United States        Office of        Publication 9240.1 -23
         Environmental Protection    Solid Waste and      DR^SS/i9o/°9°
         Agency          Emergency Response    PB95-963519
         * '            a i t-      December 1994
         Superfund

v/EPA    USEPA CONTRACT
          LABORATORY PROGRAM

          NATIONAL FUNCTIONAL
          GUIDELINES FOR ORGANIC
          DATA REVIEW

          MULTI-MEDIA,
          MULTI-CONCENTRATION
          (ILMOLO)AND
          LOW CONCENTRATION WATER
          (OLC01.0)

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                                     9240.1-23
                                     PB95-963519
                                     E?A540/R-94/090
          USEPA CONTRACT LABORATORY PROGRAM
NATIONAL FUNCTIONAL GUIDELINES


                    FOR


        ORGANIC DATA REVIEW
           Multi-Media, Multi-Concentration (OLMOI.O)


                     »nd


             Low Concentration Water (OLCOl.O)
                  DRAFT

                  December, 1990
                 Revised June, 1991

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                                                          CONTENTS
                                                                                                   Page
              INTRODUCTION  	 1
              PRELIMINARY REVIEW  	 3
              DATA QUALIFIER DEFINITIONS  	 4
             VOLATILE DATA REVIEW	 5
              I.      Technical Holding Times  	 6
             II.     GC/MS Instrument Performance Check  	 9
             III.    Initial Calibration  	12
             IV.    Continuing Calibration  	16
             V.     Blanks   	18

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 X.     Internal Standards   	66
 XL    Target Compound Identification	 68
 XII.   Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)  . . 70
 XIII.   Tentatively Identified Compounds (TICs)	71
 XTV.   System Performance  	75
 XV.   Overall Assessment of Data  	77
APPENDIX A: Contractual Requirements and Equations, Multi-media Multi-concentration  ....  A-l
APPENDIX B: Contractual Requirements and Equations, Low Concentration Water	B-l
APPENDIX C Contractual Requirement Comparison Tables 	C-l
APPENDIX D: Proposed Guidance for Tentatively Identified Compounds (VOA and SV)	  D-l
APPENDIX Es Glossary of Terms	E-l
                                                                               DRAFT 12/90
                                                                                Revised 6/91

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                                          INTRODUCTION
         This document is designed to offer guidance on EPA Contract Laboratory Program (CLP) analytical
 data evaluation and review. In some applications it may be used as a Standard Operating Procedure (SOP).
 In other, more subjective areas, only general guidance is offered due to the-complexities and uniqueness of
 data relative to specific samples. For example, areas where the application of specific SOPs are possible are
 primarily those  in which definitive performance criteria are established.  These criteria are concerned with
 specifications that are not sample dependent; they specify performance requirements that should fully be under
 a laboratory's control  These specific areas include blanks, calibration standards, performance evaluation
 standard materials, and instrument performance checks (tuning).

         These Guidelines have been updated to include the requirements in the Statement of Work (SOW)
 for Organic Analysis  Multi-Media  Multi-Concentration (SOW OLM01.0),  and  the  SOW  for  Low
 Concentration Water Organic Analysis (SOW OLC01.0). To ensure that the data review guidelines that are unique
 to the Low Concentration  Water SOW an easily identified, these requirements and procedures art presented in "«/"-T and
 contained within brackets ({ J) throughout the document.

         This update includes changes  to instrument performance checks (formerly referred to as tuning)
 including changes to instrument performance checks and calibration criteria as a result of the Response Factor
 Workgroup. Minor revisions  to the Data  Qualifier Definitions from the previous National  Functional
 Guidelines are also included in this document.

         This document  is intended to assist in  the technical review of analytical data generated through the
 CLP. Determining contract compliance is not the intended objective of these guidelines or the regional data
 review process.  The data review process  provides information on analytical limitations of  data based on
 specific quality control (QC) criteria.  In order to provide more specific useabiliry statements, the reviewer
 must have a complete understanding of the intended use of the data. For this reason, it is recommended that
 whenever possible the reviewer obtain usability issues from the user prior to reviewing the data.  When this
 is not possible, the user should be encouraged  to communicate any questions to the reviewer.

        At times, there  may be an urgent need to use data which do not meet all contract requirements and
 technical criteria. Use of these data does not constitute either a new requirement standard or full acceptance
 of the data.  Any decision to  utilize data  for which performance criteria have not been met is strictly to
 facilitate the progress of projects requiring  the availability of the data.  A contract laboratory submitting data
 which are out of specification may be required to rerun samples or resubmit data even if  the previously
 submitted data have been utilized due to urgent program needs; data which do not meet specified requirements
 are never fully acceptable. The only exception to this requirement is in the area of requirements for individual
 sample analysis; if the nature of the sample itself limits the attainment of specifications, appropriate allowances
 must be  made. The overriding concern of the Agency is to obtain data which are technically valid and legally
 defensible.

        Appendix A is  based on  the Multi-media Multi-concentration SOW and contains appropriate
 contractual  requirements and  equations  for  verifying  various calculations.   Appendix B contains the
corresponding contractual requirements and equations from the Low Concentration Water SOW. Appropriate
equations are presented for easy reference and to allow the reviewer to verify calculations  as needed.
Contractual requirements are provided  to facilitate comparisons with the technical requirements.  For each
analytical fraction. Appendix C contains a table comparing contractual requirements of the Multi-media, Multi-
concentration with those of the Low Concentration Water  SOWs.  Appendix D contains proposed  guidance
for Tentatively identified Compounds (VOA and SV), and Appendix E contains a glossary of commonly used
terms.

                                                                                      DRAFT 12/90
                                                 1                                     Revised 6/91

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        The data review should include comments that clearly identify the problems associated with a Case
or Sample Delivery Group and to state the limitations of the data. Documentation should include .the sample
number, analytical method, extent of the problem, and assigned qualifiers.

        A data review narrative generally accompanies the laboratory data forwarded to the intended data
recipient (client) or user to promote communication.  A copy of the data review narrative should be submitted
to the CLP Quality Assurance Coordinator (QAC), the Regional CLP  Technical Project Officer (TPO)
assigned oversight responsibility for the laboratory producing the data, and the Environmental Monitoring
Systems Laboratory in Las Vegas, Nevada (EMSL-LV).

        It is the responsibility of the data reviewer to notify the appropriate Regional CLP TPO concerning
problems and deficiencies with regard to laboratory data.  If there is an urgent requirement, the TPO may be
contacted by telephone to expedite corrective action. It is recommended that all items for TPO action be
presented at one time.
                                                                                     DRAFT 12/90
                                                                                      Revised 6/91

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                                      PRELIMINARY REVIEW


         In order to use this document effectively, the reviewer should have a general overview of the sample
  delivery group (SDG) or case at hand. The exact number of samples, their assigned numbers, their matrix.
  and the number of laboratories involved in their analysis are essential information.  Background information
  on the site is helpful but often this information may be difficult to locate. The site manager is the best source
  for answers to questions or further direction.

         Contract Compliance Screening (CCS) is a source of summarized information regarding contract
  compliance. If available, it can be used to alert the reviewer to problems  in the SDG data package.

         Sample cases (SDGs) routinely have unique samples which require special attention by the reviewer.
  These include field blanks, field duplicates, and performance audit samples which need to be identified.  The
  sampling records should provide:

                1. Project Officer for site.

                2. Complete list  of samples with information on:

                       a. sample matrix
                       b. field blanks,
                       c field duplicates,
                       d. field spikes,
                       e. QC audit samples,
                       f. shipping dates, and
                       g. laboratories involved.

        The chain-of-custody record includes sample descriptions and date(s) of sampling. The reviewer must
 take into account lag times between sampling and receipt for analysis when assessing  technical sample holding
 times.

        The laboratory's SDG Narrative is another source of general information.  Notable  problems  with
 matrices, insufficient sample volume for analysis or reanalysis, samples received in broken containers, and
 unusual events should be found in the SDG Narrative.

        The SDG Narrative for the sample data package must include a Laboratory Certification Statement
 (exactly as stated.in the SOW), signed by the laboratory manager or his designee. This statement authorizes
 the validation and release of the sample data results.  In addition, the laboratory must also provide comments
 in the SDG narrative describing in detail any problems encountered in processing the samples in the  data
 package.

        For every data package, the reviewer must verify that the laboratory certification statement is present.
exactly stated as in the SOW (Le^ verbatim to the statement in  the SOW), and signed by the Laboratory
Manager or designee.   The reviewer must further verify  that  the  data package is consistent with the
laboratory's certified narrative. Also, the reviewer should check the comments provided in the narrative to
determine if they are sufficient to describe and explain the associated problem.
                                                                                     DRAFT 12/90
                                                                                      Revised 6/91

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                                 DATA QUALIFIER DEFINITIONS


        The following definitions provide brief explanations of the national qualifiers assigned to results in
the data review process. If the Regions choose to use additionaT qualifiers, a complete explanation of those
qualifiers should accompany the data review.
 U      •      The analyte was analyzed for, but was not detected above the reported sample quantitation
               Unit
J      -       The analyte was positively identified; the associated numerical value is the approximate
               concentration of the analyte In the sample.


N      •       The analysis indicates the presence of an analyte for which there is presumptive evidence to
               make a 'tentative identification.'
NJ    •       The analysis indicates the presence of an analyte that has been "tentatively identified* and
               the associated numerical value represents its approximate concentration.


UJ    •       The analyte was not detected above the reported sample qnantitation limit However, the
               reported qnantitation limit is approximate and may or may not represent the actual limit of
               quantitation necessary to accurately and precisely measure the analyte in the sample.
               The sample results are rejected due to  serious deficiencies in the ability to analyze the
               sample and meet quality control criteria.  The presence or absence of the analyte cannot be
               verified.
                                                                                     DRAFT
                                                                                       Revised 6/91

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                                                                                            VGA
                                   VOLATILE DATA REVIEW    .

 •"• Data review guidelines that are unique to data generated through the Low. Concentration Water SOW an contained
 within brackets ({ J) and written in italics. M*


 The volatile data requirements to be checked are listed below

        I.       Technical Holding Times (CCS - Contractual holding times only)

        II.      GC/MS Instrument Performance Check (CCS)

        IIL      Initial Calibration (CCS)

        IV.      Continuing Calibration (CCS)

        V.      Blanks

        VL     System Monitoring Compounds (Surrogate Spikes) (CCS)

        VII.    Matrix Spikes/Matrix Spike Duplicates

        Vttl.    Laboratory Control Samples (CCS)

        DC     Regional Quality Assurance and Quality Control

        X.     Internal Standards (CCS)

        XI.     Target Compound Identification

        XII.    Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)

        XIII.   Tentatively Identified Compounds

        XIV.   System Performance

        XV.    Overall Assessment of Data
NOTE: "CCS" indicates that the contractual requirements for these items will also be checked by CCS:
       CCS requirements are not always the same as the data review criteria.
                                                                                    DRAFT 12/90
                                                                                     Revised 6/91

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                                                                                            VOA


                                    L  Technical Holding Times
        Review Items:  Fora I VOA [Fern ILCVJ, 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.

        Criteria

        Technical requirements for sample holding times have only been established for water matrices.
        The holding times for soils (and other non-aqueous matrices such as sediments, oily wastes, and
        sludge) are currently under investigation.  When the results are available they will be incorporated
        into the data evaluation process.  Additionally, results of holding time studies will be incorporated
        into the data review criteria as the studies are conducted and approved.

        The holding time criteria for water samples, as stated in the current 40 CFR Pan 136 (Clean
        Water Act)  is as follows:

               For non-aromatic volatile compounds in cooled (@ 4*C) water samples,
               the  maximum holding time is 14 days from sample collection.

               Maximum holding times for  purgeable aromatic hydrocarbons in cooled
               (@  4°C +. 2*Q, acid-preserved (pH 2 or below) water samples is 14 days
               from sample collection.

               Water samples that have  not been maintained at 4°C (+. 2°C) and
               preserved to a  pH of 2 or below should be analyzed within 7 days from
               sample collection.  If insufficient ice is used to ship samples, the
               laboratory may receive samples with no ice left in the cooler.  Under
               these circumstanes, the temperature of the samples may exceed 4°C.

        It is funher  recommended that volatile compounds in properly preserved non-aqueous samples be
        analyzed within 14 days of sample collection.

        The contractual maximum holding times, which differ from the technical maximum  holding times,
        state that water and soil samples are to be analyzed within 10 days from the validated time of
        sample receipt (VTSR) at the laboratory.
D.     Evaluation
       Technical holding times are established by comparing the sampling dates on the EPA Sample
       Traffic Report with dates of analysis on Form I VOA (Form ILCV] and the raw data.  Information
       contained in the complete SDC file (formerly called the  purge file) should also be considered in
       the determination of holding times. Verify that (he analysis dates on the Form Is and the raw


                                                6                                    DRAFT 12/90
                                                                                      Revised 6/91

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Technical Holding Times
                                                                               VGA
       data/SDG file are identical.  Examine the sample records to determine if samples were preserved.
       If adequate documentation on sample preservation is not available, contact the sampler.  If the
       sampler cannot be contacted, then it must be assumed that the samples are unpreserved. If there
       is no indication in the SDC  narrative or the sample records that there was a problem with the
       samples (e.g., samples not maintained @ 4*C or containing headspace in the samples), then the
       integrity of samples can be assumed to be good. If it is  indicated that there were problems with
       the samples, then the integrity of the sample may have been compromised and professional
       judgement should be used to evaluate the effect of the problem on the sample results.
       Action
       1.
If technical holding times are exceeded, document in the data review narrative that
holding times were exceeded and qualify the sample results as follows (also see Table 1):

a.      If there is no evidence that the samples were property preserved and the technical
        holding times exceeded 7 days, qualify positive results for aromatic compounds
        with T and sample quantitation limits with "UJ". Use professional judgement to
        determine if and how non-aromatic volatile compounds should also be qualified.

b.      If the samples were properly preserved but the technical holding times exceeded
        14 days, qualify positive results with "J" and sample quantitation limits with "UJ".
            Table 1. Qualification of Volatile Analytes Based on Technical Holding Times
MATRIX
Water

Non-aqueous
PRESERVED
No
Yes
No/Yes
> 7 DAYS
All Aromatics*
None
Professional
Judgement
> 14 DAYS
All Compounds
All Compounds
Professional
Judgement
                      Reviewer should use professional judgement to determine if data for
                      additional compounds require qualification.
              If technical holding times are grossly exceeded (e.g., by greater than two times the
              required time for volatiles) either on the first analysis or upon re-analysis, the reviewer
             •must use professional judgement to determine the reliability of the data and the effects of
              additional storage on the sample results. Should the reviewer determine that qualification
              is necessary, non-detected volatile target compounds may be qualified unusable (R).
              Positive results are considered approximates and are qualified with "J".
                                                                                     DRAFT 12/90
                                                                                      Revised 6/91

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Technical Holding rimes                        •                                           .    VOA


        3.      Due to limited information concerning holding times for non-aqueous samples, it is left to
               the discredon of the data reviewer to apply water holding times or other information that
               is available.

        4.      Whenever possible, the reviewer should comment on the effect of the holding time
               exceedance on the resulting data in the data review narrative.

        5.      When contractual and/or technical holding times are grossly exceeded, this should be
               noted for TPO action.

        6.      The reviewer should also be aware of the scenario in which the laboratory has exceeded
               the "^"fral holding times, but met contractual holding times. In  this case, the data
               reviewer should notify the Regional TPO (where samples were collected) and/or RSCC
               that shipment delays have occurred so that the field problem can be corrected. The
               reviewer may pass this information on to the laboratory's TPO, but should explain that
               contractually the laboratory met the requirements.
                                                                                     DRAFT 12/90
                                                                                      Revised 6/91

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                                                                                        VGA


                            EL   GC/MS Instrument Performance Check


        Review Items:  Form V VOA (Farm V LCVJ, BFB mass spectra and mass listing.

        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.

        Criteria

        The analysis of the instrument performance check solution must be performed at the beginning of
        each 12-hour period during which samples or standards are analyzed. The instrument
        performance check, bromofluorobenzene (BFB) for volatile analysis, must meet the ion abundance
        criteria given below.



                     Bromofluorobenzene (BFB)

                     m/z           ION ABUNDANCE CRITERIA

                     50             8.0 - 40.0% of m/z 95
                     75             mo - 66.0% of m/z 95
                     95             Base peak, 100% relative abundance
                     96             5.0 - 9.0% of m/z 95
                     173            Less than 10% of m/z 174
                     174           50.0 - 120.0% of m/z 95
                     175            4.0 - 9.0% of mass  174
                     176           93.0 - 101.0% of m/z 174
                     177            5.0 - 9.0% of m/z 176
       NOTE: All ion abundances must be normalized to m/z 95, the nominal base peak, even though
              the ion abundance of m/z 174 may be up to 120 percent that of m/z 95.
D.     Evaluation
       1.      Compare the data presented for each Instrument Performance Check (Form V VOA
              /Form VLCVJ) with each mass listing submitted to ensure the following:

              a.      Form V VOA /Form VLCV] is present and completed for each 12-hour period
                     during which samples were analyzed.
                                                                                 DRAFT 12/90
                                                                                  Revised 6/91

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 GC/MS Instrument Performance Check          •                              .             •    VOA


               b.      The laboratory has not made transcription errors between the data and the form.
                       If there are major differences between the mass listing and the Form Vs, a more
                       in-depth review of the data is required. This may include obtaining and reviewing
                       additional information from the laboratory.

               c.      The appropriate number of significant figures has been reported (number of
                       significant figures given for each ion in the ion abundance criteria column) and
                       that rounding is correct.

               d.      The laboratory has not made calculation errors.

        2.      Verify from the raw data (mass spectral listing) that the mass assignment is correct and
               that the mass listing is normalized to m/z 95.

        3.      Verify that the ion abundance criteria was met. The criteria for m/z 173,176, and  177 are
               calculated by normalizing to the specified m/z.

        4.      If possible, verify that spectra were generated using appropriate background subtraction
               techniques. Since the BFB spectrum is obtained from chromatographic peaks that should
               be free from coelution problems, background subtraction  should be done in accordance
               with the following procedure. .Three scans (the peak apex scan and the scans immediately
               preceding and following the apex) are acquired and averaged and background subtraction
               must be accomplished using a single scan prior to the elution of BFB.


        NOTE: All instrument conditions must be identical to those used in the sample analysis.
               Background subtraction actions resulting in spectral distortions for the sole  purpose of
               meeting the contract  specifications are  contrary to the quality assurance objectives  and are
               therefore unacceptable.


£.      Action

        1.      If the  laboratory has made minor transcription errors which do not significantly affect the
               data, the data reviewer should make the necessary corrections on a copy of the  form.

        2.      If the  laboratory has failed to provide the correct forms or has made significant
               transcription or calculation errors, the  Region's designated representative should contact
               the laboratory and request corrected data.  If the information is not available, then the
               reviewer must use professional judgement to assess the data. The laboratory's TPO
               should be notified.

        3.      If mass assignment is in error (such as  m/z 96 is indicated as the base peak rather  than
               m/z 95), classify all associated data as unusable (R).

        4.      If ion  abundance criteria are not met, professional judgement may be applied to determine
               to what  extent the data may be utilized. Guidelines to aid in the application of
               professional judgement to this topic are discussed as follows:


                                                10                                     DRAFT 12/90
                                                                                       Revised 6/91

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GC/MS. Instrument Performance Check         '                             •              '    VOA
               The most important factors to consider are the empirical results that are relatively
               insensitive to location on the chromatographic profile and the type of instrumentation.
               Therefore, the critical ion abundance criteria for BFB are the m/z 95/96. 174/175, 74/176,
               and 1767177  ratios. The relative abundances of m/z 50 and 75 are of lower importance.

       5.      Decisions to use analytical data associated with BFB instrument performance checks not
               meeting contract requirements should be clearly noted on the data review narrative.

       6.      If the reviewer has reason to believe that instrument performance check criteria were
               achieved using techniques other than those described in Q.O.4, then additional
               information on the instrument performance checks should be obtained.  If the techniques
               employed are found to be at variance with the contract requirements, the performance and
               procedures of the  laboratory may merit evaluation.  Concerns or questions regarding
               laboratory performance should be noted for TPO  action. For example,  if the reviewer has
               reason to believe that an inappropriate technique was used to obtain background
               subtraction (such as background subtracting from  the solvent front or from another region
               of the chromatogram rather than the BFB peak),  then this should be noted for TPO
               action.
                                               11                                    DRAFT 12/90
                                                                                     Revised 6/91

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                                                                                                 VOA
 A.      Review Items: Form VI VOA (Form VILCV], 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 (TOL).  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

         I.      Initial calibration standards containing both volatile target compounds and system
                monitoring compounds are analyzed at concentrations of 10,20,50,100, and 200 ug/L at
                the beginning of each analytical sequence or as necessary if the continuing calibration
                acceptance criteria are not met. The initial calibration (and any associated samples and
                blanks)  must be analyzed within 12 hours of the associated instrument performance check.

                [Far data generated through the La* Concentration Water SOW: Initial calibration standards containing
                both volatile target compounds and surrogate ire catalyzed at concentrations of I, 2, 5, 10, and 25 ug/L
                far non-kaones and S, 10, 25, 50, and 125 ug/L for ketones a the beginning of each anatmcai sequence
                or as necessary if die continuing calibration acceptance criteria are not met.  The initial calibration (and
                any associated samples and blanks) must be analyzed within 12 hours of the associated BFB tuning
                cheek.}

        2.      Separate initial calibrations must be performed for water samples (or medium level soil
                samples) and for low level  soil samples.  The calibration for water samples and medium
                level soil samples is performed with an unheated. purge and the calibration for low level
                soil samples is performed with a heated purge.

        3.      Initial calibration standard Relative Response Factors (RRFs) for all volatile target
                compounds and system monitoring compounds (surrogates) must be greater than or equal
                to 0.05.  (Contractual initial calibration RRF criteria are listed in Appendix A [Appendix
                B])

        4.      The Percent Relative Standard Deviation (%RSO) from the initial calibration must be
                less than or equal to 30.0% for all compounds.

O.      Evaluation

        1.       Verify that the correct concentration  of standards  were used for the initial calibration (i.e.,
                10, 20, 50, 100, and 200 ug/L for water).

                [Verify that the correct concentration of standards were used for the initial calibration (Le., 1, 2. 5. 10.
                and 25 ug/L for non-ketones and 5, 10, 25, 50, and 125 ug/L for ketones).]
                                                  12                                     DR.\FT 12/90
                                                                                          Revised 6/91

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Initial Calibration                              •                                            •    VOA
       2.      Verify that the correct initial calibration was used for water and medium level soil samples
               (Le~, unheated purge) and for low level soil samples (Le., heated purge).

       3.      If any sample results were calculated using an initial calibration, verify that the correct
               standard (Le^ 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.

               (If any ample results wen calculated using on aiiaol calibration, verify that the correct standard (Le..
               the 5 ug/L for non-ketones and 25 ug/L for ketones) was used far calculating sample results and that the
               samples were analyzed within 12 hours of the associated instrument performance check.]

       4.      Evaluate the initial calibration RRFs and  KRT" for all volatile target compounds and
               system monitoring compounds (surrogates):

               a.      Check and recalculate the RRFs and KEF" for at least one volatile target
                      compound associated with each internal standard; verify that the recalculated
                      value(s) agrees with the laboratory reported value(s).

               b.      Verify that for all volatile target compounds and system monitoring compounds
                      (surrogates), the initial calibration RRFs are greater than or equal to 0.05.

       NOTE:  Because historical performance data indicate poor response and/or erratic behavior, the
              volatile compounds in Table 2 have no contractual maximum %RSD criteria.
               Contractually they must meet a minimum  RRF criterion of 0.01, however, for data review
              purposes, the "greater than or equal to 0.05* criterion is applied to all volatile compounds.
                   Table 2. Volatile Target Compounds Exhibiting Poor Response

                      Acetone                              1.2-Dichloropropane
                      2-Butanone                           2-Hexanone
                      Carbon disulfide                       Methylene chloride
                      Chloroethane                          4-Methyl-2-pentanone
                      Chloromethane                        Toluene-48 f
                      U-Dichloroethene (total) f             l,2-Dichloroethane
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Initial Calibration
               b.      Verify that all volatile target compounds have a %RSD of less than or equal to
                      30.0%. The contractual criteria for an acceptable initial calibration specifies that
                      up to any 2 volatile target compounds may fail to meet minimum RRF or
                      mariniuTn %RSD as long as they have RRFs that are greater than or equal to
                      0.010, and %RSD of less than or equal to 40.0%. For data review purposes,
                     •however,  all compounds must be considered tor 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.

               If errors are detected in the calculations of either the RRFs or the %RSD, perform a
               more comprehensive  recalculation.
      Action
              All volatile target compounds, including the 12 'poor performers* will be qualified using
              the following criteria:

              a.      If the %RSD is greater than 30.0% and all initial calibration RRFs greater than
                     or equal to O.OS, qualify positive results with T, and non-detected volatile target
                     compounds using professional judgement.

              b.      If any initial calibration RRF is less than O.OS, qualify positive results that have
                     acceptable mass spectral identification with T, using professional judgement, and
                     non-detected analytes as unusable (R).

              At the reviewer's discretion, a more in-depth review to minimize the qualification of data
              can be accomplished by considering the following:

              a.      If any of the required volatile compounds have a %RSD greater than 30.0%, and
                     if eliminating either the  high or the low point of the curve does not restore the
                     %RSD to less than or equal to 30.0%:

                     i.       Qualify positive results for that compound(s) with "J*.

                     ii.      Qualify non-detected volatile target compounds based on professional
                             judgement

              b.      If the high point of the curve is outside of the linearity criteria (e.g. due to
                     saturation):

                     i.       No qualifiers are required for positive results in the linear portion of the
                             curve.
                                               14                                    DRAFT 12/90
                                                                                     Revised 6/91

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Initial Calibration                             '                        ,                     •    VGA


                       ii.      Qualify positive results outside of the linear portion of the curve with a
                               "J".

                       iiL      No qualifiers are needed volatile target compounds that were not
                               detected.

               c.       If the low end of the curve is outside of the linearity criteria:

                       i.       No qualifiers are required for positive results in the linear portion of the
                               curve.

                       ii.      Qualify low level positive results in the area of non-linearity with "J*.

                       iil      Qualify non-detected volatile target compounds based on professional
                               judgement

       3.       If the laboratory has failed to provide adequate calibration information, the designated
               representative should contact the laboratory and request the necessary information.  If the
               information is not available, the reviewer must use professional judgement to assess the
               data,

       4.       Whenever possible, the potential effects on the data due to calibration criteria exceedance
               should be noted in the data review narrative.

       5.       If calibration criteria are grossly exceeded,  this should be noted for TPO action.
                                                 15                                     DRAFT '.2/90
                                                                                         Revised 6/91

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                                                                                             VGA


                                    IV.  Continuing Calibration


A.      Review Items:  Form Vn VOA [Farm W LCVJ, quantitation reports, and chromatograms.

B.      Objective-

        Compliance requirements for satisfactory instrument calibration are established to ensure that the
        instrument is capable of producing acceptable qualitative and quantitative data. Continuing
        calibration establishes the 12-hour relative response factors on which the quantitations are based
        and checks satisfactory performance of the instrument on a day-to-day basis.

C.      Criteria

        1.      Continuing calibration standards containing both target compounds and system
               monitoring compounds (surrogates) are analyzed at the beginning of each 12-hour analysis
               period following the analysis of the instrument performance check and prior to the
               analysis of the method blank and samples.

        2.      The continuing  calibration RRF for volatile target compounds and system monitoring
               compounds (surrogates) must be greater than or equal to 0.05.

        3.      The percent difference (%D) between the initial calibration RRF" and the continuing
               calibration RRF must be within  ± 25.0%.

               [far data generated rtroagft the Law Concentration Water SOW: The percent difference (%D) between
               the initial calibration RRF and the continuing calibration RRF must be within ± 30.0%.]

D.      Evaluation

        1.      Verify that the continuing calibration was run at the required  frequency and that the
               continuing calibration was compared to the correct initial calibration.

        2.      Evaluate the continuing calibration RRF for all volatile target compounds and system
               monitoring compounds:

               a.       Check and recalculate the continuing calibration RRF for at least one volatile
                       target compounds associated with each internal standard; verify that the
                       recalculated value(s) agrees with  the laboratory reported value(s).

               b.       Verify that all volatile target compounds and system monitoring compounds meet
                       the RRF specifications.


        NOTE: Because historical performance data indicate poor response and/or erratic behavior, the
               compounds listed in Table 2 (Section IILD.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.


                                               16                                   DRAFT 12/90
                                                                                      Revised 6/91

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Continuing Calibration                       '                        .                    '    VGA


        3.      Evaluate the %D between initial calibration RRF  and continuing calibration RRF for
               one or more compouad(s).

               a.      Check and recalculate the %O for one or more volatile target compound(s)
                       associated with each internal standard; verify that the recalculated value(s) agrees
                      - with the laboratory reported value(s).

               b.      Verify that the %D is within ± 25.0% for all volatile target compounds and
                       system monitoring compounds. Note those compounds which have a %D outside
                       the i 25.0% criterion.  The contractual criteria for an acceptable continuing
                       calibration specifies that up to any 2 volatile target compounds may fail to meet
                       minimum RRF or maximum %D as long as they have RRFs that are greater than
                       or equal to 0.010, and %D of less than or equal to 40.0%. For data review
                       purposes, however, all compounds must be considered for qualification when the
                       %O exceeds the +. 25.0% criterion.

        4.      If errors are detected in the calculations of either the continuing calibration RRF or the
               %D, perform a more comprehensive recalculation.

E.      Action

        1.      The reviewer should use professional judgement to determine if it is necessary to qualify
               the data for any volatile target compound. If qualification of data is required, it should be
               performed using the following guidelines:

               a.       If the %D is outside the +, 25.0% criterion and the continuing calibration RRF is
                       greater than or equal to 0.05, qualify positive results with  *J".

               b.       If the %D is outside the ± 25.0% criterion and the continuing calibration RRF is
                       greater than or equal to 0.05. qualify non-detected volatile target compounds with
                       •ur.

               c.       If the continuing  calibration RRF is less than 0.05, qualify positive results that
                       have acceptable mass spectral identifications with "J" or use professional
                      judgement

               d.       If the continuing  calibration RRF is less than 0.05, qualify non-detected volatile
                      target compounds as unusable (R).

       2.      If the laboratory has failed to provide adequate calibration information, the designated
               representative should contact the laboratory and request the necessary information. If the
               information is not available, the reviewer must use professional judgement to assess the
             •data.

       3.      Whenever possible, the potential effects on the data due to calibration criteria exceedance
               should be noted in the data review narrative.

       4.      If calibration criteria are grossly exceeded, this should be noted for TPO  action.


                                                17                                    DRAFT 12/90
                                                                                       Revised 6/91

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                                                                                              VGA
                                            V.  Blanks
        Review Items: Form I VOA {farm ILCVJ, Form IV VGA {Form lYLCyj, chromatograms. and
        quantiution reports.

        Objective

        The purpose of laboratory (or field) blank analysis is to determine the existence and magnitude of
        contamination resulting from laboratory (or field) activities. The criteria for evaluation of blanks
        apply to any blank associated with the samples (e.g« method blanks, instrument blanks, trip
        blanks, and equipment blanks). If problems with anv blank exist, all associated data must be
        carefully evaluated to determine whether or not there is an inherent variability in the data, or if
        the problem is an isolated occurrence not affecting other data.

        Criteria

        1.      No contaminants should be found in the blanks.

        2.      A method blank analysis must be performed after the calibration standards and once for
               every 12-hour time period beginning with the injection of BFB.

        3.      The method blank must be analyzed on each GQMS system used to analyze samples for
               each type of analysis, Le., unheated purge (water and medium level soil) and heated purge
               (low level soil).

        4.      An instrument blank should be analyzed after any sample that has saturated ions from a
               given compound to check that the blank is free of interference and the system is not
               contaminated.

        [5.      For data generated through the Low Concentration Water SOW: A storage blank must be prepared upon
               receipt of the first samples from art SDC, and stored with samples until analysis.  The storage blank musi
               be analyzed once per SDC.]
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 (Form IV LCvf) to
               identify the samples associated with each method blank.

        3.      Verify that the instrument blank analysis has been performed following any sample
               analysis where a target analyte(s) is reported at high concentration^).
                                                18                                    DRAFT 12/90
                                                                                       Revised 6/91

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Blanks                                       •                                            •    VQA
       (4.      Verify that a storage blank has been analyzed and included with tack SDG and that the storage blanks
               an free of contamination.]

       Action

       If the appropriate blanks were not analyzed with the frequency described in Criteria 2, 3, and 4,
       [and 5] then the data reviewer should use professional judgement to determine if the associated
       sample data should be qualified.  The reviewer may need to obtain additional information from
       the laboratory. The situation should be noted for TPO action.

       Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
       Positive sample results should be reported unless the concentration of the compound in the
       sample is less  than or equal to 10 times (lOx) the amount in any blank for  the common volatile
       laboratory contaminants (mettarlene chloride, acetone, and 2>butanone), or 5 times (5x) the
       amount for other volatile target compounds.  In instances where more than one  blank is associated
       with a given sample, qualification should be based upon a comparison with the associated blank
       having the highest concentration of a contaminant.  The results must not be corrected by
       subtracting any blank value.
       Specific actions are as follows:

       1.       If a volatile compound is found in a blank but not found in the sample, no action is taken.
               If the contaminants found are volatile target compounds (or interfering non-target
               compounds) at significant concentrations above the CRQL, then this should be noted for
               TPO action.

       2.       Any volatile compound detected in the sample (other than the common volatile laboratory
               contaminants), that was also detected in any associated blank, is qualified if the sample
               concentration is less than five times (5x) the blank concentration.  The quantitation limit
               may also be elevated. Typically, the sample CRQL is elevated to the concentration found
               in the sample.  The reviewer should use professional judgement to determine if further
               elevation of the CRQL is required.  For the common volatile laboratory contaminants, the
               results are qualified by elevating the quantitation limit to the concentration found in the
               sample when the sample concentration is less than 10 times (lOx) the blank concentration.

               The reviewer should note that blanks may  not involve the same weights, volumes, or
               dilution factors as the associated samples.  These factors must be taken into consideration
               when applying the *5x" and "lOx" criteria, such that a comparison of the total amount of
               contamination is actually made.

               Additionally, there may be instances where little or no contamination was present in the
               associated blanks, but qualification of the sample is deemed necessary. If the reviewer
              determines that the contamination is from a source other than the sample, he/she  should
              qualify the data. Contamination introduced  through dilution water is one example.
               Although  it is not always possible to determine, instances of this occurring can be
              detected when contaminants are found  in the diluted sample  result, but are absent in the
               undiluted  sample result  Since both results are not routinely reported, it may be
               impossible to verify this source of contamination.  In this case, the "5x" or "10x" rules may

                                               19                                    DRAFT 12/90
                                                                                       Revised 6/91

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Blanks                                          '                                -              '     VGA
                not apply;  the target compound should be reported as not detected, and an explanation of
                the data qualification should be provided in  the data review narrative.
        3.       If gross contamination exists (Le., saturated peaks by GC/MS), all affected compounds in
                the associated samples should be qualified as unusable (R) due to interference.  This
                should be noted for TPO action if the contamination is suspected of having an effect on
                the sample results.

        4.       If inordinate numbers of other target compounds are found at low levels in the blank(s), it
                may be indicative of a problem and should be noted for TPO action.

        5.       The same consideration given to the target compounds should also be given to Tentatively
                Identified Compounds (TTCs), which are found in both the sample and associated
                blanks).  (See VOA Section XTJ for TIC guidance.)

        6.       If an instrument blank was not analyzed following a sample analysis which contained an
                analyte(s) at high concentrations), 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.

        [7.       If contaminants are found in the storage blanks, the following action is recommended.

                a.      The associated method blank data should  be reviewed to determine ifthecoruammant(s)was
                       also present at the method blank.  If die anatyu was present at a comparable level in the
                       method blank, then the source of the contamination may be in the anatyacal system and the
                       action recommended for the method blank would apply.

                       If the anofyie was not present in the method blank, then the source of contamination may be in
                       the storage and all associated samples should be considered for possible cross-contamination.

                b.      If the storage blank contains a volatile TCL compound(s) at a concentration greater than the
                       CRQL then all positive results for that compounds(s) should be qualified with "J".  If the
                       concentration level in the blank is significantly high, then positive sample results may require
                       rejection and be qualified with  "R". Non-detected volatile target compounds should not require
                       <7Tffl/'jff-ff'ffT unless the contamination is so high that it interferes with the analysts of the nan-
                       detect compounds.}
                                                  20                                      DRAFT 12!90
                                                                                            Revised 6/91

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Blanks
                                                               VGA
       The following are examples of applying the blank qualification guidelines. Certain circumstances
       may warrant deviations from these guidelines.
               Example 1:
              Example 2:
              Example 3:
Sample result is greater than the Contract Required Quantitation Limit
(CRQL). but is less than the 5x or IQx multiple of the blank result.
                             Blank Result
                             CRQL
                             Sample Result
                             Final Sample Result
                                     10x

                                      7
                                      5
                                      60
                                      60U
                                                                          Rule
5*

7
5
30
SOU
                             In the example for the "10x" rule, sample results less than 70 (or 10 x 7)
                             would be qualified as not detected.  In the case of the "5x* rule, sample
                             results less than 35 (or 5 x 7) would be qualified as not detected.
Sample result is less than the CRQL, and is also less than the 5x or IOx
multiple of the blank result
                             Blank Result
                             CRQL
                             Sample Result
                             Final Sample Result
                                     IOx

                                       6
                                       5
                                      4J
                                      5U
                                                                          Rule
5*

6
5
4J
5U
                             Note that data are not reported as 4U, as this would be reported as a
                             detection limit below the CRQL.
Sample result is greater than the 5x or IOx multiple of the blank result.

                                            Rule
                             Blank Result
                             CRQL
                             Sample Result
                             Final Sample Result
                                      10
                                       5
                                      120
                                      120
 10
 5
 60
 60
                             For both the "IOx" and "5x" rules, sample results exceeded the adjusted
                             blank results of 100 (or 10x10) and 50 (or 5x10), respectively.
                                               21
                                                       DRAFT 12/90
                                                        Revised 6/91

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                                                                                             VGA


                                VI.  System Monitoring Compounds
                                          (Surrogate Spikes)

A.      Review Items:  Form II VOA (Form U LCV]t quantitatioa reports, and chromatograms.

B.      Objective

        Laboratory performance on individual samples is established by means of spiking activities. All
        samples are spiked with system monitoring compounds (formerly referred to as surrogates) prior
        to sample purging.  The evaluation of the results of these system monitoring compounds is not
        necessarily straightforward. The sample itself may produce effects due to such factors as
        interferences and high  concentrations of anaiytes. Since the effects of the sample matrix are
        frequently outside the control of the laboratory and may present relatively unique problems, the
        evaluation  and review of data based on specific sample results is frequently subjective and
        demands analytical experience and professional judgement Accordingly, this section consists
        primarily of guidelines, in some cases with several optional approaches suggested.

C.      Criteria

        1.      Three system monitoring compounds (1.2-dichloroethane-d4. bromofluorobenzene, and
               toluene-d8) are added to all samples and blanks to measure their recovery in
               environmental  samples in sample and blank matrices.

               [far data generated through the Low Concentration Water SOW: A single surrogate,
               oromofluaroberaeru, is added to all samples and blanks to measure the recovery in sample and blank
               matrices.)

        2.      Recoveries for system monitoring compounds (surrogates] in volatile samples and blanks
               must be within the limits specified in Appendix A (Appendix B] and  the SOW.

D.      Evaluation

        1.      Check raw data (e.g., chromatograms and quaniitation reports) to verify the recoveries on
               the System Monitoring Compound Recovery Form -  Form II VOA (Surrogate Recovery Form
               • Farm IILCVJ.  Check for any calculation or transcription errors.

        2.      Check that the system monitoring compound {surrogate] recoveries were calculated
               correctly. The equation can  be found in Appendix A [Appends B).

        3.      The following should be determined from the System Monitoring Compound [Surrogate]
               Recovery form(s):

               .a.      If any system monitoring {surrogateI 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 [surrogate] recoveries followed
               by  successful re-analyses, the laboratories are required to report only the successful run.

                                                22                                    DRAFT 12/90
                                                                                       Revised 6191

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 System .Monitoring Compounds                '                       .                    '    VOA
      (Surrogates)


               b.      The laboratory Eailed to perform acceptably if system monitoring compounds
                       [surrogate] are outside criteria with no evidence of re-analysis. Medium soils must
                       first be re-eztnctracted prior to re-analysis when this occurs.

               c.     .Verify that no blanks have system monitoring compounds [surrogate] outside the
                       criteria.

        4.      Any time there are two or more analyses for a particular sample, the reviewer must
               determine which are the best data to report. Considerations should include but are not
               limited to:

               a.      System monitoring compound [surrogate/ recovery (marginal versus gross
                       deviation).

               b.      Technical holding times.

               c.      Comparison of the values of the target compounds reported in each sample
                       analysis.

               d.      Other QC information, such as performance of internal standards.

E.     Action

       Data are qualified based on system monitoring compounds [surrogate) results if the recovery of any
       volatile system monitoring compound [aarogau] is oat of specification.  For system monitoring
       compound [surrogate] recoveries out of specification, the following approaches are suggested based
       on a review of all data from the package, especially considering the apparent complexity of the
       sample  matrix.


       1.      If a system monitoring compound [surrogate] in the volatile sample has a recovery greater
               than  the upper acceptance limit (UL):

               a.      Detected volatile target compounds are qualified "J.".

               b.      Results for non-detected volatile target compounds should not be qualified.

       2.      If a system monitoring compound [sumgau] in the volatile sample has a recovery greater
               than  or equal to 10% but less than the lower acceptance limit (LL):

               a.      Detected volatile target compounds are qualified "J."

               b.      For non-detected volatile target compounds, the sample quantitation limit is
                      qualified as approximated  (UJ).
                                               23                                    DRAFT 12/90
                                                                                      Revised 6/91

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System Monitoring Compounds
      (Surrogates)
                                                                              VGA
       3.      If a system monitoring compound (sumgauj in a volatile sample shows less than 10%
               recovery:

               a.      Detected volatile target compounds are qualified T.

               b.      Non-detected volatile target compounds may be qualified as unusable (R).
                        Table 3. Qualification of Volatile Analytes Based on
                        System Monitoring Compound (Surrogate] Recoveries

Detected anaiytes
Non-detected anaiytes
SMGSurrogate Recovery
» UL 10% 10 LL < 10%
J
No
Qualification
J
UJ
J
R
      5.
In the special case of a blank analysis with system monitoring compounds {surrogate} out of
specification, the reviewer most give special consideration to the validity of associated
sample data. The basic concern is whether the blank problems represent an isolated
problem with the blank alone, or whether there is a fundamental problem with the
analytical process.  For example, if one or more samples in the batch show acceptable
system monitoring compound [surrogate] recoveries, the reviewer may choose to consider
the blank problem to be an isolated occurrence.  However, even if this judgment allows
some use of the affected data, analytical problems should be noted for TPO action.  Also
note if there are potential contractual problems associated with the lack of reanalysis of
samples that were out of specification.

Whenever possible, potential effects of the data resulting from system monitoring
recoveries not meeting the advisory limits should be noted in the data  review narrative.
                                               24
                                                                      DRAFT 12/90
                                                                       Revised 6/91

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                                                                                           VGA
                            VH.  Matrix Spikes/Matrix Soike Duplicates
                           (Not Required for Low Concentration Water Data)


 A.      Review Items: Form III VOA-1 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 analysts. These data atone cannot be
        used to evaluate the precision and accuracy of individual samples.  However, when exercising
        professional judgement, this data should be used in conjunction with other available QC
        information.

 C.      Criteria

        1.      Matrix spikes (MS)  and matrix spike duplicate (MSD) samples are analyzed at frequency
               of one MS and MSD per 20 samples of similar matrix.

        2.      Spike recoveries should be within the advisory limits provided on Form III VOA-1 and 2.

        3.      Relative percent difference (RPD) between MS and MSD recoveries must be within the
               advisory limits provided on Form III VOA-1 and VOA-2.

 D.      Evaluation

        1.      Verify that MS and  MSD samples were analyzed at the required frequency and that results
               are provided  for each sample matrix.

        1      Inspect results for the MS/MSD Recovery on Form III VOA-1 and VOA-2 and verify that
               the results for recovery and RPD are within the advisory limits.

        3.      Verify transcriptions from raw data and verify calculations.

        4.      Check that the matrix spike recoveries and RPD were calculated correctly.

        5.      Compare %RSD results of non-spiked compounds between the original result. MS, and
               MSD.

E.      Action

        1.     'No action is taken on  MS/MSD data alone.  However, using informed professional
               judgment the data reviewer may use the MS and MSD results in conjunction with other
               QC criteria and determine the need for some qualification of the data.
                                               25                                  DRAFT 12/90
                                                                                     Revised 6/91

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Matrix Spikes/Matrix Spike Duplicates           '                             .             •    VOA


       2.      The data reviewer should first try to determine to what extent the results of the MS/MSD
               affect the associated data. This determination should be made with regard to the
               MS/MSD sample itself as well as specific analytes for all samples associated with the
               MS/MSD.

       3.      In those instances where it can be determined that the results of the MS/MSD affect only
               the sample spiked, then qualification should be limited to this sample alone.  However, it
               may be determined through the MS/MSD results that a laboratory is having a systematic
               problem in the analysis of one or more analytes, which affects all associated samples.

       4.     The reviewer must use professional judgement to determine the need for qualification of
              positive results of non-spiked compounds.

       NOTE: If a field blank was used  for the MS/MSD. a statement to that effea must be included for
              theTPO.
                                              26                                    DRAFT 12/90
                                                                                     Revised 6/91

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                                                                                                           VGA
                                      VTTT-  I-ahoratory Control Samples
                                             (Low Concentration Water)

 (A.      Rene* Items:  Form HI LCV-1, LCS chromatograms and quanntotion reports.

 B.      Objective

         Data for laboratory control samples (LCS) are generated to provide information on the accuracy of the analytical
         method and on the laboratory performance.

 C      Criteria

         1.       A laboratory control sample (LCS) must be analyzed once per SDC and concurrently with the samples
                 intheSDG.

         2.       The LCS contains (he following volatile compounds, in addition to the required surrogate:

                          Vinyl chloride                     Benzene
                          1,2-Dichloroethane                 cis-IJ-Dichloropropene
                          Carbon tarachloride               Bromoform
                          1.2-DuMoropropane               Tarachloroetheru
                          Trichloroethene                    1,2-Dibromoethane
                          l,J.2-Trichloroethane               1,4-Dichloroberaene


         3.       The percem recoveries for fo LCS compounds must be within 60-140%.  The LCS must meet this
                 recovery criteria for the sample data to be accepted.

         4.       The criteria for surrogate recovery and internal standard performance also appfy.

D.       Evaluation
         1.       Verify tha LCS samples were analyzed at the required frequency and that results are provided for each
                 SDC.

         2.       Inspect results for die LCS Recovery on Farm /// LCV-l and verify that the results for recovery are
                 within the QC limits of 60 to 140 percent.

         3.       Verify transcriptions from raw data and verify calculations.

         4.       Check that the LCS recovery was calculated correctly by using the correct equation.

         Action

         If the LCS criteria an not met, then the laboratory performance and method accuracy are in question.
         Professional judgement should be used to determine if the data should be qualified or rejected. The following
        guidance 'is suggested for qualifying sample data for which the associated LCS does not meet the required criteria.

         1.      Action on the LCS recovery should be based on both the number of compounds that are outside of the
                recovery criteria and the magnitude of the exceedance of the criteria.

        2,      If the LCS recovery criteria are not met, then the LCS results should be used to qualify sample data for
                the specific compounds that are included in the LCS solution. Professional judgement should be  used to

                                                       27                                        DRAFT 12/90
                                                                                                   Revised 6/91

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Laboratory Control Samples                     '                                  .               •     VOA


                qualify data for compounds other than those compounds that are included in the LCS.  Professional
                judgement to qualify non-LCS compounds should take into account the compound class, compound
                recovery efficiency, jnafydcal problems asmciateri with each compound, and comparability in
                ptrfanitance of the LCS compound to the non-LCS compound.

        J.       // the LCS recovery is greater than 140%, then positive sample results for the affected compound(s)
                should be qualified with a V.

        4.       If the mass spectral criteria are met but  the LCS recovery is less than 60%, then the associated detected
                target compounds should be qualified V and the associated non-detected target compounds should be
                qualified'Jf.

        5.       If more than half of the compounds in tru L(3 are rm within the nqumd rcc
                the associated detected target compounds should be qualifier! T and alt associated non-detected target
                compounds should be qualified "R.*

        6.       Action on non-compliant surrogate recovery and internal standard performance should follow the
                procedures provided in VIE and 3LE, respeemefy.  Professional judgement should be used to evaluate
                the impact that non-compliance for surrogate recovery and internal standard performance in the LCS has
                on the associated sample data.

        7.       It should be noted for TPO action if a laboratory fails to analyze an LCS with each SDG, or if a
                laboratory consistently fails to generate acceptable LCS recoveries.]
                                                     28                                        DRAFT 12/90
                                                                                                 Revised 6/91

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                                                                                             VGA
                         DC  Regional Quality Assurance and Quality Control


A.      Review Items:   Form  I VOA /Form / LCV], chromatograms, and quantitaiion reports.

B.      Objective

        Regional Quality Assurance and Quality Control (QA/QC) refer to any QA and/or QC samples
        initiated by the Region, including field duplicates. Performance Evaluation (PE) samples, blind
        spikes, and blind blanks. It is highly recommended that Regions adopt the use  of these.

C      Criteria

        Criteria are determined by each Region.

        1.      Performance evaluation sample frequency may vary.

               [Far daa generated through the Low Concentration Water SOW: A performance evaluation (PE)
               sampit may bt required as frequently as once per SDG.j

        2.      The analytes present in the PE sample must be correctly identified and  quantified.

D.      Evaluation

        Evaluation procedures must follow the Region's SOP for data review.  Each Region will handle
        the evaluation of PE samples on an individual basis. Results for PE samples should be compared
        to the acceptance criteria for the specific PE samples, if available.

E.      Action

        Any action must be in  accordance with Regional specifications and the criteria  for acceptable PE
        sample results.  Unacceptable results for PE samples should be noted for TPO  action.
                                               29                                   DRAFT 12/90
                                                                                      Revised 6/91

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                                                                                                VGA


                                        X.  Internal Standards


 A.      Review Items:  Fonn VIII VOA [Farm VH1LCV], 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.

                [Far data generated through the Low Concentration Water SOW: Internal standard area counts must not
                vary by more than a factor of t 40.0% from the associated calibration standard.}

        2.       The retention time of the internal standard must not vary more than ±30 seconds from
                the retention time of the associated calibration standard.

                [For data generated through the Low Concentration Water SOW: The retention time of the internal
                standard must not vary more than +. 20LO seconds from the retention time of the associated calibration
                standard.]

D.      Evaluation

        1.       Check raw data (e.g.t chromatograms and quantitation lists) to verify the internal standard
                retention times and areas reported on the Internal Standard Area Summary (Form VIII
                VOA [Form Ylll LCVJ).

        2.       Verify that all retention times and IS areas  are within criteria.

        3.       If there are two analyses for a particular fraction, the reviewer  must determine which are
                the best data to report. Considerations should include:

                a.      Magnitude and direction of the IS area shift

                b.      Magnitude and direction of the IS retention time shift

                c.       Technical holding times.

               d.      Comparison of the values of the target compounds reported in each fraction.

               e.       Other QC
                                                 30                                     DRAFT 12/90
                                                                                         Revised 6/91

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Internal Standards
        Action

        1.       If an IS area count for a sample or blank is outside -50% or +100.% of the area for
                associated standard:

                a.      Positive results for compounds quantitated using that IS should be qualified with
                       V-

                b.      Non-detected compounds quantitated using an IS area count greater than 100%
                       should not be qualified.

                c      Non-detected compounds quantitated using an IS area count less than 50% are
                       reported as the associated sample quantitarion limit and qualified with "UJ".

                d.      If extremely tow area counts are reported, or if performance exhibits a major
                       abrupt drop-off, then a severe loss of sensitivity is indicated. Non-detected target
                       compounds should then be qualified as unusable (R).


               {If an IS ana count far a sample or blank is outside t 40.0% of the area for associated standard:

               a.       Positive results for compounds quantitated using that IS should be qualified with T.

               b.       Non-detected compounds quantitated using an IS area count greater than 40% should not be
                       qualjfird

               c.       Non-detected compounds quantitated using an IS area count less than 40% are reported as the
                       associated sample quantuaaon limit and qualified with "UJ*.

               d.       If earemefy low area counts are reported, or if performance exhibits a major abrupt drop-off.
                       then a severe loss of sensitivity a indicated. Non-detected target compounds should then be
                       qualified as unusable (R).]

       2.       If an IS retention time varies by more than 30 seconds:

               /// an IS retention time varies by more than 20.0 seconds:/

               The chromatographic profile for that sample must be examined  to determine if any false
               positives or negatives exist. For shifts of a large magnitude,  the reviewer may consider
               partial or total rejection of the data for that sample fraction.  Positive results should not
               need to be qualified as "R" if the mass spectral criteria are met.

       3.       If the  internal standards performance criteria are grossly exceeded,  then this should be
               noted for TPO action. Potential effects on the data resulting from  unacceptable internal
              standard performance should be noted in the data  review narrative.
                                                 31                                      DRAFT  12/90
                                                                                          Revised 6/91

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                                                                                              VGA


                                JQ>  Target ConiDO"nd Identification


A.      Review Items: Form I VOA (Form ILCVJ, quantitation reports, mass spectra, and chroma tograms.

B.      Objective

        The objective of the criteria for GC/MS qualitative analysis is to minimi^ the number of
        erroneous identifications of compounds.  An erroneous identification can either be a false positive
        (reporting a compound present when it is not) or a false negative (not reporting a compound that
        is present).

        The identification criteria can be applied more easily in detecting false positives than false
        negatives. More information is available for false positives due to the requirement for submittal
        of data supporting positive identifications. Negatives, or non-detected compounds, on the other
        hand represent an absence of data and are, therefore, more difficult to assess. One example of
        detecting false negatives is the not reporting of a Target Compound that is reported as a TIC

C      Criteria

        1.      The relative retention times (RRTs) must be within ±0.06 RRT units of the standard
               RRT.

        2.      Mass spectra of the sample compound and a  current laboratory-generated standard  (i.e.,
               the mass spectrum from the associated calibration standard) must  match according to the
               following criteria:

               a.      All ions present in the standard mass spectrum at a relative  intensity greater than
                       10% must be present in the sample spectrum.

                       [For data generated through the Low Concentration Water SOW: All ions present in the
                       standard mass spearum at a relative intensity greater than 25% must  be present m 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 spearum, the corresponding sample ion abundance must be
                       between 30% and 70%.)

              c.      Ions present at greater than 10% in the sample mass spectrum  but not present in
                       the standard spectrum must be considered and accounted  for.

                       [For data generated through the Low Concentration Water SOW: Ions present at greater than
                       23% in the sample mass spectrum but not present in the standard spectrum must be considered
                       and accounted for.]
                                                32                                    DRAFT 12/90
                                                                                       Revised 6/91

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Target Compound Identification                '                         .      -              '    VGA
D.      Evaluation

        1.       Check that the RRT of reported compounds is within +. 0.06 RRT units of the standard
                RRT.

        2.       Check the sample compound spectn against the laboratory standard spectra to see that it
                meets the specified criteria.

        3.       The reviewer should be aware of situations (e.g., high concentration samples preceding
                low concentration samples) when sample carryover is a possibility and should use
                judgment to determine if instrument cross-contamination has affected any positive
                compound identification.  The SOW specifies that an instrument blank must be ran after
                samples in which a target anaiyte ion(s) saturates the detector.

                {The reviewer should be aware of situations when sample carryover is a possibility and should use
               judgment to downline if immanent cross-contamination has affected any posieve compound
                identification. The SOW specifies that an instrument blank naai be run after samples which contain
                target compounds at levels exceeding the initial calibration range (25 ug/L for nenJtetones, 125 ug/L for
                kaona) or non-target compounds at concentrations greater than 100 ug/L or saturated ions from a
                compound (aciuding the compound ptaia in the solvent front).]

        4.       Check the chromatogram to verify that peaks are accounted for, Le., major  peaks  are
                either identified as target compounds, TICs, system monitoring compounds [surrogate], or
                internal standards.

E.      Action

        1.       The application of qualitative criteria for GC/MS analysis of target compounds requires
                professional judgement.  It is up to the reviewer's discretion to obtain additional
                information from the laboratory.  If it is determined  that incorrect identifications were
                made, all such data should be qualified as not detected (U) or unusable (R).

        2.       Professional judgement must be  used to qualify the data  if it is determined  that cross-
               contamination has occurred.

        3.      Any changes made to the reported compounds or concerns regarding target compound
               identifications should be clearly indicated  in the data review narrative.  The necessity for
               numerous or significant changes should be noted for TPO action.
                                                 33                                    DRAFT 12/90
                                                                                         Revised 6/91

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                                                                                            VOA


                        XIL  Compound Ouantitation and Reported CROLs
        Review Items; Form I VOA [Form ILCY], sample preparation sheets, SDC narrative, quamitation
        reports, and chroma tograms.

        Objective

        The objective is to ensure that the reported quantitation results and Contract Required
        Quantitation Limits (CRQLs) are accurate.

        Criteria

        1.      Compound quantitation, as well as the adjustment of the CRQLs, must be calculated
               according to the correct equation.

        2.      Compound RRFs must be calculated based on the internal standard (IS) associated with
               that compound, as listed in Appendix A [Appendix B] (also as specified in the Statement of
               Work) for packed column analyses. For analyses performed by capillary column method
               (EPA Method 5242). the target compounds will not necessarily be associated with the
              same internal standard as in the packed column, depending on the compound eiution
              order. Quantitation must be based on the quantitation ion (m/z) specified in the SOW
              for both the IS and target analytes. The compound quantitation must be based on the
              RRF from the appropriate daily standard.
D.     Evaluation
       1.      For all fractions, raw data should be examined to verify the correct calculation of all
               sample results reported by the laboratory. Quantitation lists and chromatograms should
               be compared to die reported positive sample results and quantitation limits. Check the
               reported values.

       2.      Verify that the correct internal standard, quantitation ion, and RRF were used to
               quantitate the compound. Verify that the same internal standard, quantitation ion. and
               RRF are used consistently throughout, in both the calibration as well as the quantitation
               process.  For analyses performed by capillary column, the reviewer should use professional
               judgement to detennine that the laboratory has selected the appropriate internal standard.

       3.      Verify that the CRQLs have been adjusted to reflect all sample dilutions and dry weight
               factors that are not accounted for by the method.
       Action •

       1.      If any discrepancies are found, the laboratory may be contacted by the designated
              representative to obtain additional information that could resolve any differences.  If a
              discrepancy remains unresolved, the reviewer must use professional judgement to decide
              which value is the best value.  Under these circumstances, the reviewer may determine
                                               34                                   DRAFT 12/90
                                                                                     Revised 6/91

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Compound Quantitation and Reported CRQLs  '                                          •     VGA


              qualification of data is warranted. A description of the reasons for data qualification and
              the qualification that is applied to the data should be documented in the data review
              narrative.

       2.     Numerous or significant failures to accurately quantify the target compound or to properly
              evaluate and adjust CRQLs should be noted for TPO action.
                                              ?5                                   DRAFT 12/90
                                                                                    Revised 6191

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                                                                                                 VGA
                               XIIL  Tentatively Identified Compounds
        Review Items: Form I VOA-TIC [Form ILCV-T1C], chromatograms, and library search printout
        and spectra for three TIC candidates.
B.      Objective
     .   Chromatographic peaks in volatile fraction analyses that are act target analytes, system monitoring
        compounds (surrogate/, or internal standards are potential tentatively identified compounds (TICs).
        TICs must be qualitatively identified by a National Institute of Standards and Technology (NIST)
        mass spectral library search and the identifications assessed by the data reviewer.

C.      Criteria

        For each sample, the laboratory must conduct a mass spectral search of the NIST library and
        report the possible identity for the 10 largest volatile fraction peaks which are not system
        monitoring compound, internal standard, or target compounds, but which have.area or height
        greater than 10 percent of the area or height of the nearest internal standard. TIC results are
        reported  for each sample on the Organic Analyses Data Sheet (Form I VOA-TIC).

        [Far data generated through the Low Concentration Water SOW: For each sample, the laboratory must conduct a
        mass spectral starch of the HIST library and report the possible identity for toe 10 largest volatile fraction peaks
        which an not surrogate, internal standard, or TCL compounds, but which have area greater than or equal to 40
        percent of the ana of the nearest internal standard.  Estimated concentrations far TICs are calculated similarh to
        the TCL compounds, using total ion areas for the TIC and the internal standard, and assuming a relative response
        factor of 1.0.  TIC remits are reported for each sample on the Organic Analyses Data Sheet (Form  I LCV-TIO.J

        NOTE: Since the SOW revision of October 1986, the CLP does not allow the laboratory to report
               as tentatively identified compounds any target compound which is properly reported in
               another fraction.  For example, late eluting volatile target compounds should  not be
               reported as semivolatile TICs.

D.      Evaluation

        1.      Guidelines for tentative identification are as follows:

               a.      Major ions (greater than 10% relative intensity)  in the reference spectrum should
                       be present in the sample spectrum.

                       [Major ions (greater than 22% relative intensity) in the reference spectrum should be present in
                       die 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.
                                                                                         DRAFT 12/90
                                                                                          Revised 6/91

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Tentatively Identified Compounds                '                              •              '    VGA


               d.      loos present in the sample spectrum but not in the reference spectrum should be
                       reviewed for possible background contamination, interference, or coclution 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.

               L       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 than 10 percent of the internal standard
               height, but present in the blank chromatogram at similar relative retention time.

               f Blank chromatograms should be examined to verify that TIC peaks present in samples an not found in
               blanks. When a lowJevei non-TCL compound that is a common artifact or laboratory contaminant is
               detected in a sample, a thorough check of blank chromatograms may require looking for peaks which
               are less than 40 percent of the internal aartdard area but present in the blank chromatogram at similar
               relative retention tone,]

       4.      All mass spectra for every sample and blank must be examined.

       5.      Since TIC library searches often yield several candidate compounds having a close
               matching score, all reasonable choices must be considered.

       6.      The reviewer should be aware of common laboratory artifacts/contaminants and their
               sources (e.g., aldol condensation products, solvent preservatives, and reagent
               contaminants).  These  may be present in  blanks and not reported as sample TTCs.

               Examples:

               a.      Common laboratory contaminants: CO2 (m/z 44), siloxanes (m/z 73), diethyl
                      ether, hexane,  certain freons (l,l,2-trichloro-l,Z2-trifluoroethane or fiuoro-
                      trichloromethane), and phthalates at levels less than 100 ug/L or 4000 ug/Kg.

              .b.      Solvent  preservatives such as cyclohexene which is a methylene chloride preser-
                      vative.  Related by-products include cyciohexanone, cyclohexenone, cyclohexanol.
                      cyclohexenol, chlorocyclohexene, and chlorocyclohexanoL

               c      Aldol condensation reaction products of acetone include: 4-hydroxy-4-methyl-2-
                      pentanone, 4-methyl-2-penten-2-one, and 5,5-dimethyl-2(5H)-ruranone.
                                                37                                    DRAFT
                                                                                        Revised 6/91

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 Tentatively Identified Compounds              '                       .                         VOA


        7.      Occasionally, a target compound may be identified in the proper analytical fraction by
               non-target library search procedures, even though it was not found on the quantitation
               list.  If the total area quantitation method was used, the reviewer should request that the
               laboratory recalculate the result using the proper quantitation ion. In addition, the
               reviewer should evaluate other sample chromatograms and check library reference
               retention times on quantitation lists to determine whether the false negative result is an
               isolated occurrence or whether additional data may be affected.

        8.      Target compounds could be identified in more than one fraction.  Verify that quantitation
               is made from the proper fraction.

        9.      Library searches should not be performed on internal standards or system monitoring
               compounds.

        10.     TIC concentration should be estimated assuming a RRF of 1.0.

E.     Action

        1.      All TIC  results should be qualified *NJ*. tentatively identified, with approximated
               concentrations.

       2.      General  actions related to the review of TIC results are as follows:

               a.      If it is determined that a tentative identification of a non-target compound is not
                      acceptable, the tentative identification should be changed to "unknown" or an
                      appropriate identification.

               b.      If all contractually required peaks were not library searched and  quantitated, the
                      designated representative could request these  data from the laboratory.

       3.      TIC results which are not sufficiently above IQx the level in the  blank should not be
               reported. (Dilutions and sample size must be taken into account when comparing the
               amounts present in blanks and samples.)

       4.      When a compound is not found in any blanks, but is a suspected artifact of common
               laboratory contaminant, the result may be qualified as unusable  (R).

       5.      In deciding whether a library search result for a TIC represents  a reasonable identification.
               professional judgment must be exercised.  If there  is more than  one possible match, the
               result may be reported as "either compound X or compound Y." If there is a lack of
               isomer specificity, the TIC result may be changed to a non-specific isomer result (e.g..
               1,3,5-trimethyl benzene to trimethyl benzene isomer) or to a compound class (e.g.. 2-
              tnethyl, 3-ethyl benzene to substituted aromatic compound).

       6.      The reviewer may elect to report all similar compounds as a total,  (e.g.. All alkanes may
              be summarized and reported as total hydrocarbons.)
                                               38                                    DRAFT 12/90
                                                                                      Revised 6/91

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Tentatively Identified Compounds              '                              -             '    VQA


       7.      Other case factors may influence TIC judgements.  If a sample TIC match is poor but
               other samples have a TIC with a good library match, similar relative retention time, and
               the same ions, identification information may be inferred from the other sample TIC
               results.

       8.      Physical constants, such as boiling point, may be factored into professional judgement of
               TIC results.

       9.      Any changes made to the reported data or any concerns regarding TIC identifications
               should be indicated in the data review narrative.

       10.     Failure to properly evaluate and report TICs should be noted for TPO action.
                                               39                                    DRAFT 12/90
                                                                                      Revised 6/91

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                                                                                               VGA
                                     XIV.   System Performance
        Review Items: Form VIE VOA [Form VUILCyj, Form III VOA-1 and VOA-2 (Form III LCV-1],
        and chromatograms.

        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.

        Criteria

        There are no specific criteria for system performance.  Professional judgement should be applied
        to assess the system performance.
D.      Evaluation
        1.      Abrupt, discrete shifts in the reconstructed ion chromatogram (RIC) baseline may indicate
               a change in the instrument's sensitivity or the zero setting.  A baseline 'shift" could
               indicate a decrease in sensitivity in the instrument or an increase in the instrument zero,
               possibly causing target compounds, at or near the detection limit, to miss detection. A
               baseline 'rise* could indicate problems such as a change in the instrument zero, a leak, or
               degradation of the column.

        2.      Poor chromatographic performance affects both qualitative and quantitative  results.
               Indications of substandard performance include:

               a.       High RIC background levels or shifts in absolute retention times of internal
                       standards.

               b.       Excessive baseline rise at elevated temperature.

               c.       Extraneous peaks.

               d.       Loss of resolution.

               e.       Peak tailing or peak splitting that may result in inaccurate quantitation.

       (3.      A drift in instrument sensinvity may occur during the 12-hour time period. This could be discerned by
               examination of the IS ana on Form VIII LCVfor trends such as a continuous or near-continuous
               increase or decrease in the IS ana over time.

       4.       The results of the LCS analysis (Form III LCSV) may also be used to assess instrument performance.!
                                                                                        DRAFT 12/90
                                                                                         Revised 6/91

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                                                                                    VGA
Action

Professional judgement must be used to qualify tne 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.
                                       41                                   DRAFT 12/90
                                                                             Revised 6(91

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                                                                                               VGA


                                   XV.  Overall Assessment of Data


A.      Review Items: Entire data package, data review results, and (if available) Quality Assurance
        Project Plan (QAPjP), and Sampling and Analysts Plan (SAP).

B.      Objective

        The overall assessment of a data package is a brief narrative in which the data reviewer expresses
        concerns and comments on the quality and. if possible, the useabiliry of the data.

C      Criteria

        Assess the overall quality of the data.

        Review all available materials to assess the overall quality of the data, keeping in  mind the
        additive nature of analytical problems.

D.      Evaluation

        1.      Evaluate any technical problems which have not  been previously addressed.

        2.      If appropriate information is available, the reviewer may assess the useabiliry of the data
               to assist the data user in avoiding inappropriate  use of the data.  Review  all available
               information, including the QAPjP (specifically the Data Quality Objectives), SAP, and
               communication with data user that concerns the  intended use and desired quality of these
               data.

E.      Action

        1.      Use professional judgement to determine if there is any need to qualify data which were
               not qualified based on the QC criteria previously discussed.

        2.      Write a brief narrative to give the user an indication of the analytical limitations of the
               data.. Any inconsistency  of the data with the SDG narrative should be noted for TPO
               action.  If sufficient information on the intended use and required quality of the data are
               available, the reviewer should include his/her assessment of the useabiliry of the data
               within the given context.
                                                 42                                    DRAFT 12/90
                                                                                         Revised 6/91

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                                                                                             sv
                                 SEMIVOIATILE DATA REVIEW

 •"• Data review guidelines that are unique to data generated through the Low Concentration Water SOW are contained
 within brackets ([ ]) and written in italics. •"


 The semivolatile data  requirements to be checked are listed below:

        I.      Technical Holding Times (CCS - Contractual holding times only)

        IL     GOMS Instrument Performance Check (CCS)

        IIL     Initial Calibration (CCS)

        IV.     Continuing Calibration (CCS)

        V.     Blanks (CCS)

        VL     Surrogate Spikes (CCS)

        VTL    Matrix Spikes/Matrix Spike Duplicates

        VUI.    Laboratory Control Samples (CCS)

        DC     Regional Quality Assurance and Quality Control

        X     Internal Standards (CCS)

        XL     Target Compound Identification

        XII.    Compound Quantitation and  Reported Contract Required Quantitation Limits (CRQLs)

        XIII.   Tentatively Identified Compounds

        XTV.   System Performance (CCS)

        XV.    Overall Assessment of Data
NOTE: "CCS" indicates that the contractual requirements for these items will also be checked by CCS;
       CCS requirements are not always the same as the data review criteria.
                                               43                                   DRAFT 12/90
                                                                                     Revised 6/91

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                                                                                               sv
                                    I.  Technical Holding Times
        Review Items:  Form I SV-1 and SV-2 {Form 1LCSV-l and LCSV-2], EPA Sample Traffic Report
        and/or chain-of-custody, raw data, and sample extraction sheets.

        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.

        Criteria

        Technical requirements for sample holding times have only been established for water matrices.
        The holding times for soils (and other non-aqueous matrices such as sediments, oily wastes, and
        sludge) are currently under investigation.  When the results are available they will be incorporated
        into the data evaluation process.  Additionally, results of holding time studies will be incorporated
        into the data review criteria as the studies are conducted and approved.

        The holding time criteria for water samples, as stated in the current 40 CFR Pan 136 (Clean
        Water Act) is as follows:

               For semivolatile compounds in cooled (@ 4*C) water samples the
               maTimiim holding time is 7 days from sample collection to extraction and
               40 days from sample extraction to analysis.

        It is recommended that semivolatile compounds  in non-aqueous samples be extracted within 14
        days of sample  collection.

        The contractual holding times, which differ from the technical holding times, state that water
        samples are to  be extracted within 5 days from the validated  time of sample receipt (VTSR) at the
        laboratory, and soil samples are to be extracted within  10 days  from the VTSR.  Also,
        contractually both water and soil sample extracts must be analyzed within 40 days of sample
        extraction. However, the contractual delivery due date is 35  days from the VTSR.

        [For data generated through the Low Concentration SOW: The contractual delivery due date is 14 days from the
        VTSR.]
D.     Evaluation
       Technical holding times for sample extraction are established by comparing the sampling date on
       the EPA Sample Traffic Report with the dates of extraction on Form I SV-i and SV-2 [Form I
       LCSV-i and LCSV-2] and the sample extraction sheets. To determine if the samples were analyzed
       within the holding time after extraction, compare the dates of extraction on the sample extraction
       sheets with the dates of analysis on Form I SV-1 and SV-2 (Form I LCSV-1 and LCSV-2].

       Verify that the traffic report indicates that the samples were received intact and iced. If the
       samples were not iced or there were any problems with the samples upon receipt, then
       discrepancies in the sample condition could effect  the data.

                                                44                                    DRAFT 12/90
                                                                                      Revised 6/91

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Technical Holding Times                       '                        ,       •                   SV
        Action

        1.      If technical holding times are exceeded, flag all positive results as estimated "J" and sample
               quantitauon limits as estimated "UJ" and document that holding limes were exceeded.

        2.      If technical holding times are grossly exceeded, either on the first analysis or upon re-
               analysis, the reviewer must use professional judgement to determine the reliability of the
               data and the effects of additional storage on the sample results.  The reviewer may
               determine that positive results or the associated quantitation limits are approximates and
               should be qualified with "J* or *UJ", respectively. The reviewer may determine that non-
               detect data are unusable  (R).

        3.      Due to limited information concerning holding times for soil samples, it is left to the
               discretion of the data reviewer to apply water holding time criteria to soil samples.
               Professional judgement is required to evaluate holding times for soil  samples.

        4.      Whenever possible, the reviewer should comment on the effect of the holding time
               exceedance on the resulting data in the data review narrative.

        5.      When contractual and/or technical holding times are exceeded, this should be noted as an
               action item for the TPO.

        6.      The reviewer should also be aware of the scenario in which the laboratory has exceeded
               the technical holding times, but met contractual holding times. In this case, the data
               reviewer should notify the Regional TPO (where samples were collected) and/or RSCC
               that shipment delays have occurred so that the field problem can be corrected.  The
               reviewer may pass this information on to the laboratory's TPO, but should explain that
               contractually the laboratory met the requirements.
                                                45                                    DRAFT 12/90
                                                                                       Revised 6/91

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                                                                                           sv
                            n. GC/MS Tn.«tr»i»nent Performance Check


 A.      Revieir Items: Form V SV (Form VLCSV], and DFTPP mass spectra and mass listing.
                                                                         »
 B.      Objective

        Gas chromatograph/mass spectrometer (COM3)  instrument performance checks (formerly
        referred to as tuning) are performed to ensure mass resolution, identification and. to some degree,
        sensitiviry.  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, decafluorotriphenyiphosphine (DFTPP) for volatile analysis, must meet the ion abundance
        criteria given below.

                             Decafluorotriphenyiphosphine (DFTPP)

                                           ION ABUNDANCE CRITERIA
                             21            30.0 - 80.0% of m/z 198
                             68            Less than 10% of m/z 69
                             69            Present
                             70            Less than 10% of m/z 69
                             127           25.0 - 75.0% of m/z 198
                             197           Less than 1.0% of m/z 198
                             198           Base peak.  100% relative abundance
                             199           5.0 - 9.0% of m/z 198
                             275           10.0 - 30.0% of m/z 198
                             365           Greater than 0.75% of m/z 198
                             441           Present, but less than m/z 443
                             442           40.0 - 110.0% of m/z 198
                             443           15.0 - 24.0% of m/z 442

       NOTE: All ion abundances must be normalized to m/z 198, the nominal base peak, even though
              the ion abundances of m/z 442 may be up to 110 percent that of m/z 198.
D.     Evaluation
       1.      Compare the data presented on each GC/MS Instrument Performance Check (Form V SV
              [Form VLCSVJ) with each mass listing submitted and ensure the following:

              a.      Form V SV [Form VLCSV] is present and completed for each 12-hour penod
                      during which samples were analyzed.
                                              16                                  DRAFT 12/90
                                                                                   Revised 6/91

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GC/MS Instrument Performance Check         •                              .             •      SV
               b.      The laboratory has not made any transcription errors between the data and the
                      form. If there are major differences between the mass listing and the Form Vs, a
                      more in-depth review of the data is required. This may include obtaining and
                      reviewing additional information from the laboratory.

               c     . The appropriate number of significant figures has been reported (number of
                      significant figures given for each ion in the ion abundance criteria column) and
                      that rounding is correct.

               d.      The laboratory has not made any calculation errors.

       2.      Verify from the raw data (mass spectral listing) that the mass assignment is correct and
               that the mass is normalized to m/z 198.

       3.      Verify that the ion abundance criteria was met The criteria for m/z 68, 70, 441, and 443
               are calcnlated by normalizing to the specified m/z.

       4.      If possible, verify that spectra were generated using appropriate background subtraction
               techniques.  Since the DFTPP spectrum  is obtained from chromatographic peaks that
               should be free from coelution problems, background subtraction should be done in
               accordance with the following procedure. Three scans (the peak apex scan and the scans
               immediately preceding and following the apex) are acquired and averaged and background
               subtraction must  be accomplished using a single scan prior to the elution of DFTPP.

       NOTE: All instrument conditions must be identical to those used in the sample analysis.
               Background subtraction actions resulting in spectral distortions for the sole purpose of
               meeting the contract specifications are contrary to the quality assurance objectives and are
               therefore unacceptable.

       Action

       1.      If the laboratory has made minor transcription errors which do not significantly affect the
               data, the data reviewer should make the  necessary corrections on a copy of the form.

       2.      If the laboratory has foiled to provide the correct forms or has made significant
               transcription or calculation errors, the Region's designated representative should contact
               the laboratory and request corrected data.  If the  information is not available, then the
               reviewer must use professional judgement to assess the data.  The laboratory's TPO
               should be notified.

       3.      If mass assignment is in error (such as m/z 199 is indicated as the base peak rather than
               m/z 198), classify  all associated data as unusable (R).

       4.      If ion abundance  criteria are not met, professional judgement may be applied to determine
               to what extent the data may be utilized.  Guidelines to aid in the application of
               professional judgement in evaluating ion abundance criteria are discussed as follows:
                                               47                                    DRAFT 12/90
                                                                                      Revised 6/91

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 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 than the
               0.75% minimum  abundance criteria, the deficiency is not as serious.

5.       Decisions to use analytical data associated with DFTPP instrument performance checks
        not meeting contract requirements should be clearly noted in the data review narrative.

6,       If the reviewer has reason to believe that instrument performance check criteria were
        achieved using techniques other than those specified in the SOW and ILD.4 above.
        additional information on the DFTPP instrument performance checks should be obtained.
        If the techniques employed are found to be at variance with contract requirements, the
        procedures of the laboratory may merit evaluation.  Concerns or questions regarding
        laboratory performance should be noted for TPO action. For example, if the reviewer has
        reason to believe that an inappropriate technique was used to obtain background
        subtraction  (such as background subtracting from the soivem front or from another region
        of the chromatogram rather than the DFTPP peak), then this should be noted for TPO
        action.
                                        48                                    DRAFT 17/90
                                                                               Revised 6/91

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                                                                                                     sv
                                              Initial Calibration
         Review Items: Form VI SV-1 and SV-2 [Form VILCSV-1 and. LCSV-2J, quantitauon reports, and
         chromatograms.

         Objective

         Compliance requirements for satisfactory instrument calibration are established to ensure that the
         instrument is capable of producing acceptable qualitative and quantitative data for compounds on
         the semivolatile Target Compound List (TCL).  Initial calibration demonstrates that the
         instrument is capable of acceptable performance in the beginning of the analytical run and of
         producing a linear calibration curve.

         Criteria

         1.      Initial calibration standards containing both semivolatile target compounds and surrogates
                are analyzed at concentrations of 20, 50, 80,120. and 160 ug/L at the beginning of each
                analytical sequence or as necessary if the continuing calibration acceptance criteria are not
                met.  The initial calibration (and any associated samples and blanks) must be analyzed
                within 12 hours of the associated instrument performance check.

                [Far data generated through the Law Concentration SOW: Initial calibration standards containing both
                semivolatile TCL compounds and surrogates art analyzed at concentrations of 5, 20, 20, SO, and 80
                ug/L at the beginning of each analytical sequence or at necessary if the continuing calibration acceptance
                criteria are not met  The usual calibration (and any associated samples and blanks) must be analyzed
                within 12 hours of the associated DFTPP tuning check. The following nine compounds require initial
                calibration a 20, SO, 80. 100, and 120 ug/L:  2.4-dinurophenol, 2,4,S-trichlorophenol, 2-nitroaruiine, 3,
                nuroaniline, 4-nitroanuine, 4-nurophenol, 4,6-dinitro-2-methylphenol,  pentachlorophenol, and 2.4.6-
                aibromophenol (surrogate).]

        2.       Minimum Relative Response Factor (RRF) criteria must be greater than or equal to 0.05.
                Contractual RRF criteria are listed  in Appendix A [Appendix BJ.

        3.       The Percent Relative Standard Deviations (%RSD) for the  RRFs in the  initial calibration
                must  be less than or equal to 30%.
D.      Evaluation
                Verify that the correct concentration of standards were used for the initial calibration (i.e.,
                20, 50, 80,120, and 160 ug/L). For the eight compounds with higher CRQLs, only a four-
                point initial calibration is required (i.e., 50, 80, 120, and 160 ug/L).

                [Verify that the comet concentration of standards were used for the initial calibration (Le., 5. 10, 20, 50.
                and 80 ug/L). For the nine compounds listed in III.C.1. with higher CRQLs, verify that a five point
                initial calibration at 20, 50, 80, 100, and 120 ug/L was performed.}
                                                  49                                     DRAFT 12/90
                                                                                            Revised 6V91

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Initial Calibration                                                                         '      SV
       2.      If any sample results were calculated using an initial calibration, verify that the correct
               standard (L&, 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.

               [If am sample render wen calrulmeei using an initial calibration, verify that the comet standard (Le.,
               the 20ug/L standard or 80 ug/L for the compounds listed in III.C2.) was used for calculating sample
               results and that the samples were analyzed within 12 hours of the associated DFTPP tuning check.]

       3.      Evaluate the RRFs for all semivolatile target compounds and surrogates:

               a.      Check and recalculate the RRF and KKF" for at least one semivoiatile target
                       compound associated with each internal standard.  Verify that the recalculated
                       value(s) agrees with the laboratory reported value(s).

               b.      Verify that ail semivolatile target compounds and surrogates have RRFs that are
                       greater than or equal to 0.05.
               Because historical performance data indicate poor response and/or erratic behavior, the
               semivolatile compounds in Table 4 have no contractual maximum %RSD criteria.
               Contractually they must meet a T"!"!!""" RRF criteria of 0.01, however, for data review
               purposes, the "greater than or equal to 0.05" criterion is applied to all semivoiatile
               compounds.

                  Table 4. Semivolatile Target Compounds Exhibiting Poor Response

                      Z2'-oxybis(l-Chloropropane)            Diethyiphthalate
                      4-Chloroaniline                        4-Nitroaniline
                      Hexachlorobutadiene                   4,6-Dinitro-2-methylphenol
                      Hexachlorocyclopentadiene             N-Nitrosodiptienylamine
                      2-Nitroaniline                          Di-n-butyipiuhalate
                      Dimethylphthalate                      Butylbenzylphthalate
                      3-Nitroaniline                          3-3'-Dichlorobenzidine
                      2,4-Dinitrophenol                      bis(2-Ethylhexyl)phthaiate
                      4-Nitrophenol                          Di-n-octyiphthalate
                      Carfaazotef                             24,6-Tribromopnenol (surr)f
                      f Multi-media, Multi-concentration only
                      tLow Concentration Water onfy
       4.       Evaluate the %RSD for all semivolatile target compounds and surrogates.

               a.      Check and recalculate the %RSD for one or more semivoiatile target
                      compound(s); verify that the recalculated value(s) agrees with the laboratory
                      reported value(s).
                                                SO                                     DRAFT 12/90
                                                                                        Revised 6/91

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Initial Calibration                             •                              .             •      SV
               b.      Verify that all semivolatile target compounds have a %RSD of less than 30%.
                      The contractual criteria for an acceptable initial calibration specifies that up to
                      any 4 semivolatile target compounds may fail to meet minimum RRF or
                      maximum %RSD as long as they have RRFs that are greater than or equal to
                      0.010, and %RSD of less than or equal to 40.0%.  For data review purposes,
                      .however, all compounds must be considered for qualification when the %RSD
                      exceeds the ± 30.0% criterion.

               c      If the %RSD  is greater than 30.0%, then the reviewer should use professional
                      judgement to  determine the need to check the points on the curve for the cause
                      of the non-linearity. This is checked by eliminating either the high point or the
                      low point and recalculating the %RSD.

       5.       If errors are detected in the calculations of either the RRF or the %RSD, perform a
               more comprehensive recalculation.
       Action
              All semivolatile target compounds, including the 19 "poor performers' will be qualified
              using the following criteria:

              a.       If the %RSD is greater than or equal to 30.0% and the RRF is greater than 0.05,
                      qualify positive results with T, and non-detected semivolatile target compounds
                      using professional judgement

              b.       If the RRF is less than 0.05, qualify positive results that have acceptable mass
                      spectral identification with *J"  using professional judgement, and non-detects as
                      unusable (R).

              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%:

                      L       Qualify positive results for that compound(s) with "J*.

                      iL      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):

                      L       No qualifiers are required for positive results in the linear portion of the
                             curve.

                     iL       Qualify positive results outside of the linear portion of the curve with "J".
                                              51                                    DRAFT 12/90
                                                                                     Revised 6/91

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Initial Calibration                            '                                            '       SV


                       til     No qualifiers are needed for non-detected target compounds.

               c      If the low end of the curve is outside-of the linearity criteria:

                       L      No qualifiers are required for positive results in the linear portion of the
                              curve.

                       ii.      Qualify low level positive results in the area of non-linearity with  *J".

                       iii.     Qualify non-detected semivolatile target compounds using professional
                              judgement

       3.      If the laboratory has failed to provide adequate calibration information, the designated
               representative should contact the laboratory and request the necessary information.  If the
               information is not available, the reviewer must use professional judgement to assess  the
               data.

       4.      Whenever possible, the potential effects on the data due to calibration criteria exceedance
               should be noted in the data review narrative.

       5.      If calibration criteria are grossly exceeded, this should be noted for TPO action.
                                                52                                     DRAFT 12/90
                                                                                        Revised 6/91

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                                                                                              sv


                                     IV.  Continuing Calibration
        Review Items:  Form VII SV-1 and SV-2 /Form VHLCSV-1 and LCSV-2], quantitation reports, and
        chromatograms.

        Objective

        Compliance requirements for satisfactory instrument calibration are established to ensure that the
        instrument is capable of producing acceptable qualitative and quantitative data for semrvolatile
        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.

        Criteria

        1.      Continuing calibration standards containing both target compounds and surrogates are
               analyzed at the beginning of each 12-hour analysis period following the analysis of the
               instrument performance check and prior to the analysis of blanks and samples.

        2.      The minimum Relative Response Factors (RRF) for semivolatile target compounds and
               surrogates must be greater than or equal to 0.05.

        3.      The percent  difference (%O) between the initial calibration RRF  and the continuing
               calibration RRF must be within +. 25.0% for all target compounds.
D.     Evaluation
       1.      Verify that the continuing calibration was run at the required frequency and that the
               continuing calibration was compared to the correct initial calibration.

       2.      Evaluate the continuing calibration RRF for all semivolatile target compounds and
               surrogates.

               a.      Check and recalculate the continuing calibration RRF for at least one
                      semivolatile target compound for each internal standard; verify that the
                      recalculated value(s) agrees with the laboratory reported value(s).

               b.      Verify that all semivolatile target compounds and surrogates have RRFs within
                      specifications.


       NOTE:' Because historical performance data indicate poor response and/or erratic behavior,  the
               compounds in Table 4 (Section IILD3) 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.
                                               53                                   DRAFT 12/90
                                                                                     Revised 6/91

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 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 semivolaUle target compound for
                      each internal standard; verify that the recalculated value agrees with the
                      .laboratory reported value(s).

               b.      Verify that the %D is within the ± 25.0% criterion, for all semivolatile target
                      compounds and surrogates.  Note those compounds which have a %D outside the
                      +, 25.0% criterion. The contractual criteria for an acceptable continuing
                      calibration specifies that up to any 4 semivolatile target compounds may fail to
                      meet minimum RRF or maximum %D as long as  they have RRFs that are greater
                      than or equal to 0.010, and %D of less than or equal  to 40.0%.  For data review.
                      purposes, however, all compounds must be considered for qualification when the
                      %D exceeds the ± 25.0% criterion.

       4.      If errors are detected in the calculations of either the continuing calibration RRF or the
               %D, perform a more comprehensive recalculation.

E.     Action

       1.      The reviewer should  use professional judgement to determine if it is necessary to qualify
               the data for any semrvolatile target compound. If qualification of data is required, it
               should be performed using the following guidelines:

               a.      If the %D is outside  the + 25.0% criterion and the continuing calibration RRF is
                      greater than or equal to 0.05, qualify positive results T.

               b.      If the %D is outside  the +. 25.0% criterion and the continuing calibration RRF is
                      greater than  or equal to 0.05, qualify non-detected semivolatile target compounds
                      •UJ-.

               c.      If the continuing calibration RRF is less than 0.05, qualify positive results that
                      have acceptable mass spectral identification with "J" or use professional
                      judgement.

               d.      If the continuing calibration RRF is less than 0.05, qualify non-detected
                      semivolatile target compounds as unusable (R).

       2.      If the laboratory has  failed  to provide adequate calibration information, the designated
               representative should contact the laboratory and request the necessary information. If the
               information is not available, the reviewer must use professional judgement to assess the
              .data.

       3.      Whenever possible, the potential effects on the data due to calibration criteria exceedance
               should be noted in the data review narrative.

       4.      If calibration criteria are grossly exceeded, this should be noted for TPO action.
                                               54                                    DRAFT 12/90
                                                                                      Revised 6191

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                                                                                              sv
                                           V.  Blanks


        Review Items: Form I SV-1 and SV-2 [Form ILCSV-1 and LCSV-2J, Form IV SV (Form IV LCSV],
        chromatograms, and quandtation reports.
B.     Objective
       The purpose of laboratory (or Seld) 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 §££ blank exist, all associated data must be
       carefully evaluated to determine whether or not there is an inherent variability in the data, or if
       the problem is an isolated occurrence not affecting other data.

       Criteria

       1.      No contaminants should be found in the blanks.

       2.      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 ISV-1 and SV-2, and raw data
               (chromatograms and quanntation 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.

       Action

       If the appropriate blanks were not analyzed with the frequency described above, then the data
       reviewer should use professional judgement to determine if the associated sample data should be
       qualified.  The reviewer may need to obtain additional information from the laboratory. The
       situation should be noted for TPO action.

       Action in the case of unsuitable blank results depends on the circumstances and origin of the
       blank.  Positive sample results should be reported unless the concentration of the compound in
       the sample is less than or equal  to 10 times (IQx) the amount in any blank for the common
       phtnalate contaminants, or 5 times the amount for other compounds.  In instances where more
       than one blank is associated with a given sample, qualification  should be based upon a comparison
       with  the associated blank having the highest concentration of a contaminant  The results must not
       be corrected by subtracting any blank value.
                                               55                                    DRAFT 12/90
                                                                                      Revised 6/91

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Blanks                                       •                                           .     SV
       Specific actions are as follows:

       1.      If a semivDlatile compound is found in a blank but not found, in the sample, no action is
               taken.  If the contaminants found are volatile target compounds (or interfering non-target
               compounds) at significant concentrations above the CRQL. then this should be noted for
               TPO action.

       2.      Any semivolatile compound detected in the sample (other than the common phthalate
               contaminants), that was also detected in any associated blank, is qualified if the sample
               concentration is less than five times (5x) the blank concentration. The quantitation limit
               may also be elevated. Typically, the sample CRQL is elevated to the concentration found
               in the sample.  The reviewer should use professional judgement to determine if further
               elevation of the CRQL is required.  For phthalate contaminants, the results are qualified
               *U* by elevating the sample quantitation limit to the sample concentration when the
               sample result is less than lOx the blank concentration.

              The reviewer should note that blanks may not involve the same weights, volumes, or
              dilution factors as the associated samples. These boon must be taken into consideration
              when applying the *5x" and *10x" criteria, such that a comparison of the total amount  of
              contamination is actually made.

              Additionally,  there may be instances where little or no contamination was present in the
              associated blanks, bnt qualification of the sample was deemed necessary. Contamination
              introduced through  dilution is one example.  Although it is not always possible to
              determine, instances of this occurring can be detected when contaminants are found in the
              diluted sample result, but are absent in the undiluted sample result Since both results
              are not routinely reported, it may  be impossible to verify this source of contamination.
              However, if the reviewer determines that the contamination is from a source other than
              the sample, he/she should qualify the data.  In this case,  the "5x* or "lOx* rules may not
              apply; the sample value should be reported as a non-detect. An explanation of the
              rationale used for this determination should be provided  in the narrative accompanying
              the Regional  Data Assessment Summary.
       3.      If gross contamination exists (i.e^ saturated peaks by GC/MS), all affected compounds in
              the associated samples should be qualified as unusable (R), due to interference. This
              should be noted for TPO action if the contamination is suspected of having an effect on
              the sample results.

       4.      If inordinate amounts of other target compounds are found at low levels in  the biank(s). it
              may be indicative of a problem and should be noted for TPO action.

       5.      The same consideration given to the target compounds should also be given to Tentatively
              Identified Compounds (TICs) which are found in both the sample and associated blank(s).
              (See SV Section XII for TIC guidance.)

       6.      If an instrument blank was not analyzed following a sample analysis which contained an
              analyte(s) at high concentration(s), sample analysis  results after the high concentration
              sample must be evaluated for carryover.  Professional judgement should be  used to
              determine if instrument cross-contamination has affected any positive compound


                                               56                                    DRAFT 12/90
                                                                                      Revised 6/91

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Blanks
                                                                SV
               identification(s). If instrument cross-contamination is suggested, then this should be
               noted for TPO action if the cross-contamination is suspeaed of having an effect on the
               sample results.

       The following are examples of applying the blank qualification guidelines. Certain circumstances
       may warrant deviations from these guidelines.
              Example 1:
              Example 1-
Sample result is greater than the Contract Required Quantitation Limit
(CRQL), but is less than the Sx or IQx multiple of the blank result
                                                                            Rule
                                    Blank Result
                                    CRQL
                                    Sample Result
                                    Qualified Sample Result
                                              7     7
                                              5     5
                                             60     30
                                             60U   30U
                             In the example for the *lQx* rule, sample results less than 70 (or 10 x 7)
                             would be qualified as non-detects.  In the case of the "Sx" rule, sample
                             results less than 35 (or 5 x 7) would be qualified as non-detects.
Sample result is less than CRQL, and is also less than the 5x or IQx
multiple of the blank result
                                               Rule
                                     Blank Result
                                     CRQL
                                     Sample Result
                                     Qualified Sample Result
                                              6
                                              5
                                             4J
                                             5U
 6
 5
4J
5U
                             Note that data are not reported as 4U, as this would be reported as a
                             detection limit below the CRQL
                             Sample result is greater than the Sx or lOx multiple of the blank result.

                                                                            Rule
                                    Blank Result
                                    CRQL
                                    Sample Result
                                    Qualified Sample Result
                                             10
                                              5
                                             120
                                             120
Sx

10
 5
60
60
                             For both the *10x" and 'Sx* rules, sample results exceeded the adjusted
                             blank results of 100 (or 10x10) and SO (or SxlO), respectively.
                                               57
                                                       DRAFT 12/90
                                                        Revised 6/91

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                                                                                                 sv


                                        VI. Surrogate Spikes


 A.      Review items: Form II SV-1 and SV-2 {Form IILCSV], chrxunatograms. and quantitation repons.

 B.      Objective

        Laboratory performance on individual samples is established by means of spiking activities.  All
        samples are spiked with surrogate compounds prior to sample preparation. The evaluation of the
        results of these surrogate spikes is not necessarily straightforward. The sample itself may produce
        effects due to such factors as interferences and high concentrations of analytes. Since the effects
        of the sample matrix are frequently outside the control of the laboratory and may present
        relatively unique problems, the evaluation and review of data based on specific sample results is
        frequently subjective and demands analytical experience and professional judgment. Accordingly,
        this section consists primarily of guidelines, in some cases with several optional approaches
        suggested.

C.      Criteria

        1.      Surrogate spikes, 4 acid compounds (3 required and 1 advisory) and 4 base/neutral
               compounds (3 required and 1 advisory) are added to all samples and blanks to measure
               their recovery in sample and blank matrices.

               (For data generated through the Low Concentration SOW: Surrogate spikes, 3 add compounds and 3
               bast/neutral compounds, art added to aO samples and Monks to measure their recovery in sample and
               blank matrices.]

        2.      Surrogate spike recoveries for semivolatile samples and blanks must be within the limits
               specified on in Appendix A and on Form II SV-1 and SV-2.

               [For data generated through the Low Concentration SOW: Surrogate spike recoveries for semivolatile
               samples and blanks must be within the limits specified in Appendix B and on Form 11LCSV.]


0.      Evaluation

        1.      Check raw data (e.g., chromatograms and quantitation reports) to verify the surrogate
               spike  recoveries on the Surrogate Recovery Form II SV-1 and SV-2 [Form II LCSV].
               deck for any transcription  or calculation errors.

        2.      Check that the surrogate spike recoveries were calculated correctly. The equation can be
               found in Appendix A [Appendix B].

        3.      The following should be determined from  the Surrogate Recovery fonn(s):

               a.       If any two base/neutral or acid surrogates are out of specification, or if any one
                       base/neutral or acid extractable surrogate has a recovery of less than  10%. then
                       there should be a reanalysis to confirm that the non-compliance is due to sample
                       matrix  effects rather than laboratory deficiencies.
                                                 58                                     DRAFT 12/90
                                                                                         Revised 6/91

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Surrogate Spikes                              '                         .                           SV


        NOTE: When there are unacceptable surrogate recoveries followed by successful re-analyses, the
                laboratories are required to report only the successful run.

                b.      The laboratory has failed  to perform satisfactorily if surrogate recoveries are out
                       of specification and there  is no evidence of reinjection of the extract, or
                       reextraction and reanatysis (if reinjeaion fails to resolve the problem).

                &      Verify that no blanks have surrogates recoveries outside the criteria.

        4.      Any time there are two or more analyses for a particular fraction the reviewer must
                determine which are the best data to report. Considerations should include but are not
                limited to:

                a.      Surrogate recovery (marginal versus gross deviation).

                b.      Technical holding  times.

                c.      Comparison of the values  of the target compounds reported in each fraction.

                d.      Other QC information, such as performance of internal standards.

E.      Action

        Data are not qualified with respect to surrogate recovery unless two or more semivolatile
        surrogates, within the same fraction (base/neutral or acid fraction), are out of specification. For
        surrogate spike recoveries out of specification, the following approaches are suggested based on a
        review of all data from the case, especially considering the apparent complexity of the sample
        matrix.

        1.      If two or more surrogates in  either semivolatile  fraction (base/neutral or acid fraction)
               have a recovery greater than  the upper acceptance limit (UL):

               a.      Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.

               b.      Detected semivolatile target compounds are qualified "J."

               c.      Results for non-detected semivolatile target compounds should not be qualified.

        2.      If two or more surrogates in  either semivolatile  fraction have a recovery greater than or
               equal to 10% but less than the  lower acceptance limit (LL):

               a.       Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.

               b.       Detected semivolatile target compounds are qualified "I.*

               c.       For non-detected semivolatile target compounds,  the sample quantitation  limit is
                       qualified as approximated  (UJ).
                                                 59                                     DRAFT 12/90
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Surrogate Spikes
                                                                                  SV
        3.      If any surrogate in either semivolatile fraction show less than 10% recovery:

               a.      Specify the fraction that is being qualified, f.e. acid, base/neutral, or both.

               b.      Detected semivolatile target compounds are qualified T.

               c      Non-detected semivolatile target compounds may be qualified as unusable (R).
                       Table 5. Qualification of Semivolatile Anaiytes Based on
                                       Surrogate Recoveries

Detected anatytes
Non-detected analytes
Surrogate Recovery
> UL 10% to LL < 10%
J
No
Qualification
J
UJ
J
R
       5.
In the special case of a blank analysis with surrogates out of specification, the reviewer
must give special consideration to the validity of associated sample data. The basic
concern is whether the blank problems represent an isolated problem with the blank
alone, or whether there is a fundamental problem with the analytical process.  For
example, if one or more samples in the batch show acceptable surrogate recoveries,  the
reviewer may choose to consider the  blank problem to be an isolated occurrence.
However,  even if this judgement allows some use of the affected data, analytical problems
should be noted for TPO action.  Also note if there are potential contractual problems
associated with the lack of re-analysis of samples that  were out of specification.

Whenever possible, the potential effects of the data resulting from system monitoring
recoveries not meeting the advisory limits should be noted in  the data review narrative.
                                                                                       DRAFT 12/90
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                                                                                              sv
                            VH.  Matrix Spikes/Matrix Soike Duplicates
                           (Not Required for Low Concentration Water Data)

 A.      Review Items:  Form 01 SV-1 and SV-2, chromatograms, and quantitation reports.

 B.      Objective

        Data for matrix spikes/matrix spike duplicates (MS/MSD) are generated to determine long-term
        precision and accuracy of the analytical method on various matrices and to demonstrate acceptable
        compound recovery by the laboratory at the time of sample analysis. These data alone cannot be
        used to evaluate the precision and accuracy of individual samples.  However, when exercising
        professional judgement, this data should be used in conjunction with other available QC
        information.

 C      Criteria

        1.      Matrix spikes and matrix spike duplicate samples are analyzed at  frequency of one MS and
               MSD per 20 samples of similar matrix.

        2.      Matrix spike and matrix spike duplicate recoveries should be within the advisory limits
               established on Form III SV-l and SV-2.

        3.      The Relative Percent Differences (RPDs) between matrix spike and matrix spike duplicate
               recoveries should be within the advisory limits listed on Form III SV-l and SV-2.

 D.      Evaluation

        1.      Verify that MS and  MSD samples were analyzed at the required  frequency and  that results
               are provided for each sample matrix.

        2.      Inspect results for the MS/MSD Recovery on  Form HI SV-l and  SV-2 and verify that the
               results  for recovery and RPD are within the advisory limits.

        3.      Verify transcriptions from raw data and verify calculations.

        4.      Check that the recoveries and RPD were calculated correctly.

        5.      Compare results (%RSD) of non-spiked compounds between the original result, MS, and
               MSD.

E      Action

        1.     .No action  is  taken on MS/MSD data alone. However, using informed professional
               judgment the data reviewer may use the matrix spike and matrix  spike duplicate results in
               conjunction with other  QC criteria and determine the need for some qualification of the
               data.

       2.      The data reviewer should  first try to determine to what extent the results of the MS/MSD
               effect the associated data. This determination should be made with regard to the


                                               61                                    DRAFT 12/90
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Matrix Spikes/Matrix Spike Duplicates           •                             .             •      SV


               MS/MSD sample itself as well as specific analytes for all samples associated with the
               MS/MSD.

       3.      In those instances where it can be determined that the results of the MS/MSD effect only
               the sample spiked, then qualification should be limited to this sample alone.  However, it
               may be determined through the MS/MSD results that a laboratory is having a systematic
               problem in the analysis of one or more analytes, which affects all associated samples.

       4.      The reviewer must use professional judgement to determine the need for qualification of
               positive results of non-spiked compounds.


       NOTE:  If a field blank was used  for the MS/MSD, a statement to that effea must be included for
               TPO action.
                                              62                                    DRAFT 12/90
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                                                                                                            sv


                                      VTTI.  Laboratory Control Sa"!ples
                                             (Low Concentration Water)


 (A.      Review Items:  Form 111 LCSV, LCS chromatagrams and qiianritarion reports.

 B.       Objective

         Data for laboratory control samples (LCS) are generated to provide information on the accuracy of the analytical
         method and the laboratory performance.

 C.       Criteria

         1.      Laboratory control samples an analyzed at frequency of once per 20 samples per SDG. The LCS must
                 be prepared and analyzed concurrently with the samples in the SDG.

         2      LCS percent recoveries mat be within the QC limits provided on Form HI LCSV.  The LCS must meet
                 the recovery criteria for the sample data to be accepted.

         3.      The LCS contains the following semivolatile target compounds, in addition to the required surrogates:

                          Phenol                                     1,2,4-Trichlorobenune
                          2-Chlorophenol                             Naphthalene
                          4-Chloroaniline                             2,4-Dinurotoiuene
                          2,4,6-Trichlorophenol                        Dietnylphthalau
                          bis(2-Chloroethyl)ether                       N-Nitrosodiphenylamine
                          N-Nitrosc^di-n-propylamine                   Heachlorobenzene
                          Hexachloroethane                           Bemo(a)pyrene
                          Isophorone

         4.      The criteria for surrogate recovery and internal standard performance also appfy.

D.       Evaluation

         1.      Verify that LCS samples wen analyzed at the required frequency.

         2.      Inspect the results for LCS Recovery on Form III LCSV and verify that the results for recovery are
                 wuhin the advisory Umits.

         3.       Verify transcriptions from raw data and verify calculations.

         4.       Check that the recoveries were calculated correctly.

E.       Action

         If the LCS criteria are not met, then the laboratory performance and method  accuracy are in question.
         Professional judgement should be used to determine if the data should be qualified or rejected. The following
         guidance is suggested for qualifying sample data for which the associated LCS does not meet the required criteria.

         I.       Action on the LCS recovery should be based on both the number of compounds that are outside of the
                 recovery criteria and the magnitude of the aceedance of the criteria.

         2.       If the LCS recovery criteria are not met, then the LCS results should be used to qualify sample data for
                 the specific compounds that are included ir. the LCS solution.  Professional judgement should be used to

                                                      63                                         DRAFT  12/90
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Laboratory Control Samples                      '                          .                      '       SV


                 qualify data for compounds other than those compounds that are included in the LCS. Professional
                 judgment to qualify non-LCS compounds should take into account the compound class,  compound
                 recovery efficiency, analytical problems associated with each compound, and comparability in
                 performance of the LCS compound to the non-LCS compound.

        3.       If the LCS recovery is greater than 140%, then positive sample results for the affected compound(s)
                 should be qualified with a V.

        4.       If the mass spectral criteria are met but the LCS recovery is less than 60%, then the associated detected
                 target compounds should be qualified  V and the associated non-detected target compounds should be
                 qualified "R".

        5.       If more than half of the compounds in the LCS are not within the required recovery criteria, then all of
                 the associated detected target compounds should be qualified V and all associated non-detected target
                 compounds should be qualified "R."

        6.       Action on non-compliant surrogate recovery and internal standard performance should follow the
                 procedures provided in Vl£ and X.E, respectively.  Professional judgement should be used to evaluate
                 the impact that non-compliance for surrogate recovery and internal standard performance in the LCS has
                 on the associated sample data.

        7.        It should be noted for TPO action if a laboratory fails to analyze an LCS with each SDC, or if a
                 laboratory consistently fails to generate acceptable LCS recoveries.]
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                                                                                               sv
                         IX. Regional Quality Assurance and Quality Control
        Review Items:  Form ISV-1 and SV-2 [Farm ILCSV-1 and LCSV-2], chromatograms, quantitation
        report, traffic repon and raw data for Regional QC samples.
 B.      Objective
        Regional Quality Assurance and Quality Control (QA/QC) refer to any QA and/or QC initiated
        by .the Region, including field duplicates, Regional Performance Evaluation (PE) samples, blind
        spikes, and blind blanks. It is highly recommended that Regions adopt the use of these.

        Criteria

        Criteria are determined by each Region.

        1.      Performance evaluation sample frequency may vary.

               [For data generated through the Low Concentration SOW: A performance evaluation (PE) sample may
               be rtaiured as frequently as once per SDG.J

        2.      The analytes present in the PE sample must be correctly identified and quantified.
0.     Evaluation
       Evaluation procedures must follow the Region's SOP for data review.  Each Region will handle
       the evaluation of PE samples on an individual basis. Results for PE samples should be compared
       to the acceptance criteria for the specific PE samples, if available.

       Action

       Any action must be in accordance with Regional specifications and the criteria for acceptable PE
       sample results.  Unacceptable results for PE samples should be noted for TPO action.
                                               65                                    DRAFT 12/90
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                                                                                                  sv
                                        X.  Interna*
 A.     Review Items:  Form VIII SV-1 and SV-2 [Form VU1 LCSV.1 and LCSV-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 4- 100%) from the associated calibration standard.

                [For data generated through the Low Concentration Water SOW: Internal standard area counts must not
                vary by more than a factor of t 40.0% from the associated calibration standard.]

        2.      The retention time of the internal standards in samples and blanks must not vary by more
                than +. 30 seconds from the retention time of the associated calibration standard.

                [for data generated through the Low Concentration SOW: The retention time of the internal standards
                in samples and blanks must not vary by more than t20.0 seconds from the retention time of the
                associated calibration standard,]

 D.     Evaluation

        1.      Check raw data (e.g., chromatograms and quantitation lists) for samples  and blanks to
                verify the internal standard retention times and areas reported on the Internal Standard
                Area Summary (Forms VIII SV-i, VIII SV-2 [Form Vlll LCSV-l and LCSV-2]).

        2.      Verify that all retention times and IS areas are within the required criteria.

        3.      If there are two analyses for a particular  fraction, the reviewer must determine which are
                the  best data to report.  Considerations should include:

                a.      Magnitude and direction of the IS area shift

                b.      Magnitude and direction of the IS retention time shift

                c.      Technical holding times.

               'd.      Comparison of the values of the  target compounds reported in each fraction.

E.      Action

        1.       If an IS area count for a sample or blank is outside - 50% or + 100% of the area  for the
                associated standard:
                                                  66                                    DRAFT 12/90
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Internal Standards
                                                                                                    sv
               a.      Positive results for compounds quantitated using that IS should be qualified with
                       V.

               b.      Non-deteaed compounds quantitated using an IS area count greater than 100%
                       should not be qualified.

               c.      Non-deteaed compounds quantitated using an IS area count less than 50% are
                       reported as the associated sample quantitation limit and qualified with "UJ".

               d.      If extremely low area counts are reported, or if performance exhibits a major
                       abrupt drop-oft then a severe loss of sensitivity is indicated. Non-detected target
                       compounds should then be qualified as unusable (R).
               /// an IS area count for a sample or blank is outside i 40.0% of the ana for associated standard:

               a.       Positive results for compounds y^'Tiri* using that IS should be qualified with V.

               b.       Non-detected compounds quantitated using an IS area count greater than 40% should not be
                       qualified.

               c.       Non-detected compounds quantitated using an IS area count less than 40% are reported as the
                       associated sample quanatation limit and qualified with "UJ*.

               a.      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:

               /// an IS retention time varies by more than 20.0 seconds:]

               The chromatographic profile for that sample must be examined to determine if any false
               positives or negatives exist  For shifts of a large magnitude, the reviewer may consider
               partial or total rejection (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.
                                                 67                                      DRAFT 12/90
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                                                                                                sv


                                 XL   Target Compound Identification
         Review Items:  Form I SV-1 and SV-2 (Form I LCSV-l and LCSV-2], quamitation reports, mass
         spectra, and chromatograms.
 B.     Objective
        Qualitative criteria for compound identification have been established to minimize the number of
        erroneous identifications of compounds. An erroneous identification can either be a false positive
        (reporting a compound present when it is not) or a false negative (not reporting a compound that
        is present).

        The identification criteria can be applied much more easily in detecting false positives than false
        negatives. More information is available due to the requirement for submittal of data supporting
        positive identifications. Negatives, or non-detected compounds, on the other hand represent an
        absence of data and are, therefore, much more difficult to assess.  One example  of detecting false
        negatives is the reporting of a Target Compound as a TIC
 C.      Criteria
        1.       Compound must be within ± 0.06 relative retention time (RRT) units of the standard
                RRT.

        2.       Mass spectra of the sample compound and a current laboratory-generated standard must
                match according to the following criteria:

                a.      All ions present in the standard mass spectrum at a relative intensity greater than
                       10% must be present in the sample spectrum

                       {For data generated through the Law Concentration SOW: All ions present in the standard
                       mass spectrum at a relative intensity greater than 25% must be present in the sample spectrum. ]

                b.      The relative intensities of these  ions must agree within ±20% between  the
                       standard and sample spectra.  (Example: For  an ion with an abundance of 50%
                       in the standard spectrum, the corresponding sample ion abundance must be
                       between 30% and 70%.)

               c,      Ions present at greater than 10% in the sample mass spectrum but not  present  in
                       the standard spectrum must be considered and accounted for.

                       [Far data generated through the Low Concentration SOW: Ions present at greater than 25% in
                       the sample mass spectrum but not present in the standard mass spectrum must be considered
                       and accounted for.}
D.      Evaluation
        1.      Check that the RRT of reported compounds is within ± 0.06 RRT units of the standard
               relative retention time.
                                                68                                     DRAFT 12/90
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Target Compound Identification                                                                  SV


        2.      Check that the sample compound spectra against the laboratory standard speara to verify
               that its meets the specified criteria.

        3.      The reviewer should be aware of situations (e.g., high concentration samples preceding
               low concentration samples) when sample carryover is a possibility and should use
               judgment to determine if instrument cross-contamination has affected any positive
               compound identification.

        4.      Check the chromatogram to verify that peaks are accounted for, i.e., major peaks are
               either identified as target compounds, TICs, surrogates, or internal standards.

E.      Action

        1.      The application of qualitative criteria for GC/MS analysis of target compounds requires
               professional judgement  It is up  to the reviewer's discretion to obtain additional
               information from the laboratory.  If it is determined that incorrect identifications were
               made, all such data should be qualified as not detected (U) or unusable (R).

       2.      Professional judgement must be used to qualify the data if it is determined that cross-
               contamination has  occurred.

       3.      Any changes made to the reported compounds or concerns regarding target compound
               identifications should be clearly indicated in the data review narrative. The necessity for
               numerous or significant changes should be noted for TPO action.
                                                69                                    DRAFT 12/90
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                                                                                              sv
                         XII.  Compound Ouandtation and Reoorted CROLS
        Review Items:  Fonn I SV-1 and SV-2 (Form ILCSV-1 and LCSV-21, sample preparation sheets, case
        narrative, sample clean-up sheets, quamitation repocts^and chromatograms.
 B.      Objective
        The objective is to ensure that the reported quantitation results and Contract Required
        Quantitation Limits (CRQLs) for semivolatile target compounds are accurate.

        Criteria

        1.      Compound quantitation, as well as the adjustment of the CRQL, must be calculated
               according to the correct equation.

        2.      Compound area responses must be calculated based on the internal standard (IS)
               associated with that compound, as listed in Appendix A [Appendix BJ (also as specified in
               the Statement of Work). Quantitation must be based on the quantitation ion (m/z)
               specified in the SOW for both the IS and target anaiytes.  The compound quantitation
               must be based on the RRF from the appropriate daily calibration standard.
D.     Evaluation
       1.      For all fractions, raw data should be examined to verify the correct calculation of all
               sample results reported by the laboratory.  Quantitation lists, chromatograms. and sample
               preparation log sheets should be compared to the reported positive sample results and
               quantitation limits. Check the reported values.

       2.      Verify that the correct internal standard, quantitation ion, and RRF were used  to
               quantitate the compound. Verify that the same internal standard, quantitation  ion. and
               RRF are used consistently throughout the  calibration and quantitation processes.

       3.      Verify that the CRQLs  have been adjusted to reflect all sample dilutions, concentrations.
               splits, clean-up aaivities, and dry weight faaors that are not accounted for by the method.

       Action

       1.      If there are any discrepancies found, the laboratory may be contacted by  the designated
               representative to obtain additional information that could resolve any differences.  If a
               discrepancy remains unresolved, the reviewer must use professional judgement to decide
               which value is the  best value. Under these circumstances, the reviewer may determine
               qualification of data is warranted. Decisions made on data quality  should be included in
               the data review narrative.  A description of the reasons for data qualification and the
               qualification that is applied to the data should be documented in the data review
               narrative.

       2.       Numerous or significant failures  to accurately quantify the target compound or to properly
               evaluate and adjust CRQLs should be noted for TPO aaion.


                                               70                                    DRAFT  12/90
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                                                                                                    sv
                                XIII.  Tentatively Identified Compounds
 A.      Review Items: Form I SV-TIC [Form ILCSV-TIC], chromatograras. 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 (MIST) mass spectral
         library search and the identifications assessed by the data, reviewer.

 C.      Criteria

         For each sample, the laboratory must conduct a mass spectral search of the NIST library and
         report the possible identity for the 20 largest semivolatile fraction peaks which are not surrogate,
         internal standard, or target compounds, but which have area or height greater than 10 percent of
         the area or height of the nearest internal standard.  TIC results are reported  for each sample on
         the Organic Analyses Data  Sheet (Form I SV-TIC).

        [For data generated through the Law Concentration SOW: For each sample, the laboratory must conduct a mass
        spectral search of the NIST library and report the possible identity for the 20 largest semivolatile fraction peaks
        which an not surrogates, internal standards, or TCL compounds, but which have an area greater than SO percent
        of the area of the nearest internal standard. Estimated concentrations for TICs are calculated similarly to the
        TCL compounds, using total ion areas for the TIC and the internal standard, and assuming a relative response
        factor of 1.0. TIC results are reported for each sample on the Organic Analyses Data Sheet (Form I LCSV-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 property reported in
                another fraction. For example, late eluting volatile target compounds should not be
                reported as semivolatile TICs.

D.      Evaluation

        1.       Guidelines for tentative identification are as follows:

                a.       Major ions (greater than 10% relative intensity) in the  reference spectrum should
                        be present  in the sample spectrum.

                       [Major ions  (greater than 25% relative intensity) in the reference spectrum should be present in
                       the sample spectrum.]

               *b.      The relative intensities of the major ions should agree within ±20% between the
                       sample and the reference spectra.

               c.      Molecular ions present in the reference spectrum should be present in the sample
                       spectrum.
                                                  71                                     DRAFT 12/90
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Tentatively Identified Compounds                                                                  SV


               
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 Tentatively Identified Compounds                                                                 SV


                c      Aldoi reaction products of acetone include:  4-hydroxy-4-methyl-2-pentanone, 4-
                       methyl-2-penten-2-one, and 5,5-dimethyl-2(5H)-furanone.

        7.       Occasionally, a target compound may be identified as a TIC in the proper analytical
                fraction by non-target library search procedures, even though it was not found on the
                .quantitation list  If the total area quantitation method was used, the reviewer should
                request that the laboratory recalculate the result using the proper quantitation ion.  In
                addition, the reviewer should evaluate other sample chromatograms and check library
                reference retention times on quantitation lists to determine whether the false negative
                result is an isolated occurrence or whether additional data may be  affected.

        8.       Target compounds may be identified in more than one fraction. Verify that quantitation
                is made from the proper fraction.

        9.       Library searches should not be performed on internal standards or surrogates.

        10.      TIC concentration should be estimated assuming a RRF of 1.0.

E.      Action

        1.       All TIC results should be qualified "NJ", tentatively identified, with approximated
                concentrations.

        2.       General actions related to the  review of TIC results are as follows:

                a.      If it is determined that a tentative identification of a non-target compound is not
                       acceptable, the tentative  identification should be changed to 'unknown" or an
                      appropriate identification.

                b.     If all contractually required peaks were not library searched and quantitated. the
                      designated representative could request these data from the laboratory.

       •3.      TIC results which are not sufficiently above the level in the blank should not be reported.
                (Dilutions and sample size must be taken into account when comparing the amounts
                present in blanks and samples.)

        4.       When a compound is not found in any blanks, but is a suspected artifact of common
                laboratory contamination, the result may be qualified as unusable (R).

        5.       In deciding whether a library search result for a TIC represents a reasonable identification,
               professional judgment must be exercised.  If there is more than one possible match, the
              . result may be reported as "either compound X or compound Y."  If there  is a  lack of
               isomer specificity, the TIC result  may be changed to a non-specific isomer result (e.g.,
                13,5-trimethyl benzene to trimethyt benzene isomer) or to a compound class (e.g., 2-
               methyl, 3-ethyl benzene to substituted aromatic compound).

       6.       The reviewer may elect to report all similar isomers as a total.  (All alkanes may be
               summarized and reported as total hydrocarbons.)
                                                73                                    DRAFT 12/90
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Tentatively Identified Compounds                                       .      •                   SV


        7.      Other case {actors may influence TIC judgments.  If a sample TIC match is poor but other
               samples have a TIC with a good library match, similar relative retention time, and the
               same ions, identification information may be inferred from  the other sample TIC results.

        8.      Physical constants, such as boiling point, may be factored into professional judgment of
               TIC results.

        9.      Any changes made to the reported data or any concerns regarding TIC identifications
               should be indicated in the data review narrative.

        10.     Failure to properly evaluate and report TICs should be noted for TPO action.
                                                74                                    DRAFT 12/90
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                                                                                                  sv
                                      XIV.  System Performance
        Review Items:  Form III SV-1 and SV-2 (Form III LCSVJ, Form VIII SV-l and SV-2 [Form
        LCSV-2 and LCSV-2], and chromatograms.
B.      Objective
        Dunng the period following Instrument Performance QC checks (e.g. blanks, tuning, calibration),
        changes may occur in the system that degrade the quality of the data. While this degradation
        would not be directly shown by QC checks until the next required series of analytical QC runs, a
        through review of the ongoing data acquisition  can yield indicators of instrument performance.
C.      Criteria
        There are no specific criteria for system performance. Professional judgement should be used to
        assess the system performance.
D.      Evaluation
        1.      Abrupt, discrete shifts in the reconstructed ion chromatogram (RIC) baseline may indicate
               a change in the instrument's sensitivity or the zero setting.  A baseline shift could indicate
               a decrease in sensitivity in the instrument or an increase in the instrument zero, possibly
               causing target compounds at or near the detection limit to be non-detects.  A baseline
               "rise" could indicate problems such as a change in the instrument zero, a leak, or
               degradation of the column.

        2.      Poor chromatographic performance affects both qualitative and quantitative results.
               Indications of substandard performance include:

               a.       High RIC background levels or shifts in absolute retention times of internal
                       standards.

               b.       Excessive baseline rise at elevated temperature.

               c.       Extraneous peaks.

               d.       Loss of resolution as suggested between by factors such as non-resolution of 2.4-
                       and 24- dinitrotoluene.

               e.       Peak tailing or peak splitting that may result in inaccurate quantitation.

       [3.    •  A drift in instrument sensitivity may occur during the 12-hour nme period.  This could be discerned by
               examination  of the IS ana on Form  VIIILCSV-1 and LCSV-2 for trends such as a continuous or near-
               conanuous increase or decrease in the IS area over tune.

       4.       The remits of the LCS analysis (Form III LCSV) may also be used to assess instrument performance./
                                                 75                                     DRAFT 12/90
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System Performance                           '                       .                   '      SV
       Action

       Professional judgement must be used to qualify the data if it is determined that system
       performance has degraded during sample analyses.  Any degradation of system performance which
       significantly affected the data should be documented for TPO action.
                                               76                                   DRAFT 12/90
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                                      .   Overall Assessment of Data
 A.      Review Items: .Entire data package, data review results, and (if available) Quality Assurance
         Project Plan (QAPjP), and Sampling and Analysis Plan (SAP).

 B.      Objective

         The overall assessment of a data package is a brief narrative in which the data reviewer expresses
         concerns and comments on the quality and. if possible, the useabiliry of the data.

 C.      Criteria

         Assess the overall quality of the data.

         Review all available materials to assess the overall quality of the data, keeping in mind the
        additive nature of analytical problems.

 0.      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 qualify  of the
               data.

E.      Action

        1.      Use professional judgement to determine if there  is any need to qualify data which were
               not qualified based on the QC criteria previously discussed.

        2.      Write a brief narrative to give the user an indication of the analytical limitations of the
               data. Any inconsistency of that data with the SDG Narrative should be noted  for TPO
               action.  If sufficient information on the intended use and  required quality of the data are
               available, the reviewer should include his/her assessment of the  useability of the data
               within the given context.
                                                 77                                     DRAFT 12/90
                                                                                         Revised 6/91

-------
               APPENDIX A

CONTRACTUAL REQUIREMENTS AND EQUATIONS

MULTI-MEDIA, MULTI-CONCENTRATION - MM/MC
                (OLM01.0)
                                                DRAFT 12/90
                                                Revised 6/91

-------
                                                                                APPENDIX A
                           MULTI-MEDIA, MULTI-CONCENTRATION
        CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR VOLATILE DATA REVIEW
 II.      GC/MS Instrument Performance Check

 Use equation III to verify that the laboratory has not made errors the calculation of the percent relative
 abundance.


                         * Relative Abundance - «*"**"*< °/* x 100%                     (II.1)
                                              abundance of Y


 For example, the percent relative abundance of m/z 96 (X) relative to m/z 95 (V) is calculated as follows:


                       % Relative Abundance -  abundance °f *k 96 x
                                             abundance of m/z 95
HI.    Initial Calibration

Data Review Criteria: All volatile target compounds and system monitoring compounds must have a
Relative Response Factor (RRF) of greater than or equal to 0.05 and a percent relative standard deviation
(%RSD) of less than or equal to 30%.

Contractual Criteria;  The maximum %RSD for volatile compounds is 20.5% and the minimum RRF
criteria vary as specified in the Table A.1 (The volatile compounds listed separately in Table 2 on page 13
are not contractually required to meet a maximum %RSD but do have to meet a contractual minimum
RRF of 0.010). The contractual criteria for an acceptable initial calibration specifies that  up to anv 2
volatile target compounds may fail to meet minimum RRF or maximum %RSD as long as they have RRFs
that are greater than or equal to 0.010, and %RSD of less than or equal to 40.0%.

                  Table A.1 Minimum RRF Criteria for Volatile Target Compunds

                     Volatile                             Minimum
                     Compound                           RRF

                     Bromomethane                       0.100
                     Vinyl chloride                        0.100
                     1,1-Dichloroethene                   0.100
                     1.1-Dichloroethane                   0.200
                     Chloroform                          0.200

                     1,2-Dichloroethane                   0.100
                     1.1,1-Trichloroethane                  0.100
                     Carbon tetrachloride                  0.100
                     Bromodichloromethane               0.200
                     cis-13-Dichloropropene               0.200


                                             A-1                                 DRAFT 12/90
                                                                                  Revised 6/91

-------
 MM/MC                                                                           APPENDIX A

              Table A.1 Minimum RRF Criteria for Volatile Target Compunds (continued)

                       Volatile                              Minimum
                       Compound                           RRF

                       Trichloroethene                       0.300
                       Dibromochloromethane                0.100
                       1,1,2-Trichloroethane                  0.100
                       Benzene                              0.500

                       trans-13-Dichloropropene              0.100
                       Bromoform                           0.100
                       Tetrachloroethene                     0.200
                       1,1^2-Tetracbloroethane               0300
                       Toluene                              0.400

                       Chlorobenzene                        0.500
                       Etbyibenzene                         0.100
                       Styrene                              0300
                       Xylenes (total)                        0.300
                       Bromofluorobenzene                  0.200


Initial calibration RRFs and RRF are calculated using equations III.1 and 111.2.


                                       RRF  -   ^i  x  ^S                                 (HI.1)
                                         	                                               (III.2)
                                         MF - —	
                       where:
                              RRFj = "i'th Relative Response Factor
                              A    = Area of the characteristic ion (EICP) measured
                              C    = Concentration
                              is   =* Internal standard
                              x   = Analyte of interest


The %RSD is calculated using equations III.3 and III.4.


                                                                                           (III.3)
                                               A-2                                  DRAFT
                                                                                      Revised 6/91

-------
 MM/MC                   ,                                                      APPENDIX A


                                        %RSD~ 4 x 100                                 (m.4)
                                               x

                      where:
                             a *  Standard deviation of 5 relative response factors
                             I =  Mean of S relative response factors

 IV.     Continuing Calibration

 Data Review Criteria;  All compounds must be considered for qualification when the %D exceeds the ±
 25.0%  criterion.

 Contratual Criteria; The percent difference (%D) between the initial calibration KKF and the
 continuing calibration RRF is +. 25% for all compounds listed in Table A.1. The contractual criteria for
 an acceptable continuing calibration specifies that up to am 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
 %O of less than or equal to 40.0%.

 Check the continuing calibration RRF calculations for volatile target compounds using equation III.1.  The
 %O between initial calibration -RRF and continuing calibration RRF is calculated using equation IV. 1.


                                                     x 100*                            crv.i)
                                             RRF,

               where:

                     RRFl = average relative response factor from initial calibration.
                     RRfc = relative response factor from continuing calibration standard.


VI.     System Monitoring Compounds

The volatile system monitoring compounds (surrogates) and their contractual recovery limits are listed in
Table A.2.

                 Table A-2 System Monitoring Compound Contractual Requirements

               System Monitoring Compound                 %Recoverv Limits
                                                   Water Samples        Soil Samples

               SMC1  Toluene-^                     88-110               84-138
               SMC2  Bromofluorobenzene             86-115               59-113
               SMC3  U-Dichloroethane-d4            76-114               70-121
                                             A-3                                  DRAFT 12/90
                                                                                   Revised 6/91

-------
 MM/MC                                                                         APPENDIX A

 Use equation VLl to check that the system monitoring compound recoveries were calculated correctly:
                                     Conccntrationlamcaua spiked



VII.    Matrix Spikes/Matrix Spike Duplicates

The 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

              1,1-Dichloroethene     61  - 145       59 - 172          <.14          <22
              Trichloroctliene        71  - 120       62 - 137          <.14          ^24
              Benzene               76  - 127       66 - 142          £.11          <.2l
              Toluene               76  - 125       59 - 139          <.13          ^21
              Chlorobenzene         75-130       60-133          <13          <21
Verify that the matrix spike recoveries and RPO were calculated correctly using equations VII. 1 and VII.2.


                                * Recovery - SSR ~ SR x 100%                          (VII.I)
                             where:
                                    SSR ^ Spiked sample result
                                    SR  zc Sample result
                                    SA  = Spike added
                               RPD.   \MSR - MSD*\   x  100%
                                     1/2 (MSR f MSDK)
                            where:
                                   RPD = Relative percent difference
                                   MSR = Matrix spike recovery
                                   MSDR = Matrix spike duplicate recovery
                                             A-4                                 DRAFT 12/90
                                                                                  Revised 6/91

-------
 MM/MC

 IX.     Internal Standards
                                              APPENDIX A
 Table A.4 contains the volatile internal standards and their corresponding target compounds.  These
 criteria have been established for packed columns only. Specific criteria for capillary columns have not
 been included in the SOW at this time.
               Table A.4 Internal Standards and Their Corresponding Target Compounds
        Bromochloromeihane
1,4-Difluorobenzene
Chlorobenzene-d*
        Chloromethane
        Bromomethane
        Vinyl Chloride
        Chloroethane
        Methylene Chloride
        Acetone
        Carbon Disulfide
        1.1-Dichloroethene
        1,1-Dichloroe thane
        U-Oichloroethene(total)
        Chloroform
        1,2-Dichloroe thane
        2-Butanone
        1.2-Dichloroethane-d4 (SMC)
1,1,1-Trichloroe thane
Carbon Tetrachloride
Bromodichloromethane
Bromoform
1,2-Dichloropropane
trans-13-Dichloropropene
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroe thane
Benzene
cis- 13-Dichloropropene
Bromoform
2-Hexanone
4-Methyl-2-Pentanone
Tetrachloroethene
1,1^2-Tetrachloroe thane
Toluene
Chlorobenzene
Ethyibenzene
Styrene
Total Xylenes
Bromofluorobenzene (SMC)
Toluene-dg (SMC)
       SMC = System Monitoring Compound
XI.    Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)

Check the reponed positive sample results and quantitation limits with the quantitation lists and
chromatograms using equations XL1, XL2, or X13. Characteristic ions for the volatile target compounds
are contained in Table A.5. Characteristic ions for System  Monitoring Compounds and Internal Standards
are contained in Table A.6.
       Concentration for waters:
                                     ugfL
                                                  /, x Df
                                            A,, x KXF x K.
                                                     (XLl)
                                              A-5
                                               DRAFT 12/90
                                                Revised 6/91

-------
 MM/MC                                                                           APPENDIX A

         Concentration for. low level soils:
         (Dry weight basis)
                                                                                           (XI.2)
        Concentration for medium level soils:
        (Dry weight basis)
                                  „     A, * 7, x K, x 1000 x Df
                                uglKg * — - - - - - -
                                        A,, x RKF x Va x  Wt x D
               where:
                      Ax  s area of characteristic ion (EICP) for compound being measured
                      A^ * area of characteristic ion (EICP) for the internal standard
                      /,  = amount of internal standard added (ng)
                      RRF  s daily response factor for compound being measured
                      VQ  ss volume of water purged (mL)
                      Ws  = weight of sample (g)
                      D   = (100 - % moisture)/100% - conversion to dry weight
                      Vl  = volume of methanol (mL)f
                      Kj  = volume of extract added (uL) for purging
                      Df  = dilution factor}
                      Vt  = volume of the aliquot of the methanol extract (uL) added to reagent water
                            for purging
               This volume is typically 10.0 mL, even though only 1.0 mL is transferred to the vial. See
               the SOW for more details.

               The dilution factor for analysis of soil/sediment samples for volatiles by the medium level
               method is defined ss the ratio of the number of microliters (uL) of methanol added to the
               reagent water for purging (Va) to the number of microliters of the methanol extract of the
               sample contained in volume Va.  If no dilution is performed, then the dilution factor
               equals 1.0.
The CRQL for a diluted sample should be calculated as follows:

               Adjusted CRQL = Non-adjusted CRQL x Sample Dilution Factor                 (XI.4)
                                               A-6                                  DRAFT 12/90
                                                                                     Revised 6/91

-------
MM/MC                                                                         APPENDIX A

       For example, the adjusted CRQL for a water sample with a 10U non-diluted CRQL and a 1 to
       100 dilution (100.0 dilution factor) would be 1000U, according to the following calculation:

                            1000U = 10U x 100
The CRQL adjustment for dry weight for a soil sample should be calculated as follows:


                            Dry Weifr CRQL -  *«^** <*»
                                               . 100 - %mouture.                        (X1.5)
                                                      100
       For example, the dry weight CRQL for a soil sample with a 10U non-adjusted CRQL and a 10%
       moisture would be 11U, according to the following calculation:
                                      IIU
                                                100
                                            A-7                                  DRAFT 12/90
                                                                                  Revised 6/91

-------
MM/MC
APPENDIX A
                   Table A£ Chancteristk Ions for Volatile Target Compounds
Analyte
Chloromethane
Bromomethane
Vinvl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1.1-Dichloroethene
1,1-Dichloroethane
1,2-Dichloroethene
Chloroform
1,2-Dichloroethane
2-Butanone
1,1.1-Trichloroethane
Carbon tetrachloride
Bromodichloromethane
1, 1,22-Tetrachloroethane
1,2-Dichloropropane
trans-13-Dichloropropene
Trichloroetheae
Dibromochloromethane
1,1,2-Trichloroetnane
Benzene
cis- 13-Dichloropropene
Bromoform
2-Hexanone
4-Methyl-2-penianone
Primary Ion*
50
94
62
64
84
43
76
96
63
96
83
62
43"
97
117
83
83
63
75
130
129
97
78
75
173
43
43
Secondary Ion(s)
52
96
64
66
49, 51, 86
58
78
61,98
65, 83, 85, 98, 100
61,98
85
64, 100, 98
57
99, 117, 119
119, 121
85
85, 131. 133, 166
65, 114
77
95, 97. 132
208. 206
83, 85, 99, 132, 134
—
77
171, 175, 250, 252, 254, 256
58, 57, 100
58, 100
                                          A-8
 DRAFT 12/90
  Revised 6/91

-------
MM/MC
APPENDIX A
              Table AJ Characteristic Ions for Volatile Target Compounds (Continued)
Analyte
Tetrachloroethene
Toluene
Chlorobenzenc
Ethyl benzene
Styrene
Total Xylenes
Primary Ion*
164
92
112
106
104
106
Secondary Ion(s)
129. 131. 166
92
114
91
78, 103
91
       While m/z 43 is used for quantitation of 2-Butanone, m/z 72 must be present for positive
       identification.

       The primary ion should be used unless interferences are present, in which case, a secondary ion
       may be used.
       Table A.6 Characteristic Ions for System Monitoring Compounds and Internal Standards
                                for Volatile Organic Compounds
Compound
Primary Ion
Secondary Ion(s)
SYSTEM MONITORING COMPOUNDS
4-Bromofluorobenzene
1.2-Dichioroethane-d4
Toluene-d8
95
65
98
174, 176
102
70, 100
INTERNAL STANDARDS
Bromochioromethane
1,4-Difluorobenzene
Chlorobenzene-dj
128
114
117
49. 130. 51
63,88
82,119
                                             A-9
 DRAFT 12/90
  Revised 6/91

-------
                                                                                 APPENDIX A

                           MULTI-MEDIA, MULTI-CONCENTRATION
     CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR SEMTVOLATTLE DATA REVIEW
 II.     GC/MS Instrument Performance Check

 Use equation II. 1 to verify that the laboratory has not made errors in the calculation of the percent
 relative abundance.

 For example, the percent relative abundance of m/z 443 (X) relative to m/z 442 (Y) is calculated as follows:
                                                      * "*     x 100%
                                            abundance of m/z 442
III.    Initial Calibration
Data Review Criteria; All sernivolatile target compounds and surrogates must have a Relative Response
Factor (RRF) of greater than or equal to 0.05 and a percent relative standard deviation (%RSD) of less
than or equal to 30%.

Contractual Criteria; The maximum %RSD for most semivolatile compounds is 20.5% and the minimum
RRF criteria vary as specified in Table A. 7 (The semivolatile compounds listed separately in Table 4 on
page 52 are not contractually required to meet a man'mnm %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-Chiorophenol               0.800
                             13-Dichlorobenzene           0.600
                             1,4-Dichlorobenzene           0.500

                             1,2-Dichlorobenzene           0.400
                             2-Methyiphenol               0.700
                             4-Methylphenol               0.600
                             N-Nitroso-di-propylamine      0.500
                             Hexachloroethane              0.300

                             Nitrobenzene                 0.200
                             Isophorone                   0.400
                             2-Nitrophenol                 0.100
                             2,4-Dimethylphenol            0.200
                             bis(-2-Chloroethoxy)methane    0.300


                                            A-10                                 DRAFT 12/90
                                                                                  Revised 6/91

-------
MM/MC                                                                          APPENDIX A

          Table A.7 Minimum RRF Criteria for Semivolatile Target Compounds (Continued)

                            Semivolatile                  Minimum
                            Compounds                   RRF

                            2,4-Dichloropfaenol            0200
                            1,2,4-Trichlorobenzene         0.200
                            Naphthalene                  0.700
                            4-Chloro-3-methylphenol       0.200
                            2-Methylnaphthalene          0.400

                            2,4,6-Trichlorophenol          0.200
                            2,4,5-Trichlorophenol          0200
                            2-Chloronaphthalene          0.800
                            Acenaphthytene               1300
                            2,6-Dinitrotoluene             0.200

                            Acenaphthene                0.800
                            Dibenzofuran                 0.800
                            2,4-Dinitrotoluene             0.200
                            4-Chlorophenyl-phenylether    0.400
                            Fluoreae                     0.900

                            4-Bromophenyl-phenylether    0.100
                            Hexachlorobenzenc            0.100
                            Peotachlorophenoi             0.050
                            Phenanthrene                 0.700
                            Anthracene                   0.700

                            Fluoranthene                 0.600
                            Pyrene                       0.600
                            Benzo(a)anthiacene            0.800
                            Chrysene                     0.700
                            Benzo(b)fluoranthene          0.700

                            Benzo(k)fluoramhene          0.700
                            Benzo(a)pyrene               0.700
                            Indeno(l,23-cd)pyrene         OJOO
                            Dibenz(a4))anthracene         0.400
                            Benzo(g4w)peryiene           OJOO

                            Nitrobenzene-dj               0.200
                            2-Buorobtphenyl              0.700
                            TerphenyW14                 OJOO
                            Phenol-d,                    0.800
                            Z-Ruorophenol               0.600

                            2-Cnlorophenol-d4             0.800
                            12-Dichlorobenzene-d4        0.400
                                            A-ll                                  DRAFT
                                                                                   Revised 6/91

-------
 MM/MC                                                                           APPENDIX A

 Initial calibration RRF and RRF are calculated using equations III.1 and III.2; %RSD is calculated
 using equations IIL3 and III.4.

 IV.     Continuing Calibration

 Data Review Criteria;  All semivolatile target compounds should meet a %D criterion of ± 25%.

 Contractual Criteria; The percent difference (%D) between the initial calibration RRF and the
 continuing calibration RRF is ± 25.0% for the compounds listed in Table A.4.  The contractual criteria
 for an acceptable continuing calibration specifies that up to any 4 semivolatile target compounds may fail
 to meet minimum RRF or maximum %D as long as they have RRFs that are greater than or equal to
 0.010, and %D of less than or equal to 40.0%.

 Check the continuing calibration RRF calculations for semivolatile target compounds using equation III.l.
 and evaluate the %D between initial calibration RRF and continuing calibration RRF using equation
 I V.I.

 VI.    Surrogate Spikes

 The semivolatile surrogate compounds and their contractual recovery limits are listed in Table A.8.

                            Table AJJ Semivolatile Surrogate Requirements

                Surrogate                             %Recoverv Limits
                                             Water Samples        Soil Samples

        SI Nitrobenzene-d5                      35-114               23 - 120
        S2 2-Fluorobiphenyl                     43-116               30-115
        S3 Terphenyl-d14                        33 - 141               18 - 137
        S4 Phenol-d5                            10-110               24-113
        S5 2-Fluorophenol                       21 - 110               25 - 121
        S6 2,4,6-Tribromophenol                  10 - 123               19 - 122
        S7 2-Chlorophenol-d4                    33 - 110*              20 - 130*
        S8 l,,2-Dichlorobenzene-d4                16 - 110*              20 - 130*

        * Advisory limits

 Use equation VL1 to verify that the surrogate recoveries were calculated correctly.

 VII.    Matrix Spikes/Matrix Spike Duplicates

 The matrix spike/matrix spike duplicate contractual requirements are listed in Table A.9.

 Verify that the matrix spike recoveries and RPD were calculated correctly using equations VII. 1 and VII.2.

 IX.     Internal Standards

Table A. 10 contains the semivolatile internal standards  and their corresponding target compounds.
                                              A-12                                  DRAFT 12/90
                                                                                      Revised 6/91

-------
MM/MC                                                                    APPENDIX A

                   Table A.9 SemhroiatUe MS/MSD Contractual Requirements

             Compound           %R • Water   %R - Soil     RPD - Water   RPD - Soil

       Phenol                     12-110       26-90         <.42          < 35
       2-Chlorophenol              27-123       25-102        <. 40          <. 50
       1,4-DichJorobenzene          36-97        28-104        <2&          < 27
       N-Nitroso-di-n-propylamine    41 -116       41-126        <. 38          <. 38
       U,4-Trichloroben2ene        39-98        38-107        <. 28          <. 23
       4-Chloro-3-methylphenol      23-97        26-103        <. 42          <. 33
       Acenaphthene               46-118       31-137        < 31          <. 19
       4-Nitrophenol               10-80        11-114        <.50          <. 50
       2,4-Dinitrotoluene            24-96        28-89         <.38          <. 47
       Pentachlorophenol            9-103       17-109        <. 50          <. 47
       Pyrene                     26 -127       35 - 142        <. 31          <. 36
                                         A-13                               DRAFT l2/9«
                                                                             Revised 6/91

-------
MM/MC
                                               APPENDIX A
        Table A.10 Semivolatile Internal Standards and Their Corresponding Target Compounds
       l,4-Dichlorobenzene-d4
Naphthalene-
-------
MM/MC                                                                            APPENDIX A

XL     Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)

Check the reported positive sample re-  ilts and quantitation limits with the quantitation lists and
chromatograms using equations XI.6, XI.7. or XI.8. Equation XL4 should be used to adjust the CRQL for
a diluted sample, and equation XLS should be used to adjust the CRQL for a soil sample.  Characteristic
ions for semivolatile target compounds  are contained in Table A. 11.  Characteristic ions for semivolatile
surrogates and internal standards are contained in Table A.1Z Characteristic ions for pesticides and
Aroclors are contained in Table A. 13.

        Concentration for waters:
                                        m    ,,,
                                          A^x RRF x  K, x Vt
       Concentration for soils/sediments:
       (Dry weight basis)
                                      .       ,,,
                                        Xto x RRF x Vt x Wt x D
              where:

                      Ax  = area of characteristic ion (EICP) for compound being measured
                      Ah  = area of characteristic ion (EICP) for the internal standard
                      /s  =  amount of internal standard added (ng)
                      RRF  - daily relative response factor for compound being measured
                      V0  = volume of water extracted (mL)
                      fj   — volume of extract injected (uL)
                      Vl   = volume of concentrated extract (uL)
                      Df  ^ dilution factor f
                      D   = (100 - % moisture)/100% - conversion to dry weight
                      Wt  = weight of sample (g)

              The dilution faaor for analysis of water samples for semivolatiles by the method specified
              in SOW OLM01.0 is  calculated  using equation XI.8. If no dilution is performed, then the
              dilution faaor equals 1.0.

                 _, m  uL of the most concentated extract used * uL of clean solvent             (XI.8)
                                 uL of the most concentrated extract used
                                              A-15                                   DRAFT 12/90
                                                                                      Revised 6/91

-------
MM/MC
APPENDIX A
                 Table A.11 Characteristic Ions for Semivolatile Target Compounds
Analyte
Phenol
bis(2-Chloroethyi)ether
2-ChlorophenoI
U-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
2»2*-oxybis( 1-ChJoropropane)
4-Methylphenol
N-Nitroso-di-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2.4-Dimethylphenol
bis(2-Chloroethoxy)methane
2.4-Dichlorophenol
1 ,2,4-Trichlorobenzene
Naphthalene
4-Chloroaoiline
Hexachlorobutadiene
4-Chloro-3-methyiphenol
2-Methylnaph'thalene
Hexachlorocyclopentadiene
2,4,6-TrichJorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
Primary Ion
94
93
128
146
146
146
108
45
108
70
117
77
82
139
107
93
162
180
128
127
225
107
142
237
1%
196
162
Secondary Ion(s)
65.66
63,95
64, 130
148, 113
148. 113
148, 113
107
77,79
107
42, 101. 130
201, 199
123,65
95,138
65, 109
121. 122
95, 123
164,98
182. 145
129. 127
129
223.227
144, 142
141
235.272
198. 200
198,200
164, 127
                                          A-16
DRAFT 12/90
 Revised 6/91

-------
MM/MC                   ,                                                   APPENDIX A

           Table A.11 Characteristic Ions for Semivolatile Target Compounds (Continued)
Parameter
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibcnzofuran
2,4-Dinitrotoluene
2.6-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenylether
Huorene
4-NitroaniIine
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Carbazole
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3'-Dichlorobenzidine
Primary Ion
65
163
152
138
153
184
109
168
165
165
149
204
166
138
198
169
248
284
266
178
178
167
149
202
202
149
252
Secondary ion(s)
92, 138
194, 164
151. 153
108,92
152, 154
63, 154
139,65
139
63. 182
89. 121
177, 150
206, 141
165. 167
92, 108
182,77
168. 167
250, 141
142. 249
264,268
179, 176
179, 176
166, 139
150, 104
101. 100
101, 100
91,206
254, 126
                                          A-17
DRAFT 12/90
 Revised 6/91

-------
MM/MC                  .                                                     APPENDIX A

           TaMe A.11 Characteristic ions for Semivoiatile Target Compounds (Continued)
Analyte
Benz(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Di-n-Octyl phthalate
Benzo(b)fluoranthene
Benzo(k)Quoranthene
Benzo(a)pyrene
Indeno( l,23-cd)pyrene
Dibenz(aJi)anthracene
Benzo(g,h,i)perylene
Primary Io&-
228
149
228
149
252
252
252
276
278
276
Secondary Ion(s)
229,226
167, 279
226,229
—
253,125
253, 125
253, 125
138,227
139, 279
138,277
                                          A-18
DRAFT 12/90
 Revised 6/91

-------
MM/MC                                                                          APPENDIX A

           Table A.12 Characteristic Ions for Semivotatile Surrogates and Internal Standards
Analyte
SURROGATES
Phenol-dj
2-Fluorophenol
2,4,6-Tribromopbenol
Nitrobenzene-dj
2-Fluorobipbenyl
Tcrphenyl
2-Chiorophenol-d4
l,2-Dichlorobenzene-d4
INTERNAL STANDARDS
l,4-DicbJorobenzene-d4
Naphthalene-d8
Acenapthene-d10
Phenanthrene-d,0
Chrysene-d12
Perylene-d12
Primary loo

99
112
330
82
172
244
132
152

152
136
164
188
240
264
Secondary Ion(s)

42,71
64
332, 141
128,54
171
122,212
68,134
115, 150

115
68
162,160
94,80
120,236
260,265
                                            A-19
DRAFT 12/90
 Revised 6/91

-------
MM/MC
APPENDIX A
                       Table A.13 CharacterisUc Ions for Pesticides/Aroclors
Analyte
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
Heptachlor
Aldrin
Heptachior epoxide
Endosulfan I
Dieldrin
4.4--DDE
Endrin
Endrin ketone
Endrin aldehyde
Endosulfan II
4,4'-DDD
Endosulfan sulfate
4,4'-DDT
Methoxychlor
Chlordane (alpha and/or gamma)
Toxaphene
ArochJor-1016
Arochlor-1221
Arochlor-1232
Arochlor-1242
Arochlor-1248
Arochlor-1254
Arochlor-1260
Primary Ion
183
181
183
183
100
66
353
195
79
246
263
317
67
337
235
272
235
227
373
159
222
190
190
222
292
292
360
Secondary Ion(s)
181, 109
183, 109
181, 109
181. 109
272, 274
263. 220
355, 351
339, 341
263, 279'
248, 176
82,81
67, 319
250.345
339, 341
237, 165
387, 422
237, 165
228
375, 377
231,233
260,292
222,260
222. 260
256.292
362, 326
362, 326
362.394
                                            A-20
 DRAFT 12/90
  Revised 6/91

-------
               APPENDIX B

CONTRACTUAL REQUIREMENTS AND EQUATIONS

     LOW CONCENTRATION WATER - LCW
                (OLC01.0)
                                               DRAFT 12/90
                                                Revised 6/91

-------
                                                                                APPENDIX B
                                LOW CONCENTRATION WATER
       CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR VOLATILE DATA REVIEW
II.     GC/MS Instrument Performance Check

Use equation II. 1 to verify that the laboratory has not made errors the calculation of the percent relative
abundance.
                         % fefarfve Abundance - abmtlaaee °    x 100*                     (H.1)
                                               abundance of Y


For example, the percent relative abundance of m/z 96 (X) relative to m/z 95 (Y) is calculated as follows:
                       * Rela** Abundance =           °f "* * x 100%
                                             abundance of m/z 95


III.    Initial Calibration

Data Review Criteria; All volatile target compounds and system monitoring compounds must have a
Relative Response Factor (RRF) of greater than or equal to O.OS and a percent relative standard deviation
(%RSD) of less than or equal to 30%.

Contractual Criteria;  The maximum %RSD for most volatile compounds is 20.5% and the minimum
RRF criteria vary as specified  in the following table (The volatile compounds listed separately in Table 2
on page 13 are not contractually required to meet a maximum %RSD but do have to meet a contractual
minimum RRF of 0.010). The contractual criteria for an acceptable initial calibration specifies that up to
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%.

Initial calibration RRFs and RRF  are calculated using equations III.l and III.2.


                                     RRF =  ^i  x   S                                (IH.I)
                                      RRF
                                               s
                                              I
                                              1-1
E **?,                                 (IIL2)
                     where:
                            RRFj as "i"th Relative Response Factor
                            A   = Area of the characteristic ion (EICP) measured
                            C   - Concentration
                            is  - Internal standard
                            jc   = Analvte of interest
                                             B-l                                  DRAFT 12/90
                                                                                  Revised 6/91

-------
LCW
                                                                               APPENDIX B
                       Table B.I. Technical Acceptance Criteria for Initial
                   and Continuing Calibration for Volatile Organic Compounds
Target Volatile Compound
Benzene
IBromochloromethane
Bromodichlorometbane
Bromofonn
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroform
Dibromochloromethane
1.2-Dibromoethane
1 ,2-Dichlorobenzene
1.3-Dichlorobenzene
1 ,4-Dichlorobenzene
1.1-Dichloroethane
1.2-Dichioroethane
1.1-Dichloroethene
cis- 1 3-Dichloropropene
trans- 1,3-Dichloropropene
Ethylbenzene
Styrene
1.1,22-Tetrachloroethane
Tetrachioroethene
Toluene
1,1,1-Trichloroethane
1,12-Trichloroethane
Trichloroethene
Vinyl Chloride
Xyienes (total)
4-Bromofluorobenzene
Minimum RRF
0.500
0.100
0200
0.100
0.100
0.100
0.500
0.200
0.100
0.100
0.400
0.600
0.500
0.200
0.10u
0.100
0.200
0.100
0.100
0300
0.500
0.200
0.400
0.100
0.100
0.300
0.100
0.300
0.200
Maximum
%RSD
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
%D
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0-
±30.0
±30.0
                                           B-2
DRAFT 12/90
 Revised 6/91

-------
                                                                                     APPENDIX B

  The %RSD is calculated using equations III.3 and III.4.
                                          „  J  f (X'"*)2
                                              N  w (»-D
                                                - -?.  x 100                                   (IH.4)
                        where:
                               a - Standard deviation of 5 relative response factors

                               x =  Mean of 5 relative response factors


 IV.     Continuing Calibration

 Data Review Criteria;  All volatile target compounds should meet a %D criterion of ± 30%.

 Contractual Criteria; The percent difference (%D) between the initial calibration R"RT" and the
 continuing calibration RRF is + 30% for all compounds listed in Table B.I (Page B-2). The contractual
 criteria for an acceptable continuing calibration specifies that up to anv 2 volatile target compounds may
 fail to meet minimum RRF or maximum %D as long as they have RRFs that are greater than or equal to
 0.010, and %D of less than or equal to 40.0%.

 Check the RRF calculations for volatile target compounds using equation III.1 (Page B-l). The %D
 between initial calibration RRF  and  continuing calibration RRF is calculated using equation IV.l.
                                                .r
                                    % D =  - /     c x 100%                               (IV.l)
                                               RRF,

               where:

                       RRFt = average relative response factor from initial calibration.

                       RRFC = relative response factor from continuing calibration standard.


VI.     Surrogate Spikes


The volatile surrogate compound and the contractual recovery limits are listed below.


               Surrogate Spike                       %Recoverv  Limits

               BFB Bromofluorobenzene                80 - 120
                                               B-3                                   DRAFT 12/90
                                                                                      Revised 6/91

-------
 LCW                                                                              APPENDIX B


 Use equation VI.2 to check that the surrogate percent recovery was calculated correctly:
                                    % Recovery « -2  x 100%                               (VI.2)
                      where:
                              QD = Quantity determined by analysis.
                              QA = Quantity added to samples/blanks.
VII.    Laboratory Control Samples (LCS)

Laboratory Control Sample compounds are listed in Table B.2.  The contractual percent recovery limits
are from 60 to L40 percent However, these limits may eventually be expanded by the Agency during the
period of performance if the limits are  found to be too restrictive.


                      Table B.2 Volatile Laboratory Control Sample Compounds

                      Vinyl Chloride
                      1,2-Dichloroethane
                      Carbon Tetrachloride
                      1,2-Dichloropropane
                      Trichloroethene
                      1,1,2-Trichloroethane
                      Benzene
                      cis- 13-Dichloropropene
                      Bromoform
                      Tetrachloroeihene
                      1,2-Dibromoethane
                      1,4-Dichloro benzene
Check that the LCS recovery was calculated correctly by using equation VI.2.



IX.     Internal Standards

Table B.3 contains the volatile internal standards and their corresponding target compounds.
                                               B-4                                  DRAFT 12/90
                                                                                      Revised 6/91

-------
 LCW
                                              APPENDIX B
                               Table B J. Volatile Internal Standards
                            and Their Corresponding Target Compounds
        1,4-Difluorobenzene
Chlorobenzene-dc
1,4-Dichlorobenzene d4
        Chloromethane
        Bromomethane
        Vinyl Chloride
        Chloroetnane
        Bromochloromethane*
        Methylene Chloride
        Acetone
        Carbon disulfide
        1,1-Dichloroethene
        1,1-Dichloroethane
        cis-U-Dichloroethene"
        trans-1,2-Dichloroethene* *
        Chloroform
        1,2-Dichloroethane
        2-Butanone
        4-Bromofluorobenzene (SUIT)
1,1.1-Trichloroethane
Carbon tetrachloride
Bromodichloromethane
1,2-Dichloropropane
cis- 1.3-Dichloropropene
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Benzene
trans- 13-Dichloropropene
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1,1,2.2-Tetrachloroethane
1,2-Dibromoe thane*
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes
Bronioforin
l,2-Dibromo-3-chloropropane*
1,2-Dichlorobenzene *
1,3-Dichlorobenzene*
1,4-Dichlorobenzene*
       * compounds not on Multi-media, Multi-concentration TCL
       "on Multi-media, Multi-concentration TCL as total 1.2-Dichioroethene
XI.    Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)

Check the reponed positive sample results and quantitation limits with the .quantitation lists and
chromatograms using equation XI. 1.  Primary and secondary Quantitation ions are listed in Table B.4
(Page B-7).
                                            A:. x RRF x K
                                                                                          (XI.1)
             ' where:
                      Ax  = area of characteristic ion (EICP) for compound being measured
                      Aa  = area of characteristic ion for the internal standard
                      /s  =  amount of internal standard added (ng)
                      RRF = relative response factor for compound being measured
                      V0  = volume of water purged (mL)
                      Df  = dilution factor
                                              B-5
                                              DRAFT 12/90
                                               Revised 6/91

-------
LCW                                                                           APPENDIX B

The CRQL for a diluted sample should be calculated as follows:


              Adjusted CRQL = Non-adjusted CRQL x Sample Dilution Factor               (XI.4)


       For example, the adjusted CRQL for a water sample with a 10U non-diluted CRQL and a 1 to
       100 dilution (100.0 dilution factor) would be lOOOU, according to the following calculation:

                            1000U = 10U x 100
                                                                                 DRAFT 12190
                                                                                 Revised 6/91

-------
LCW
APPENDIX B
                             TABLE B.4 Volatile Quantitation Ions
Volatile Target Compounds
Acetone
Benzene
Bromochlororaethane
Bromodichloromethane
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Cblorobenzene
Chloroethane
Chloroform
Chloromethane
Dibromochloromethane
l,2-Dibromo-3-chloropropane
1 .2-Dibromoethane
1,2-Dichlorobenzene
1 ,3- Dichlorobenzene
1 ,4- Dichlorobenzene
1.1-Dichloroethane
1.2-Dichloroethane
1,1-Dichioroethene
cis- 1,2-Dichloroethene
trans- 1.2-Dichloroethene
1.2-Dichloropropane
cis- 13-Dichloropropene
Primary Quantitation
Ion
43
78
128
83
173
94
43
76
117
112
64
83
50
129
75
107
146
146
146
63
62
96
96
96
63
75
Secondary Ions
58
_.
49, 130
85, 127
175, 254
%
72'
78
119
77,114
66
85
52
127
155, 157
109, 188
111. 148
111. 148
111, 148
65,83
98
61.63
61,98
61.98
112
77
      Quantuation ot this analyte is based on m/z 4j out m/z 72 must be present in the spectrum.
                                            B-7
 DRAFT 12/90
  Revised 6/91

-------
LCW
APPENDIX B
                       TABLE B.4 Volatile Quantitation Ions (Continued)
Volatile Target Compounds
trans- 1 J-Dichloropropene
Ethyibenzene
2-Hexanone
Methylcne chloride
4-Methyl-2-pentanone
Styrene
1,1^2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1,1.2-Trichloroethane
Trichloroethene
Vinyl chloride
Xylenes (total)
Primary Quantitation
Ion
75
91
43
84
43
104
83
166
91
97
97
95
62
106
Secondary Ions
77
106
58, 57, 100
86,49
58,100
78
131.85
168, 129
92
99,61
83, 85, 99, 132, 134
130, 132
64
91
SURROGATE COMPOUND AND INTERNAL STANDARDS:
4-Bromofluorobenzene
Chlorobenzene-d;
1 ,4-Dichlorobenzene-d4
1.4-Difluorobenzene
95
117
150
114
174, 176
82, 119
115, 152
63,88
                                           B-8
DRAFT 12/90
 Revised 6/91

-------
Lcw                                                                           APPENDIX B

                               LOW CONCENTRATION WATER
     CONTRACTUAL REQUIREMENTS AND EQUATIONS FOR SEMIVOLATILE DATA REVIEW


n.     GC/MS Instrument Performance Check

Use equation II. 1 (Page B-l) to verify that the laboratory has not made errors the calculation of the
percent relative abundance.

For example, the percent relative abundance of m/z 443 (AT) relative to m/z 442 (Y) is calculated as follows:


                                            «*"•*«• *•* *43
                                            abundance of mfz 442
                        * Relative Abundance - «*"•*«• *•* *43 x 100%
 lU.    Initial Calibration

 Data Review Criteria; All semivolatile target compounds and surrogates must have a Relative Response
 Factor (RRF) of greater than or equal to 0.05 and a percent relative standard deviation (%RSD) of less
 than or equal to 30%.

 Contractual Criteria; The maximum %RSD for most semivolatile compounds is 2O5% and the minimum
 RRF criteria vary as specified in the following table (The semivolatile compounds listed separately in table
 4 on page 52 are not contractually required to meet a maximum %RSD but do have to meet a contractual
 minimum RRF of 0.010). The contractual criteria for an acceptable initial calibration specifies that up to
 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%.

 Initial calibration  RRFs and RRF are calculated using equations III.1 and III.2 (Page B-l); %RSD is
 calculated using equations III3 and III.4 (Page B-3).


 IV.     Continuing Calibration

 Data Review Criteria: All semivolatile target  compounds should meet a %D criterion of  +. 25%.

 Contractual Criteria; The percent difference  (%D) between the initial calibration RRF and the
 continuing calibration RRF is ± 25.0% for the compounds listed in Table B.5. The contractual criteria
 for an acceptable continuing calibration specifies that up to anv 4 semivolatile target compounds may fail
 to meet  minimum  RRF or maximum %D as long as they have RRFs that are greater than or equal to
0.010, and %D'of less than or equal to 40.0%.

Check the RRF calculations for semivolatile target compounds using equation III.1 (Page B-l), and
evaluate the %D between initial calibration RRF and continuing calibration RRF using equation I V.I
(Page B-3).
                                             B-9                                  DRAFT 12/90
                                                                                  Revised 6/91

-------
LCW
                                                                               APPENDIX B
                     Table B.5. Acceptance Criteria tor Initial and Continuing
                         Calibration for Semivolatile Organic Compounds
1 Semivolatile Compounds
Phenol
bis(-2-Chloroethyl)ether
2-Chlorophenoi
2-Meihylpbenol
4-Mcihyiphenol
IN-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzcne
Naphthalene
4-Chloro-3-metnylphenol
2-Methylnaphthalene
2.4.6-Trichlorophenol
1 2.4.5-Trichlorophenol
II 2-Chloronaphtoalene
j| Acenaphthylene
|| Acenaphthene
|| Dibenzofuran
|| 2.4-Oinitrotoluene
1 2.6-Dinitrotoluene
|| 4-Chlorophenyl-phenyiether
|| Fluorene .
|| 4-Bromophenyl-phenyiether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Fluoranthene
Minimum RRF
0.800
0.700
0.700
0.700
0.600
0.500
0300
0.200
0.400
0.100
0200
0.300
0.200
0.200
0.700
0.200
0.400
0.200
0.200
0.800
1300
0.800
0.800
0.200
0.200
0.400
0.900
0.100
0.100
0.050
0.700
0.700
0.600
Maximum %RSD
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
30.0
30.0
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
30.0
20.5
20^
20.5
20^
20^
20J
20.5
20.5
20.5
%D
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±30.0
±30.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±30.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
                                           B-10
DRAFT 12/90
 Revised 6/91

-------
 LCW
                               APPENDIX B
                      Table B.5.  Acceptance Criteria for Initial and Continuing
                     Calibration for Semivolatile Organic Compounds (continued)
Semivolatile Compounds
Pyrene
Benz(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoraothene
Benzo(a)pyrene
Indeno(1^3-cd)pyrene
Dibenz(aji)anthracene
Benzo(g4u)perylene
Phenol-dj (sun)
2-Fluorophenol (surr)
Terphenyl-di4 (surr)
2-Fluorobiphenyl (surr)
Minimum RRF"
0.600
0.800
0.700
0.700
0.700
0.700
0.500
0.400
0.500
0.800
0.600
0.500
0.700
Maximum %RSD
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
%D
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
VI.     Surrogate Spikes

Surrogate spike recoveries for semivolatile samples and blanks must be within the limits specified in Table
B.6.

                       Table B.6 Semivolatile Surrogate Recovery Requirements
                      Surrogate Compound

                      Nitrobenzene-d5
                      2-Fluorobiphenyl
                      p-Terphenyl-d14
                      Phenol-d;
                      2-Ruorophenol
                      2,4,6-Tribromophenol
% Recovery

40- 112
42 - 110
24- 140
17 - 113
16 - 110
18- 126
Use equation VI.2 to verify that the surrogate recoveries were calculated correctly.
                                              B-ll
                                DRAFT 12/90
                                 Revised 6/91

-------
 LCW                                                                               APPENDIX B

 VD.    Laboratory Control Samples (LCS)

 The percent recovery for each of the compounds in the LCS spiking solution must be within the recovery
 limits listed in Table B.7.  However, these limits may eventually be expanded by the Agency during the
 period of performance if the limits are found to be too restrictive.

           Table B.7 SemhrolatUe Laboratory Control Sample Compounds and Recevery Limits

                       Compound                     %Recovery

                       Phenol                        44 -120
                       2-Chlorophenol                58 •  110
                       4-Chloroaniline                35 -  98
                       2,4,6-Trichlorophenol           65 -110
                       bis(2-Chloroethyl)ether         64 -110
                       N-Nitroso-di-n-propylamine      34 •  102
                       Hexachloroethane              32 -  77
                       Isophorone                    49 -ilO
                       1,2,4-Trichlorobenzene          44 -  96
                       Naphthalene                   56 -160
                       2,4-Dinitrotoluene              61 -140
                       Diethylphthalate                76 -104
                       N-Nitrosodiphenyiamine        35 -120
                       Hexachlorobenzene             30 -  95
                       Benzo(a)pyrene                55 -  92


Check that the recoveries were calculated correctly by using equation VI.2 (Page B-4).


IX.     Internal Standards

Table B.8 (Page B-14) contains the semivolatile internal standards and their corresponding target
compounds.


XI.     Compound Quantitation and Reported Contract Required Quantitation Limits (CRQLs)

Check the reported positive sample results and quantitation limits with the quantitation lists and
chromatograms using equation  XI.6.  Equation XI.4 (Page B-6) should be used to adjust the CRQL for a
diluted sample.  Table B.9  (Page B-15,16,17) contains the semivolatile primary and secondary Quantitation
ions.
                                   ug/L
                                           A,, x RRF x
                                               B-12                                  DRAFT 12/90
                                                                                      Revised 6791

-------
LCW                                                                              APPENDIX B
              where:
                      Ax  = area of characteristic ion (EICP) for compound being measured
                      AU  m area of characteristic ion (EICP) for the internal standard
                      /,  =  amount of internal standard added (ng)
                      RRF  » daily relative response factor for compound being measured
                      VQ  = volume of water extracted (mL)
                      y(   * volume of extract injected (uL)
                      Vt   » volume of concentrated extract (uL)
                      Df  = dilution factor
                                             B-13                                 DRAFT 12/90
                                                                                    Revised 6191

-------
LCW
                                              APPENDIX B
                             Table BA Semivoiatile Internal Standards
                            and Their Corresponding Target Compounds
       l,4-Dichlorobenzene-d4
Naphtbalene-dg
       Acenaphthene-d10
       Phenol
       bis(2-Chloroethyl)ether
       2-Chlorophenol
       2-Meihylphenol
       2£'-oxybis-(l-Chloropropane)
       4-Methylphenol
       N-Nitroso-di-n-propylamine
       2-Huorophenol (SUIT)
       Phenol-d5 (surr)
Nitrobenzene
Isopborone
2-Nitrophenol
2,4-Dimethylphenol
bis(2-Chloroethojcy)methane
2,4-Dichlorophenol
1,2,4-Tricblorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-methyiphenol
2-Methylnaphthalene
Nitrobenzene-dj (surr)
Hexachlorocyclopentadiene
2,4,6-Trichlorophenoi
2,4,5-Tricblorophenol
2-ChIoronaphthalene
2-Nitroaniline
Dimethyl pbthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenoi
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitro toluene
Diethyl phthalate
4-Chlorophenyl-phenyl ether
Fluorene
4-Nitroaniline
2-Fluorobiphenyl (surr)
2,4,6-Tribromophenol (surr)
       surr = surrogate compound
       Phenamhrene-dj0
        Chrysene-d12
        Perylene-di;
       4,6-Dinitro-2-methylphenol
       N-Nitrosodiphenylamine
       4-Bromophenyl phenyl ether
       Hexachlorobenzene
       Pentachlorophenol
       Phenamhrene
       Anthracene
       Di-n-buiyl phthaiate
       Fluoranthene
        Pyrene
        Butylbenzyl phthalate
        33'-Dichlorobenzidine
        Benzo(a)anthracene
        bis(2-Ethylhexyl)phthalate
        Chrysene
        Terphenyl-di4 (surr)
        Di-n-octyl phthalate
        Benzo(b)fluoramhene
        Benzo(k)fluoranthene
        Benzo(a)pyrene
        Indeno( l,2j-cd)pyrene
        Dibenz(a,h)anthracene
        Benzo(g.h,i) perylene
       SUIT = surrogate compound
                                              B-14
                                                                                      Revised 6/91

-------
LCW
                                                                               APPENDIX B
                            Table B.9 Semivolatile Quantitation Ions
BAnalyte
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1.4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
2,2'-oxybis(l-Chloropropane)
4,-Methylphenol
IN-nitroso-di-n-propylamine
Hexachloroe thane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
bis(-2-Chloroethoxy)methane
2,4-Dichlorophenoi
1 ,2,4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-raethylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
1 2-Nitroaniline
Primary Ion
94
93
m
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
Secondary Ion(s)
65.66
63,95
64, 130
148, 113
148, 113
148. 113
107
77,79
107
42. 101, 130
201, 199
123,65
95, 138
65,109
121. 122
95, 123
164,98
182, 145
129, 127
129
223.227
144, 142
141
235.272
198, 200
198, 200
164, 127
92, 138
                                          B-15
DRAFT 12/90
 Revised 6/91

-------
LCW
                                                                              APPENDIX B
                      Table B.9 Semivolatile Quantitation Ions (Continued)
Anaiyte
Dimethyl phthalate
Acenaphthylene

3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitropbenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenylether
Huorene
4-Nuroaniline
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachloropbenol
Phenanthrene
Anthracene
Oi-n-butylpbthalate
Fluoranttaene
Pyrene
Butylbenzylphthalate
3,3'Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylbexyl)phthalate
Chrysene
Di-n-octyl phthalate
Primary Ion
163
152
138
153-
184
109
168
165
165
149
204
166
138
198
169
248
284
266
178
178
149
202
202
149
252
228
149
228
149
Secondary Ion(s)
194,164
151, 153
108.92
152, 154
63,154
139,65
139
63,182
89, 121
177, 150
206, 141
165, 167
92,108
182.77
168, 167
250, 141
142, 249
264,268
179, 176
179, 176
150. 104
101. 100
101, 100
91.206
254, 126
229,226
167, 279
226, 229
—
                                                                              DRAFT 12/90
                                                                               Revised 6/91

-------
LCW
APPENDIX B
                      Table B.9 Semivolatile Quantitation Ions (Continued)
Analyte
Benzo(b)fluorantnene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno( l,23-cd)pyrene
Dibenz(aji)anthracene
Benzo(g,h4)perylene
Primary Ion
252
252
252
276
278
276
Secondary Ion(s)
253.125
253,125
253,125
138. 227
139, 279
138, 277
Surrogates
Phenol-ds
2-Fluorophenol
2,4,6-Tribromophenol
d-5 Nitrobenzene
2-Fluorobiphenyl
Terphenyi
99
112
330
82
172
244
42,71
64
332, 141
128,54
171
122,212
Internal Standards
1 .4-Dichlorobenzene-d4
Naphthalene-ds
Acenaphthene-d10
Phenanthrene-d10
Chrysene-dT2
Perylene-dj2
152
136
164
188
240
264
115
68
162, 160
94,80
120. 236
260, 265
                                          B-17
 DRAFT 12/90
  Revised 6/91

-------
                APPENDIX C




CONTRACTUAL REQUIREMENT COMPARISON TABLES
                                                 DRAFT 12/90

-------
                                                    APPENDIX C
Table Cl. Corr.parison of Requirements for
         Volatile Data Review
REQUIREMENT
Target Compound List
Data Turnaround
Technical Holding Time
Initial Calibration
Continuing Calibration
Blanks
SMC/Surrogates
MS/MSD
LCS
Regional QA/QC
Internal Standards
CRQL
TICS
MULTI-MEDIA, MULTI-
CONCENTRATION
33 Target Compounds
35 days
7 days if not preserved
14 days if preserved
5 levels: 10 - 200 ug/L
mid-level: SO ug/L
Method Blanks
Instrument Blanks
SMC:
1.2-Dichloroethane-d4
Bromofluorobenzene
Toluene-dg
Frequency: 1 per 20 samples,
per matrix
N/A
PEs - variable
IS Area: - 50% to -I- 100%
IS RT Shift: ± 30 sec.
3 compounds:
Chlorobenzene-d;
1.4-Difluorobenzene
Bromochloromethane
10 ppb (water/low soil)
1200 ppb (med soil)
largest 10 j> 10% of nearest IS
LOW CONCENTRATION
WATERS
40 Target Compounds
14 days
7 days if not preserved
14 days if preserved
5 levels: 1 - 25 ug/L
(5 - 125 for Ketones)
mid-level: 5 ug/L
(25 for Ketones)
Method Blanks
Instrument Blanks
Storage Blanks
Surrogate: Bromofluorobenzene
N/A
i per SDG
PEs - 1 per SDG
IS Area: + 40%
IS RT Shift: ± 20 sec.
3 compounds:
Chlorobenzene-ds
1,4-Difluorobenzene
1,4-Dichlorobenzene
1 - 5 ug/L
largest 10 .>40% of nearest IS
                 C-l
DRAFT 12/90

-------
                                                    APPENDIX C
Table C.2.  Comparison of Requirements for
        Semivoiatile Data Review
REQUIREMENT
Target Compound List
Data Turnaround
Technical Holding Time
Initial Calibration
Continuing Calibration
Blanks
Surrogates
MS/MSD
LCS
Regional QA/QC
Internal Standards
CRQLs
TICs
MULTI-MEDIA, MULTI-
CONCENTRATION
64 Target Compounds
35 days
Extraction - 5 days
Analysis • 40 days after
extraction
5 levels: 20 • 160 ug/L
mid-level: 50 ug/L
Method Blanks
Instrument Blanks
8 compounds
Frequency: 1 per 20 samples,
per matrix
N/A
PEs - variable
IS Area: - 50% to + 100%
IS RT Shift: ± 30 sec.
10 - 50 ppb (water)
330 - 1700 ppb (low soil)
10,000 - 50.000 (med soil)
largest 20 >.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 per SDG
PEs - 1 per SDG
IS Area: - 50% to 100%
IS RT Shift: + 20 sec.
5 - 20 ug/L
largest 20 ^50% of nearest IS
                 C-2
DRAFT 12/90

-------
          APPENDIX D

     PROPOSED GUIDANCE FOR
TENTATIVELY IDENTIFIED COMPOUNDS
          (VOAANDSV)
                                           DRAFT #90

-------
                    Proposed Guidance for Tentatively Identified Compounds (VOA)


A.      Review Items:   Form IVOA-TIC, chromatograms, library search printout and spectra for three TIC
                       candidates, and GC retention time data.
B.      Objective

        Chromatographic  peaks in volatile analyses that are not  TCL compounds, system monitoring
        compounds, or internal standards are potential tentatively identified compounds (TICs) or library
        search compounds (LSCs). TICs must be qualitatively identified by a library search of the National
        Institute of Standards and Technology (NIST) mass spectral library, and the identifications assessed
        by the data reviewer.

C.      Criteria

        For each sample, the laboratory must conduct a library search of the NIST mass spectral library and
        report the possible identity for the 10 largest volatile fraction peaks which are not surrogates, internal
        standards, or TCL compounds,  but which have a peak area greater than 40 percent of the peak area
        of the nearest internal standard. TIC results are reported for each sample on the Organic Analysis
        Data Sheet (Form I VOA-TIC).

        Note:  Since the SOW revision of October 1986, the CLP does not allow the laboratory to report
               as tentatively identified  compounds any TCL compound which is property reponed in another
               fraction.   (For example, late eluting volatile TCL  compounds must not be reponed as
               semivolatile TICs.)

D.      Evaluation

        1.      Guidelines for Tentative' Identification are as follows:

               The interpretation of library search compounds (LSCs) is one of the aspects of data review
               which calls for the  fullest exercise of professional judgement.   The reviewer must  be
               thoroughly familiar with the principles and practice of mass spectral interpretation and of gas
               chromatography.  Because  the interpretation process is  labor-intensive, it is important to
               document  the  process involved in arriving at a tentative identification.

               Worksheets for Tentative  Identification  of Library Search Compounds" are provided in
               Appendix B for the volatile GC/MS fractions to assist in generating the information needed
               to  make a reasonable tentative identification of the LSCs.

               The process involved  in tentatively identifying a library search compound may be summarized
               as  follows:

             •  a.       Identify all samples in the related group (Case. SAS  or SDG) in which the unknown
                      compound occurs. Calculation of relative retention times  (RRT) and comparison of
                      RRT and  mass spectral data across samples is extremely helpful in  identifying
                      unknowns that occur repeatedly in related samples. Use one worksheet per unknown
                      for all samples  in which it occurs.

               b.      Inspect the library search spectrum retrieved for each  unknown, to determine if
                      detailed mass spectral interpretation is  necessary.   Often, it is  obvious  that  the


                                                                                       DRAFT 6/90

-------
Tentatively Identified Compounds                                                              VGA

                      correct match is among the spectra retrieved for the unknown from the several
                      samples in which it is found. It may only be necessary to check the unknown's RRT
                      versus a reference list of VOA (generated under similar  conditions and after
                      accounting for bias in the sample) to arrive at a satisfactory tentative identification.
                      Some references  are  provided.  If a reference RRT  is not available, then  a
                      comparison of the unknown's RRT or boiling point to the RRT or boiling point of
                      a closely related compound may also provide a satisfactory tentative identification.
                      Within a compound class, retention time increases with increasing  boiling point.

               c.      In the event that serious ambiguity still exists after cramming the library spectra and
                      RRT data, a full mass spectral interpretation can narrow down the  possibilities.
                      While a full  discussion of manual mass spectral interpretation is beyond the scope
                      of this document, several key points may be mentioned as important objects:

                      o      Determine a likely molecular weight. Depending on the unknown, the MW
                             may or may not be apparent due to the extent of fragmentation.  The MW
                             of the retrieved library spectra, interpreted in light  of the RRT, may be
                             helpful if the molecular ion is not present.

                      o      Determine the isotope ratios (M+1)/M,  (M+2)/M (M+4VM, 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-t-dbl:

                                            (r+db) = C-H-X + N 4-1
                                                         222

                                            where: C * no. of carbons
                                                   H = no. of hydrogens
                                                   X = no. of halogens
                                                   N * no. of nitrogens

                                            Note:  oxygen and sulfur do not need to be accounted for.
                                                   An aromatic ring counts as  four rings and double
                                                   bonds.

                      o      Calculate the  mass losses represented  by major peaks  in the unknown
                             spectrum, and relate these to the fragmentation of neutral moieties from the
                             molecular ion  or other daughter ions.

                      o      Using the information gathered on molecular weight,  molecular formula.
                             degree of unsaturation, and mass losses in the unknown spectrum, combined
                             with the RRT data, grve as precise a description of the unknown as possible.
                             including an exact identification if it is justified.


                                              D,2                                    DRAFT 6/90

-------
Tentatively Identified Compcrinda                                                              VOA

               d.      In the event that the unknown spectrum is not that  of a pure compound, mass
                      spectral interpretation may not be possible.  However, in some instances, a mixed
                      spectrum may be recognised as two compounds having very similar relative retention
                      times. Target compounds, surrogates and internal standards may also be responsible
                    .  for extra ions in an unknown spectrum.

       2.      Check the raw data to verify that the laboratory has generated a library search spectrum for
               all required peaks  in the chromatograms for samples and blanks.

       3.      Blank chromatograms should be examined to verify that TIC peaks present in samples are not
               found in  blanks.  When a  low-level  non-TCL compound that  is a common artifact or
               laboratory contaminant is detected in a sample, a thorough check of blank chromatograms
               may require looking for peaks which are less than 40 percent of the internal standard peak
               area or height, but present in the blank chromatogram at similar relative retention time.

       4.      All mass spectra for every sample and blank must be examined.

       5:      The reviewer should be aware of common laboratory artifacts/contaminants and their sources
               (e.g., aldol condensation products, solvent preservatives, and reagent contaminants). These
               may be present in  blanks and not reported as sample TICs.

               Examples:

               a.      Common laboratory contaminants: CO2 (m/z 44), siloxanes (m/z 73), diethyl ether.
                      hexane,   certain   freons   (l,l,2-mchloro-l,2^-trifluoroethane   or  fluoro-
                      trichloromethane), and phthalates at levels less than 100 ug/L or 4000 ug/Kg.

               b.      Solvent preservatives such as cyclohexene which is a methylene chloride preservative.
                      Related   by-products   include  cyclohexanone,  cyclohexenone,  cyclohexanol.
                      cyclohexenol, chlorocyclohexene, and chlorocyclohexanol.

               c.      Aldol condensation reaction products of acetone include:  4-hydroxy-4-methyl-2-
                      pentanone, 4-methyl-2-pemen-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 thai 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 quantuauon is
               made from the proper fraction.

       8.       Library searches should not  be performed on  internal standards or surrogates.

       9.       TIC concentration should be estimated assuming a RRF of 1.0.
                                               D-3
                                                                                      DRAFT 6/90

-------
Tentatively Identified Compounds                                                              VOA

E.     Action

       1.      All TIC results should be qualified as tentatively identified (N>with estimated concentrations
               (J)or(NJ).

       2.     .General actions related to the review of TIC results are as follows:

               a.      A non-TCL compound is not considered to be "tentatively identified" until the mass
                      spectrum and retention time data have been reviewed according to the evaluation
                      guidelines in XIILD.   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, S AS. or SDG.
                      It may also be used in writing a Special Analytical Service Statement of Work to
                      identify the unknown, or if the sample is sent to an EPA research laboratc      r-SC
                      identification by multiple spectral techniques.

               b.      If  all contractually required peaks  were  not  library  searched,  the desig	
                      representative could request these data from the laboratory.

       3.       TIC results which are not sufficiently above the level in  the blank should not  be reported.
               (Dilutions and sample size must be taken into account when comparing the amounts present
               in blanks and samples.)

       4.       When a compound is not  found in any blanks, but is a suspected artifact  or common
               laboratory contaminant, the result may be qualified as unusable (R).

       5.       The reviewer  may elect to report all  similar isomers as a total.  (All alkanes  may be
               summarized and reported as total hydrocarbons.)

       6.       The data reviewer should state the degree of confidence (high, medium, low) in  the tentative
               identification after completing the review process.

       7.       The complete "Tentative Identification of Library Search Compound" worksheet should be
               attached to the final data review report.
                                               D.4                                    DRAFT 6/90

-------
 Tentatively Identified Compounds                                                           VOA

                                         APPENDIX


 Equation 1:

 RI - 100      RTunk - RTz + 100Z
               RTz+1-RTz

 where:  RTunk is the retention time of the unknown
               RTz is the retention time of the proceeding retention index standard
               RTz+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(g4U)    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 calibntion may be used.  Retention time shifts and bias must be accounted
        for.

 Equation 2

 Number of rings-plus-double bonds (r+db):

 (r+db) = C-H-X + N +1
            222

where:   C = no. of carbons
              H  =  no. of  hydrogens
              X  »  no. of halogens
              N  m  no. of nitrogens

Note:  oxygen and sulfur do not need to be accounted for. An aromatic ring counts as four rings and double
       bonds.
                                            D-5                                  DRAFT 6/90

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Tentatively Identified Compounds                                                    .        VOA

                                        REFERENCES


1.     Lee, ML. Vassilaros, D.U White. CM., and Novotny. M., "Retention  Indices for Programmed-
       Temperature Capillary-Column  Gas  Chromatography of Polycyclic Aromatic  Hydorcarbons".
       Analytical Chemistry. V. 51, no. 6,1979, pp. 768-773.

2.     Rostad, G&, and  Pereira, W.E,  'Kovats  and  Lee  Retention Indices  Determined  by Gas
       Chromatograpny/Mass Spectrometry fo Organic Compounds of Environmental Interest,' l! High
       Resolution Carom, and Chrom. Commun.. voL 9,1986, pp. 328*334.

3.     Silverstein. RJM. Bassler. G.C. and Morrill. T.C. Spectrometric Identification of Organic Compounds
       4th ed., Wiley, New York, 1981.

4.     Vassilaros, D.M..  Kong, R.C, Later. D.W. and Lee.  M.L.. "Linear  Retention Index System for
       poiycyclic Aromatic Compounds.  Critical Evaluation and Additional Indices*. J. of Chromatoeraphv.
       252 (1982) pp. 1-20.
                                                                                   DRAFT 6/90

-------
                                                                                               sv

                     Proposed Guidance for Tentatively Identlflfd Coi?'DonnH« jj?V)


 A.     Review Items:  Form I SV-TIC, chromatograms, library search printout and spectra for three TIC
                       candidates, and GC retention time data.
 B.     Objective

        Chromatographic peaks in semivolatile analyses that are not TCL compounds, surrogates, or internal
        standards are potential tentatively identified compounds (TICs) or library search compounds (LSCs).
        TICs must be qualitatively identified by a library search of the National Institute of Standards and
        Technology (NIST) mass spectral library, and the identifications assessed by the data reviewer.

 C.      Criteria

        For each sample, the laboratory must conduct a library search of the NIST mass spectral library and
        report the possible identity for the 20 largest semivolatile fraction peaks which are not surrogates,
        internal standards, or TCL compounds, but which have a peak area greater than 50 percent of the
        peak area of the nearest internal standard.  TIC results are reported for each sample on the Organic
        Analysis Data Sheet (Form I SV-TIC).

        Note:   Since the SOW revision of October 1986, the CLP does not allow the laboratory to report
               as tentatively identified compounds any TCL compound which is properly reported in another
               fraction.   (For example, late eluting volatile TCL compounds must not be reported as
               semivolatile TICs.)

D.      Evaluation

        1.      Guidelines for Tentative Identification are as follows:

               The interpretation  of library search compounds (LSCs) is one of the aspects of data review
               which calls for the fullest  exercise of professional judgement.   The reviewer must  be
               thoroughly familiar with the principles and practice of mass spectral interpretation and of gas
               chromatography.  Because the interpretation process  is labor-intensive, it is important to
               document the process  involved in arriving at a tentative identification.

               Worksheets for Tentative Identification of Library Search Compounds" are provided in
               Appendix B for the semivolatile GC/MS fractions to  assist in generating the information
               needed to make a reasonable identification of the TICs.

              The process involved in tentatively identifying a library search compound may be summarized
              as follows:

              a)      Identify all samples in the related group (Case, SAS or SDG) in which the unknown
                      compound  occurs.  Calculation of retention indices (RI) and comparison of RI and
                      mass spectra across samples is extremely helpful in identifying unknowns that occur
                      repeatedly in related samples. Use one worksheet per unknown for all samples in
                      which it occurs. Retention indices are calculated according  to the following example:
                                               D-7                                    DRAFT 6/90

-------
Tentatively Identified Compounds                                                                SV

                             RI « 100      RTunk - RTz  4- 1002
                                           . RTz-t-1 - RTz

                      where: RTunk is the retention time of the unknown
                              RTz is the retention time of the proceeding retention index standard
                              RTz4-1 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,lu)    z»5    RI-500.00
                             perylene


                      Note:   when these compounds are not dound in the sample of interest. RT data for
                             the deuterated internal standards or most recent calibration may be used.
                             Retention time shifts and bias must be accounted for.
              b)     Inspect the library search spectrum retrieved for each  unknown, to determine if
                     detailed mass spectral interpretation is necessary.  Often, it  is obvious that  the
                     correct match is  among  che spectra retrieved for the unknown from the several
                     samples in which it is found.  It may only be necessary to check the unknown's RI
                     versus a reference list of SV (generated under similar conditions and after accounting
                     for bias in the sample) to arrive at a satisfactory tentative identification.  Some
                     references are provided. If a reference RI is not available, then  a comparison of the
                     unknown's RI or boiling point  to the  RI or boiling point of a closely related
                     compound may also  provide  a satisfactory  tentative  identification.   Within a
                     compound class, retention time increases with increasing boiling point.

              c)     In the event that serious ambiguity still exists after examining the library spectra and
                     RI data, a full n
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Tentatmly Identified Compounds                                                               SV

                      o      Calculate the total number of rings-plus-double-bonds in the unknown by
                             applying the follwing equation to the likely molecular formulas, to determine
                             the degree of unsaturation.

                                            Number of rings-plus-double bonds (r+db):

                                            (r+db) -C-H-X + £+1
                                                         222

                                            where: C » no. of carbons
                                                   H » no. of hydrogens
                                                   X • no. of halogens
                                                   N » no. of nitrogens

                                            Note:  oxygen and sulfur do not need to be accounted for.
                                                   An aromatic ring, counts as four rings and double
                                                   bonds.

                      o      Calculate  the  mass losses represented by  major peaks in the unknown
                             spectrum, and relate these to the fragmentation of neutral moieties from the
                             molecular ion or other daughter ions.

                      o      Using the information gathered on molecular weight, molecular formula,
                             degree of unsaturaoon, and mass losses in the unknown spectrum, combined
                             with the RI data, give as precise a description of the unknown as possible,
                             including an exact identification if it is justified.

              d)      In the event that  the unknown spectrum is not  that of a pure compound, mass
                      spectral interpretation may not be possible. However,  in some instances, a mixed
                      spectrum may be recognized as two compounds having very similar retention indices
                      (for example, ortho-terphenyl, RI»317.43 and nonadecane. RI=317.20).  This
                      particular coeiution  would  result in an unknown spectrum having a polycyclic
                      aromatic pattern at m/z 230, the MW of terphenyl. with an hydrocarbon type pattern
                      at m/z 43,57,71, etc Target compounds, surrogates and  internal standards may also
                      be responsible for extra ions in an unknown spectrum, and may be treated similarly.

      2.      Check the raw data to verify that the laboratory has generated a library search spectrum tor
              all required peaks in  the chromatograms for samples and blanks.

      3.      Blank chromatograms should be examined to verify that TIC peaks present in samples are not
              found in blanks.  When a low-level non-TCL compound  that  is a  common  artifact or
              laboratory contaminant is detected in a sample, a thorough check of blank chromatograms
            • may require looking for peaks which are less than 10 percent of the internal standard peak
              area or height, but present in the blank chromatogram at similar relative retention  time.

      4.      All mass spectra for every sample and blank must be examined.
                                                                                     DRAFT 6/90

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 Tentatively Identified Compounds                              •                         -         SV

        5.      The reviewer should be aware of common laboratory artifacts/contaminants and their sources
               (e.g^ aldol condensation products, solvent preservatives, and reagent contaminants). These
               may be present in blanks and not reported as sample TICs.

               Examples:

               a.      Common laboratory contaminants: CO2 (m/z 44), siloxanes (m/z 73), diethyl ether.
                       hexane,  certain   freons   (I,l,2-trichloro-l.l2-trifluoroethane  or   fluoro-
                       trichloromethane),-and phthalates at levels less than 100 ug/L or 4000 ug/Kg.

               b.      Solvent preservatives such as cyclohexene which is a methylene chloride preservative.
                       Related  by-products   include   cyclohexanone,   cyciohexenone,   cyclohexanol,
                       cyclohexenol, chlorocyciohexene, and chlorocyclohexanoL

               c.      Aldol  condensation reaction products of acetone include:  4-hydroxy-4-methyl-2-
                       pentanone, 4-methyl-2-penten-2-one. and 5,5-dimethyl-2(5H)-furanone.

        6.      Occasionally, a TCL compound may be identified in the proper analytical fraction by non-
               target library search procedures, even though it was not found on the quanutation list. If the
               total area quanutation method was used, the reviewer should request that the laboratory
               recalculate the result using the proper quanutation ion.   In addition, the reviewer should
               evaluate  other sample chromatograms and check library reference retention times on
               quanutauon lists to determine whether the false negative result is an isolated occurrence or
               whether additional data may be affected.

        7.      TCL compounds may  be identified in more than one fraction.  Verify that quantitation  is
               made from the proper fraction.

        8.      Library searches should not be performed on internal standards or surrogates.

        9.      TIC concentration should be estimated assuming a RRF of 1.0.

E.      Action

        1.      All TIC results should be qualified as tentatively identified (N) with estimated concentrations
               (J) or (NJ).

        2.      General actions related to  the review of TIC results are as follows:

               a.      A non-TCL compound is not considered to be "tentatively identified" until  the mass
                      spectrum and  retention time data have been reviewed as per section XIII O.  The
                      review  should be  documented on the  Tentative  Identification  of  Library Search
                      Compound worksheet. The worksheet will be useful if a better library match tor 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.
                                               D.lo                                    DRAFT 6/90

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Tentatively Identified Compounds                                                                SV

               b.      If ail contractually required  peaks were  not library searched,  the  designated
                      representative could request these data from the laboratory.

       3.      TIC results which are not sufficiently above the level in the blank should not be reported.
               (Dilutions and sample size must be taken into account when comparing the amounts present
               in blanks and samples.)

       4.      When a compound is not found in any blanks, but is a suspected artifact or common
               laboratory contaminant, the result may be qualified as unusable (R).

       5.      The reviewer may elect  to report all similar  isomers as  a total  (All alkanes may be
               summarized and reported as total hydrocarbons.)

       6.      The data reviewer should state the degree of confidence (high, medium, low) in the tentative
               identification after completing the review process.

       7.      The complete Tentative Identification of Library Search Compound" worksheet should be
               attached to the final data review report.
                                             D-ll                                    DRAFT 6/90

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    APPENDIX E

GLOSSARY OF TERMS
                                       DRAFT 12/90
                                        Revised 6/91

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                                                                                 MM'ENDIX I

                                    GLOSSARY OF TERMS


 A?O          Administrative Project Officer

 BFB           Bromofluorobenzene - volatile instrument performance check compound
     s
 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 j
               particular site. A Case consists of one or more Sample Delivery Group(S).

 CCS           Contract Compliance  Screening -  process  in which  SMO inspects analytical  data  tor
               contractual compliance and provides results to the Regions, laboratories and EMSL/LV.

 CF            Calibration Factor

 CRQL         Contract Required Quantitation Limit

 CSF           Complete SDG File

 DFTPP        Decafluoromphenyiphosphine - semivolatile instrument performance check compound

 DPO          Deputy Project Officer

 EICP          Extracted Ion Current  Profile

 GC/EC        Gas Chromatography/Electron Capture Detector

 GC/MS        Gas Chromaiograph/Mass Spectrometer

GPC           Gel Permeation Chromatography •  A sample clean-up technique that separates compound*
               by size and molecular weight.  Generally used to remove oily materials from sample extracts

 IS             Internal Standards - Compounds added to every VOA and BNA standard, blank, matrix spike
               duplicate, and sample extract at a  known concentration, prior  to instrumental analysis.
               Internal standards are used as the basis for quantitation of the target compounds.

LCS           Laboratory Control Sample

 MS/MSD  .    Matrix Spike/Matrix Spike Duplicate

m/z            The ratio of mass (m) to charge (z) of ions measured by GC/MS

OADS         Organic Analysis Data Sheet (Form I)

ORDA        Organic Regional Data Assessment - from earlier version of the Functional Guielines

NIST          National Institute of Standards and Technology
                                             £.1
                                                                                  DRAFT 11/90

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 CI.OSSARY                                                                        \PPEM)IX I

 PCS           Polychlonnated biphenyl (Arochlor i> u trademark)

 PE            Sample Performance Evaluation Sample

 QA           Quality .Assurance • Total program tor assuring the reliability of data.

 QC           Quality Control - Routine application of procedures for controlling the monmmne proce-^

 R1C           Reconstructed Ion Chromatoeram

 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 firsv

               •       Case of field samples

               •  .     Each 20 field samples within a Case

               •       Each 14-day calendar period during which field samples in  a Case are received.
                      beginning with receipt of the first sample in the SDG.  (For VOA contracts, ihe
                      calendar period is 7-day.)

SMC           System Monitoring Compound - formerly surrogates for volatile analysis.

SMO           Sample Management Office

SOP           Standard Operating Procedure

SOW           Statement of Work

SV             Semivolatile analysis - Method based on analysis by GC/MS for BNA organic compounds.

TCL           Target Compound List

TIC           Tentatively Identified Compound - A compound tentatively identified from search of the
               NIST mass spectral  library that is not on the TCL.

TPO           Technical Project Officer



                                              E-2                                  DRAFT tl/90

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GLOSSARY                                                        .                MM'KNDIX i:

VOA           Volatile  Organic Anahsis  - Method hjied v>n ine .purue  and  trap iccnmquv.* -ior organic
               compound analysis.

               Validated Time ol Sample Receipt - Time ol -ample receipt at the lahorator. .1- recorded on
               the shipper's deliver.- receipt and Sample Trainc Report.
                                             E-3                                  DRAFT 11/90

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