with higher CRQLs, only a four-
point initial calibration is required-(i.e., 50, 80, 120, and 160 ug/L). (See Appendix A for
list).
2. If any sample results were calculated using an initial calibration, verify that the correct
standard (i.e., the 50 ppb standard) was used for calculating sample results and that the
samples were analyzed within 12 hours of the associated instrument performance check.
3. Evaluate the RRFs for all semivolatile target compounds and surrogates:
a. Check and recalculate the RRF and RRF for at least one semivolatile target compound
associated with each internal standard. Verify that the recalculated value(s) agrees with
the laboratory reported value(s).
45
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Region HI ModificatiocM
Initial Calibration SV
b. Verify that all semivolatile target compounds and surrogates have RRFs that are greater
than or equal to 0.05. If problems are suspected with low response factor or compound
identification, also check elution order.
NOTE: Because historical performance data indicate poor response and/or erratic behavior, the
semivolatile compounds to Table 4 have no contractual maximum %RSD criteria.
Contractually they must meet a minimum ERF 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
2,2'-oxybis(l-Chloropropane) Diethylphthalate
4-Chloroaniline~ 4-Nitroaniline
Hexachlorobutadiene 4,6-Dinitro-2-methylphenol
Hexachlorocyclopentadiene N-Nitrosodipbenylamine
2-Nitroaniline Di-n-butylphthalate
Dimethylphthalate Butylbenzylphthalate
3-NitroaniIine 3-3'-Dichlorobenzidine
2,4-Dinitrophenol bis(2-Ethylhexyl)phthalate
4-Nitrophenol Di-n-octylphthalate
Carbazole
4. Evaluate the %RSD for all semivolatile target compounds and surrogates.
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).
b. Verify that all semivolatile target compounds have a %RSD of less man or equal to 30%.
The contractual criteria for an acceptable initial calibration specifies that up to any 4
semivoiatile target compounds may fail to meet minimum RRF or maximum %RSD as long
as they have RRFs mat are greater man or equal to 0.010, and %RSD of less man 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 man 30.0%, men 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.
46
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Region III Modification!
Initial Calibration SV
E. Action
I. All semivolatile target compounds, including the 19 "poor performers" (see Table 4) will be
qualified using the following criteria:
a. If die %RSD is greater than 30.0% and the RRF is greater than or equal to O.OS, qualify
positive results with "J", and non-detected semivolatile target compounds using professional
judgement.
b. If the RRF is less than O.OS, 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 "I".
tii. No qualifiers are needed for non-detected target compounds.
c. If the low end of the curve is outside of the linearity criteria:
i. No qualifiers are required for positive results in the linear portion of the curve.
ii. Qualify low level positive results in the area of non-linearity with "J".
iii. Qualify non-detected semivolatile target compounds using professional judgement.
3. If the laboratory has failed to provide adequate calibration information, the designated
representative should contact the laboratory and request the necessary information. If the
information is not available, the reviewer must use professional judgement to assess the data.
4. Whenever possible, the potential effects on the data resulting from a failure to meet calibration
criteria should be noted in the data review narrative.
4?
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Region QI Modification!
Initial Calibration SV
5. When it is suspected that relative response factors were incorrectly generated from misidentified
peaks or incorrect area measurements, the laboratory should be contacted to requantitate these
RRFs and associated sample results. Hie report narrative should identify affected results and
document the cause of the reviewer's suspicions. In addition, a CLP telephone log must be
completed.
6. Positive results for compounds flagged for blank contamination *B" will not need a separate flag
"J" in the data summary form for minimum RRF, %RSD, or %D outside criteria. However,
these situations should be addressed in the data review narrative.
48
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Region in Modification*
IV. Continuing Calibration SV
A. Review Items: Form VH SV-1 and SV-2, quantitation reports, and chromatograms.
B. Objective
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data for semivolatile target
compounds. Continuing calibration establishes the 12-hour relative response factors on which the
quantitations are based and checks satisfactory performance of the instrument on a day-to-day basis.
C. Criteria
1. Continuing calibration standards containing both target compounds and surrogates are analyzed
at the beginning of each 12-hour analysis period following the analysis of die 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 mat 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 m.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.
49
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Region ID Modifications
Continuing Calibration SV
3, Evaluate the %D between initial calibration RRF and continuing calibration RRF for one or
more semivolatile compounds.
a. Check and recalculate the %D for at least one semivolatile target compound for each internal
standard; verify that the recalculated value agrees with die 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.
Hie 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 mat 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
man or equal to 0.05, qualify positive results "I*.
b. If the %D is outside the ±_ 25.0% criterion and the continuing calibration RRF is greater
than or equal to 0.05, qualify non-detected semivolatile target compounds based on
professional judgement.
c. If the continuing calibration RRF is less than 0.05, qualify positive results mat have
acceptable mass spectral identification with "I" or use professional judgement.
d. If the continuing calibration RRF is less man 0.05, qualify non-detected semivolatile target
compounds as unusable "R".
2. If the laboratory has railed 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 die data resulting from a failure to meet calibration
criteria should be noted in the data review narrative.
50
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Region m ModiGulicmx
Continuing Calibration SV
4. When it is suspected that relative-response factors were incorrectly generated from misidentified
peaks or incorrect area measurements, the laboratory should be contacted to requantitate these
RRFs and associated sample results. The report narrative should identity affected results and
document the cause of the reviewer's suspicions. In addition, a CLP telephone log must be
, completed.
5. Positive results for compounds flagged for blank contamination "B" will not need a separate flag
"3" in the data summary form for minimum RRF, %RSD, or %D outside criteria. However,
these situations should be addressed in the data review narrative.
51
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Region 01 Modification*
sv
V. Blanks
A. Review Items: Form I SV-1 and SV-2, Form IV SV, chromatograms, and quantitation reports.
B. Objective.
The purpose of laboratory (or field) blank analyses is to determine the existence and magnitude of
contamination problems resulting from laboratory (or field) activities. The criteria for evaluation of
blanks apply to any blank associated with the samples (e.g., method blanks, instrument blanks, trip
blanks, and equipment blanks). If problems with 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, men 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.
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 (lOx) 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
52
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Region m Modification!
Blanks SV
is associated with a given sample, qualification should be based upon comparison with the associated
blank* having the highest concentration of a contaminant. Toe results must not be corrected by
subtracting any blank value.
Field blanks measure contamination introduced not only in the field but also from the laboratory.
In general, evaluation of the impact on specific sample results is handled as with laboratory blanks.
The reviewer should use caution in attributing contamination to the field as opposed to laboratory
sources. However, when field-introduced contamination is suspected, it is helpful for the reviewer
to consult the sampling group to identify possible sources and prevent future reoccurrences. Verified
field sources of contamination should be noted in the data review narrative. If a field blank has a
highest concentration of a contaminant, then all samples in the associated case are qualified "B",
using the 5x and lOx rule. Other field blanks associated with the case are not qualified.
Specific actions are as follows:
1. If a semivolatile compound is found in a blank but 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, men this should be noted in the report narrative.
2. Any semivolatile compound detected in the sample (other man the common phthalate
contaminants), that was also detected in any associated blank, is qualified "B" if the sample
concentration is less than five times (5x) the blank concentration. For phthalate contaminants,
the results are qualified IB* when the sample result is less than lOx the blank concentration.
In using the 5x/10x rule Jo compare blank results to sample results which were calculated using
different weights, volumes, or dilution factors, the reviewer must choose between comparing the
levels detected with die instrument, the total amount of compound (ug of contamination) present
in the extracts, or the final concentration of the contaminant in the sample aliquots. Often, more
than one approach will be acceptable and will yield the equivalent flagging of sample results.
a. Comparisons involving sample dry weight correction factors, but with all other calculation
factors the same for sample versus blank:
o In this case, the reviewer can compare the wet weight concentrations, instrument levels,
or the total amount of compound (ug of contaminant) in the extracts. All of these
approaches will be acceptable and will yield equivalent flagging of sample results.
b. When the sample has a smaller initial aliquot size than the blank (purge or extraction
weight/volume), but all other calculation factors beyond this analytical step are identical (i.e.,
* For qualification purposes, to determine the highest concentration of a contaminant, consider all blanks
in a case associated with all samples.
53
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Region ffl Modification!
Blanks SV
same final extract volumes, injection volumes, and extract dilution factors for sample versus
blank):
o In this case, it is acceptable and equivalent to compare either instrument levels, the total
amount of compound (ug of contaminant) in the extracts, or the concentration of
contaminant in the extracts.
o Final concentrations of sample versus blank should not be compared.
c. When the sample has a larger final extract volume or a greater dilution factor than the blank:
o If the laboratory contaminant may have been introduced after or during the sample
dilution step, then a direct comparison of instrument levels is appropriate. For
example, comparing the instrument level result for a water sample mat was diluted
1:100 prior to injection would take into account possible laboratory contamination of
the syringe, instrument, or dilution solvent.
o On the other hand, if it is highly probable that the contamination originated before the
dilution step, then it is more appropriate to calculate and compare the total amount of
compound (ug of contaminant) present in the undiluted extract of the sample versus the
blank. For example, a BNA extract diluted 1:100 prior to injection may only be subject
to phthalate contamination prior to the dilution step (i.e., during
extraction/concentration).
o If the results of a dilution run are to be flagged "B" because of blank contamination,
the reviewer should attempt to determine whether an undiluted run was also performed.
If so, the undiluted run may be used to verify the presence of a compound detected at
levels too high to be questioned or, conversely, to prove that a compound was actually
not present at levels multiplied by a dilution factor.
The reviewer should note that blanks may not involve the same weights, volumes, or dilution
factors as the associated samples. These factors must be taken into consideration when applying
the "5x" and " lOx" criteria, such that a comparison of the total amount of contamination is
actually made.
Additionally, mere 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 die diluted sample
result, but are absent in the undiluted sample result. Since both results are not routinely
reported, it may be impossible to verify mis source of contamination. However, if the
reviewer determines that the contamination is from a source other man the sample, he/she
should qualify the data. An explanation of the rationale used for this determination should be
provided in the narrative accompanying the Regional Data Assessment Summary.
54
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Region M Modifications
Blanks SV
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^), 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 mis should be noted for TPO action if the
cross-contamination is suspected of having an effect on the sample results.
7. Blanks or samples run after a matrix spike or standard should be carefully examined to
determine the occurrence of instrument or syringe carry-over. Since the efficiency of sample
transfer can vary dramatically according to apparatus and operator techniques, professional
judgment should be used in each case to determine whether sample or blank results are
attributable to carry-over. Some common examples are as follows:
o Zero to .one percent syringe carry-over occasionally in BNA runs.
o Higher percentages of carry-over following BNA runs that are saturated.
Sample results which are possible artifacts of carry-over should be flagged as unusable, "R".
8. When there is convincing evidence mat contamination is restricted to a particular instrument,
matrix, or concentration level, the 5X/10X rule will only be applied to compare contaminated
blanks to certain associated samples (as opposed to all samples in the case). Some examples are
as follows:
o Column bleed (siloxanes) may be localized to a particular instrument.
o Common laboratory contaminants, such as methylene chloride and phthalates, are generally
too unpredictable to safely assume contamination is restricted to a particular instrument,
matrix, or concentration level.
55
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Region ID Modifications
Blanks SV
Hie 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.
Rule
Blank Result 7 7
CRQL 5 5
Sample Result 60 30
Qualified Sample Result 60S 30B
In the example for the "10x" rule, sample results less than 70 (or 10 x 7) would be
qualified "B". In the case of the *5x* rule, sample results less than 35 (or 5x7)
would be qualified "B".
Example 2: Sample result is less than CRQL, and is also less than the 5x or lOx multiple of
the blank result.
Rule
JO* &
Blank Result 6 6
CRQL 5 5
Sample Result 4J 4J
Qualified Sample Result 4B 4B
Note that data are reported as 4B, indicating that the qualitative presence is not
confirmed.
Example 3: Sample result is greater man the 5x or lOx multiple of the blank result.
Rule
Blank Result 10 10
CRQL 5 5
Sample Result 120 60
Qualified Sample Result 120 60
For both the * IQx" and "5x" rules, sample results exceeded the adjusted blank results
of 100 (or 10x10) and 50 (or 5x10), respectively.
56
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Region m ModiGcAliooi
sv
VI. Surrogate Spikes
A. Review Items: Form n SV-1 and SV-2, chromatograms, and quantitation reports.
B. Objective
Laboratory performance on individual samples is established by means of spiking activities. All
samples are spiked with surrogate compounds prior to sample preparation. The evaluation of the
results of these surrogate spikes is not necessarily straightforward. The sample itself may produce
effects because of such factors as interferences and high concentrations of analytes. Since the effects
of the sample matrix are frequently outside the control of the laboratory and may present relatively
unique problems, the evaluation and review of data based on specific sample results is frequently
subjective and demands analytical experience and professional judgment. Accordingly, this section
consists primarily of guidelines, in some cases with several optional approaches suggested.
C. Criteria
1. Surrogate spikes, 4 acid compounds (3 required and 1 advisory) and 4 base/neutral compounds
(3 required and 1 advisory) are added to all samples and blanks to measure their recovery in
sample and blank matrices. .
2. Surrogate spike recoveries for semivolatile samples and blanks must be within the limits
specified in Appendix A and on Form n SV-1 and SV-2 or SOW.
D. Evaluation
1. Check raw data (e.g., chromatograms and quantitation reports) to verify the surrogate spike
recoveries on the Surrogate Recovery Form tt-SV-1 and SV-2-. Check for any transcription or
calculation errors.
2. Check that the surrogate spike recoveries were calculated correctly. The equation can be found
in Appendix A.
3. The following should be determined from the Surrogate Recovery form(s):
a. If any two base/neutral oj acid surrogates are out of specification, or if any one base/neutral
or acid extractable surrogate has a recovery of less than 10%, then there should be a
reanalysis to confirm mat the non-compliance is because of sample matrix effects rather man
laboratory deficiencies.
]No|e: When there are unacceptable surrogate recoveries followed by successful re-analyses, the
laboratories are required to report only the successful run.
57
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Region m Modification*
Surrogate Spikes SV
b. Hie laboratory has failed to perform satisfactorily if surrogate recoveries are out of
specification and there is no evidence of re-injection of the extract, or re-extraction and
reanalysis (if re-injection fails to resolve the problem).
c. Verify that no blanks have surrogates recoveries outside the criteria.
4. Any time there are two or more analyses for a particular traction the reviewer must determine
which are the best data to report. Considerations should include but are not limited to:
a. Surrogate recovery (marginal versus gross deviation).
b. Technical holding times.
c. Comparison of the values of the target compounds reported in each fraction.
d. Other QC information, such as performance of internal standards.
5. When both the initial analysis and the reanalysis have surrogate recoveries outside of criteria,
the data summary should normally contain the highest concentration obtained for each compound
detected, provided that surrogate recoveries in the analysis being reported do not suggest a high
bias. However, if a demonstrated laboratory contaminant is detected in one analysis but not the
other, the negative result may be more appropriate to report.
When the reanalysis of a fraction is within surrogate recovery criteria, the laboratory is required
to provide only data for the acceptable analysis. If both sets of data are provided, and if a
compound was detected in the initial analysis but not the reanalysis, then the positive result
should be reported (provided the compound is not a demonstrated laboratory contaminant). The
reported result should be flagged as estimated "J", due to possible sample inhomogeneity.
6 If advisory surrogates are outside established criteria, professional judgement will be used in
qualifying the sample results. If the results are outside the criteria, then qualification would only
affect similar target compounds.
E. Action
Data are not qualified with respect to surrogate recovery unless two or more semivolatile surrogates,
within the same traction (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 me case, especially considering the apparent complexity of the sample matrix.
fstote: These actions apply to all surrogates, except for "advisory* surrogates. Professional
judgement should be used in qualifying sample results based on advisory surrogate
recoveries. Qualification based on advisory surrogate recoveries should be applied to similar
compounds in the sample only. Specify in the narrative any actions taken based on advisory
• surrogate recovery.
58
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Region IB Modifications
Surrogate Spikes
SV
1. If two or more surrogates in either semivolatile fraction (base/neutral or acid fraction) have a
recovery greater than the upper acceptance limit (UL):
a. Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.
b. Detected semivolatile target compounds are qualified biased high, "K".
c. Results for non-detected semivolatile target compounds should not be qualified.
2. If two or more surrogates in either semivolatile fraction have a recovery greater man or equal
to 10% but less than the lower acceptance limit (LL):
a. Specify the fraction mat is being qualified, i.e. acid, base/neutral, or bom.
b. Detected semivolatile target compounds are qualified biased low, "L".
c. For non-detected semivolatile target compounds, the sample quantitation limit is qualified as
biased low, "UL".
3. If any surrogate in either semivolatile fraction show less man 10% recovery:
a. Specify the fraction mat is being qualified, i.e. acid, base/neutral, or both,
b. Detected semivolatile target compounds are qualified biased low, "L*.
c. Non-detected semivolatile target compounds may be qualified as unusable "R". (If advisory
surrogate limits are not met, use professional judgement to qualify non-detected compounds).
Table 5. Qualification of Semivolatile Anal vies Based on
Surrogate Recoveries
SURROGATE RECOVERY
Detected analytes
Non-detected analytes
2 or 3
all high
K
i
none
2 or 3
all low
L
UL
2 or 3
mixed high/low
J
UJ
1 or more
< 10% rec.
L
R
4. If two or more surrogate recoveries in either semivolatile fraction (base/neutral or acid fraction)
are outside surrogate recovery limits, and one of the recoveries is below the lower limit (but
> 10%) and the other recovery is above the upper limit:
a. Specify the fraction that is being qualified, i.e., acid, base/neutral, or bom.
59
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Region ID Modifications
Surrogate Spikes SV
*•
b. Detected semivolatile target compounds are qualified as estimated, "J".
c. Non-detected semivolatile target compounds are qualified as estimated, "UJ".
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 mere
is a fundamental problem with the analytical process. For example, if one or more samples in
the batch show acceptable surrogate recoveries, the reviewer may choose to consider the blank
problem to be an isolated occurrence. However, even if this judgement allows some use of the
affected data, analytical problems should be noted for TPO action. Also note if there are
potential contractual problems associated with the lack of re-analysis of samples that were out
of specification.
6. Whenever possible, the potential effects of the data resulting from surrogate recoveries not
meeting the advisory limits should be noted in the data review narrative.
7. Positive results for compounds already flagged for blank contamination will not need a separate
flag for surrogate recoveries. However, these situations should be addressed in die narrative
or the support documentation.
8. When dilutions are performed which prevent detection of BNA surrogate compounds, the
narrative or support documentation should indicate that extraction efficiency/method accuracy
cannot be verified.
9. Although semivolatile surrogate recoveries cannot usually be correlated with specific analytes,
in the following cases specific action will be allowed based upon a particular surrogate:
a. When a semivolatile surrogate is the deuterated analog of a TCL analyte (for example, d3-
phenol and phenol), a low recovery for the surrogate can be used to flag positive results and
quantitation limits as biased low for the undeuterated analog. (This applies even if no other
surrogates are outside criteria or if other surrogates are biased high instead of low.)
b. When d12-terphenyl is biased low, positive results and quantitation limits for the heavier
polyaromatic hydrocarbons (those which elute starting with fluorathene) can be considered
as biased low. (This applies even if no other surrogates are outside criteria or if other
• surrogates are biased high instead of low.)
c. When 2,4,6-tribromophenol is biased low,positive results and quantitation limits for
trichlorophenols and pentachlorophenol can be considered as biased low. (mis applies even
if no other surrogates are outside criteria or if other surrogates are biased high instead of
low.)
60
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Region HI Modification*
sv
VH. Matrix Spikes/Matrix Spike Duplicates
A. Review Items: Form in 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 die analytical method on various matrices and to demonstrate acceptable
compound recovery by the laboratory at the tune of sample analysis. These data alone cannot be
used to evaluate the precision and accuracy of individual samples. However, when exercising
professional judgement, this data should be used in conjunction with other available QC information.
C. Criteria
1. Matrix spike 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 in SV-1 and SV-2 and in the SOW..
3. Hie Relative Percent Differences (RPDs) between matrix spike and matrix spike duplicate
recoveries should be within the advisory limits listed on Form in SV-1 and SV-2 and in the
SOW.
D. Evaluation
1. Verify that MS and MSD samples were analyzed at the required frequency and that results are
provided for each sample matrix.
2. Inspect results for the MS/MSD Recovery on Form HI SV-1 and SV-2 and verify mat 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 RPDs were calculated correctly.
5, Compare results (%RSD) of non-spiked compounds between the original result, MS, and MSD.
E. Action
1. No action is taken on MS/MSD data alone. However, using informed professional judgment
the data reviewer may use the matrix spike and matrix spike duplicate results in conjunction with
other QC criteria and determine the need for some qualification of the data.
61
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Region m Modi6cttioiu
Matrix Spikes/Matrix Spike Duplicates SV
2. The data reviewer should first try to determine to what extent the results of the MS/MSD effect
the associated data. This determination should be made with regard to the MS/MSD sample
itself as well as specific analytes for all samples associated with the MS/MSD.
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 analytes, which affects all associated samples.
4. The reviewer must use professional judgement to determine the need for qualification of positive
results of non-spiked compounds.
5. When extremely low % recoveries are noted, qualify data for all affected compounds using
professional judgement.
6. When non-spiked compounds are present in either the MS or MSD results, a table in the data
review narrative is constructed showing original (unspiked) sample results for non-spiked
compounds, non-spiked compounds present in the MS and MSD and the calculated %RSD.
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Region m Modi fuatioiu
sv
VBi. Regional Quality Assurance and Quality Control
A. Review Items: Form I SV, Chromatograms, and Quantitation reports.
B. Objective
Regional Quality Assurance and Quality Control (QA/QC) refer to any QA and/or QC samples
initiated by die Region, including field duplicates, Performance Evaluation (PE) samples, blind
spikes, and blind blanks.
C. Criteria
Criteria are dependent on the type of QC sample. Frequency may vary.
1. The analytes present in the PE sample must be correctly identified and quantitated.
D. Evaluation
1. Evaluation of Performance Evaluation (PE) Samples are not to be presented as part of the data
review. All forms associated .with the Performance Evaluation Samples are to be sent (with a
cover memo stating the case number and laboratory information) directly to the Quality
Assurance Branch in Region M.
U.S. Environmental Protection Agency
Region III, Central Regional Laboratory
Quality Assurance Branch
201 Defense Highway, Suite 200
Annapolis, MD 21401
Attn: Program Support Section
2. Percent difference between target compounds present in the field duplicate samples shall be
determined. Evaluation of the percent difference compared to those specified in the site Quality
Assurance Project Plan may be presented in the data review narrative.
E. Action
1. Field duplicate results are to be presented in a table form in the data review narrative. If target
compounds were not present in either of the field duplicate samples, men a table is not required.
The percent difference is to be calculated and presented in the table, (if one of the field
duplicates was also used as a matrix spike/matrix spike duplicate sample, then the table should
include any non-spiked compounds detected, along with the % relative standard deviation.)
63
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Regton ID ModiDcationi
Regional Quality Assurance and Quality Control SV
No action is taken based on percent difference of field duplicate sample data alone. However,
using informed professional judgement, the data reviewer may use the field duplicate results in
conjunction with other QC criteria and determine the need for some qualification of the data.
2. Other types of Regional QC Samples
Professional judgement is needed for evaluating other types of QC samples that may be
associated with a particular case of samples. This information may be used in conjunction with
other QC criteria to determine the need for qualification of data.
64
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Region HI Modification!
sv
IX. Internal Standards
A. Review Items: Form Vffl SV-1 and SV-2 , quantitation reports, and chromatograms.
B. Objective
Internal Standards (IS) performance criteria ensure that GC/MS sensitivity and response are stable
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.
2. Hie retention time of the internal standards in samples and blanks must not vary by more than
+_ 30 seconds from the retention time of the associated calibration standard.
D. Evaluation
1 . Check raw data (e.g. , chromatograms and quantitation lists) for samples and blanks to verify the
internal standard retention times and areas reported on the Internal Standard Area Summary
(Forms Vm SV-1, Vffl SV-2).
2. Verify that all retention times and IS areas are within the required criteria.
3. If there are two analyses for a particular fraction, the reviewer must determine which ate the
best data to report. Considerations should include:
a. Magnitude and direction of the IS area shift.
b. Magnitude and direction of the IS retention time shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each fraction.
E. Action
1. If an IS area count for a sample or blank is outside - 50% or + 100% of the area for the
associated standard:
a. Positive results for compounds quantitated using that IS should be qualified with "1*.
b. Non-detected compounds quantitated using an IS area count greater than + 100% or less man
50% should be qualified with "UF.
65
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Region IQ Modification!
Internal Standards SV
c. If extremely low area counts are reported, or if performance exhibits a major abrupt drop-
off, men a severe loss of sensitivity is indicated, Non-detected target compounds should men
be qualified as unusable "R".
2. If an IS retention time varies by more man 30 seconds:
The chromatograpbic profile for mat sample must be examined to determine if any false
positives or negatives exist. For shifts of a large magnitude, the reviewer may consider partial
or total rejection (R) of the data for that sample fraction. Positive results should not need to be
qualified with "R* if the mass spectral criteria are met.
3. If the internal standards performance criteria are grossly exceeded, then this should be noted for
TPO action. Potential effects on the data resulting from unacceptable internal standard
performance should be noted in the data review narrative.
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Region ID Modification!
sv
X. Target Compound Identification
A* Review Items: Form I SV-1 and SV-2 quantitation reports, mass spectra, and chromatograms.
B. Objective
Qualitative criteria for compound identification have been established to minimize the number of
erroneous identifications of compounds. An erroneous identification can either be a false positive
(reporting a compound present when it is not) or a false negative (not reporting a compound that is
present).
The identification criteria can be applied much more easily in detecting false positives than false
negatives. More information is available due to the requirement for submittal of data supporting
positive identifications. Negatives, or non-detected compounds, on the other hand represent an
absence of data and are, therefore, much more difficult to assess. One example of detecting false
negatives is the reporting of a Target Compound as a TIC.
C. Criteria
1. Compound must be within ± 0.06 relative retention time (RRT) units of the standard RRT.
2. Mass spectra of the sample compound and a current laboratory-generated standard must match
according to the following criteria:
a. All ions present in the standard mass spectrum at a relative intensity greater than 10% must
be present in the sample spectrum.
b. The relative intensities of these ions must agree within ± 20% between the standard and
sample spectra. (Example: For an ion with an abundance of 50% in the standard spectrum,
the corresponding sample ion abundance must be between 30% and 70%.)
c. Ions present at greater than 10% in the, sample mass spectrum but not present in the standard
spectrum must be considered and accounted for.
D. Evaluation
1. Check that the RRT of reported compounds is within ± 0.06 RRT units of the standard relative
retention time.
2. Check the sample compound spectra against the laboratory standard spectra to verify that its
meets the specified criteria.
3. The reviewer should be aware of situations (e.g., high concentration samples preceding low
concentration samples) when sample carryover is a possibility and should use judgment to
determine if instrument cross-contamination has affected any positive compound identification.
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4. Check the chromatograra to verify that peaks are accounted for, i.e., major peaks are either
identified as target compounds, TICs, surrogates, or internal standards.
E. Action
1. The application of qualitative criteria for GC/MS analysis of target compounds requires
professional judgement. It is up to the reviewer's discretion to obtain additional information
from the laboratory. If it is determined .that incorrect identifications were made, all such data
should be qualified as not detected "U" or unusable "R".
2. Professional judgement must be used to qualify the data if it is determined that cross-
contamination has occurred.
3. Any changes made to the reported compounds or concerns regarding target compound
identifications should be clearly indicated in the data review narrative. The necessity for
numerous or significant changes should be noted for TPO action.
4. If it is determined mat incorrect identifications were made, all such data should be reported as
not-detected, and the narrative and the support documentation should indicate this action. In
addition, the reviewer should verify that the misidentified peak was library searched as a TIC,
if appropriate.
5. If the presence of a target compound is strongly suggested by raw data, but its mass spectrum
contains minor inadequacies, the compound may be added to the data summary and qualified as
a tentative identification "N". The reviewer should address corroborating evidence in the
narrative, such as the presence of the compound in closely related compounds in the same
sample.
6. If the laboratory did not report a compound of acceptable matching quality, the reviewer should
add this compound to the sample data summary. The narrative and the support documentation
should indicate this action, as well as the ORDA. The reviewer should request the laboratory
to re-examine and resubmit the result, particularly if the value is greater than the CRQL.
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Region in Modification*
sv
XI. Compound Ouantitation and Reported CROLS
A. Review Items: Form I SV-1 and SV-2, sample preparation sheets, case narrative, sample clean-up
sheets, quantitation reports, and chromatograms.
B. Objective
The objective is to ensure that the reported quantitation results and Contract Required Quantitation
Limits (CRQLs) for semivolatUe 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 (also as specified in the Statement of Work). Quantitation
must be based on the quantitation ion (m/z) specified in the SOW for bom 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. Calculation errors can sometimes be revealed by abnormally high
surrogate recoveries, matrix spike recoveries, or inappropriately high results for certain
compounds.
2. Verify that the correct internal standard, quantitation ion, and RRF were used to quantitate the
compound. Verify that the same internal standard, quantitation ion, and RRF are used
consistently throughout the calibration and quantitation processes.
3. Verify that the CRQLs have been adjusted to reflect all sample dilutions, concentrations, splits,
clean-up activities, and dry weight factors that are not accounted for by the method.
E. Action
1. If there are any discrepancies found, the laboratory may be contacted by the designated
representative to obtain additional information that could resolve any differences. If a
discrepancy remains unresolved, the reviewer must use professional judgement to decide which
value is the best value. Under these circumstances, the reviewer may determine
qualification of data is warranted. Decisions made on data quality should be included in the data
review narrative. A description of the reasons for data qualification and the qualification that
is applied to the data should be documented in the data review narrative.
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Compound Quantitation and Reported CRQLS SV
2. Numerous or significant failures to accurately quantify the target compound or to properly
evaluate and adjust CRQLs should be noted for TPO action.
3. The reviewer must assure that any results in error by more than 10 percent are identified and
corrected on the sample data summary. If laboratory resubmission is not performed, the
reviewer should document his/her changes to the data in the narrative or support documentation.
Calculation errors should also be noted on the ORDA.
4. If a sample concentration is above the highest standard and contract required dilutions were not
performed, the TPO should be informed on the ORDA. The chromatogram and mass spectrum
should be examined for signs of a saturated signal. If the ion used for quantitation was
saturated, then the result should be flagged as biased low, "L". If the ion used for quantitation
was not saturated, the result should be flagged as estimated, "I*.
5. When sample results were quantitated using RRFs from the wrong calibration standard, the
laboratory should resubmit these results. The ORDA should identify affected results and
document the error. In addition, a CLP telephone log must be completed.
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sv
XII. Tentatively Identified Compounds
A. Review Items: Form ISV-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 (HIST) 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 MIST library and report
the possible identity for the 20 largest semivolatile fraction peaks which are not surrogate, internal
standard, or target compounds, but which have area or height greater than 10 percent of the area or
height of the nearest internal standard. TIC results are reported for each sample on the Organic
Analyses Data Sheet (Form I SV-TIC).
Note: Since the SOW revision of October 1986, the CLP does not allow the laboratory to report
as tentatively identified compounds any target compound which is properly reported in
another fraction. For example, late eluting volatile target compounds should not be reported
as semivolatile TICs.
D. Evaluation
1. Guidelines for tentative identification are as follows:
a. Major ions (greater than 10% relative intensity) in the reference spectrum should be present
in the sample spectrum.
b. The relative intensities of the major ions should agree within .±20% between the sample and
the reference spectra.
c. Molecular ions present in the reference spectrum should be present in the sample spectrum.
d. Ions present in the sample spectrum but not in the reference spectrum should be reviewed
for possible background contamination, interference, or coelution of additional TIC or target
compounds.
e. When the above criteria are not met, but in the technical judgment of the data reviewer or
mass spectra! interpretation specialist the identification is correct, the data reviewer may
report the identification.
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Tentatively Identified Compounds SV
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.
3. Blank chromatograms should be examined to verify mat TIC peaks present in samples are not
found in blanks. When a low-level non-target compound that is a common artifact or laboratory
contaminant is detected in a sample, a thorough check of blank chromatograms may require
looking for peaks which are less than 10 percent of the internal standard height, but present in
the blank chromatogram at a similar relative retention time.
4. All mass spectra for 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: CC^ (m/z 44), siloxanes (m/z 73), diethyl ether, hexane,
certain ft eons (1,1,2-trichloro-1,2,2-trifluoroethaneor fluorotrichloromethane), and phthalates
at levels less man 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 reaction products of acetone include: 4-hydroxy-4-methyl-2-pentanone, 4-methyl-2-
penten-2-one, and 5,5-dimethyl-2(5H)-ruranone.
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, die 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 tunes 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 man one fraction. Verify that quantitation is made
from the proper fraction.
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9. Library searches should not be performed on internal standards or surrogates.
10. TIC concentration should be estimated assuming a RRF of 1.0.
E. Action
1. All TIC results should be qualified "J", estimated concentration on the Laboratory
Form I-TlCs.
2. General actions related to the review of TIC results are as follows:
a. If it is determined that a tentative identification of a non-target compound is not acceptable,
the tentative identification should be changed to "unknown" or an appropriate identification.
b. If all contractually required peaks were not library searched and quantitated, the designated
representative could request these data from the laboratory.
3. Blank Results
Form I-TIC which contain sample results that are questioned by blank results, should be flagged
"B" and a line drawn through these data for emphasis (initialed and dated).
To be considered questionable, a sample TIC concentration must be within 10 times the
concentration of one of the blank results. If different volumes/weights are used, the total
amount of compound in the extract must be compared for sample versus blank. In general,
blanks analyzed within the same case, by the same lab, may be cross-applied to either soil or
water samples extracted or analyzed on other days.
To question a sample result, only presumptive evidence for the presence of the compound in the
blank is necessary. The presence of the TIC in the blank is suggested in any of the following
situations:
a. Relative retention times (RRTs) match for sample versus blank, and the sample library search
result matches the same compound oj compound class as the library search result for the
blank.
b. RRTs match, but library search results do not list the same compound or class for sample
versus blank. However, some of the largest ions in the sample are also in the blank, and a
direct comparison of sample versus blank spectra suggests mat the TIC in the sample is quite
possibly the same compound as that in the blank.
c. A peak at the same RRT as the sample TIC is present in the chromatogram of the blank, but
no library search was performed or included in the data. (The labs do not have to library
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Tentatively Identified Compounds SV
search peaks less than 10% of the height of the nearest internal standard, although these peaks
may still be important to identify low-level blank contaminants that can question sample results
at levels above 10% of the nearest internal standard height.)
All blank results must be attached in the support documentation section of the data review.
4. When a compound is not found in any blanks, but is a suspected artifact of common laboratory
contamination, the reviewer should cross off the reported TIC result on the copy of the Form
I-TIC and note the reason(s) hi the narrative.
5. In deciding whether a library search result for a TIC represents a reasonable identification,
professional judgment must be exercised. If there is more than one possible match, the result
may be reported as "either compound X or compound Y". If there is a lack of isomer
specificity, the TIC result may be changed to a non-specific isomer result (e.g., 1,3,5-trimethyl
benzene to trimethyl benzene isomer) or to a compound class (e.g., 2-methyl, 3-ethyl benzene
to substituted aromatic compound). These changes may be made directly on a copy of the Form
I-TIC, as long as changes are initialed and dated.
6. Other case factors may influence TIC judgments. If a sample TIC match is poor but other
samples have a TIC with a good library match, similar relative retention time, and the same
ions, identification information may be inferred from the other sample TIC results.
7. Physical constants, such as boiling point, may be factored into professional judgment of TIC
results.
8. Any changes made to the reported data or any concerns regarding TIC identifications should be
indicated in the data review narrative. Any changes made regarding TIC identifications or
qualifications are to be made on copies of the laboratory generated Form I-TIC and not the
originals.
9. Failure to properly evaluate and report TICs should be noted for TPO action.
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sv
Xin. System Performance
A. Review Items: Form in SV-1 and SV-2, Form Vffl SV-I ami SV-2, and ehromatograms.
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 mis 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-delects. 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 m absolute retention times of internal standards.
b. Excessive baseline rise at elevated temperature.
c. Extraneous peaks.
d. Loss of resolution as suggested by factors such as non-resolution of 2,4- and 2,5-
dinitrotoluene.
e. Peak tailing or peak splitting that may result in inaccurate quantitation,
E. Action
Professional judgement must be used to qualify the data if it is determined that system performance
has degraded during sample analyses. Any degradation of system performance which significantly
affected the data should be documented for TPO action.
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sv
XIV. Overall Assessment of Data
A. Review Items: Entire data package, data review results, ami (if available) Quality Assurance Project
Plan (QAPjP), and Sampling and Analysis Plan (SAP).
B. Objective
Hie overall assessment of a data package is a brief narrative in which the data reviewer expresses
concerns and comments on the quality and, if possible, the useability of the data.
C. Criteria
Assess the overall quality of the data.
Review all available materials to assess the overall quality of the data, keeping in mind the additive
nature of analytical problems.
D. Evaluation
1. Evaluate any technical problems which have not been previously addressed.
2. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
3. If appropriate information is available, the reviewer may assess the useability of the data to assist
the data user in avoiding inappropriate use of the data. Review all available information,
including the QAPjP (specifically the Data Quality Objectives), SAP, and communication with
data user that concerns the intended use and desired quality of the data.
E. Action
1. Use professional judgement to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
2. Write a brief narrative to give the user an indication of die analytical limitations of the data.
Any inconsistency of mat data with the SDG Narrative should be noted for TPO action. If
sufficient information on the intended use and required quality of die data are available, the
reviewer should include his/her assessment of the useability of the data within the given context.
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PEST
PESHCIDE/AROCLOR DATA REVIEW
Hie pesticide/Aroclor data requirements to be checked are listed below.
I. Technical Holding Times (CCS-Contractual holding times only)
H. GC/ECD Instrument Performance Check
m. Initial Calibration (CSS)
IV. Continuing Calibration (CCS)
V. Blanks
VI. Surrogate Spikes (CCS)
VII. Matrix Spikes/Matrix Spike Duplicates
Vm. Regional Quality Assurance and Quality Control
IX. Pesticide Cleanup decks
X. Target Compound Identification
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
XIL Overall Assessment of Data
Nofe: "CCS* indicated mat 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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PEST
I. Technical Holding Times
A. Review Items; Form I PEST, EPA Sample Traffic Report, and/or chain-of-custody, raw data, SDG
Narrative, 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 sediment, oily wastes, and sludge)
are currently under investigation. When the results are available they will be incorporated into die
date evaluation process. Additionally, results of holding time studies will be incorporated into the
data review criteria as die 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 pesticides and Aroclors in cooled (@ 4°C) water samples, the technical holding time is 7 days
from sample collection to extraction and 40 days from sample extraction to analysis.
It is recommended that pesticides and Aroclors in soil samples in properly preserved non-aqueous
samples be extracted within 7 days of sample collection and extracts analyzed within 40 days from
sample extraction.
The contractual holding times, which differ from the technical holding times, state that extraction of
water samples by separatory funnel must be completed within 5 days of validated time of sample
receipt (VTSR), extraction of water samples by continuous liquid-liquid extraction procedures must
be started within 5 days of VTSR, and soil/sediment samples are to be extracted within 10 days of
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 either 14 days or 35 days after
receipt in the laboratory of the last sample in the SDG, depending on die contract.
D. Evaluation
Technical holding times for sample extraction are established by comparing the sample collection date
on the EPA Sample Traffic Report with the dates of extraction on Form I PEST and the sample
extraction sheets. To determine if the samples were analyzed within die holding time after extraction,
compare the dates of extraction on the sample extraction sheets with the dates of analysis on Form
I PEST.
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Technical Holding Times PEST
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, the discrepancies in the
sample condition could affect die data,
E, Action
1. If technical holding times are exceeded, qualify all detected compound results as estimated "J"
and sample quantitation limits as estimated "UJ", and document in the data review narrative mat
holding times were exceeded. However, please note that some extractable compounds are
extremely persistent in the environment (e.g., PCBs) in non-aqueous matrices and would not be
expected to degrade significantly during sample storage. The reviewer must use professional
judgement in the application of data qualifiers to those compounds in non-aqueous matrices.
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 effect
of additional storage on the sample results. The reviewer may determine that detected compound
results or the associated quantitation limits are approximates and should be qualified with "J" or
"UJ", respectively. The reviewer may determine that non-detected target compound data are
unusable (R).
3. Whenever possible, the reviewer should comment on the effect of exceeding the holding time on
the resulting data in the data review narrative.
4. When contractual and/or technical holding times are exceeded, mis should be noted as an action
item for the TPO.
5. 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 mis case, the data reviewer should
notify the Regional TPO (where samples were collected) and/or RSCC indicating mat shipment
delays have occurred so mat the field and/or shipping problems can be corrected. The reviewer
may pass this information on to the laboratory's TPO, but should explain mat contractually the
laboratory met the requirements.
6. When there are other quality control problems in conjunction with exceeded holding times (such
as suspected laboratory contamination), the reviewer should follow the hierarchy of qualifiers.
In particular, if for any reason the reviewer doubts the presence of a compound, die data
summary should display only the "B" or "R" qualifier, and not the "J" qualifier.
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Region ID Modificitioni
PEST
II. GC/ECP Instrument Performance Check
A. Review Items: Form VI PEST-4, Form VD PEST-1, Form Vm PEST, chromatograms, and data
system printouts.
B. Objective
Performance checks on the gas chromatograph with electron capture detector (GC/ECD) system are
performed to ensure adequate resolution and instrument sensitivity. These criteria are not sample
specific. Conformance is determined using standard materials, therefore, these criteria should be met
in all circumstances.
C. Criteria
1. Resolution Check Mixture
a. The Resolution Check Mixture must be analyzed at the beginning of every initial calibration
sequence, on each GC column and instrument used for analysis. The Resolution Check
Mixture contains the following pesticides and surrogates:
gamma-Chlordane Endrin ketone
Endosulfan I Methoxychlor
4,4'-DDE Tetrachloro-m-xylene
Dieldrin Decachlorobiphenyl
Endosulfan sulfate
b. The depth of the valley between two adjacent peaks in the Resolution Check Mixture must be
greater man or equal to 60.0 percent of the height of the shorter peak.
2. Performance Evaluation Mixture
a. The Performance Evaluation Mixture (PEM) must be analyzed at the beginning (following the
resolution check mixture) and at the end of the initial calibration sequence. The PEM must
also be analyzed at the beginning of every other 12-hour analytical period. The PEM contains
the following pesticides and surrogates:
gamma-BHC Endrin
alpha-BHC Methoxychlor
4,4*-DDT Tetrachloro-m-xylene
beta-BHC Decachlorobiphenyl
b. The resolution of adjacent peaks for the PEM injections in' each calibration (initial and
continuing) must be 100 percent for both GC columns.
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Region QI Modifications
GC/ECD Instrument Performance Check PEST
c. The absolute retention times of each of the single component pesticides and surrogates in all
PEM analyses mtist be within the specific retention time windows centered around the mean
retention times determined from the three-point initial calibrations
using the Individual Standard Mixtures. A list of the retention time windows is included in
Appendix A.
For example, for a given pesticide the mean retention time is first determined from the initial
calibration and found to be 12.69 minutes. The retention time window for mis pesticide is ±
0.05 minutes. Therefore, the calculated retention time window would range from 12.64 to
12.74
d. The relative percent difference (RPD) between the calculated amount and the true amount for
each of the single component pesticides and surrogates in the PEM analyses must be less than
or equal to 25.0 percent.
e. The percent breakdown is the amount of decomposition that 4,4'-DDT and Endrin undergo
when analyzed on the GC column. For Endrin, the percent breakdown is determined by the
presence of Endrin aldehyde and/or Endrin ketone in the GC chromatogram. For 4,4'-DDT,
the percent breakdown is determined from the presence of 4,4'-DDD and/or 4,4'-DDE in the
GC chromatogram. The equations used to verify these calculations are provided in Appendix
A.
i. The individual percent breakdown for both 4,4'-DDT and Endrin in each PEM must be less
than or equal to 20.0 percent for both GC columns.
ti. The combined percent breakdown for 4,4'-DDT and Endrin hi each PEM must be less man
or equal to 30.0 percent for both GC columns.
D. Evaluation
1. Resolution Check Mixture
a. Verify from the Form Vffl PEST that the resolution check mixture was analyzed at the
beginning of the initial calibration sequence on each GC column and instrument used for
analysis.
b. Check tfie resolution check mixture data and Form VI PEST-4 to verify that the resolution
criterion between two adjacent peaks for the required compounds is less than or equal to 60%.
The resolution criteria requires that the depth of the valley between two adjacent peaks in the
resolution check mixture must be greater than or equal to 60% of the height of the shorter
peak.
2. Performance Evaluation Mixture
a. Verify from the Form Vm PEST mat the Performance Evaluation Mixture (PEM) was
analyzed at the proper frequency and position sequence.
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GC/ECD Instrument Performance Check PEST
b. Check the PEM data from the initial and continuing calibrations to verify that the resolution
between adjacent peaks is 100 percent on both GC columns.
c. Check the PEM data from the initial and continuing calibrations and Form VII PEST-1 to
verify that the absolute retention times for the pesticides in each analysis are
within the calculated retention time windows based on the mean RT from the three-point initial
calibration using equations and examples found in Appendix A.
d. Verity that the relative percent difference (RPD) between the calculated amount and the true
amount for each of the pesticides and surrogates is less man or equal to 25,0 percent.
e. Verity that the individual breakdown on each GC column for 4,4'-DDT and Endrin is less than
or equal to 20.0 percent, and that the combined breakdown is less man or equal to 30.0
percent.
E. Action
1. Resolution Check Mixture: If resolution criteria are not met, the quantitative results may not be
accurate due to inadequate resolution. Detected target compounds that were not adequately
resolved should be qualified with "J". Qualitative identifications may also be questionable if
coelution exists. Non-detects with retention times in die region of coelution may not be valid,
depending on the extent of the problem. Professional judgement should be used to determine the
need to qualify data as unusable (R).
2. Performance Evaluation Mixture Retention Times: Retention tune windows are used in
qualitative identification. If the retention times of the pesticides in the PEM do not fall within
the retention time windows, the associated sample results should be carefully evaluated. All
samples injected after the last in-control standard are potentially affected.
a. For the affected samples, check to see if the sample chromatograms contain any peaks that are
close to die expected retention time window of the pesticide of interest. If no peaks are
present either within or close to the retention time window of the deviant target pesticide
compound, then there is usually no affect on the data (i.e., non-detected values can be
considered valid). Sample data mat are potentially affected by standards not meeting the
retention time windows should be noted in the data review narrative.
b. If the affected sample chromatograms contain peaks which may be of concern (i.e., above the
CRQL and either dose to or within the expected retention time window of the analyte
of interest), then the reviewer should determine the extent of the effect on the data and may
choose to qualify detected target compound "Ml" and non-detected target compounds "R". In
some cases, additional effort by the reviewer may be necessary to determine if sample peaks
represent the compounds of interest, for example:
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i. The reviewer can examine the data package for the presence of three or more standards
containing the pesticide of interest that were run within a 72-hour period during which the
sample was analyzed.
ii. If three or more such standards are present, the mean and standard deviation of the
retention time window can be re-evaluated.
iii. If all standards and matrix spikes fall within the revised window, the valid positive or
negative sample results can be determined using this window.
iv. The narrative should identify the additional efforts taken by the reviewer and the
resultant impact on data usability. In addition, the support documentation should contain
all calculations and comparisons generated by the reviewer.
c. If the reviewer can not resolve the problem of concern with the available data, all positive
results and quantitation limits should be qualified "R".
3. If PEM resolution criteria are not met, quantitative results for compounds in the region where the
criteria is not met may not be accurate due to inadequate resolution. Positive sample results for
compounds that were not adequately resolved should be qualified "J". If in the professional
judgement of the reviewer, qualitative identifications are questionable due to poor resolution,
positive sample results should be qualified "NJ". Non-detected target compounds that would elute
in the region of coelution may not be valid depending on the extent of the coelution problem.
Professional judgement should be used to qualify detection limits unusable "R".
4. If RPD criteria are not met, qualify all associated positive results generated during the analytical
sequence with "J" and the sample quantitation limits for non-detected target compounds with
"UJ".
5. 4,4'-DDT/Endrin Breakdown:
a. If 4,4'-DDT breakdown is greater than 20.0 percent:
i. Qualify all positive results for DDT with "L" (biased low). If DDT was not detected, but
DDD and DDE are detected, then qualify the quantitation limit for DDT as unusable (R).
ii. Qualify positive results for DDD and/or DDE as presumptively present at an approximated
quantity (NJ).
b. If Endrin breakdown is greater than 20.0 percent:
i. Qualify all positive results for Endrin with "L" biased low. If Endrin was not detected, but
Endrin aldehyde and Endrin ketone are detected, then qualify the quantitation limit for
Endrin as unusable (R).
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GC/ECD Instrument Performance Check PEST
ii. Qualify positive results for Endrin ketone and Endrin aldehyde as presumptively present
at an approximated quantity (NJ).
c. If the combined 4,4*-DDT ami Endrin breakdown is greater man 30.0 percent:
i. Qualify ill positive results for DDT and Endrin, "J* estimated. If Endrin was not detected,
but Endrin aldehyde and Endrin ketone are detected, then qualify the quantitation limit for
Endrin as unusable (R). If DDT was not detected, but DDD and DDE are detected, then
qualify the quantitation limit for DDT as unusable (R).
ii. Qualify positive results for Endrin ketone and Endrin aldehyde as presumptively present
at an approximated quantity (HI). Quality positive results for DDD and/or DDE as
presumptively present at an approximated quantity (NJ),
6. Potential effects on the sample data resulting from the initial calibration problems should be noted
in the data review narrative.
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Region ID Modification*
PEST
III. Initial Calibration
A. Review Items: Form VI PEST-1,2,3, and 4, Form VH PEST-I, Form VHI PEST, chromatograms,
and data system printouts.
B. Objective
Compliance requirements for satisfactory initial calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data for pesticide and
Aroclor target compounds. Initial calibration demonstrates that the instrument is capable of
acceptable performance at the beginning of the analytical sequence and of producing a linear
calibration curve.
C. Criteria
1. Individual Standard Mixtures
a. Individual Standard Mixtures A and B (containing all of the single component pesticides and
surrogates) must be analyzed at low, midpoint, and high levels during the initial calibration,
on each GC column and instrument used for analysis.
b. The resolution between any two adjacent peaks in the midpoint concentration of Individual
Standard Mixtures A and B in the initial calibration must be greater than or equal to 90.0
percent on both columns.
c. The absolute retention times of each of the single component pesticides and surrogates are
determined from three-point initial calibration using the Individual Standard Mixtures. A list
of the retention time windows and an example for calculating retention tune windows is given
in section m in Appendix A. • ~ -
d. At least one chromatogram from each of the Individual Standard Mixtures A and B must yield
peaks that give recorder deflections between SO to 100 percent of full scale.
e. The concentrations of the low, medium, and high level standards containing all of the single
component pesticides and surrogates (Individual Standard Mixtures A and B) must meet the
following criteria on bom GC columns.
The low point corresponds to the CRQL for each analyte. The midpoint concentration must
be 4 times the low point. The high point must be at least 16 times the low point, but a higher
concentration may be chosen.
f. The Percent Relative Standard Deviation (%RSD) of the calibration factors for each of the
single component pesticides and surrogates in the initial calibration on both columns for
Individual Standard Mixtures A and B must be less than or equal to 20.0 percent, except as
noted below. For the two surrogates, the %RSD must be less than or equal to 30.0 percent.
85
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Region m Modifications
Initial Calibration PEST
Up to two single component target pesticides (other than the surrogates) per column may
exceed die 20.0 percent limit but the %RSD must be less than or equal to 30.0 percent,
Note: Either peak area or peak height may be used to calculate die calibration factors that are,
in turn, used to calculate %RSD. However, the type of peak measurement used to
calculate each calibration factor for a given compound must be consistent. For example,
if peak area is used to calculate the low point calibration factor for endrin, men the mid and
high point calibration factors for endrin must also be calculated using peak area.
2. Multi-component Target Compounds
a. The multi-component target compounds (the 7 Aroclors and Toxaphene) must each be analyzed
separately at a single concentration level during the initial calibration sequence. The analysis
of the multi-component target compounds must also contain the pesticide surrogates.
b. For each multi-component analyte, the retention times are determined for three to five peaks.
A retention time window of ± 0.07 minutes is used to determine retention time windows for
all multi-component analyte peaks.
c. Calibration factor data must be determined for each peak selected from the multi-component
analytes.
D. Evaluation
1. Individual Standard Mixtures
a. Verify from the Form VTD PEST mat the Individual Standard Mixtures A and B were analyzed
at the proper frequency on each GC column and instrument used for analysis. Check the raw
data (chromatograms and data system print outs) for each standard to verify that each of the
standards was analyzed at the required concentration levels.
b. Check the raw data and determine that the midpoint standard's concentration is 4 times the
concentration of the tow point standard's concentration and verify mat resolution is greater
than 90%.
c. Check the Individual Standard Mixtures A and B data and Form VI PEST-1 and review the
calculated retention time windows for calculation and transcription errors.
d. Check the Individual Standard Mixtures A and B data and Form VI PEST-2 to verify mat the
%RSD for the calibration factors in each of the single component pesticides and surrogates in
the initial calibration analyses on both columns are in compliance with the criteria in Section
m.C. Check and recalculate the calibration factors and %RSD for one or more pesticides;
verify mat the recalculated values agree with the reported values. If errors are detected, more
comprehensive recalculation should be performed.
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Initial Calibration PEST
2. Multi-component Target Compounds
a. Verify from the Form VIII PEST that each of the multi-component target compounds were
analyzed at the required frequency. Check the raw data for the standards to verify that the
multi-component analytes were analyzed at the required concentration.
b. Check the data for the multi-component target compounds and Form PEST VI-3 to verify that
at least three peaks were used for calibration and that retention time and calibration factor data
are available for each peak.
E. Action
1. If the initial calibration sequence was not followed as required, then professional judgement must
be used to evaluate the effect of the non-compliance on the sample data. If the requirements for
the initial calibration sequence \vere_ not met, then mis should be noted for TPO action on the
ORDAS. If the non-compliance has a potential effect on the data, then the data should be
qualified according to the professional judgement of the reviewer and this should be noted in the
data review narrative.
2. If resolution criteria are not met, then the quantitative results may not be accurate due to peak
overlap and lack of adequate resolution. Positive sample results for compounds that were not
adequately resolved should be qualified with "J". Qualitative identifications may be questionable
if coelution exists. Non-detected target compounds that elute in the region of coelution may not
be valid depending on the extent of the coelution problem. Professional judgement should be
used to qualify data as unusable (R).
3. If the %RSD linearity criteria are not met for the compound(s) being quantified, qualify all
associated positive quantitative results with "I". When the %RSD is grossly exceeded (i.e.,
> 50%), use professional judgement for qualifying non-detects as "UJ".
4. Potential effects on the sample data due to problems with calibration should be noted in the data
review narrative. If the data reviewer has knowledge that the laboratory has repeatedly failed to
comply with the requirements for frequency, linearity, retention time, or resolution, mis
information should be documented in the report narrative.
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PEST
IV. Continuing Calibration
A. Review Items: Form VH PEST-I and 2, Form Vffl PEST, chTOmatograms, and data system
printouts.
B. Objective
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data. Continuing calibration
checks and documents satisfactory performance of the instrument over specific time periods during
sample analysis. To verify the calibration and evaluate instrument performance, continuing
calibration is performed, consisting of the analyses of instrument blanks, the PEM, and the midpoint
concentration of Individual Standard Mixtures A and B.
C. Criteria
1. An instrument blank and the PEM must bracket one end of a 12-hour period during which
samples are analyzed, and a second instrument blank and the midpoint concentration of Individual
Standard Mixtures A and B must bracket the other end of the 12-hour period.
2. The resolution between any two adjacent peaks in the midpoint concentration of Individual
Standard Mixtures A and B must be greater than or equal to 90.0 percent.
3. The absolute retention time for each single component pesticide and surrogate in the midpoint
concentration of Individual Standard Mixtures A and B must be within the retention time windows
determined from the initial calibration.
4. The RPD between the calculated amount and the true amount for each of the pesticides and
surrogates in the midpoint concentration of the Individual Standard Mixtures A and B must not
exceed 25.0 percent.
D. Evaluation
1. Check the Form VHI PEST to verify that die instrument blanks, PEMs, and Individual Standard
Mixtures were analyzed at the proper frequency and that no more than 12 hours elapsed between
continuing calibration brackets in an ongoing analytical sequence.
2. Check the data for the midpoint concentration of Individual Standard Mixtures A and B to verify
that the resolution between any two adjacent peaks is greater than or equal to 90.0 percent.
3. Check the data for each of the single component pesticides and surrogates in the midpoint
concentration of Individual Standard Mixtures A and B and Form VH PEST-2 to verify that the
absolute retention times are within the appropriate retention time windows.
4. Check that the data from the midpoint concentration of Individual Standard Mixtures A and B and
Form VII PEST-2 between the calculated amount and the true amount for each of the pesticides
and surrogates is less than or equal to 25.0%.
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Continuing Calibration PEST
E. Action
1. If die continuing calibration sequence was not followed as required, then professional judgement
must be used to evaluate the effect of the non-compliance on the sample data. If the requirements
for the continuing calibration sequence were not met, men this should be noted in the report
narrative. If the non-compliance has a potential effect on the data, then the data should be
qualified according to the professional judgement of the reviewer and mis should be noted in the
data review narrative.
2, If resolution criteria are not met then the quantitative results may not be accurate due to
inadequate resolution. Positive sample results for compounds that were not adequately resolved
should be qualified with T. Qualitative identifications may be questionable if coelution exists.
Non-detected target compounds mat elute in the region of coelution may not be valid depending
on the extent of the coelution problem. Professional judgement should be used to qualify data
as unusable (R).
%
3. Retention time windows are used in qualitative identification. If the standards do not fall within
the retention time windows, the associated sample results should be carefully evaluated. All
samples injected after the last in-control standard are potentially affected.
a. For the affected samples, check to see if the sample chromatograms contain any peaks that are
close to the expected retention time window of the pesticide of interest. If no peaks are
present either within or close to the retention time window of the deviant target pesticide
compound, then non-detected values can be considered valid. Sample data that is potentially
affected by the standards not meeting the retention time windows should be noted in the data
review narrative.
b. If the affected sample chromatograms contain peaks which may be of concern (i.e., above the
CRQL and either dose to or within the expected retention time window of the pesticide of
interest), then the reviewer should follow the guidelines provided in Section Q.E.2 to
determine the extent of the effect on the data.
4, If the RPD is greater man 25% for the compound(s) being quantified, qualify all associated
positive quantitative results with "J" and the sample quantitation limits for non-detects with "UJ"
when the RPD is grossly exceeded (i.e., >50%).
5. Potential effects on the sample data due to problems with calibration should be noted in the data
review narrative. If the data reviewer has knowledge mat the laboratory has repeatedly failed to
comply with the requirements for frequency, linearity, retention time, resolution, or DDT/Endrin
breakdown, the data reviewer should note this in the report narrative.
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PEST
V. Blanks
A. Review Items: Form I PEST, Form IV PEST, chromatograms, and data system printouts.
B. Objective
The purpose of laboratory (or field) blank analyses is to determine the existence and magnitude of
contamination problems resulting from laboratory (or field) activities. The criteria for evaluation of
laboratory blanks apply to any blank associated with the samples (e.g., method blanks, instrument
blanks, field generated blanks, and sulfur cleanup blanks). If problems with any blank exist, all
associated data must be carefully evaluated to determine whether or not mere 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 present in the blanks.
2. Frequency:
a. Method Blanks - A method blank analysis must be performed for each 20 samples of similar
matrix in each sample delivery group (SDG) or whenever a sample extraction procedure is
performed.
b. Instrument Blanks - An acceptable instrument blank must be run at least once every 12 hours
and immediately prior to the analysis of either the performance evaluation mixture or
Individual Standard Mixtures, A and B, depending on the place in the analysis sequence.
c. Sulfur Cleanup Blanks - A sulfur cleanup blank must be analyzed whenever part of a set of
samples extracted together requires sulfur cleanup. If the entire set of samples associated with
a method blank requires sulfur cleanup, men the method blank also serves the purpose of a
sulfur blank and no separate sulfur blank is required.
d. Field Generated Blanks - Equipment rinsate blanks and/or field blanks may be collected and
analyzed with each set of samples collected. The QAPjP will specify the type and frequency
for the collection of these blanks.
D. Evaluation
1. Review the results of all associated blanks.. Form I PEST and Form IV PEST, and raw data
(chromatograms and data system printouts) to evaluate the presence of target pesticides/PCBs.
2. Verify mat method blank analysis has been reported per SDG, per matrix, per concentration level,
for each GC system used to analyze samples, and for each extraction batch.
3. Verify that the method blank analyses do not contain any target pesticide or Aroclor/Toxaphene
at greater man its Contract Required Quantitation Limits (CRQL).
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Region ID ModiGc*tions
Blanks PEST
4. For the surrogates in each method blank, verify that the observed retention times are within the
appropriate retention time windows calculated from the initial calibration.
5, Verify that the instrument blank analysis has been performed every 12 hours as part of the
continuing calibration and following a sample analysis which contains an analyte(s) at high
concentration(s), and that the instrument blanks do not contain any target analytes above one-half
the CRQL, assuming that die material in the instrument resulted from the extraction of a 1-L
water sample.
6. Verify that the sulfur cleanup blanks were analyzed at the required frequency and that they do not
contain any target compound above the CRQL, assuming that the material in the instrument
resulted from the extraction of a 1-L water sample. If a separate sulfur cleanup blank was
prepared, one version of Form IV PEST should be completed associating all the samples with the
method blank, and a second version of Form IV PEST should be completed listing only those
samples associated with the separate sulfur cleanup blank.
E. Action
If the appropriate blanks were not analyzed with die frequency described in Section V.C.2, 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.
Action in the case of unsuitable blank results depends on the circumstances and the origin of the
blank. Detected compound results should be reported and qualified "B" if the concentration of the
compound in the sample is less than or equal to 5 times (Sx) die amount in the blank. In instances
where more man 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. For
qualification purposes, to determine the highest concentration of a contaminant, consider all blanks
in a case associated with all samples, except for instrument blanks, which only affect the samples
bracketed by the contaminated instrument blank. The results must not be corrected by subtracting
the blank value.
Specific actions are as follows:
1. If a target pesticide or Aroclor/Toxaphene is found in die blank but not found in the samples),
no qualification is required. If the contaminants) is found at level(s) significantly greater than
the CRQL, then this should be noted in the report narrative.
2. Any pesticide or Aroclor/Toxaphene detected in the sample, that was also detected in any
associated blank, is qualified "B" if the sample concentration is less than five times (5x) the blank
concentration.
The reviewer should note mat analyte concentrations calculated for method 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 "Sx" criteria, such that a comparison of the
total amount of contamination is actually made.
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Region m Modification!
Blanks PEST
Additionally, there may be instances when little or no contamination was present in die associated
blanks, but qualification of die sample was deemed necessary. Contamination introduced through
dilution is one example. Although it is not always possible to determine, instances of mis
occurring can be detected when contaminants are found in the diluted sample result, but 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 mat die
contamination is from a source other man die sample, he/she should qualify die data. In this
case, die "Sx" rule does not apply, die sample value should be reported and qualified "B" and a
note should be added to die narrative.
3. If gross contamination exists (i.e., saturated peaks), all affected compounds in the associated
samples should be qualified as unusable (R), due to interference. This should be noted in die data
review narrative if die contamination is suspected of having an effect on me sample results.
4. If inordinate amounts of other target pesticides or Aroclors/Toxaphene are found at low levels in
die blank(s), it may be indicative of a problem at the laboratory and should be noted in the data
revie6w narrative.
5. If an instrument blank was not analyzed following a sample analysis which contained an analyte(s)
at high concentration^), sample analysis results after the high concentration sample must be
evaluated for carryover. Professional judgement should be used to determine if instrument cross-
contamination has affected any positive compound identification(s), and if so, detected compound
results should be qualified. If instrument cross-contamination is suggested, dien diis should be
noted in die data review narrative if die cross-contamination is suspected of having an effect on
die sample results.
The following are examples of applying die blank qualification guidelines. Certain circumstances
may warrant deviations from these guidelines.
Example I: Sample result is greater than die CRQL, but is less dian die 5x multiple of me
blank result.
Sx
Blank Result 1.0
CRQL 0.5
Sample Result 4.0
Qualified Sample Result 4.0B
In diis case, sample results less man 5.0 (or 5 x 1.0) would be qualified as a blank
contaminant, "B".
Example 2: Sample result is less man die CRQL, and is also less man me 5x multiple of me
blank result.
22.
Blank Result 1.0
CRQL 0.5
Sample Result 0.4J
Qualified Sample Result 0.4B
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Region HI Modification*
PEST
Example 3: Sample result is greater than the 5x multiple of the blank result,
Blank Result
CRQL
Sample Result
Final Sample Result
1.0
0.5
10.0
10.0
In this case, die sample result exceeded the adjusted blank result (5 x 11) and the sample
result is not qualified.
6, In pesticide analyses by GC/EC, contractually compliant laboratory blanks can sometimes contain
interferences which obscure detection of target pesticide compounds (since the interfering
compound may not actually be a pesticide). If sample quantitation limits are flagged as biased
low (UL) or unreliable (R) due to interferences attributable to such laboratory blank
contamination, men mis issue should be addressed in the narrative.
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Region m Modifications
VI. Surrogate Spikes PEST
A. Review Items: Form 0 PEST, Form VE PEST, chromatograms, and data system printouts.
B. Objective
Laboratory performance on individual samples is established by means of spiking samples prior to
extraction and analysis to determine surrogate spike recoveries. All samples are spiked with
surrogate compounds prior to sample extraction to measure extraction efficiency. The evaluation of
the recovery results of these surrogate spikes is not necessarily straightforward. The sample itself
may produce effects due to such factors as interferences and high concentrations of target and/or non-
target 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. Two surrogate spikes, tetrachloro-m-xylene and decachlorobiphenyl, are added to all samples,
Individual Standard Matures, PEMs, blanks, and matrix spikes to measure their recovery in
sample and blank matrices.
2. The advisory limits for recovery of the surrogates tetrachloro-m-xylene (TCX) and
decachlorobiphenyl (DCB) are 60-150 percent for both water and soil samples.
3. The retention times of both of the surrogates in the PEM, Individual Standard Mixtures, and
samples must be within the calculated retention time windows. TCX must be within ± 0.05
minutes, and DCB must be within ± 0.10 minutes of the mean retention time determined from
the initial calibration.
D. Evaluation
1. Check raw data (e.g., chromatograms and data system printouts) to verify that the recoveries on
the Surrogate Recovery Form II PEST are accurate and within die advisory limits and mat die
retention times on the Pesticide Analytical Sequence Form vm PEST are accurate and within the
retention time limits.
2. Check that the surrogate spike recoveries were calculated correctly and free from transcription
errors.
3. If surrogate spike recoveries are not within limits, check the raw data for possible interferences
which may have affected surrogate recoveries.
4. If retention time limits were not met, check the raw data for possible misidentificauon of GC
peaks. Non-recovery of surrogates may be due to shite in RT.
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Region CO Modi6c*lioai
PEST
5. If low surrogate recoveries are observed, the reviewer should investigate whether the low
recoveries were a result of sample dilution.
6. In the special case of a blank analysis with surrogates out of specification, the reviewer must give
special consideration to the validity of associated sample data. Hie 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 die
batch show acceptable surrogate recoveries, the reviewer may choose to consider the blank
problem to be an isolated occurrence.
E. Action
1. If surrogate spike recoveries are outside of advisory limits (60-150%), the following guidance is
suggested. Professional judgement must be used in applying these criteria.
TABLE X - Guidance for qualifying data based on surrogate recoveries outside the advisory limits
(60-150%) but greater than 10%. In instances where detection limits require
qualification, the qualifier begins with a U and is listed hi the column titled "Value
reported from the column with non-conformance".
#of
outliers
1 out
2 out
3 out
4 out
Recovery
High
Low
2 high same column
2 low same column
Mixed same column -
2 high different column
2 low different column
Mixed different column
All high
All low
2 high 1 low
2 low 1 high
Other mix of
high and low
All high
All low
Mixed
Value reported from
the column with
non-conformance
No action
No action
K
L, UL
J,UJ
J
J,UJ
Prof, judgement
K
L, UL
K (2 high)
L, UJ (2 low)
J, UJ
K
L, UL
J,UJ
Value reported from
the column without
non-conformance
No action
No action
No action
No action
No action
Not applicable
Not applicable
Not applicable
Not applicable
Not applicable
J (1 low 2nd column)
J (1 high 2nd column)
Not applicable
Not applicable
Not applicable
Not applicable
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Regioa ID Modificitiotu
Surrogate Spikes PEST
a. If either pesticide surrogate recovery is reported >0% but <10%, the reviewer should
examine the sample chromatogram to assess the qualitative validity of the analysis. If low
surrogate recoveries are found to be due to sample dilution, then professional judgement
should be used to determine if the resulting data should be qualified. If sample dilution is not
a factor, then detected target compounds may be qualified "L", and non-detected target
compound results should be qualified unusable (R).
b. If zero pesticide surrogate recovery is reported, the reviewer should examine the sample
chromatogram to determine if the surrogate may be present, but slightly outside its retention
time window. If this is the case, in addition to assessing surrogate recovery for quantitative
bias, the overriding consideration is to investigate the qualitative validity of the analysis. If
the surrogate is not present, qualify all non detected target compounds as unusable (R).
2. If surrogate retention times in PEMs, individual standards, and samples are outside of the
retention time limits, qualification of the data is left up to the professional judgement of the
reviewer. Refer to section n E.2 for more guidance.
3. Potential effects of the data resulting from surrogate recoveries not meeting the advisory limits
should be noted in the data review narrative.
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Region m Modificalioai
PEST
VII. Matrix Spikes/Matrix Snike Duplicates
A. Review Items: Form in PEST-i and PEST-2, chromatograms, and data system printouts.
B. Objective
Data for Matrix spikes (MS) and Matrix spike duplicates (MSD) are generated to determine long-term
precision and accuracy of the analytical method on various matrices. These data alone cannot be used
to evaluate the precision and accuracy of individual samples. However, when exercising professional
judgement, MS/MSD 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 a frequency of at
least one MS and MSD per 20 samples of each matrix.
2. Matrix spike recoveries should be within die advisory limits provided on Form III PEST-1 and
PEST-2 and in Appendix A.
3. Relative percent difference (RPD) between MS and MSD recoveries must be within the advisory
limits provided on Form HI PEST-1 and PEST-2 and in Appendix A.
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 M PEST-1 and PEST-2 and verify that die
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 judgement 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.
2. The data reviewer should first try to determine to what extent die results of die MS/MSD affect
die associated sample data. The determination should be made with regard to die MS/MSD
sample itself, as well as specific analytes for all samples associated with the MS/MSD.
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Matrix Spikes/Matrix Spike Duplicates PEST
3. In some 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. For example, if die
recoveries for MS and MSD are consistently low for bom water and soil samples, mis could be
indicative of a systematic problem in the laboratory and recoveries should be examined in all
associated samples.
4. The reviewer must use professional judgement to determine the need for qualification of positive
results of non-spiked compounds.
5. When extremely low % recoveries are noted, qualify data for all affected compounds using
professional judgement.
6. When non-spiked compounds are present in either the MS or MSD results, a table in the data
review narrative is constructed showing original (unspiked) sample results for non-spiked
compounds, non-spiked compounds present in the MS and MSD and the calculated % RSD.
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Region ffl Modificuiam
Vin. Regional Quality Assurance and Quality Control PEST
A. Review Items: Form I PEST, chromatograms, Data system printouts, traffic reports and raw data
for Regional QC samples.
B. Objective
Regional Quality Assurance and Quality Control (QA/QC) refers 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 dependent on the type of QC sample. Frequency may vary.
1. The analytes present in the PE sample must be correctly identified and quantified.
D. Evaluation
1. Evaluation of Performance Evaluation (PE) Samples are not to be presented as part of the data
review. All forms associated with the Performance Evaluation Samples are to be sent (with a
cover memo stating the case number and laboratory information) directly to the Quality Assurance
Branch in Region HI:
U.S. Environmental Protection Agency
Region HI, Central Regional Laboratory
Quality Assurance Branch
201 Defense Highway, Suite 200
Annapolis, MD 21401
Attn: Program Support Section—
E, Action
1. Field duplicate results are to be presented in a table form in the data review narrative. If target
compounds were not present in either of the field duplicate samples, then a table is not required.
The percent difference is to be calculated and presented in the table. (If one of the field
duplicates was also used as a matrix spike/matrix spike duplicate sample, men the table should
include any non-spiked compounds detected, along with the % relative standard deviation.)
2. No action is taken based on percent difference of field duplicate sample data alone. However,
using informed professional judgement, the data reviewer may use the field duplicate results in
conjunction with other QC criteria and determine the need for some qualification of the data.
3. Other types of Regional QC Samples
Professional judgement is needed for evaluating other types of QC samples that may be associated
with a particular case of samples. This information may be used in conjunction with other QC
criteria to determine the need for qualification of data.
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PEST
IX. Pesticide Cleanup Checks
A. Review Items: Form DC PEST-1 and 2, chromatograms, and data system printouts.
B. Objective
Pesticide cleanup procedures are utilized to remove matrix interferences from sample extracts prior
to analysis. The use of the Florisil cartridge cleanup procedure significantly reduces matrix
interferences caused by polar compounds. Gel permeation ehroraatography (GPC) is used to remove
high molecular weight contaminants mat can interfere with the analysis of target analytes. Pesticide
cleanup procedures are checked by spiking the cleanup columns and cartridges and verifying the
recovery of pesticides through the cleanup procedure.
C. Criteria
1. Florisil Cartridge Cleanup
a. Florisil cartridges must be used for the cleanup of all sample extracts.
b. Every lot number of Florisil cartridges used for sample cleanup must be checked by spiking
with 2,4,5-trichlorophenol and the midpoint concentration of Individual Standard Mixture A.
These compounds are listed in Appendix A.
c. The lot of Florisil cartridges is acceptable if the recoveries for all of the pesticides and
surrogates in Individual Standard Mixture A are within 80 and 120 percent, if the recovery
of 2,4,5-trichlorophenol is less than 5. percent, and if no peaks interfering with the target
analytes are detected.
2. Gel Permeation Chromatography (GPC)
a. GPC is used for the cleanup of all SOU sample extracts and for water sample extracts mat
contain high molecular weight components that interfere with the analysis of the target
analytes.
b. At least once every 7 days, die calibration of the GPC unit must be checked by spiking with
two check mixtures: the matrix spiking solution and a mixture of 0.2 ug/mL Aroclors 1016
and 1260. The matrix spiking solution compounds for the GPC Check are:
Pesticide Ug/mL
gamma-BHC(Lindane) 0.5
4,4'-DDT 1.0
Endrin 1.0
Heptachlor 0.5
Aldrin 0.5
Dieldrb 1.0
100
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Region m Modification*
Pesticide Cleanup Checks PEST
c. The GPC calibration is acceptable if the recovery of the pesticides in the matrix spiking
solution are within 80 to 110 percent, and the Aroclor patterns should match those generated
for previously run standards.
d. A GPC blank must be analyzed after each GPC calibration and is acceptable if the blank does
not exceed one-half the CRQL for any target analytes.
D. Evaluation
1. Florisil Cartridge Check
Check the data from the Florisil cartridge solution analyses and the Form DC-PEST-1 and
recalculate some of the percent recoveries to verify mat the percent recoveries of the pesticides
and surrogates in Individual Standard Mixture A are within 80-120%, the recovery of 2,4,5-
trichloropheno! is less than 5%, and no interfering peaks are present. Compare the raw data to
the reported results and verify that no calculation or transcription errors have occurred.
2. Gel Permeation Chromatography (GPC)
Check the data from the GPC calibration check analyses and the Form DC PEST-2 and recalculate
some of the percent recoveries to verify that the percent recoveries of the pesticides in the matrix
spike solution are within 80-110% and that the Aroclor patterns are similar to those of previous
standards. Check to make sure that no transcription errors have occurred.
£, Action
1. If Florisil Cartridge Check criteria are not met, the raw data should be examined for the presence
of polar interferences and professional judgement should be used in qualifying the data. If a
laboratory chooses to analyze samples under an unacceptable Florisil Cartridge Check, then this
should be noted in the data review narrative.
2. If Gel Permeation Criteria are not met, the raw data should be examined for the presence of high
molecular weight contaminants and professional judgement should be used in qualifying the data.
If a laboratory chooses to analyze samples under an unacceptable Gel Permeation Criteria, then
8th is should be noted in the data review narrative.
3. If zero recovery was obtained for the pesticide compounds and surrogates during either check,
then the non-detected target compounds may be suspect and the data may be qualified unusable
(R).
4. If high recoveries (i.e., greater than 120%) were obtained for the pesticides and surrogates during
either check, use professional judgement to qualify detected target compounds as biased high (K).
Non-detected target compounds do not require qualification.
5, Potential effects on the sample data resulting from the pesticide cleanup analyses not yielding
acceptable results should be noted in the data review narrative.
101
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Region ID Modific*tkmi
PEST
X. Target Compound Identification
A. Review Items: Form I PEST, Form X PEST-1 and PEST-2, chromatograms, and data system
printouts,
B. Objective
Qualitative criteria for compound identification have been established to minimize the number of false
positives (reporting a compound present when it is not) and false negatives (not reporting a compound
mat is present).
C. Criteria
1. The retention times of both of the surrogates, matrix spikes, and reported compounds in each
sample must be within the calculated retention time windows on bom columns. TCX must be
within ± 0.05 minutes of the mean retention time determined from the initial calibration and
DCS must be within ± 0.10 minutes of the mean retention time determined from the initial
calibration.
2. GC/MS confirmation is required if the concentration of a compound exceeds 10 ng/uL in the final
sample extract. Pesticides mat are confirmed by GC/MS should be identified with a *C" in the
Q column on Form I PEST.
3. When no analytes are identified in a sample, the chromatograms from the analyses of the sample
extract must use the same scaling factor as was used for the low point standard of the initial
calibration associated with those analyses,
4. Chromatograms must display single component pesticides detected in the sample and the largest
peak of any multicomponent analyte detected in the sample at less than full scale.
5. If an extract must be diluted, chromatograms must display single component pesticides between
10 and 100 percent of full scale, and multicomponent analytes between 25 and 100 percent of full
scale.
6. For any sample, the baseline of the chromatogram must return to below 50 percent of full scale
before the elution time of alpha-BHC, and also return to below 25 percent of full scale after the
elution time of alpha-BHC and before the elution time of decachlorobiphenyl.
7. If a chromatogram is replotted electronically to meet these requirements, the scaling factor used
must be displayed on die chromatogram, and both the initial chromatogram and the replotted
chromatogram must be submitted in the data package.
D. Evaluation
1. Review Form I PEST, the associated raw data (chromatograms and data system printouts) and
Form X PEST-1 and PEST-2. Confirm reported detected analytes by comparing the sample
102
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Region m Modification
Target Compound Identification PEST
chromatograms to the tabulated results and verifying peak measurements and retention times.
Confirm reported non-detected analytes by a review of the sample chromatograms. Check the
associated blank data for potential interferences (to evaluate sample data for false positives) and
check the calibration data for adequate retention time windows (to evaluate sample data for false
positives and false negatives).
2. For multi-component target compounds (Toxaphene and Aroclors), the retention times and relative
peak heights ratios of major component peaks should be compared against the appropriate
standard chromatograms.
3. Verify that GC/MS confirmation was performed for pesticide concentrations in the final sample
extract which exceeded 10 ng/uL.
E. Action
1, If the qualitative criteria for both columns were not met, all target compounds that are reported
detected should be considered non-detected. The reviewer may use professional judgement to
qualify reported compounds "N", tentatively identified, or "R", rejected. In the case of multi-
component compounds, the reviewer can accept the reported compound based on pattern
recognition and relative peak height ratios. The reviewer should use professional judgement to
assign an appropriate quantitation limit using the following guidance:
a. If the misidentified peak was sufficiently outside the target pesticide retention time window,
then the reported values may be a false positive and should be replaced with the sample CRQL
value.
b. If the misidentified peak poses an interference with potential detection of a target peak, then
the reported value should be considered and qualified as unusable (R),
2. If the data reviewer identifies a peak in both GC column analyses that falls within the appropriate
retention time windows, but was reported as a non-detect, then die compound may be a false
negative. Professional judgement should be used to decide if the compound should be included.
All conclusions made regarding target compound identification should be included in the data
review narrative.
3. If multi-component target compounds exhibit marginal pattern-matching quality, professional
judgement should be used to establish whether die differences are due to environmental
"weathering" (i.e., degradation of die earlier eluting peaks relative to die later eluting peaks).
If die presence of a multi-component pesticide is strongly suggested, results should be reported
as presumptively present (N). If an observed pattern closely matches more than one Aroclor,
professional judgement should be used to decide whether die neighboring Aroclor is a better
match, or if multiple Aroclors are present.
4. If it is determined that qualitative criteria for two-column confirmation were not met, all such data
should be reported as not detected and it should be clearly noted in die narrative.
103
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Region III Modification
Target Compound Identification PEST
5, When all qualitative criteria for identification have been met, single-peak pesticides which are not
confirmed by GC/MS should be noted in the narrative, indicating that supporting data may be
necessary to rely upon these results. If supporting data exist (site-related records, GC/MS
confirmations of other samples, etc.), the reviewer should discuss the type of supporting data in
the narrative. Whenever single-peak pesticides are confirmed by an acceptable GC/MS spectrum
and retention time match against standards, confirmation should be noted in the narrative.
104
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Region DI Modifiutioai
PEST
. CompOTnd QuanfMtUiQn and ReporteJ C
A. Review Items: Form I PEST, Form X PEST-i and PEST-2, sample preparation log sheets,
chromatograms, case narrative, and data system printouts.
B. Objective
The objective is to ensure that the reported quantitative results and contract required quantitation limits
(CRQLs) are accurate.
C. Criteria
Compound quantitation, as well as the adjustment of the CRQL, must be calculated according to the
equations provided in Appendix A (also found in Section D/Pest of the Statement of Work).
D. Evaluation
1. Raw data should be examined to verify the correct calculation of all sample results reported by
the laboratory. Data system printouts, chromatograms, and sample preparation log sheets should
be compared to the reported positive sample results and quantitation limits. Verify that die
sample values are reported correctly. Calculation errors can sometimes be revealed by
abnormally high surrogate recoveries, matrix spike recoveries, or inappropriately high results for
certain compounds.
2. Verify that the CRQLs have been adjusted to reflect all sample dilutions, concentrations, splits,
clean-up activities, and dry weight factors that are not accounted for by the method.
E. Action
1. Quantitation limits affected by large, off-scale peaks should be qualified as unusable (R). If the
interference is on-scale, the reviewer can provide an approximated quantitation limit (UJ) for each
affected compound.
Note: Single-peak pesticide results are checked for rough agreement between quantitative results
obtained by the two GC columns. The potential for co-elution should be considered and the
reviewer should use professional judgement to decide whether a much larger concentration
obtained on one column versus the other indicates the presence of an interfering compound.
If an interfering compound is indicated, professional judgement must be used to determine how
best to report, and if necessary, qualify die data. Contractually the lower of the two values
is reported.
2. 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 decide which value is the best value. Under these
105
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Rtgion HI Modification*
Compound Quantitation and Reported CRQLS PEST
circumstances, die reviewer may determine if qualification of the 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.
3. If the calculated concentrations of detected compounds do not agree ±25% on both columns,
qualify the reported value "J", estimated.
106
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Region HI Modification!
PEST
XII. Overall Assessment
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 die overall quality of the data.
Review all available materials to assess the overall quality of the data, keeping in mind the additive
nature of analytical problems
D. Evaluation
1. Evaluate any technical problems which have not been previously addressed.
2. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
3. If appropriate information is available, the reviewer may assess the useability of the data to assist
the data user in avoiding inappropriate use of the data. Review all available information,
including the QAPjP (specifically the Data Quality Objectives), SAP, and communication with
data user that concerns the intended use and desired quality of the data.
E. Action
1. Use professional judgement to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
2. Write a brief narrative to give the user an indication of the analytical limitations of the data. 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.
Reference the Region HI Data Validation Reports Requirements, found in Appendix B.
107
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APPENDIX A
CONTRACTUAL REQUIREMENTS AND EQUATIONS
MULTI-MEDIA, MULTI-CONCENTRATION - MM/MC
(OLM01.0)
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Region HI Modifications
APPENDIX A
MULTI-MEDIA, MULTI-CONCENTRATION
CONTRACTUAL REQUIREMENTS AM) EQUATIONS FOR VOLATILE DATA REVIEW
n. GC/MS Instrument Performance Check
Use equation n.l to verify that the laboratory has not made errors in the calculation of the percent
relative abundance.
% tetative Abundance = x m%
abundance of Y
For example, the percent relative abundance of m/z 96 (X) relative to m/z 95 (Y) is calculated as follows:
«*"•**» °/ ^ %
abundance of mjz 95
% Jfetofre Abundance - «*"•**» °/ ^ % * 100%
III. Initial Calibration
Data|^jejy_C.riterji; All volatile target compounds and system monitoring compounds must nave a
Relative Response Factor (RRF) of greater than or equal to 0.05 and a percent relative standard deviation
(%RSD) of less man or equal to 30%.
Contractual Criteria: The maximum %RSD for volatile compounds is 20.5% and the minimum RRF
criteria vary as specified in Table A.I (The volatile compounds listed separately in Table 2 on page 13
are not contractually required to meet a maximum %RSD but do nave to meet a contractual minimum
RRF of 0.010). The contractual criteria for an acceptable initial calibration specifies mat 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%.
Table A-l Minimum RRF Criteria for Volatile Target Compounds
Volatile Minimum
Compound RRP
Broroomethane 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-TnchJoroethane 0.100
Carbon tetracMoride 0.100
Bromodichloromethane 0.200
cis-t,3-Dichloropropene 0.200
A-l
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Region in Modification*
MM/MC APPENDIX A
Table A.I Minimum RRF Criteria for Volatile Target Compounds (continued)
Volatile Minimum
Compound EKE
Trichloroethene 0.300
Dibromochloromethane 0.100
1,1,2-Trichloroethane 0.100
Benzene 0.500
trans-1,2-Dichloropropene 0.100
Bromofonn 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 ELI and ffl.2
c*
where:
IMF, = "i'th Relative Response Factor
A a: Area of the characteristic ion (EICP) measured
C = Concentration
is - Internal standard
x = Analyte of interest
The %RSD is calculated using equations EQ.3 and QI.4.
a *
N
A-2
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Region ffl Modificationi
MM/MC APPENDIX A
%RSD - ^ Jt 100 (777.4)
x
where:
a = Standard deviation of 5 relative response factors
I = 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% criterion.
Contractual Criteria: The percent difference (%D) between the initial calibration RRF and the continuing
calibration RRF is ± 25% for all compounds listed in Table A.l, The contractual criteria for an
acceptable continuing calibration specified that up to aqyJE 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 HL1.
The %D between initial calibration RRF and continuing calibration RRF is calculated using equation
IV. 1.
RRK-KRF
% D - ' * x 100% (IK1)
RRF
where:
RRF, = 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 % Recovery Limits
Water Samples Soil Samples
SMC1 Toluene-d, 88-110 84 -138
SMC2 Bromofiuorobenzene 86 -115 59-113
SMC3 l,2-Dichloroethane-d4 76-114 70 -121
A-3
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Region m ModificatioW
MM/MC APPENDIX A
Use equation VI.l to check that the system monitoring compound recoveries were calculated correctly:
% Recovery .
Concentrationjamoura spiked
VH. Matrix Spikes/Matrix Spike Duplicates
Hie matrix spike/matrix spike duplicate contractual requirements are listed in Table A.3.
Table A3 MS/MSD Contractual Requirements
Compound %R - Water %R - Soil RPD - Water RPD - Soil
U-DicMoroethene 61 -145 59-172 £ 14 £22
Trichloroetliene 71 -120 62 -137 £ 14 £24
Benzene 76-127 66-142 £11 £21
Toluene 76-125 59-139 £13 £21
CMorobenzene 75 -130 60 - 133 £ 13 £21
Verity that the matrix spike recoveries and RPD were calculated correctly using equations VH.1 and
VTL2.
% Recovery - SSR " SR x 100% (WO)
ura
where:
SSR = Spiked sample result
SR - Sample result
SA = Spike added
where:
RPD = Relative percent difference
MSR = Matrix spike recovery
MSDR= Matrix spike duplicate recovery
A-4
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Region ED Modification*
MM/MC APPENDIX A
IX. Internal Standards
Table A.4 contains the volatile internal standards and their corresponding target compounds. These
criteria nave 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.
Chloromethane 1,1,1-Trichloroethane 2-Hexanone
Bromomethane Carbon tetrachloride 4-Methyl-2-pentanone
Vinyl chloride Bromodichloromethane Tetrachloroethene
Chloroethane Bromoform 1,1^^-Tetrachloroethaoe
Methylene chloride 1,2-DichJoropropane Toluene
Acetone trans-l,3-Dichloropropene Chlorobenzene
Carbon disulfide Trichloroethene Ethylbenzene
1,1-Dichloroethene Dibromochloromethane Styrene
1,1-Dichloroethane 1,1,2-Trichloroethane Total Xylenes
1,2-Dichloroethene (total) Benzene BromofluorDbenzEne{SMQ
Chloroform cis-l,3-Dichloropropene Toluene-d, (SMC)
1,2-Dichloroethane Bromoform
2-Butanone
l,2-DichJoroethane-d4 (SMC)
SMC - System Monitoring Compound
XI. Compound Quantltatlon and Reported Contract Required Quantitatlon Limits (CRQLs)
Check die reported positive sample results and quantitation limits with die quantitation lists and
chromatograms using equations XI. 1, XI .2, or X1.3. Characteristic bus 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*
A, x L x Df
Concentration for low level soils:
(Dry weight basis)
^ " A^xRKFx WtxD *
A-5
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Region HI Modifications
MM/MC APPENDIX A
Concentration for medium level soils:
(Dry weight basis)
A, x I, x Vt x 1000 x Df
where:
A. = area of characteristic loo (EICP) for compound being measured
Aj, = area of characteristic ion (EICP) for the internal standard
I, = amount of internal standard added (ng)
RRF = daily response factor for compound being measured
V, = volume of water purged (ml)
W. = weight of sample (g)
D = (100 - % moisture)/100%
V, = volume of memanol (ml)*
V, = volume of extract added (ul) for purging
Dr = dilution factor**
V, = 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 analysts of soil/sediment samples for volatiles by the medium level method
is defined as the ratio of the number of microliters (ul) of memanol added to the reagent water
for purging (VJ to the number of mictoliters of the metnanol extract of the sample contained in
volume V.. If no dilution is performed, then the dilution factor equals 1.0.
The CRQL for a diluted sample should be calculated as follows:
Ad/ustedCRQL - Non-adjustedCRQL x Sample Dilution Factor (X1.4)
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:
1000C/ « IOC? x
The CRQL adjustment for dry weight for a soil sample should be calculated as follows:
Dry Weight CSQL
- .
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:
1QU
100
A-6
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MM/MC
Region ID Modiftcotioni
APPENDIX A
Table A.5 Characteristic Ions for Volatile Target Compounds
Analyte
CnJoromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1 , 1 -Dichloroethene
1 , 1 -D ichloroethane
1,2-Diehloroetfaene
Chloroform
1 ,2-Dichloroethane
2-Butaoone
1,1, 1-Tr ichloroethane
Carbon tetrachloride
BromodichJoroemethane
1 , 1 ,2 ,2-TetrachJoroethane
1 .2-Dichloropropane
trans- 1,3-Dichloropropene
Trichloroethene
Dibromochloromethane
1 , 1 ,2-Trichloroethane
Benzene-
els- 1 ,3-Dichloropropene
Bromofonn
2-Hexanone
4-Methyl-2-pentanone
Primary Ion*
50
94
62
64
84
43
76
96
63
96
83
62
43**
i 97
117
83
83
63
75
130
129
97
78
75
173
43
43
Secondary Ion(s)
52
%
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-7
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MM/MC
Region ID Modification*
APPENDIX A
Table A.5 Characteristic Ions for Volatile Target Compounds (Continued)
Analyte
Tetrachloroethene
Toluene
Chlorobenzene
Ethyl benzene
Styrene
Total Xylenes
Primary Ion* II Secondary Ion(s)
164
91
112
106
104
106
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
1 ,2-Dichloroethane-d4
Toluene-d,
Bromochloromethane
1 ,4-Difluorobenzene
Chlorobenzene-dj
95
65
98
INTERNAL STANDARDS
128
114
117
174, 176
102
70, 100
49, 130, 51
63,88
82,119
A-8
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Region HI Modifications
APPENDIX A
MULTI-MEDIA, MULTI-CONCENTRATION
CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR SEMIVOLATILE DATA REVIEW
n. GC/MS Instrument Performance Check
Use equation II. I 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:
or D i ^ JL j abundance of mlz 443 tnna
% Relative Abundance ~ - l — — - x 100%
abundance of mlz 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 tor 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-Chloroethyl)ether 0.700
2-Chlorophenol 0.800
1 .3-Dichlorobenzene 0.600
1 .4-Dichlorobenzene 0.500
I.2-Dichlorobenzene 0.400
2-Methylphenol 0.700
4-Methylphenol 0.600
N-Nitroso-di-n-propyiamine 0.500
Hexachloroethane 0.300
Nitrobenzene 0.200
Isophorone 0.400
2-Nitrophenol 0.100
2, 4-Dimethy (phenol 0.200
bis(-2-Chloroethoxy)methane 0.300
A-9
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Region HI Modifications
MM/MC APPENDIX A
Table A.7 Minimum RRF Criteria for Semivolalile Target Compounds (Continued)
Semi volatile Minimum
Compounds RRF
2,4-Dichlorophenol 0.200
1,2,4-Trichlorobenzene 0.200
Naphthalene 0.700
4-Chloro-3-methylphenoi 0.200
2-MethylnaphthaJene 0.400
2,4,6-Trichlorophenol 0.200
2,4,5-Trichlorophenol 0.200
2-ChIoronaphthalene 0.800
Acenaphthylene 1.300
2,6-Dinitrotoluene 0.200
Acenaphthylene 0.800
Dibenzoftiran 0.800
2,4-Dinitrotoluene 0.200
4-ChorophenyI-phenyIether 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
lndeno(l,2,3-cd)pyrene 0.500
Dibenz(a,h)anthracene 0.400
Benzo(g,h,i)perylene 0.500
Nitrobenzene-d, 0.200
2-FluorobiphenyI 0.700
Terpheny!-dw 0.500
Phenol-d, 0.800
2-FluorophenoJ 0.600
2-Chlorophenol-d4 0.800
1,2-Dichiorobenzene-d4 0.400
Initial calibration RRF and RRF are calculated using equations III. 1 and III.2; %RSD is
calculated using equations III.3 (pg.A-2, Appendix A) and III.4 (pg.A-3, Appendix A).
A-10
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Region 10 Modifications
MM/MC APPENDIX A
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_4jemivolatile 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 ID. 1
(reference p.A-2), and evaluate the %D between initial calibration RRF and continuing calibration RRF
using equation IV.I (reference p.A-3).
VI. Surrogate Spikes
The semivolatile surrogate compounds and their contractual recovery limits are listed in Table A.8.
Table A.8 Semivolatile Surrogate Requirements
Surrogate %Recovery Limits
Water Samples Soil Samples
SI Nitrobenzene-d, 35 - 144 23 - 120
S2 2-Fluorobiphenyl 43 - 116 30 - 115
S3 Terphenyl-d14 33 - 141 18 - 137
S4Phenol-d< 10-110 24-113
S5 2-Fluoprophenol 21-110 25 - 121
S6 2.4.6-Tribromophenol 10 - 123 19 - 122
S7 2-Chlorophenol-d4 33 - 110* 20 - 130*
s8 U-Dichlorobenzene-d, 16-110* 20-130*
* Advisory limits
Use equation VI. I to verify that the surrogate recoveries were calculated correctly.
VII. Matrix Spikes/Matrix Spike Duplicates
The matrix spike/matrix spike duplicate contractual requirements are listed in Table A.9.
Verify that the matrix spike recoveries and RPD were calculated correctly using equations VII. 1 and
VU.2. (Reference p.A-4)
DC. Internal Standards
Table A. 10 contains the semivolatile internal standards and their corresponding target compounds.
A-ll
-------
Region IQ Modifications
MM/MC APPENDIX A
Table A.9 Semivolatile MS/MSD Contractual Requirements
Compound %R - Water %R - Soil RPD - Water RPD - Soil
'k
Phenol 12-110 26-90 £42 £35
2-CUorophenol 27 - 123 25 - 102 £40 £50
1,4-DicMorobenzene 36-97 28-104 £28 £27
N-Nitroso-di-n-proplyamine 41-116 41-126 £38 £38
1,2,4-TriehJorobenzene 39 - 98 38 - 107 £28 £23
4-Chloro-3-methylphenoI 23 - 97 26-103 £42 £33
Acenaphthene 46-118 31-137 £31 £19
4-Nitrophenol 10-80 1! - 114 £50 £50
2,4-DJnitrotoIuene 24-96 28-89 £38 £47
Pentachlorophenol 9 - 103 17 - 109 £50 £47
Pyrene 26 - 127 35-142 £31 £36
A-12
-------
MM/MC
Region III Modifications
APPENDIX A
Table A.10 Semivolatile Internal Standards and Their Corresponding Target Compounds
1,4-Dichlorobenzene-d4
Naphthalene-dg
Acenaphthene-d
10
Phenol
bis(2-Chloroethyl)ether
2-ChJorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
2,2*-oxybis-( 1 -Chlorapropane)
4-Methylphenol
N-Nitroso-Di-n-propylamine
Hexachloroethane
2-FIurorophenol (SUIT)
PhenoWj (surr)
2-Chloroben2ene-d4 (surr)
1,2-Dichlorobenzene-d4 (surr)
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-DimethyIphenol
bis(2-Chioroethoxy)methane
2,4-DiehlorophenoI
1,2,4-Triehlorobenzene
Napththalene
4-ChIoroaniline
Hexachlorohutadiene
4-Chloro-3-methylphenol
2-Methy I naphthalene
2-Nitrobenzene-d, (SUIT)
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
2-NitroIaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitroto!uene
2,6-Dinitrotoluene
Diethyl phthalate
4-Chlorophenyl-phenyl ether
Fluorene
4-Nitroaniline
2-FluorobiphenyI (SUIT)
2,4,6-TribromophenoI (surr)
Phenanthrene-d
10
Chrysene-d12
Perylene-d,2
4,6-Dinitro-2-methylphenoI
N-Nitrosodiphenylamine
4-Bromophenyl pheoyl ether
H exachlorobenzene
Pentachlorophenol
Phenanthrene
Carbazole
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butylbenzyl phthalate
3-3*-Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Terphenyl-d,4 (surr)
Di-n-octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(l ,2,3-«l)
Dibenz(a,h)anthracene
Benzo(g,h ,i)perylene
surr = surrogate compound
A-13
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Region III Modifications
MM/MC APPENDIX A
XI. Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)
Check the reported positive sample results and quantitation limits with the quantitation lists and
chromatograms using equations XI.6, XI.7, or XI,8 below. Equation X1.4 (reference p.A-6) should be
used to adjust the CRQL for a diluted sample, and equation XI.S should be used to adjust the CRQL for
a soil sample. Characteristic ions for semi volatile 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 Arolclors are contained in Table A. 13.
Concentration for waters:
A, x L x Vt x Df
Concentration for soils/sediments:
(Dry weight basis)
x
where:
Ax = area of characteristic ion (EICP) for compound being measured
Aj, = area of characteristic ion (EICP) for the internal standard
I, — amount of internal standard added (ng)
RRF = daily relative response factor for compound being measured
V0 = volume of water extracted (MI)
Vj = volume of extract injected (Ul)
V, = volume of concentrated extract (Ul)
Df = dilution factor*
D = (100 - % moisture)/ 100%
W. = 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.S. If no dilution is performed, then the dilution
factor equals 1.0.
nf uL of the most concentrated extract used * uL of dean solvent /vro\
JJT s - * - _ - — — - - - f - - - \Al.O)
uL of the most concentrated extract used
A-14
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Region ID Modification*
MM/MC APPENDIX A
Table A.11 Characteristic Ions for Semivolatile Target Compounds
Analyte | Primary Ion | Secondary Ion(s)
Phenol 94
bis(2-Chloroethyl)ether | 93
2-ChlorophenoI
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
2-Methylpheaol
2,2'-oxybis(l -Chioropropane)
4-MethylphenoI
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2.4-Dimethylphenol
bis(2-Chloroethoxy)methane
2,4-DichlorophenoI
1 ,2 ,4-Trichlorobenzene
Naphthalene
4-Chloroaniliiie
Hexachlorobutadiene
4-Chloro-3-methyIpheQol
2-Methylnaphthalene
Hexachlorocydopentadiene
2,4,6-TrichlorophenoI
2,4,5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline .
128
146
146
146
108
45
108
70
117
77
82
139
107
93
162
180
128
127
225
107
142
237
196
1%
162
65
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
128, 127
129
223, 227
144, 142
141
235,272
198, 200
198, 200
164, 127
92,138
A-15
-------
MM/MC
Regkm HI Modifications
APPENDIX A
Table A.11 Characteristic Ions for SemivolatUe Target Compounds (Continued)
Parameter
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethylphthalate
4-ChJorophenyl-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'-DichJorobenzidine
Benz(a)anthracene
bis(2-Ethylhexyl)phthalate
Primary Ion II Secondary Ion(s)
163
152
138
153
1*4
109
168
165
165
149
204
166
138
198
169
248
284-
266
178
178
167
149
202
202
149
252
228
149
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
229, 226
167, 279
A-16
-------
MM/MC
Region m Modification*
APPENDIX A
Table A.11 Characteristic Ions for Semivolatile Target Compounds (Continued)
Analyte
Chrysene
Di-n-Octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo{a)pyrene
Indeno(l , 2,3-cd)pyrene
Dibenz(a,h)authracene
Benzo(g,h,i)perylene
Primary Ion
228
149
252
252
252
276
278
276
Secondary Ion(s)
226, 229
—
253,125
253, 125
253, 125
138, 227
139, 279
138, 277
A-17
-------
Region ID Modifications
MM/MC APPENDIX A
Table A.12 Characteristic Ions for Semivolatile Surrogates and Internal Standards
Analyte | Primary loo
[ Secondary Ion(s)
SURROGATES
Phenol-d3
2-Fluorophenol
2,4,6-Tribromophenol
Nitrobenzene-d,
2-Fluorobiphenyl
Terphenyl
2-Chlorophenol-d^
1 ,2-Dichlorobenzene-d4
1 .4-DicbJorobenzene-d4
Naphthalene-
-------
MM/MC
Region ID Modification*
APPENDIX A
Table A.13 Characteristic Ions for Pesticides/Arodors
Analyte
aipha-BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
Heptachlor
Aldrin
HeptachJor expoxide
Endosulfan I
Dieldrin
4,4'-DDE
Endrin
Endrin ketone
Endrin aldehyde
Endosulfan n
1,4'-DDD
Endosulfan sulfate
4,4'-DDT
Methoxychlor
Chlordane (alpha and/or gamma)
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-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-19
-------
Region in Modifications
MM/MC APPENDIX A
Calibration standards are prepared at a minimum of five concentration levels (20, 50, 80, 120, and 160
total ng). Eight compounds listed below require only a four-point initial calibration at 50, 80, 120 and
160 total ng.
2,4- Dinitro phenol 4- Nitroaniline
2,3,4 - Trichlorophenol 4 - Nitrophenol
2 - Nitroaniline 4,6 - Dinitro-2-methylphenol
3 - Nitroaniline Pentachlorophenol
A-20
-------
Region HI Modifications
APPENDIX A
MULTI-MEDIA, MULTI-CONCENTRATION
CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR PESTICIDE DATA REVIEW
Q. GC/ECD Instrument Perfonnance Check
Check the Perfonnance Evaluation Mixture calculations to ensure correct calculation of DDT and Endrin
breakdown. When using equations 0.2 and 0.3, values for the amount found and the amount injected
should be reported in nanograms (ng). The breakdown of DDT and Endrin in both of the PEM injections
must be less than 20.0 percent, and the combined breakdown of DDT and Endrin must be less than 30.0
percent.
% Breakdown DDT - *™»»* P™* {DDD+DDE) x 100
Amount of DDT injected
% Breakdown Ewfrin = *""""* •*"""* (J5afriB oldg/^fe * Eadrin ****"**> * 10° (ff.3)
Amount of Endrin injected
Combined % Breakdown = % Breakdown DDT + % Breakdown Endrin (17.4)
All peaks in both injections of the Performance Evaluation Mixture must be 100 percent resolved on bom
columns. The relative percent difference of the calculated amount and the true amount for each of the
single component pesticides and surrogates in the PEMs must be less man or equal to 25.0 percent using
equation O.5.
|C - C^J
** x 100
Where:
= True concentration of each analyte
~ Calculated concentration of each analyte from the analysis of the standard
A-21
-------
Region DB Modification*
APPENDIX A
ID. Initial Calibration
Retention time windows for each analyte and surrogate are calculated using Table A. 14, Windows are
centered around the mean absolute retention time for die analyte established during the initial calibration.
For example, for a given pesticide die mean retention time is first determined from the initial calibration
is found to be 12,69 minutes. The retention time window for this pesticide is ± 0.05 minutes.
Therefore, the calculated retention time window would range from 12.64 to 12.74 minutes.
Table A.14 Retention Time Windows for Pesticide Target Compounds
Pesticide Compounds Retention Time Windows in Minutes
alpha-BBC ±0.05
beta-BHC ±0.05
gamma-BBC ±0.05
delta-BBC ±0.05
HepatachJor ±0.05
Aldrin ±0.05
alpha-Chtordane ±0.07
gamma-Chlordane ±0.07
Heptachlor epoxide ±0.07
Dieldrin ±0.07
Endrin ±0.07
Endrin aidehyde ±0.07
Endrin ketone ±0.07
ODD ±0.07
DDE ±0.07
DDT . ±0.07
Endosulfan I ±0.07
Endosulfan n ±0.07
Endosulfan sulfate ±0.07
Methoxychlor ±0.07
Aroclors ±0.07
Toxaphene ±0.07
Tetrachloro-m-xylene ±0.05
Decachlorobiphenyl ±0.10
A-22
-------
Region ID Modification*
APPENDIX A
Hie % RSD of the calibration factors for each single component target must be less than or equal to 20.0
percent. The % RSD for toe two surrogates must be less than or equal to 30.0 percent. Up to two single
component target compounds per column may exceed the 20.0 percent limit for % RSD, but those
compounds must nave a % RSD of less man or equal to 30.0 percent. Calibration factors are calculated
using equations HI. 5 and ffl.6 and the % RSD is calculated using equations in. 3 and DI.4.
%KSD . x joo (Jff.3)
Mean
where,
Standard Deviation - |— f/2 (flf.4)
Where:
5i = each individual value used to calculate the mean
x = the mean of n values
n — me total number of values
Area of the Standard
"— - - -
mass injected
n
SF-E ^
i-I *
Where: _
CF = Mean calibration factor of a n values
CF, = i* calibration factor
n = Total number of values
IV. Continuing Calibration
The retention time (RT) for each target compound and surrogate must be within RT window as calculated
above using the mean absolute RT established during the three-point initial calibration. The relative
percent difference of the calculated amount and the true amount for each of the compounds in the mid
point concentration of the individual Standard mixtures must be less than or equal to 25.0 percent, using
equation D.S.
A-23
-------
Region ffl Modifications
APPENDIX A
VI. Surrogate Spikes
The advisory limits lor recovery of tetrachloro-m-xylene (TCX) and decachlorobiphenyl (DCB) are 60-
150 percent for both water and soil samples. The surrogate percent recovery is calculated using equation
VI. 1 . The retention time of bom surrogates must be within the calculated retention time windows, i.e.,
TCX must be within ±0.05 minutes of the mean retention time determined from the initial calibration
and DCB must be within ±0.10 minutes of the mean retention time determined from the initial
calibration.
J
Surrogate Percent Recovery « — - x 100
v«
Where:
Qi = Quantity determined by analysis
Q, = Quantity added to sample/blank
A-24
-------
Region HI Modifications
APPENDIX A
VH. Matrix Spikes/Matrix Spite Duplicate
Tie matrix spike/matrix spike duplicate recovery and RPD requirements are listed in Table A. 15. The
matrix spike recoveries and RPD are calculated using equations VQ.l and VH.2.
Table A. IS MS/MSD Contractual Requirements
Compound
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4'-DDT
% Recovery
Water
56-123
40-131
40-120
52-126
56-121
38-127
RPD
Water
15
20
22
18
21
27
% Recovery
Soil
46-127
35-130
34-132
31-134
42-139
23-134
RPD
Soil
50
31
43
38
45
50
Spike Recovery
SSR-SR
SA
x 100
Where:
SSR - Spike sample result
SR = Sample result
SA = Spike added
RPD
\MSR - MSDR\
1/2 (MSR + MSDR)
100
(VU2)
Where:
RPD = Relative percent difference
MSR = Matrix spike recovery
MSDR = Matrix spike duplicate recovery
The vertical bars in me formula above indicate the absolute value of the
difference, hence RPD is always expressed as a positive value.
A-25
-------
Region ID Modifications
APPENDIX A
IX. Pesticide Cleanup Check
Every lot number of Florisil cartridges used for sample cleanup must be checked by spiking with 2,4,5-
trichlorophenol and midpoint concentration of Individual Standard Mixture A. Hie recoveries for all of
die pesticides and surrogates in Individual Standard Mixture A must be within 80 to 120 percent, the
recovery of 2,4,5-trichJorophenol must be less than 5 percent, and no peaks oust interfere with the target
analytes. Percent recovery is determined using equation DLL
Percent Recovery - — x 100 (/X.I)
Where:
Q4 = Quantity determined by analysis
Q. — Quantity added to sample/blank
The gel permeation chromatography (GPC) apparatus must be calibrated every 7 days. The calibration
is acceptable if the recovery of each single component analyte is within 80-110 percent and the Aroclor
patterns match patterns previously generated by standards.
X. Target Compound Identification
Retention times of surrogates, matrix spikes, and reported compounds must fall within the retention time
windows established using the initial three-point calibration.
A-26
-------
Region in Modifications-
APPENDIX A
XI. Compound Quantitation and Reported CRQLs
The concentration of the single component pesticides are calculated using equations XI. 1 and XI.2, as
appropriate. The dilution factor for both soil and water samples is calculated using equation XI.3 and
the adjusted CRQL is calculated using equation XI.4. Equation XI.5 is used to adjust the CRQL for the
sampies's dry weight. The percent difference (%d) is calculated comparing calculated concentrations for
both columns using equation XI.6.
Concentration for water samples:
Concentration uglL = ^ ^ ' (JO.l)
Where:
A, = Area of the peak for the compound to be measured.
CF = Calibration factor for the mid point concentration external standard (area per ng).
V0 = Volume of water extracted in milliliters (mL).
V; = Volume of extract injected in micro!iters (uL). (If a single injection is made on
to two columns, use one half the volume in the syringe as the volume injected
on to each column.)
Vt = Volume of the concentrated extract in microliters (uL) (this volume must be
10000 uL, see Section E, 7.2.3).
Df = Dilution Factor. The dilution factor for analysis of water samples by this method
is defined as follows:
uL most cone, extract used for dilution + uL clean solvent ty. ^
uL most cone, extract used for dilution
If no dilution is performed, Df = 1.0
If GPC is performed on a water sample extract, V, becomes 5000 uL, and a factor of 2
must be added to the numerator, as described below for soil/sediment samples.
A-27
-------
Region M Modifications
APPENDIX A
Concentration for soil samples (Dry weight basis)
Concentration ug/Kg * (XI.2)
Where:
A, and CF are as given for water, above,
Vt =< Volume of the concentrated extract in microliters (uL) (this volume must be 5000
uL, see Section n, 7.2.3)
V; = Volume of extract injected in microliters (uL) (If a single injection is made on
to two columns, use one half the volume in the syringe as the volume injected
on to each column.)
D = 100 - % moisture
100
W. = Weight of sample extracted in grams (g).
Df = Dilution Factor. The dilution factor for analysis of soil samples by this method
is defined as follows:
Dilution factor (Dr):
n - «£ most cone, extract used for dilution + uL clean sovcnt .„. „.
f uL meat cone, extract used for dilution
If no dilution is performed, Df = 1.0.
The factor of 2.0 in the numerator is used to account for the amount of extract that is not
recovered from the mandatory use of GPC cleanup. Concentrating the extract collected
after GPC to 5.0 mL rather man 10.0 mL-for water samples not subjected to GPC (see
Section n. 7.2.3 in the CLP SOW OLM01.0 or subsequent revision), maintains the
sens|tiyi|y of die soil method comparable to that of the water method, but correction of
the numerical result is still required.
Dilution factor (Df):
n - "*• "»*** conc- extract used for dilution + uL clean solvent
f uL most conc. extract used for dilution
CRQL (Adjusted for dilution)
(CRQL) (D) = Adjusted CRQL (XI. 4)
Where:
CRQL = contract required quantitation limit
Df = Dilution factor
A-28
-------
Region ID Modificalkmi
APPENDIX A
CRQL (Adjusted for samples dry weight)
Where:
D = 100 - % moisture
100
CRQL = contract required quantitation limit
D, = dilution factor
If no dilution is performed, D, = 1.0
If a sample extract cannot be concentrated to the protocol-specified volume, this fact must be accounted
for in reporting the sample quantitation limit. (SOW: Exhibit C)
Percent difference:
ConcL
Where:
COUCH = The higher of the two concentrations for the target compound in question
= The lower of the two concentrations for the target compound in question
A-29
-------
-------
APPENDIX B
REGION III STANDARD OPERATING PROCEDURE
FOR DATA VALIDATION REPORTS
-------
-------
Appendix Bp
Page 1 of 6
ORGANIC DATA VALIDATION REPORT PREPARATION
1.0 Purpose
The purpose of this procedure is to establish a report format for organic
data review report writing according to EPA Region III protocol and is
based on and applies to organic data review level M3 only.
2.0 Discussion
After completion of data review, the data reviewer will be responsible
for compiling review notes and writing a report. The outline below
describes the steps to follow in preparing the organic data review
report.
3.0 Procedure
3.1 Organic Data Validation Narrative
The validation narrative is for the data user. Because the data
user may not be familiar with EPA abbreviations, it is necessary
to write out commonly used acronyms such as RAS, DAS, etc..
3.1.1 The first page of the report should be printed on
letterhead. The address of the report should include the
following information and be in the established format
for Region III, as:
Date: Month DO, YEAR (Date report is sent to EPA)
Subject: Organic Data Validation for Case {case #)
Site (write site name)
From: Reviewer Name Oversight Reviewer Name
Reviewer Title Reviewer Title
To: Remedial Project Manager
EPA Region III
3.1.2 Overview
The first section of the report is the overview, and is
presented in paragraph form after the title "OVERVIEW".
Information in this paragraph should include:
Case or DAS (Delivered Analytical Services) Number
Analytes
Number of samples
Matrix (or matrices and number of samples of each
matrix)
Number of QC samples (field and/or equipment blanks,
trip blanks, field duplicates, etc.)
- The SOW under which the laboratory performed the
analyses
Laboratory name and its CLP Code
A statement should also be made that the samples were
analyzed through the Contract Laboratory Program (CLP),
-------
Appendix B
Page 2 of 6
and whether they were performed as a Routine Analytical
Services (RAS) or Delivered Analytical Services (DAS).
If results exceeded the levels identified in the EPA
10-day Chemical Health A'dvisory Levels (Attachment A),
such exceedances are* mentioned in the overview
paragraph(s).
3.1.3 ««•»» »-y
The summary section, written below the title "SUMMARY",
is a general statement noting whether the samples were
successfully analyzed or if there were any analyses
determined unsuccessful (e.g., data were qualified
unusable}.
3.1.4 Maior Problems
After the section title, "MAJOR PROBLEMS", any problems
identified during the validation that seriously affect
data usability and any data that are qualified unusable,
"R", is noted in this portion of the narrative.
Identification of the support documentation included in
the appendices of the report (see Section 3.1.8) which
identifies each problem is referenced. Each identified
problem is reported in a separate paragraph.
NOTE: Paragraphs in the major and minor problems sections
and the "Notes" section are presented in "bulleted"
format.
3.1.5 Minor Problems
The section title, "MINOR PROBLEMS" is followed by a
series of bulleted paragraphs describing biases
identified during the data review which may qualify data
as "J", "UJ", "K", "L", or "UL". Examples of these
problems are discussed thoroughly in the Functional
Guidelines for Organic Data Validation as Modified by
Region III. As in the reporting of major problems,
support documentation is referenced for each problem
described.
Problems listed in this section of the narrative are
listed according to the hierarchy of qualifiers,
beginning with the most serious ("J", "UJ") first. If
problems are identified in more than one organic
fraction, each fraction is identified.
Notes
This section follows the minor problems section and is
used to Identify issues and information which may be
beneficial to the data user, and includes a paragraph
describing any blank contamination found and its possible
effects on sample results. Maximum levels of the blank
contaminants are listed in tabular form. Common lab
contaminants are identified with an asterisk (*)• Other
Information which shall be included in the "Notes"
section includes, but is not limited to: variances in
methodology which did not affect samples, dilutions used,
non-spiked MS/MSD comparisons, a field duplicate
-------
Appendix B
Page 3 of 5
comparison summary (In tabular form with relative percent
differences [RPDe]), and a general statement regarding
actions taken during the review of tentatively identified
compounds (TlCe) . As in the problems descriptions,
reference is made to support documentation included in
the appendices of the report.
3.1.7 Report Content Statement
A short paragraph, not bulleted, follows the notes
section stating that the data were reviewed in accordance
with the Functional Guidelines for Evaluating Organic
Analyses, as modified for use in Region III, and that the
text of the report only addresses those problems which
affect data usability.
3.1.8
Under the sectio'n title "ATTACHMENTS" . a list of
appendices and their contents is included. The
appendices normally listed and their order are:
Appendix A - Glossary of Data Qualifiers
Appendix B- - Data Summary Forms
Appendix C - Laboratory Reported Results
Appendix D - Laboratory Reported TICs
Appendix E - Support Documentation
3.2 Appendices
Appendices are separated from the main body of the report by title
pages containing, centered on the page, the appendix name and
title.
3.2.1 Appendix A - glossary of Data Qualifier Codas
A listing of all organic data qualifiers used in Region
III and their definitions is included in Attachment D.
3.2.2 Appendix B ~ Data S"twarv Forms
3.2.2.1 The full title of this appendix is
"Data Summary. These Include:
(a) All positive results for target compounds
with qualifier codes where applicable.
(b) All unusable detection limits (qualified
"R")."
3.2.2.2 Included are Data Summary Forms for all
fractions analyzed, sequentially numbered
beginning with the volatile organic fraction,
for all samples analyzed. Information on the
Data Summary Forms includes: organic fraction
identified, sample matrix, concentration units,
site, case number, SDG number if multiple SDGs
are reported, sampling date(s), sample numbers,
dilution factors used (if none, identified as
1.0), sample locations, sample Identifications
(e.g., trip blank, field duplicate), contract
required quantitation limit for each analyte,
all target analytes, all positive results and
-------
Appendix B
Page 4 of 5
quantitatton limits with qualifier codas where
applicable, and all unusable detection limits
qualified "R".
NOTE: Standard generation of the Data Summary Forms
can be done on a spreadsheet program. Blank Data
Summary Forms for both aqueous and solid samples are
included in Attachment E.
3.2.3 Appendix C - Results as Reported bv toe Laboratory for
all Target Compounds
After the title page, Appendix C contains photocopies of
all of the Form Is. The Form Zs for all samples for the
volatile organica fraction are included first, followed
by Form Is for all samples for semivolatile organic
compounds and pesticides/PCBs. The sample order of the
Form Zs should match the sample order as listed on the
Data Summary Forms.
3.2.4 Appendix P ~ Reviewed and Accepted ICorrectedI
Tentatively Identified Compounds
Appendix D contains photocopies of the Tentatively
Identified Compounds forms (Form I VOA - TIC and Form I
SV - TIC) for each sample, with all volatile organics
forms preceding ail semivolatiie organics forms. If
corrections to the TIC forms are made during validation,
use the word "corrected* in the appendix title. All TIC
forms are included even if no TICs were identified by the
laboratory.
3.2.5 Appendix F — Support Documentation
Appendix. F for the organic data review report includes
all support documentation needed to substantiate the
findings described in the narrative. In addition to
copies of specific supporting forms from the data
package, the appendix will includes
3.2.5.1 Table I, "Calibration Outliers", is a
compilation of all Response Factors (RFs),
percent Relative Standard Deviations (%RSDs),
and percent Differences (%Ds) which were outside
of the control limits for both volatile and
semivolatile organic compounds. Examples of
Table I are included in Attachment F. Table I
also includes the qualifiers applied during
validation to compound results because of these
outliers, and the definitions of the qualifier
codes used.
3.2.5.2 Initial and continuing calibration data are
included for all volatile and semivolatile
compounds (Forms VI VGA, VII VOA, VI SV-1 and -
2, and VII SV-1 and -2), with a reviewer-written
list of samples affected by each calibration.
3.2.5.3 Copies of the laboratory case narrative, sample
traffic report/chain of custody (TR/COC), and
EPA Shipping Log.
-------
Appendix B
Page 5 of 5
*itiftHliiici tiic Report
The organic report shall be assembled in the order presented in Sections
3.1 and 3.2 of this document. The narrative is followed by the
Appendices as described.
5.0 Review and Distribution
After the report is completed and assembled, it should be reviewed
internally by optional peer review(s), oversight chemist review(s), and
team manager review.
5.1 The report should be submitted to a senior oversight chemist for
its first internal review. The internal review may be assigned
to another validator or be performed by the oversight chemist.
5.-1.1 The reviewer will review the document. Any deficiencies,
inconsistencies, or other comments should be returned to
the validator.
5.1.2 The reviewer will return the review to the validator, who
will make the required corrections.
5.1.3 The process will continue (Steps 5.1 - 5.1.2) until the
document requires no further revision.
5.1.4 The validator will initial the first page of the
narrative next to his/her name.
5.1.5 The final review is performed by the team manager, who
will read and review the document. If the report is
acceptable to the team manager, he will initial the
narrative next to his name.
5.2 The completed report is submitted .to the EPA oversight chemist for
review.
5.2.1 All internal review checklists are removed, and the rest
of the document is" copied for the validator files. The
internal review checklists and document copy are then
placed in a filing area.
5.2.2 The original, document is placed in an inter-office
envelope addressed to the EPA RPM.
5.3 Upon completion of review by the EPA oversight chemist, the
document will either be approved as submitted or revisions will
be required.
5.3.1 If revisions are required by the EPA oversight chemist,
the validator must complete those revisions and submit
the document for internal review as outlined above
beginning in section 5.1.
5.3.1.1 All resubmissions are labelled as revision 1 (or
subsequent).
-------
-------
ATTACHMENT A
Qraanics
Water ftta/Ll
Chemical Tan Dav Health Advisory List
Metals
Water fticr/Ll
Arsenic
Cadmium
Chromium
Lead
Nickel
Soil fppml
Lead
Inorganics
Nitrate
Nitrite
Cyanide
Acrylamide 300
Alachior 15000
Aldicarb 12
Benzene 233
Carbofuran, 50
Carbon Tetrachloride 160
Chlordane 63
Chlorobenzene 1800
2,4-D 300
DBCP 50
1,3-diclilorobenzene 8930
1,4-dichlorobenzene 10700
1,2-dichloroethane 740
1,1-dichloroethylene 1000
cis-1,2-dichloroethylene 1000
trans-i,2-dichloroethylene2720
D i chloromethane 1500
1,2-dichloropropane 9 0
p-Dioxane 568
Dioxin 1 x 10**
EDB 8
Endrin 5
Epichlorohydrin 140
Ethylbenzene 2100
Ethylene glycol 5500
Heptacblor 10
Hexachlorobenzene 50
n-Hexane 4000
Lindane 1200
Methoxychlor 2000
Methyl ethyl ketone
(2-butanone) 7500
Oxamyl 350
Pentachlorophenol 300
Styrene 200OO
Tetrachloroethylene 34000
Toluene 6000
Toxaphene 80
2,4,5-TP (Silvex) 200
1,1,1-trichloroethane 35000
Vinyl chloride 2600
Xylenes 7800
PCB hundreds
50
8
1400
20
1000
500
10 mg/L - 4 kg
111 mg/L - other
1 mg/L - 1 kg
11 mg/L - other
220
RD0073A23.LIS
-------
-------
ATTACHMENT B
GLOSSARY OF DATA QUALIFIER CODES (ORGANIC)
CODES KBtfATED TO IDENTIFICATION
(confidence concerning presence or absence of compounds)
U = Not detected. The associated number indicates
approximate sample concentration necessary to be
detected.
HO CODE - Confirmed identification.
B « Not detected substantially above the level reported
in laboratory or field blanks.
R - Unusable result. Analyte may or may not be present
in the sample.
t
N B Tentative identification. Consider present.
Special methods may be needed to conform its
presence or absence in future sampling efforts.
CODES RELATED TO OUANTITATION
(can be used for both positive results and sample quantitation
limits):
3 = Analyte present. Reported value may not be
accurate or precise.
K = Analyte present. Reported value may be biased
high. Actual value is expected to be lower.
L « Analyte present. Reported value may be biased low.
Actual value is expected to be higher.
UJ = Not detected. Quantitation limit may be inaccurate
or imprecise.
UL = Not detected. Quantitation limit is probably
higher.
OTHER CODES
NJ • Qualitative identification questionable due to poor
resolution. Presumptively present at approximate
quantity.
Q - No analytical result.
-------
-------
Attachment C
Data Summary Forms
-------
-------
DATA SUMMARY FORM: VOLATILES 1
Page
of
Site Na
Case i:
HATER SAMPLES
Cug/L)
Sampling Oate(s):
To calculate sample quant)tat Ion UralIB:
(CROL * Dilution Factor)
CRQL
to_
10
19
10
10
10
10
10
10
10
!0_
1
-------
-------
DATA SUMMARY FORK; VOLATILES 2
Page
of
Site Na
Cut f:
WATER SAMPLES
(ug/0
Sampling Date(s):
To calculate aanple quant Station Knits:
(CRDL * Dilution Factor)
OWL
10
10
10
10
10
10
10
10
10.
10
10
10
10
10
10
10
10
Sanple No.
Dilution Factor
Location
COMPOUND
•1 ,2-Dichlorowooar*
CU-1 .3-Dlchloroprooene
Trlchloroethene
Dlbromochloroawthana
1 .1 .2-Tridiloroctharw
*B«nzerM
Trana-1 .3-01 dildropropana
Brooofom
4-Rathvl -2-Dantanoiw
2-Mcxanofw
*Tetrachloroethene
1.1.2.2-Tatrachloro*than«
*Toluene
*Chlorobenzene
•Ethvlbanzana
•Stvrene
•Total XvlenM
,
.
_
.
CROL • Contract Required Quantitatloti Halt
•Action Level Exlata
SEE NARRATIVE FOR CODE DEFINITIONS
revised 07/90
-------
-------
DATA SUMMARY FORM: VOLATILES 1
Page
of
Sit* Ha
Cat* f:
SOIL SAMPLES
(ug/Kg)
SanpUng Date(»):
To calculate swiple quantitatIon Units:
(CRQL * Dilution factor / ((100 • X*o«Bture)/100)
CRQL
W_
18
10
to
10
10
16
10
10
10
10
18
10
M-
10
10
Sanple »0.
Dilution Factor
X Moisture
Location
COMPOUND
Chlorenethane
Brojwmethan*
Vlnvl Chloride
Chloroethane
ttethvlana Chloride
Acetone;
Carbon Oitutf Ida
1.1-Dichtoro*thane
1.1-Dlchtoroethane
Total 1.2-Dichloro«thene
Chloroforv
1.2-Oidiloroethen*
2-ftutenone
1.1.1-THdilarMthane
Carbon Tetrachloride
Bronodlchloromethane
.
mmmmmmmmmmm
.-••••••••I
.
. .
mmmmmmmmmmn
•........-•
.___
"•"
,
I
CRQL • Contract Required Ouantitation Linit
SEE NARRATIVE FOR CODE DEFINITIONS
revised 07/90
-------
-------
DATA SUMMARY FORM: VOLATILES 2
Pag*
of
Site Da
Case f:
SOIL SAMPLES
(ug/Kg)
Date(s):
To calculate sanple quantltatlon limits:
(CROL * Dilution factor / ((100 - XMolsture)/100)
CRQL
to
10
10
10
10
10
10
10
10
10
_ WL
w_
10_
10_
10_
10_
10
Sanple No.
Dilution Factor
% Moisture
Location
COMPOUND
1.2-Dichloroorooene
Cfa-LS-Dlcfiloropfopene
Trtehloroetltem
Dfbrooochlon*«thar»«
I.I.Z-THchlerocthaiM
ianzerw
Trana- 1 , 3-DlcMoropropene
Broaofona
4-Mathvl -Z-oentanoiM
2-N«xanon«
Tetrachloroethane
1 f 1.Zf 2-T«trachloro«th«n»
Toluene
Chlorobenzene
Ethvlbanz«ne
Stvr«M
Total Xvlanea
B
.
'•
-
1-
L
.
CROL • Contract Required Quantltatien Llalt
SEE NARRATIVE FOR CODE DEFINITIONS
revised 07/90
-------
-------
DATA SUMARV FORM: B N A
Page
of
Sit* Ha
Cam f:
WATER SAMPLES
(ug/L)
Sampling Date(s):
To calculate sample quantitation limits:
(CRDL * Dilution Factor)
CRQL
10
10_
16
10_
10
10
10
10
10
10
10
10
10
10
10
«L
10
10
10
10
Saapl* No.
Dilution Factor
Location
COMPOUND
Phenol
bl •(2-Ch I oroethvl lather
• 2-Chloroohenol
•1.3-Dicnlorabenzene
•1,4-Dichloroberuene
1.2-Diehlorobenzene
2-Hethvluhenol
2.2'-oxvblt<1-ehloropropene)
4-Hethvlrtienol
N-Nltrmo-dl -n-woovlamine
Hexactiloroathana
Nitrobenzene
Ivochororw
2-HttroDhenol
2,*-D««ethvloher»l
biB(2-Chtoroethoxv)«ethar»
2.4-Dlchlorochenol
1.2.4-Trichlorobenzene
HeDhthalene
4-ChloroaniUne
I-
CRQL • Contract Required Aiantltatlon Limit
•Action Level ExUt«
SEE NARRATIVE FOR CODE DEFINITIONS
revised 07/90
-------
-------
DATA SUMMARY FORM: I N A
Sit* Name:
Case *:
MATER SAMPLES
(Ufl/L)
Sanpllna Date(s):
To calculate taspte quant I tat ion Units:
(CRDL * DIHjtton Factor)
CRQL
10
10
10
10
10
25
11« No.
OJlutJon Factor
Location
COMPOUND
Hwtaditorobutadtan*
4-Chloro-3-«Bthvloh«nol
2-NcthvtnaehthalWMi
Hax*chlorocyclop«ntadf«nt
2.4.6-Trlchloroch«nol
2.4.5-Tr«chlorooh«nol
2-CtiloronaDthatene
2-NitroanUfrw
DlMthyletttlulate
Acenaehthvltn«
2.6-Dlnltrotoluam
S-Nitrewi(ltrw
Acmwiithcne
2.4-Dtnitroohcnol
*-Nltroohenol
Otbeniofuran
2.4-Olnltrotolueoe
Diathvlphthalata
4-Chloroc*«nyl-i*enYl«th«r
Fluorww
4-N1trotnlllm
4.6-01nltro-2-nethylp»i«K)t
(SOL • Contract Required Quantltatlon
•Action l*v*l Ixltta
SEE NARRATIVE FOR CODE DEFINITIONS
revised 07/90
-------
-------
DATA SUMMARY FORM: SNA
Page
of
Site Name:
Case f:
WATER SAMPLES
(ug/L)
Sampling Date(t):
To calculate sanple quantltatlon limits:
(CRDL * Option Factor)
CftQL
10
10
10
25.
1
-------
-------
DATA SUWARV FORM: IMA
Pag*
of
Sit* Mane:
Case «:
SOIL SAMPLES
(ug/Kg>
Sampling Dat«(s):
To calculate tangle quantltatlon Units:
(CRQL * Dilution factor / ((100 - Xn»lsture)/100)
CRQL
.330.
530.
330_
330.
330_
.330.
.330.
.330.
330.
.330.
330.
.330.
.330.
.338.
.330.
.330.
.330.
.330.
.330.
330
Sanpla No.
Dilution Factor
X Moisture
Location
COMPOUND
Phanot
blt(2-Ch loroathvl )»th«r
2-Chloroeh*nol
1 .3-Dlchlorobenz«n*
1 ,4-0 Idilorobenzarw
! .2-0 Ichlorobanzane
2-Methylrfwnol
2r2'-oxvbli(1-chloropropan«)
4-H«thvloh«x>l
N-i 1 trosa-df -n-0ropy la»l na
Ncxachloroetharw
nitrobenzene
IcoDhoron*
2-Mltroohenol
2.4-0 iMttwlehanol
bla(2-ailefoathoxy)Mthana
2.4-Dlchloroohenol
t .2.4-Tr Ichlorobanzena
Nachthalene
4-Chloroanlllne
'
___________
...........
'
CRQL • Contract Required Quant I tatIon Limit
SEE NARRATIVE FOR CODE DEFINITIONS
revised 07/90
-------
-------
DATA SUMMARY FORM: SNA
Pas*
of
Site Name:
Case •:
SOIL SAMPLES
Cug/Kg)
Sampling Date(«):
To calculate sample quantI tatIon limits:
(CRQL * Dilution factor / ((100 - X«»l8ture>/100)
OWL
330
.330
330
330
330
800
330
800
330
330
JS30
MO
330
800
800
330
330
330
330
330
BOO
800
Sarnpla Ho.
Dilution Factor
% Mofaturt
Location
COMPOUND
Haxachlorofautadlana
*-Chloro-3-nethytDhtnol
2-H«thylnaohthalene
Haxachlorocvclooentadltna
2.4.4-Trlchlorochenol
2.*.5-Trlchloroohenol
2-Chtoronanthalen*
2-Nltremlllm
DlwathvlDhthalata
Acanachthvlene
2.6-BlnltratoluaM
3-Kltroantltne
|' Aetntohthmt
| 2>-D1n1tr«*anol
i-Nltroohenol
Olbamofuran
2,4»DlnttrototiMrw
Dlathylphthalat*
4-ChlorophenYl-ph*ftylathar
Fluorana
4-MltroaflUlM
4.6-D1n1tro-2-«athylphanol
.
-
-
CROl • Contract Raqulred Quantltatlon Llilt
SEE NARRATIVE FOR CODE DEFINITIONS
revUed 07/90
-------
-------
DATA SUMMARY FORM: B N A
Page
of
Sit* Dane:
CM* f;
SOIL SAMPLES
(ug/Kg)
Sampling Date(s):
To calculate senple quantitation Halts:
(CRttL • Dilution factor / ((100 - Xmolature)/100)
CROL
330
330
330
800
330
330
330
330
.330
330
330
330
330
330
330
330
330
330
330
330
330
330
Staple lo.
Dilution Factor
X Motatura
Location
COMPOUND
N-Nitroaodfeh*nylanfne
4-Brofflcehenyl-phenylether
Hexachloroberuene
Pentachloroohenol
Phenenthrene
Anttiracana
Carfaezole
Dl -n-butvichtlialat*
FlueranthwM
Pvrafw
ButvlbenzvlDhthalat*
3.3'-i>fchlorobenzidinc
Benzo(a)anthracena
Chrvsane
bf t(Z-Ethvlhexvl )phthalat*
Dl-n-octvluhthalate
Bamofblf luorantKena
Benzo( k) f luoranthana
Benzo(a)Bvr«n«
Indeno(1.2.3-cd)Dvrefw
Dfb«nz(a.h)anthracene
Beftto(g.h.l)D*rvl«n«
•
mmmmmmmmmmm
mmmmmmmmmmm
-
1
1
CROL » Contract Required Quantttatlon Limit
SEE NARRATIVE FOR COD! DEFINITIONS
revised 07/90
-------
-------
DATA SUMMARY FORM: PESTICIDES AND P C • S
Pag*
of
Sit* Nam:
f:
HATER SAMPLES
(ug/U
Sampling Date(s):
To calculate sample quant I tat ion Units;
(CftDl * Dilution Factor)
Sanpla Ho,
Dilution Factor
Location
CRQL COMPOUND
0.05| elcht-BHC
0.05 ( bita-BHC
0.05 | etelta-iKC
0.05) *oanwa-IKC (lindana)
0.05) " *Naetachlor
0.05 | Aldrln
0.05 1 Hwtachlor EooKida
0.05) Endoauifan I
0.10) Dtaldrln
0.10) 4.4'-DDi
0.10| *Endrin
0.10) Endoauifan 11
0.10) 4,4'-DDO
0.10J Endoauifan Sulfata
0.10| *.4'-DOT
0.50 | *N*thQXvehlor
0.10| Endrin Ketooe
0.10| Endrin Aldehyde
0.05) *aloha-Chlord«ne
0.05 1 *gaBwa-Chlortten*
5.0 *Toxaphan*
1.0 *Aroclor-1016
2.0 *Aroclor-1221
.0 *Aroelor-lS2
.0 *Aroclor-1Z42
.0 *Aroeler-tZ48
.0 *Aroelor-1S4
.0 *Aroclor-1260
CROL * Contract l*quir*d Quantitatton Lli
•it
•••••••••_•
mmmmmmmmmm,
V
.
...
•Action I
^
lava
'
I Exiata
SEE
NARRATIVE
FOR (
*t
3»E DEFIKll
nous
revised 07/90
-------
-------
DATA SUWARY FORK: PESTICIDES AND P C i S
Page
of
Sit* NBIWJ
CMC f:
SOIL SAMPLES
(ug/Kg)
Sanpling Date(s):
To calculate sanple quant i tat I on Units:
(CRQL * Dilution factor / ((100 - Xmoistup*)/100)
CRQL
1.7
1.7
1.7
1.7
J-7_
1.7
J«7_
1.7
3.3
3.3
3.3
.3.3.
_3.3.
3.3
_3'3L
17
3.3
3.3
1.7
1.7
170
33
67
33
33
33
33
33
CSQL •
Sample No.
Dilution Factor
X MoUtura
Location
COHPOUNO
aloha-BHC
b«ta-BHC
delta-BHC
ganna-BHC (Llndant)
Heotachlor
Aldrln
Heotachlor Eooxlde
EndoMjlfan I
Dleldrin
4.*'-DOE
Endrin
EndOMJlfan II
4.4' -DOB
Endoaulfan Sulfate
4.4' -DOT
Nethoxvchler
Endrfn Katone
Endrln Aldehyde
alpha-Chlordane
ganiM- Ch I ordana
Toxachen*
Aroclor-1016
Aroeler-1H1
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Contract Raquirad Quant Itatl on Lit
•It
mmmmmmmmmmm
mm*mmmmmmmt
.
,
_-_„,_--„..
SEE
NARRATIVE 1
r« 1
^
•
DODE DEFINI1
news
revised 07/90
-------
-------
Attachment D
Table I
-------
-------
TABLE I
Page of
.CASE/SAS No..
ENVIRONMENTAL PROTECTION AGENCY REGION III
CALIBRATION OUTLIERS
VOLATILE HSL COMPOimDS
CONTRACTOR
| Instrument* Unit. Cal. Cont. Cal.
! DATE /TIME: I
1 SRF %RSD * RF !%D *
! Chlorome thane ! '
f Bromomethane ! !
Vinvl Chloride ! !
Chloroethane ! i
Methvlene Chloride i
Acetone !
Carbon Dieulfide 1 ! ! !
1,1-Dichloroethene ! ! ! !
1,1-Dichloroethane ! ! If ! !
Total-1.2-Dichloroethene ! ! ! ! ! !
Chloroform \ ! ! ! !
1,2-Dichloroethane I : ! ! !
2-Butanone ! ! \ [ ! !
1.1.1-Trichloroethane !!!!!!
Carbon Tetrachloride i ! !
Bromodichlororaethane ! ! ! ! ! !
1,2-DichlorooroDane ! ! ! ! !
cis-1, 3-DichloroDrooene ! ! 1
Trichloroethene ! !
Dibromochloromethane t !
1. 1,2-Trichloroethane ! !
Benzene ! 1 i
trana-1 . 3-DichloroDrooene !!;!!!
Bromoform ! ! ! !
4-Methvl-2-Pentanone ! ! ! ! !
2-Hexanone ! ! ! ! !
Tetrachloroethene ! ! ! ! !
I 1,1.2.2-Tetrachloroethane ! ! ! !
! Toluene ! ! !
Chlorobenzene f ! ! ! !
Ethvlbenzene ! !
Stvrene ! j
Total Xvlenes 1 ! f ! !
i i
•
AFFECTED j
SAMPLES: ! !
! Cont .
!
!RF
!
i
|
J
[
i
i
!
1
i
Cal. !
{
%D f * !
i i
J j
j j
i ^
i i
i i
i i
i i
i t i
I 1 1
I j j
j J
i i
j j
j [
j j
i i
i i
j j
t i
j !
• j
!
1
I
! i
i i
i i
i i
i i
t i
1 1
|
1 !
j
i
i
Reviewer
Initials/Date:.
* See last pace of this table for DEFINITION OF CODES.
-------
-------
CASE/SAS No..
TABLE I
ENVIRONMENTAL PROTECTION AGENCY REGION III
CALIBRATION OUTLIERS
SEMIVOLATILE HSL COMPOUND 'Part 1 of 2}
CONTRACTOR
Page of
Instrument/
DATE /TIMEs
Phenol
bis r 2-Chloroethvl lether
2-Chloroohenol
1 , 3-Dichlorobenzene
1 . 4-Dichlorobenzene
1 , 2-Dichloroben rene
2-MethYlpherjol
bie(2-ChloroiBODroDvl 1 ether
4-Methvluhenol
N-Nitroso-di-n-DroDvlamine
Hexachloroethane
Nitrobenzene
Isoohorone
2-NitroDhenol
2 . 4— Dimethvlohenol
! bis f2-Chloroethoxv> methane
1 2 .4-Dichloroohenol
1. 2 . 4-Trichlorobenzene
Naohthalene
4-Chloroan i 1 ine
Hexach lorobut ad iene
4-Ch loro-3-Met hv iDheno 1
! 2-Methvlnachthalene
Hexachlorocvclooentadiene
2.4. 6-Trichloroohenol
2,4. 5-TrichloroDhenol
2-Chl oronaoht ha Iene
! 2-Nitroaniline
DimethvlDhthalate
! Acenachthvlene
I 2 . 6-Dinitrotoluene
1 3-NitroanM.ine
Acenaohthene
2 . 4-DinitrophenoJ.
4-Nitrot>henol
AFFECTED
SAMPLES:
le viewer j
nitiala/Date:
llnit
j
!RF
i
J
!
I
i
i
i
*
j
i
•
|
j
!
i
i
}
!
!
t
t
\
. Cal.
!%RSD
I
J
!
i
t
!
•
j
i
I
\
i
i
i
i
ICont. Cal. ICont. Cal. 'Cont. Cal.
[ ! j
! * ! RF %D ! * ! RF ! %D ! * ! RF ! %D *
it iii iii
! ! ! ! ! ! !
ii iii ii
I ! ! ! ! ! i J
ii iii iii
iii iii iii
iii iji iii
iii iii iii
• ' t 1 ' ' i . t i
1 j 1 1 1 1 1 1 1
II 1 'II 1 II 1
III III III
II III III
! ! ! ! ! ! ! ! ! - |
i i i i i i i i
i iii iii
! 5 ! ! ! J
. ! ! ! ! ! ! i
it i i i i
j i ii iii
(ill ! !
! ! i ! i !. ! i
i iii iii i
• j i j j !S 1 J
ij j j i ! ! ! ! !
ii i j i | i j
i i i i i
1 ' i ! !
it ii
I !
1 ! ! !
i ii i i
i iii iii i
! ! ! ! ! ! !
! } ! i ! ! !
! ! ! ! III!
J >
i i i
! !
i i
i ! i
i
i
- - "
* See last page of this tablefor DEFINITION OF CODES.
-------
-------
TABLE I
Page of
ENVIRONMENTAL PROTECTION AGENCY REGION III
CALIBRATION OUTLIERS
SEHIVOLATILE HSL COMPOUNDS (Part 2 Of 2)
j Instrument/ flnit. Cal.
1 DATE/TIMEt
i
t
Cont
« Cal. Icont. Cal*
1
|RF SiRSD !* RF
_i_ Dibenzofuran !
2,4-Dtnitrotoluen0 !
Diethylphthalate !
4-Chloronhenvl-ofienvlether !
Fluorene !
4-Nitroaniline !
4 , 6-Dinitra-2-methvlohenol !
N-Nitroaodiphenvlamine !
4-BromoBhenvl-ohenvlefcher 1
Hexachlorobenzene !
Pentachlorophenol !
Phenanthrene !
Anthracene
Carbazole
Oi— n-butvlohthalate !
Fluoranthene !
Pvrene
Butvlbenzylphthalate !
3 , 3 ' -Dichlorobenzidine !
Benzof a) anthracene !
Chrvaene
bis ( 2-ethvlhexvl 1 phtha late
L Di-n-octvlchthalate 1
Beqzo ( b \ f luorant hene
Benzo ( k ) f luorant hene
Benzo f a 1 uvrene !
Indeno (1.2,
Dibenzfa.h]
Benzofa.h, :
, 3-cdlovrene j
anthracene !
. loervlene
f%0 » RF !%D
i
! !
! !
|
t
!
j
|
!
i
t
j
i
J
i
I
I \
!
! !
i
4 j
1
[
J
!
i
i i
j
!
J
S
AFFECTED
t
i
!
s
{
t
i
i
!
i
i
i
i
<
t
j
i
' j
»
i
i i
*
i i i
L i
! 1 !
i < i
I i
i i i
| ' !
j
j
i
iii i
1
i
i
SAMPLES! ! !
Reviewer
[nitiala/Datc
** -- _,,„,
j
j
j
i i
\
Cont. Cal.
RF S%D * i
i
j
j
j
j
{
\
j
!
i
i
j
! _j
i
p
s
i
i
i
i
i
i
!
j
j
1
j
i
f
J
t
i
i i
J 1
I ! !
1 11
] [
i i
J
!
j j
i j
! t
1
i
j
i
i
i
i
* See last pace ofthis table for DEFINITION OF CODES.
-------
-------
Page of
DEFINITION OF CODES USED IN TABLE I
%RSD exceeded 30% in the initial calibration, positive
results are qualified "J". When the %RSD exceeded 50%,
quantitation limits are qualified "UJ",
%D exceeded 25% .in the continuing calibration, positive
results are qualified "J". When the %D exceeded 50%,
quantitation limits are qualified "UJ",
RF less than 0.05 in the calibration. All quantitation
limits are qualified "R" and positive results are qualified
ML".
The "B" qualifier, denoting blank contamination, supersedes
the qualifier issued in this table.
The "R" qualifier, denoting unusable results, supersedes the
qualifier issued in this table.
-------
-------
Region 01 Modifications
APPENDIX C
CONTRACTUAL REQUIREMENT COMPARISON TABLES
-------
-------
Region m Modifications
APPENDIX C
Table C.I. Comparison of Requirements for
Volatile Data Review
REQUIREMENT
Target Compound List
Data Turnaround r
Technical Holding Time
Initial Calibration
Continuing Calibration
Blanks
SMC/Surrogates
MS/MSD
LCS
Regional QA/QC
Internal Standards
CRQL
ncs
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: SO ug/L
Method Blanks
Instrument Blanks
SMC:
1 ,2-Dichloroethane-
-------
Region ID Modification*
APPENDIX C
Table C.2. Comparison of Requirements for
SemivolatHe 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: SO 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 soU)
10,000 - 50,000 (med soil)
largest 20 2 10% 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 perSDG
PEs - 1 per SDG
- IS Area: - 50% to 100%
IS RT Shift: ±20 sec.
5 - 20 ug/L
largest 20 2 50% of nearest IS
C-2
-------
APPENDIX D
PROPOSED GUIDANCE TOR
TENTATIVELY IDENTIFIED COMPOUNDS
(VOA AND SV)
-------
-------
in Modific«tk>m
APPENDIX D
PROPOSED GUIDANCE TOR 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 mat are not TCL compounds, system monitoring
compounds, or internal standards are potential tentatively identified compounds (TICs) or library
search compounds (LCSs). 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 report the possible identity for the 10 largest volatile fraction peaks which are not surrogates,
internal standards, or TCL compounds, but which have a peak area greater man 40 percent of
the peak area of the nearest internal standard. TIC results are reported for each sample on the
Organic Analysis Data Sheet (Form I VOA-TIC).
Note: Since the SOW revision of October 1986, the CLP does not allow the laboratory to report
as tentatively identified compounds any TCL compound which is properly reported in
another fraction. (For example, late eluting volatile TCL compounds must not be
reported as 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 hi 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 (KIT) and comparison of
RRT and mass spectral data across samples Is extremely helpful in identifying
D-l
-------
Region III Modification*
VGA APPENDIX D
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 "A is obvious mat 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 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, men 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 Ml mass spectral interpretation can narrow down the possibilities. While
a full discussion of manual mass spectral interpretation is beyond the scope of mis
document, several key points may be mentioned as important objects:
o Determine a likely molecular weight (MW). 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+i)/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-- + + l
where: C = no. of carbons
H — no. of hydrogens
X = no. of halogens
N = no. of nitrogen
Note: oxygen and sulfur do not need to be accounted for. An
aromatic ring counts as four rings and double bonds.
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 otter daughter ions.
D-2
-------
Region III Modifkabom
VGA APPENDIX D
o Using the information gathered on molecular weight, molecular formula, degree
of unsaturation, and mass losses in the unknown spectrum, combined whh the
RRT data, give as precise a description of the unknown as possible, including an
exact identification if it is justified.
d. In the event mat 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 th& 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 the 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 man 40 percent of the internal standard peak
area or height, but present in the blank chromatogram at similar relative mention time.
4. All mass spectra for every sample and blank must be examined.
5. The reviewer should be aware of common laboratory artifacts/contaminants and their
sources (e.g., aldol condensation products, solvent preservatives, and reagent contaminants).
These may be present in blanks and not reported as sample TICs.
Examples:
a. Common laboratory contaminants: CO^m/z 44), siloxanes (m/z 73), diethyl ether,
hexane, certain freons (l,l,2-trichloro-l,2,2-trifluoroethane or fluoro-
trichloromenthane), and phthatates at levels less man 100 ug/L or 4000 ug/Kg.
b. Solvent preservatives such as cyclohexene which is a methylene chloride preservative.
Related by-products include cydohexanone, cyclohexenone, cyclohexanol,
cyclohexenol, chlorocyclohexene, and chlorocyclohexanol.
c. Aldol condensation reaction products of acetone include: 4-hydroxy-4-metbyI-2-
pentatone, 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.
D-3
-------
Region ID Modifications
VGA APPENDIX D
7. TCL compounds may be identified in more than one fraction. Verify that quantitation is
made from the proper fraction.
8. Library searches should not be performed on internal standards or surrogates.
9, TIC concentration should be estimated assuming a RRF of 1.0.
E. Action
1. All TIC results should be qualified as tentatively identified (N) with estimated concentrations
g)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 XD.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 hi another Case, SAS, or SDG. It may also
be used in writing a Special Analytical Service Statement of Work to identify the
unknown, or if the sample is sent to an EPA research laboratory LSC identification by
multiple spectral techniques.
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-4
-------
VGA
R«gk>n in Modifmtkxu
APPENDIX D
APPENDIX
Equation 1:
RTunk - RTz
- RTz
1002
where: RTunk is the retention time of the unknown
RTz Is the retention time of the preceding retention index standards
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
pbenanthrene
chrysene
Benzo(g,h,i)
perylene
z-2
z-S
R]=200.00
RI=300.00
RI=400.00
RI-500.00
when these compounds are not found in the sample of interest, RT data for
die 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 - — -£ + ^*i
222
Note:
where: C = no. of carbons
H - no. of hydrogens
X — no. of halogens
N = no. of nitrogens
oxygen and sulfur do not need to be accounted for. An aromatic ring counts
as four rings and double bonds.
D-5
-------
Region ffl Modifications
VGA APPENDIX D
REFERENCES
1. Lee, MX. Vassilaros, D.L., White. C.mM., and Novotny, M., "Retention Indices for
Programmed-Temperature Capillary-Column Gas Chromatography of Polycyclic Aromatic
Hydorcarbons", Analytical Qieipistry. V.51, no. 6» 1919, pp. 768-T73.
2. Rostad, C.E., and Pereira, W.E., "Kovats and Lee Retention Indices Determined by Gas
Chromatography/Mass Spectrometry for Organic Compounds of Environmental Interest*
J, High Resolution Chrom. and Chromf Commun... vol.9,1986, pp. 328-334.
3. Silverstein, R.M., Bassier, G.C., and Morrill, T.C. Spectrometric Identification of Organic
Compounds 4tn ed.. Wilev. New York, 1981.
4. Vassilaros, D.M., Kong, R.C., Later, D.W. and Lee, MX,, :Linear Retention Index System for
polyclyclic Aromatic Compounds. Critical Evaluation and Additional Indices". |. of
Chromatographv. 252 (1982) pp. 1-20,
D-6
-------
Region in Modi
APPENDIXD
PROPOSED GUIDANCE FOR TENTATIVELY IDENTIFIED COMPOUNDS (SV)
A. Review Items: Form ISV-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 1 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 SDG) in which the unknown
compound occurs. Calculation of retention indices (R) and comparison of RI and mass
spectra across samples is extremely helpful in identifying unknowns that occur
D-7
-------
Region ID Modificationi
SV APPENDED
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:
RI
- RTz
where: RTunk is the retention time of the unknown
RTz is 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 z=2 RI= 200.00
phenanthrene z=3 RI= 300.00
chrysene z»4 RI =400.00
Benzo(g,h,i) z=5 RI=500.00
perylene
Note: when these compounds are not dound in the sample of interest, RT data for
the deuterated internal standards or most recent calibration may be used.
Retention tune 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 mat the correct match
is among the spectra retrieved for the unknown from the several samples in which it
is found. It may only be necessary to check the unknown's RI versus a reference list
of SV (generated under similar conditions and after accounting for bias in the sample)
to arrive at a satisfactory tentative identification. Some references are provided. If a
reference RI is not available^ then a comparison of the" unknown's RI or boiling point
to the RI or boiling point of a closely related compound may also provide a
satisfactory tentative identification. Within a compound class, retention time increases
with increasing boiling point.
c) In the event mat serious ambiguity still exists after examining the library spectra and
RI data, a full mass spectral interpretation can narrow down the possibilities. While
a Ml discussion of manual mass spectral interpretation is beyond the scope of mis
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 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-8
-------
Repon IH ModificBtkiai
SV APPENDIX D
Calcuiate the total number of rings-plus-double-bonds in die 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):
where: C = no. of carbons
H •= no. of hydrogens
X *= no. of halogens
N = no. of nitrogens
Ifote: 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 die 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 ffie 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«=317.10). 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 mat the laboratory has generated a library search spectrum for
all required peaks in die chromatograms for samples and blanks.
3. Blank chromatograms should be examined to verify mat 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 man 10 percent of the internal standard peak
area or height, but present in the blank chromatogram at similar relative retention time.
4. All mass spectra for every sample and blank must be examined.
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VS APPENDIX D
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 man 100 ug/L or 4000 ug/KG.
b. Solvent preservatives such as cyclohexene which is a methylene chloride preservative.
Related, byproducts include cyclohexanone, cyclohexenone, cyclohexanol,
cyclohexenol, chlorocyclohexene, and chiorocyclohexanol.
c. Aldol condensation reaction products of acetone include:. 4-hydroxy-4-methyl-2-
pentatone, 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 "A was not found on the quantitation list. If
the total area quantitation method was used, the reviewer should request mat the laboratory
recalculate the result using the proper quantitation ion. In addition, the reviewer should
evaluate other sample chromatograms and check library reference retention times on
quantitation lists to determine whether the false negative result is an isolated occurrence or
whether additional data may be affected.
7. TCL compounds may be identified in more than one fraction. Verify that quantitation is
made from the proper fraction.
8. Library searches should not be performed on internal standards or surrogates.
9. TIC concentration should be esthflaiedissuming a RRFDfl .0; ~ ~
£. Action
1. Ail TIC results should be qualified as tentatively identified (N) with estimated concentrations
(J)or(NJ).
2. General actions related to the review of TIC results are as follows:
a. A non-TCL compound is not considered to be "tentatively identified: until the mass
spectrum and retention time data have been reviewed as per section Xffl D. The
review should be documented on the Tentative Identification of Library Search
Compound worksheet. The worksheet will be useful if a better library match for the
unknown is retrieved in another Case, SAS, or SDG. It may also be used in writing
a Special Analytical Service Statement of Work to identify the unknown, or if the
sample is sent to an EPA research laboratory for LSC identification by multiple
spectral techniques.
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VS APPENDIX D
b. If all contractually required peaks were not library searched, die designated
representative could request these data from the laboratory.
3. TIC results which are not sufficiently above the level in die blank should not be reported.
(Dilutions and sample size must be taken into account when comparing die 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, die result may be qualified as unusable (R).
5. Hie reviewer may elect to report all similar isomers as a total. (All alkanes may be
summarized and reported as total hydrocarbons.)
6. Hie data reviewer should state die degree of confidence (high, medium, low) in die tentative
identification after completing die review process.
7. The complete "Tentative Identification of Library Search Compound" worksheet should be
attached to die final data review report.
D-ll
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APPENDIX E
GLOSSARY OF TERMS
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APPENDIX E
GLOSSARY OF TEEMS
APO Administrative Project Officer
%
BFB Bromofluorobenzene - volatile instrument perfonnance 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 Group(s).
i
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 Ffle
DFTPP Decafluorotriphenylphosphine - semivolatile instrument performance check compound
DPO Deputy Project Officer
EICP Extracted Ion Current Profile
GC/EC Gas Chromatograph/Electron capture
t
GC/MS Gas Chromatograph/Mass Spectrometer
GPC Gel Permeation Chromatography - A sample clean-up technique mat 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
t
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 Guidelines
NIST National Institute of Standards and Technology
PCB Polychlorinated biphenyl (Aroclor is a trademark)
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GLOSSARY APPENDIX E
PE Performance Evaluation Sample
QA Quality Assurance - Total program for assuring the reliability of data.
QC Quality Control - Routine application of procedures for controlling die monitoring process.
RIC Reconstructed Ion Chromatogram
RPD Relative Percent Difference (between matrix spike and matrix spike duplicate)
RRF Relative Response Factor
RRF Average Relative Response Factor
RRT Relative Retention Time (with relation to internal standard)
RSD Relative Standard Deviation
RT Retention Time
SDG Sample Delivery Group - Defined by one of the following, whichever occurs first:
* Case of field samples
* Each 20 field samples within a Case
* Each 14-day calendar period during which field samples hi 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 :
VOA Volatile Organic Analysis - Method based on the purge and trap technique for organic compound analysis.
VTSR Validated Time of Sample Receipt - Time of sample receipt at the laboratory as recorded on the shipper's
delivery receipt and Sample Traffic Report.
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