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                          USEPA CONTRACT LABORATORY PROGRAM
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                                    STATEMENT OF WORK
                           r



                                       DIOXIN ANALYSIS

                                          Multi-Media

                                       Multi-Concentration



                                           SOW. 9/86

                                           Rev. 8/87


                                  Form IFB Series:  WA86-K357
        55                            HEADQUARTERS LIBRARY
        -                            ENVIRONMENTAL PROTECTION AGENCY
       ±                             WASHINGTON, D.C. 20460

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                               STATEMENT OF WORK

                               TABLE OF CONTENTS


                                                                         No. of
                                                                         Pages

PREFACE:     Scope of Work	    ii

             Summary of Dioxin SOW Changes	   ill

EXHIBIT A:   Summary of Requirements	   A-1-5

EXHIBIT B:   Reporting Requirements and Deliverables	   B-l-20

EXHIBIT C:   Sample Rerun Requirements	   C-l-3

EXHIBIT D:   Analytical Methods	   D-l-35

EXHIBIT E:   Quality Assurance/Quality Control Requirements	   E-l-25

EXHIBIT F:   Specifications for Chain-of-Custody, Document Control
             and Standard Operating Procedures	   F-l-8

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                                 SCOPE OF WORK
The purpose of this contract Is to provide EPA with chemical analytical
services usiag selected Ion monitoring (SIM) gas chromatography/mass
spectrometry/data system (GC/MS/DS) techniques for the analysis of 2,3,7,8-
Tetrachlorodibenzo-p-dioxin (TCDD) in soil or sediment and water samples.  The
majority of these samples are from areas of suspected 2,3,7,8-TCDD contami-
nation.  The methods required in this contract are effective for a concen-
tration range of 1 to 1000 pacts per billion for soil or sediment and 0.01 to
10 parts per billion for water.

The Contractor shall use safe handling procedures and generally accepted good
laboratory practices to prepare and analyze for the presence of 2,3,7,8-
tetrachlorodibenzo-p-dioxin (TCDD) in soil or sediment and water samples.

The data obtained T&tll be used by EPA to determine the existence and extent of
threats to the public and the environment posed by hazardous waste disposal
sites.  The data may be used in civil and/or criminal litigation, therefore the
strictest adherence of chain-of-custody protocol, document control, and quality
assurance procedures is required.
                                       LL

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                         SUMMARY OF DIOXIN SOW CHANGES

                 In  Updating the 9/83 Version to the 9/86 Version


 The method changes  that have  been made resulted  In a  large number of  changes
 throughout the text.   A summary of the changes  is  given  below,  a line by  line
 listing  of all changes has not been made.

 I.   The  method has  been extended  to Include water  samples by  adding the
     extraction and  concentration  steps from Method 613.

 2.   Spiking solutions are  now mixed with 1.5 mL  of acetone before addition to
     samples and blanks.  This was required by the  inclusion of  water  in the
     method.

 3.   The  surrogate concentration has been changed and  it  is now  used to
     monitor method  detection  limits.

 4.   The  S/N ratios' "of the  13C12-TCDD and native TCDD  are no longer
     reportables. The S/N  ratio of 37Cl4-2,3,7,8-TCDD m/e 328 is a
     reportable.

 5.   The  "Detection  Limit"  has been retitled "Maximum  Possible Concentration"
     and  redefined.  The'formula remains the same.
 6.
 7.
Concentration Calibration (CC) solution 5 has been eliminated, reducing
the number of CC solutions to .four and reducing the calibration range and
working range of the method to 1 to 1000 ug/kg for soil/sediment and
0.01 to 10 ug/L for water.  The working range includes using a smaller
sample aliquot for the higher concentration samples (Exhibit D Section 1.1).
                   kfls been added as a recovery standard; added to the
extract just before analysis to monitor performance of the analytical
train.  It is present in the CC solutions at 60% of the internal standard
(  C,2~2,3,7,8-TCDD) concentration, an advisory recovery window of
40-lioZ has been set for Internal standard recovery.
may be set when sufficient data is avalable.
                                                           An action window
 8.   The confirmatory period scan requirement and the DFTPP tune requirement
     have been dropped.

 9.   The forms have been redesigned.

10.   The requirements for an acceptable method blank have been modified.

11.   Two concentration calibration options have been provided to facilitate'
     the Inclusion of the recovery standard and use of existing stocks of CC.
     solutions.                                                           •'  • -

12.   Numerous changes have been made for clarity and consistency with other
     CLP methods.  .
                                       ill

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       EXHIBIT A




SUMMARY OF REQUIREMENTS

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                   Exhibit A - Summary of Requirements


I.    The Contractor shall provide appropriate equipment  and experienced
     personnel to Identify and measure 2,3,7,8-tetrachlorodibenzo-p-dioxln
     (TCDD) in soil/sediment and water samples.   These analyses require GC/MS/DS
     instrumentation Including the capability to acquire,  store, and retrieve
     selected-ion-monitoring data for six ions.   Required  equipment and exper-
     tise is specified in 1FB Pre-Award Bid Confirmations.   Samples to be
     analyzed may contain high levels of toxic or hazardous materials and must
     be stored and handled with appropriate precautions.

     Specific analytical procedures to be used are provided in Exhibit D.
     Specific QA/QC Requirements are specified in Exhibit  E.  These procedures
    •must be followed explicitly without deviation, except as authorized in
     writing by the Contracting Officer.  Required activities Include:

     1.1  Sample receipt and handling under Chain-of-Custody procedures.

     1.1.1  Adherence to Chain-of-Custody procedures described in Exhibit G.
            Documentation described therein shall be required to show that
            all procedures are being strictly followed.  This documentation
            shall be reported as the complete Case File Purge.

     1.2  Extract samples, perform column chromatography procedures, and con-
          centrate extracts.  Analyze extract allquots with GC/MS procedures.
          Required equipment:   capillary column, low resolution MS, and
          selected Ion-monitoring data acquisition software.  (See Exhibit D.)

     1.3  Acquire appropriate selected-ion-current profiles from MS data files.
          (See Exhibit D.)

     1.4  Using criteria specified in Exhibit D, determine the presence or
          absence of 2,3,7,8-TCDD in each sample.  If present, calculate its
          concentration; if absent, calculate the maximum  possible
          concentration.

     1.5  For each sample extract or blank, measure signal to noise ratio of
          the surrogate compound,   Cl^-2,3,7,8-TCDD, and  determine if the
          analyte detectability requirement has been met.   (See Exhibit E.)
                   sample extract or blank calculate the percent recovery of
          the internal standard (13C12~2,3,7,8-TCDD) using the recovery
                   (13C19-1,2,3,4-TCDD).
1.6  For each sample extract
     the internal standard (
     standard (13C12-1,2,3,4-TCD5).
     1.7  Periodically analyze performance check solution and appropriate QC
          samples (blanks, duplicates, fortified samples, and performance
          evaluation samples), as specified In Exhibit E.

     1.8  Perform all required sample rerun extractions and analyses, as
          specified in Exhibit C.
                                     A - 1


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     1.9  Provide all reports and documentation within the applicable delivery
          requirement, as specified In Exhibit B.

     1.10 After receipt of samples, retain unused portions of samples and
          sample extracts for six months as specified In Exhibit B.

2.  The Contractor shall receive field samples In groups designated as sample
    "batches."  There will be up to twenty-four (24) samples In a batch,  as
    defined below.

    2.1  Sample;  A sample is defined as a solid material (soil or sediment)
         or a liquid material (water or rlnsate) that is shipped to the
         Contractor for detection and measurement of 2,3,7,8-tetrachloro-
         dibenzo-p-dioxln (TCDD).

    2.2  Field Blanks (described in Exhibit E, Sections 4.2 and 4.2.2):  One or
         more field blank samples will be included in each sample batch.

         2.2.1  Field Blank for Spiking — One field blank for each matrix
              -  will be designated for spiking.  The Contractor shall fortify
                this field blank with 2,3,7,8-TCDD at a concentration of  1
                ug/kg for soil/sediment or 10 ng/L for water.  After spiking,
                this field blank shall be analyzed by SIM GC/MS; it shall not
                be analyzed prior to spiking.  If a sample is not designated
                for spiking,  the laboratory shall call SMO immediately.

         2.2.2  Unspiked Field Blanks — Other field blanks, if any are
                included in the batch, shall be extracted and analyzed as
                routine samples per contract requirements.

    2.3  Rinsate Sample (described in Exhibit E, Section 4.2.3):  Normally, one
         rinsate sample will be Included in each batch of samples, though more
         than one may be included.  The rinsate sample is a portion of organic
         solvent that was used to rinse sampling equipment, and therefore, will
         be liquid in nature, rather than soil/sediment.  The rinsate sample is
         to be prepared and analyzed as a routine sample per contract require-
         ments.

3.  Extraction/Analysis Requirements;  Each sample in a batch shall be
    extracted and analyzed with selected ion-monitoring (SIM) GC/MS procedures.
    Additionally, for each batch of samples, three other analyses are required:

    3.1  Laboratory Method Blank (described in Exhibit E, Section 4.1):  The
        Contractor shall extract and analyze a laboratory method blank for
        each matrix in each batch of samples (or each time a group of samples
        are extracted) using contract-specified extraction and analysis
        procedures.  NOTE: Method blank analysis is considered part of the
        required Internal laboratory QA/QC (included in the sample unit price);
        method blank analysis is not considered as a separate sample analysis
        for contract accounting and/or billing purposes.

                                     A - 2

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    3.2  Duplicate Sample Analysis (described in Exhibit E,  Section 5):   One
         sample of each.matrix In each batch will be designated for duplicate
         analysis.  (In the event that no sample in the batch is marked  for
         duplicate analysis, then the Contractor shall select sample(s)  from
         the batch and perform duplicate analysis.  DO NOT USE THE FIELD BLANK
         FOR DUPLICATE ANALYSIS.)  A duplicate aliquot of this sample shall be
         extracted and analyzed using contract-specified extraction and  analysis
         procedures.  NOTE:  Duplicate sample analysis is accountable and
         billable as a separate sample analysis.

   3.3   Fortified Field Blank Analysis:  One sample for each matrix in  each
         batch should be identified as a field blank for spiking (see Exhibit A
         section 2.2.1).  If no sample(s) are so designated  the laboratory
         should contact SMO immediately.


4.  Automatic Rerun Analyses (described in Exhibit C):   Certain samples  may
    require sample reruns (reextraction and/or reanalysis) either due to
    problems, with the sample matrix or Contractor insufficiencies.   NOTE:  Sam-
    ple reruns may be considered either as billable or non-billable under the
    terms of this contract, as defined in Exhibit C.  For the purposes of this
    contract, the terra "automatic rerun" shall signify only billable rerun
    analyses.

5.  Summary of Batch Analyses:

    5.1  Extractions —

               24 or less field samples (including field blanks spiked at 1
                ug/kg or 10 ng/L as appropriate)
               1 or more laboratory method blanks*
               1 or 2 duplicate samples
           Plus, undetermined number of rerun samples.**


    5.2  Analyses —

               24 or less field samples (including field blanks
                spiked at 1 ug/kg or lOng/L as appropriate)
               1 or more laboratory method blanks*
               1 or 2 duplicate samples
           Plus, undetermined number of rerun samples.**
   *Not billable as separate sample extraction/analysis (see Section 3.1).
  **A11 sample reruns may not be billable as separate sample
    extraction/analyses, depending on basis for rerun (see Section 4).
                                     A - 3

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6.  Contract Bid Lot:  One bid lot consists of analysis of a maximum number
    of three thousand (3,000) samples, which will be received and analyzed
    In batches of less than or equal to twenty-four (24) field samples.   The
    contractor will be required to perform a maximum number of 200 sample
    analyses per calendar month period.

7.  Sample shipments to the Contractor's facility will be scheduled and
    coordinated by the EPA CLP Sample Management Office (SMO).

    7.1  The Contractor shall communicate with SMO personnel by telephone as
         necessary throughout the process of sample scheduling, shipment,
         analysis and data reporting, to ensure that samples are properly
         processed.  This shall Include Immediately notifying SMO personnel of
         any Irregularities with samples or sample paperwork received (noting
         discrepancies from verbal order placed by SMO), problems encountered
         In sample analyses that will affect the data produced, and laboratory
         conditions that Impact on timeliness of analyses and data reporting.
         In particular, the Contractor shall notify SMO personnel In advance
         regarding sample data that will be late and shall specify an estimated
         delivery date.

    7.2  Sample analyses will be scheduled by groups of samples, each defined
         as a Case and Identified by a unique EPA Case and Batch number.   A
         Case signifies a group of samples collected at one site or geo-
         graphical area over a predetermined time period, and will include one
         or more field samples with associated blanks.  Samples may be shipped
         to the Contractor in a single shipment or multiple shipments over a
         period of time, depending on the size of the Case.   If a Case consists
         of multiple shipments, each shipment is considered a Batch.

    7.3  Each sample received by the Contractor should be labeled with an EPA
         sample number, and accompanied by a Dtoxin Shipment Record bearing the
         sample number and descriptive information regarding each sample.  The
         Contractor shall complete and sign the Dloxin Shipment Record,
         recording the date of sample receipt and sample condition on receipt
         for each sample container.  The Contractor shall submit the signed
         copy of each Shipment Record to SMO within seven (7) calendar days
         following sample receipt (see contract delivery schedule).  If there
         are problems either with the samples (e.g., mixed media, containers
         broken or leaking) or paperwork (e.g., Shipment Record not with
         shipment, sample and Shipment Record numbers do not correspond)  the
         Contractor shall immediately contact SMO for resolution.

    7.4  The EPA Case and sample numbers shall be used by the Contractor  in
         identifying samples received under this contract both verbally and
         in reports/correspondence.                                         :

    7.5  Samples will routinely be shipped to the Contractor through an over-
         night delivery service.  However, as necessary, the Contractor shall b
         responsible for any handling or processing required for the receipt.o«;
         sample shipments, including pick-up of samples at the nearest
       ,  servicing airport, bus station or other carrier service within  the

                                     A - 4

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     Contractor's geographical area.  The Contractor shall be available
     to receive sample shipments at any time the delivery service Is
     operating, Including Saturdays.

7.6  The Contractor shall accept all samples scheduled by SMO, provided
     that the total number of samples received in any calendar month does
     not exceed the monthly limitation expressed in the contract.  Should
     the Contractor elect to accept additional samples, the Contractor
     shall remain bound by all contract requirements for analysis of those
     samples accepted.

7.7  The Contractor shall be required to return sample shipping containers
     (e.g., coolers) to the return addressee indicated oh or within the
     container, within a period of fourteen (14) days following receipt of
     the sample shipment.  The government will pay reasonable costs for the
     return of sample shipping containers by ground carrier service.

                                 A - 5

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               EXHIBIT B




REPORTING REQUIREMENTS AND DELIVERABLES

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          Exhibit B  -  Reporting Requirements and Deliverables


1.    The Contractor shall provide reports and other deliverables as specified
     in the Contract Schedule.   These reports are described below.   All reports
     shall be submitted in legible form or resubmission shall be required.
     All reports and documentation required,  including chromatograms,  shall be
     clearly labeled with the EPA Case number, Batch number and associated
     sample/Dioxin Shipment Record number(s).   If documentation is  submitted
     without the required identification, as  specified above, resubmission
     shall be required.

     The Contractor shall provide all reports and deliverables as described
     below.  The Contract Reporting Schedule  (Section 2) specifies  the number
     of  copies required,  delivery schedule and distribution of all  required
     deliverables.

     1.1  Dioxin"shipment Record:  Copy of SMO Dioxin Shipment Record  with  lab
          receipt information and original Contractor signature.

     1.2  Sample Data Summary Package:   Hard  copy analytical data and  documenta-
          tion are required from the Sample Data  Package (Section 1.3).

          1.2.1  Case Narrative

          1.2.2  Completed data  reporting sheets  consisting of Forms B-l, B-2,
                 B-3,  and B-4.   Original and  rerun sample data shall be  provided
                 on Form  B-l.

     1.3  Sample Data  Package:   Hard copy analytical data and documentation
          are required as described below. NOTE:  This analytical  protocol is
          designed for receipt and analysis of samples by batch.  Therefore,  it
          is desired that sample data from samples in one batch be  reported
          together,  i.e.,  on the same reporting form.   However, contract
          accounting and  billing are based on the sample unit.

          1.3.1  Case  Narrative  (laboratory cover letter) contains  the Case
                 number,  Dioxin  Shipment Record numbers, Contract number and
                 detailed documentation of any Quality Control,  sample,  ship-
                 ment  and/or analytical problems  encountered in a specific
                 Case. Also included should  be documentation of  any internal
                 decision tree process  used along with a summary  of corrective
                 actions  taken.   The Case narrative must be signed  in  original
                 signature by the Laboratory  Manager or his designate.

          1.3.2  Copies of completed Dioxin Shipment Records for all samples
                 reported in data package.

          1.3.3  Results  of initial triplicate analyses of four (4) concentra-
                 tion calibration solutions,  including all Selected Ion  Current
                                     B - I

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            Profiles (SICPs),  Calculated Response Factors,  plotted concen-
            tration calibration curves (see Section 9.2.6.5.7, Exhibit D),
            and computer generated quantitation reports.

     1.3.4  Completed data reporting sheets (Forms B-l, B-2, B-3, and B-4)
            with appropriate SICPs.  Data results of levels less than 10
            ug/kg or 100 ng/L shall be reported to two (2)  significant
            figures; results greater than 10 ug/kg or 100 ng/L shall be
            reported to three (3) significant figures.  Apply the rounding
            rules found in Section 7.2.2, "Handbook for Analytical Quality
            Control in Water and Wastewater Laboratories,"  EPA-600/4-79-
            019.  Each SICP must include the following header information:
            date and time of analysis; instrument ID; and sample ID, i.e.,
            EPA sample number, calibration solution number  (CC1, CC2, CC3,
            or CC4) or column performance check solution (PC).  When
            samples are analyzed more than once, all sample data shall be
         .- ^reported.  (Note:   Original and rerun data must be submitted.)

     1.3.5  SXCPs generated during each performance check solution analysis
            and each concentration calibration solution analysis.

     1.3.6  A chronological list of all analyses performed.  If more than
            one GC/MS system is used,  a chronological list  is required for
            each system.   The  list must provide the Data System File Name,
            the EPA sample number, and (if appropriate) the contractor
            laboratory sample  number for each sample, blank, concentration
            calibration solution,  and performance check solution.  This
            list shall specify date and time of beginning of analysis.  All
            sample/blank analyses performed during a 12-hour period must
            be accompanied by  two performance check solution analyses, one
            preceding and one  following sample/blank analyses.  If multiple
            shifts are used, the ending performance check sample analysis
            from one 12-hour period may serve as the beginning analysis
            for the next 12-hour period.

1.4  Monthly Sample Status Report;  The Monthly Sample Status Report shall
     provide the status of all samples the Contractor has received or has
     had in-house during the calendar month.   Required status information
     includes:  samples received,  samples extracted, samples analyzed,
     samples rerun.  All samples shall be identified by appropriate EPA
     Sample, Case and Batch/Shipment numbers.

1.5  Daily Sample Status Report:  In response to verbal request from the
     Sample  Management Office  or the Project  Officer, the Contractor must
     verbally provide sample status information on a same-day basis.
     Should  written confirmation be requested, the Contractor must send
     daily sample status information in a written form that same day using
     first-class mail service.  Required Daily Sample Status information
     shall include the items noted for the Monthly Sample Status Report
     and, in addition, shall require information on sample  analysis reports
     in progress and analysis reports submitted/mailed.
                                B-2

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1.6  GC/MS Tapes:  The Contractor must store all raw GC/MS data  (includ-
     ing samples, blanks, concentration calibration solutions, performance
     check solutions, and performance evaluation samples) on magnetic tape
     in appropriate instrument manufacturer's format.  The Contractor
     shall maintain a written reference/Logbook of tape files to EPA
     sample number, calibration data, standards and blanks.  The reference
     must include EPA*sample numbers identified by Case numbers and
     batch numbers.  This reference/logbook shall accompany tapes when
     submitted.

     The Contractor shall submit GC/MS tapes and associated reference/
     logbook within 7 days following receipt of written request by the EPA
     Project Officer or Sample Management Office.  The Contractor shall
     retain tapes for at least 365 days after data submission unless
     submission is requested during that time.

1.7  Extracts and Unused Sample Volume:  Unused portions of samples and
     all sample extracts shall be retained by Contractor for a period of
     365 days after data is submitted.  Extracts shall be stored at 4°C;
     unused portions of samples can be sealed and stored at ambient
     temperature.  Extracts and unused sample volume containers shall be
     labeled with EPA sample number, Case number and Batch number.   A
     logbook of stored extracts and sample volume shall be maintained,
     listing EPA sample numbers and associated Case and Batch numbers.

     The Contractor shall submit sample extracts and/or unused sample
     volume and associated logbook(s) within 7 days following receipt of
     written request by the EPA Project Officer or Sample Management
     Office.  The Contractor shall retain extracts and unused sample
     volume for at least 365 days after data submission unless submission
     is requested during that time.

     NOTE:   The Contractor is responsible for shipment of these materials
     in accordance with applicable Department of Transportation regulations.
     Whenever the Contractor disposes of such materials, the Contractor
     is responsible for disposition of these materials in accordance with
     applicable environmental regulations.

1.8  Complete Case File Purge: (formerly called the Document Control and
     Chain-of-Custody  Package)  The Complete Case File Purge package includes
     all laboratory records received or generated for a specific Case or
     sample batch, that have not been previously submitted to EPA as a
     deliverable.  These items include but are not limited to:  sample
     tags,  custody records, sample tracking records, analysts logbook
     pages, bench sheets, chromatographic charts, computer printouts, raw
     data summaries, instrument logbook pages, correspondence, and  the
     document inventory.  (See Exhibit F.)

2.    The following table (2.1) reiterates the contract reporting and
     deliverables requirements specified in the Contract Schedule and
     specifies the distribution that is required for each deliverable.
     Recipients include the CLP Sample Management Office, EMStr/LV QA.

                                B - 3

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          Division, the appropriate Regional Technical Officer, and NEIC
          Contract Evidence Audit Team.   NOTE:  Specific recipient names and
          addresses are subject to change during the term of the contract.
          The Project Offier will notify the contractor in writing of such
          changes when they occur.

     2.1  Contract Reporting Schedule

                        CONTRACT REPORTING SCHEDULE
ITEM
 NO.
REPORT
COPIES
DELIVERY
SCHEDULE
  REPORT DISTRIBUTION
SMO EMSL/LV REGION  NEIC
  I  Dioxin Shipment
       Record
  2  Sample Data
     Summary Package

  3  Sample Data
     Package

  4   Monthly Sample
      Status Report

  5   Daily Sample
      Status Report
  6   GC/MS Tapes    Lot
                 7 Days After Validated
                 Time of Sample Receipt
                 (VTSR)

                 21 days after VTSR
                 21 days after VTSR
                 5 days following end of
                 each calendar month

                 Verbal and/or written;
                 upon request by PO or
                 SMO; maximum frequency
                 is daily

                 Retain for 365 days after
                 data submission or submit
                 within 7 days after receipt
                 of written request by PO or
     Extracts & Unused Lot
     Sample Volume
      Complete Case   1
      File Purge     Pkg
                                      As Directed
                                      As Directed
                                                       SMO
                  Retain for 365 days after      As Directed
                  data, submission or submit
                  within 7 days after receipt
                  of written request by PO or SMO

                 Submit 180 days after data
                 submission or within 7 days
                 after receipt of written
                 request by PO or SMO
NOTE: ALL RESULTS SHALL BE REPORTED TOTAL AND COMPLETE.
      items 2 and 3 is required.
                                               Concurrent delivery of
                                     B - 4

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2.2  Addresses for Distribution
     SMO

     CLP Sample Management Office
     P. 0. Box 818
     Alexandria, VA  22313
     For overnight deliveries, use
       street address:
     300 N. Lee St., Suite 200
     Alexandria, VA  22314
EMSL/LV

USEPA EMSL/LV QA Division
Box 15027
Las Vegas, NV  89114
 ATTN:  Data Audit Staff

For overnight deliveries, use
  street address:
944 E. Harmon Ave.
Executive Center, Km. 226
Las Vegas, NV  89109
     Region        "*           •

     Following contract award and prior to Contractor's receipt of the first
     batch of samples, the Sample Management Office, acting on behalf of the
     Project Officer, will provide the Contractor with the list of Deputy Project
     Officers for the 10 EPA Regions.  SMO will provide the Contractor with
     updated Regional address/name lists as necessary throughout the period of
     the contract.
     NEIC

     NE1C Contract Evidence
     Audit Team (CEAT)
     12600 West Colfax, Suite C310
     Lakewood, CO  80215
                                       B - 5

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Lab:
Case/Batch No:

Instrument ID:
 FORM B-1S.   TCDD SOIL DATA REPORT FORM

	           Report Date:	

                        Column:
                                                                    Page 1 of 2
EPA
Sample No.


*














Extr.
Date

















Wet wt



	













ug/kg
Meas.

















TCDD
MPC

















GC/MS Analysis
Date

















Time

















Surr.
S/N Ratio

















*
Z REC(IS)

















 MB  =  Method Blank                               FB
  N  =  Native TCDD Spike                          IS
  D  =  Duplicate/Fortified Field Blank           RR
 PE  =  EMSL-LV Performance Evaluation Sample      RS
MPC  =  Maximum Possible Concentration            ND
*Note:  Relative to 13C12~1,2,3,4-TCDD
                                  Field Blank
                                  Internal Standard
                                  Rerun
                                  Recovery Standard
                                  Not Detected
                                      B - 7
                                                                           9/86

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Lab;
Case/Batch No:

Instrument ID:
               FORM B-1S.  TCDD SOIL DATA REPORT FORM

               	           Report Date:	

                                        Column:
                                                                    Page 2 of 2
  EPA
       Rel.
Response Ratios
Response
Sample
Number
















320/
322
















332/
334 IS
















332/
334RS
















259
















320
















322
















328












•



332IS
















334IS
















332RS
















334RS














-. 1

 MB  =  Method Blank                               FB
  N  =  Native TCDD Spike                          IS
  D  =  Duplicate/Fortified Field Blank            RR
 PE  »  EMSL-LV Performance Evaluation Sample      ND
MFC  =  Maximum Possible Concentration             RS
                                                   Field Blank
                                                   Internal Standard
                                                   Rerun
                                                   Not Detected
                                                   Recovery Standard
                                     B - 8
                                                                    9/86

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Lab:
Case/Batch No:
               FORM B-1W.   TCDD WATER DATA REPORT FORM

                                       Report  Date:	

                                       Column:
                                                                    Page 1  of 2
Instrument ID:
EPA
Sample No.

















Extr.
Date

















volume



—













ng/L
Meas.





-











TCDD
MPC

















GC/MS Analysis
Date

















Time












•




Surr.
S/N Ratio
•
















*
Z REC(IS)

















 MB  =
  N  =
  D  =
 PE  =
MFC  =
*Note:
Method Blank                              FB
Native TCDD Spike                         IS
Duplicate/Fortified Field Blank           RR
EMSL-LV Performance Evaluation Sample     RS
Maximum Possible Concentration            ND
Relative to 13C12~1,2,3,4-TCDD
Field Blank
Internal Standard
Rerun
Recovery Standard
Not Detected
                                     B - 9
                                                                   9/86

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Lab:
Case/Batch No:_

Instrument ID:
 FORM B-1W.   TCDD WATER DATA REPORT FORM

	           Report Date:	

                           Column:
                                                                    Page 2 of 2
              Rel.
  EPA  Response Ratios
                        Response (Area)
Sample
Number
















320/
322
















332/
334 IS
















332/
334RS
















259











-




320















-
322
















328
















332IS
















334IS












-



332RS
















334 RS














• !
1

 MB  =  Method Blank                               FB
  N  =»  Native TCDD Spike                          IS
  D  =  Duplicate/Fortified Field Blank            RR
 PE  =  EMSL-LV Performance Evaluation Sample      ND.
MFC  =  Maximum Possible Concentration             RS
                                      Field Blank
                                      Internal Standard
                                      Rerun
                                      Not Detected
                                      Recovery Standard
                                     B -  10
                                                       9/86

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A.   TCDD REPORT FORM (Form B-l)

     This form is used for tabulating and reporting case results.

     Complete the header Information at the top of the page Including Instru-
ment ID, laboratory name, case/batch number, report date, and column used.

     EPA sample number Is tabulated along with date sample was extracted, and
weight (wet) extracted to the nearest tenth (O.I) of a gram or volume extracted
(water) to the nearest 10 milliliters.

     Calculate the concentration of 2,3,7,8-TCDD using the formula:

                      A
           Ais
   Ais . RRFn . W

 -2,3,7,8-TCDD concentration in ug/kg or ug/L

  the sum of Integrated ion abundance detected for m/z 320
  and 322

  the sum of integrated ion abundances detected for m/z 332
  and 334 (characteristic ions of 13C12-2,3,7,8-TCDD the
  internal standard).
                   quantity (In ng) of 13C12~2,3,7,8-TCDD added to the sample
                   before extraction
                   calculated
                   relative to
             mean response factor for unlabeled 2,3,7,8-TCDD
             '   C12~2»3»7»8"TCDD
             V  =  The weight (in g) of soil/sediment extracted or volume of
                   water extracted (in roL)

     Positive samples are quantitated with values >10.0 ug/kg or 100 ng/L
     recorded to three (3) significant figures and those values <10.0 ug/kg or
     100 ng/L reported to two (2) significant figures.

     For samples in which unlabeled 2,3,7,8-TCDD was not detected calculate
the estimated maximum possible concentration, which is the concentration
required to produce a signal with a peak height of 2.5 times the background  •<
signal height.

     Use the formula:                                                     :  •.  •

                 2.5 . Hx . Qls                                           ••.•.:
         MFC  =
     where:  MFC
Hls .  RRFn . w                                          •;;.;.

    maximum possible concentration of unlabeled 2,3,7,8-TC'UP
    required to produce Hx.

                    B - 11

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       Hx  =  peak height for m/z 320 or 322 in the same group
              of >5 scans used to measure A^s.

      ^is  =  peak height for the appropriate ton characteristic of the
              Internal standard, m/z 332 when 320 is used to determine Ax,
              and m/z 334 when 322 is used to determine Ax.

      Qis  =  quantity (In ng) of 13C12-2,3,7,8-TCDD added to the
              sample before extraction.
     RRF,
        U
calculated mean response factor for unlabeled 2,3,7,
relative to 13C12-2,3,7,8-TCDD.
8-TCDD
 weight (in g) of wet soil/sediraent sample or volume of water
extracted (in mL).
Report GC/MS Instrument ID, the date and time the analysis was performed,
and the signal'to noise ratio for the surrogate compound.
                                 B -  12

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                                    FORM B-2

                          INITIAL CALIBRATION SUMMARY
                        Page 1 of 2
Laboratory:
Case/Batch No,:
CC Solution Alternative:

Instrument ID:
                                                AREA

Date















Time














Sol.
ID
CC1
CC1
CC1
CC2
CC2
CC2
CC3
CC3
CC3

CC4
CC4
CC4


320















322















328






*


t /
t /
/
/ t
/ t

332IS















334IS















332RS















334RS














Solution ID Codes;

CC1 •= Concentration calibration solution Si
CC2 - Concentration calibration solution $2
CC3 ** Concentration calibration solution #3
CC4 = Concentration calibration solution #4
  * Not present in CC Solution
    Alternative One.
                                     B - 13
                               9/86

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Laboratory:
Case/Batch No.:
                                    FORM B-2

                          INITIAL CALIBRATION SUMMARY
                                      Page 2 of 2
              CC Solution Alternative:
              Instrument ID:


Date














Time













Sol.
ID
CC1
CC1
CCl
CC2
CC2
CC2
CC3
CC3
CC3
CC4
CC4
CC4
Measured
RRFn













Mean
RRFn













Measured
RRFi













Mean
RRFi













Solution ID Codes:

CC1 « Concentration calibration solution tfl
CC2 = Concentration calibration solution #2
CC3 = Concentration calibration solution 93
CC4 = Concentration calibration solution #4
ZRSD: RRFj,
 CCl=	
 CC2=	
 CC3=	
 CC4=
Native Mean
of Means:
                                                    IS Mean
                                                    of Means:
                                     B -  14
                                             9/86

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B.   Initial Calibration Summary (Form B-2)

     Record all routine calibrations (PCS and CC1) performed during initial
calibration on form B-3.

     Complete all header information including laboratory, case/batch number,
and instrument ID and EPA CC Solution Alternative.

     Date and time along with response for each ion is recorded for each cali-
bration solution.  The response factors are calculated with the following
equations:
RRFn (native Response Factor)
                            RRFj (internal Standard Response Factor)
RRF_
         Ax
                                              RRF,
          is •
Ais

ATS
Where:
 rs
the sum of integrated ion abundance of m/z 320 and 322 for unlabeled
2,3,7,8-TCDD

the sum of integrated ion abundancces of m/z 332 and m/z 334 for
13C12-2,3,7,8-TCDD

the sum of integrated ion abundance of m/z 332 and m/z 334 for
13C12-1,2,3,4-TCDD

quantity of unlabeled 2,3,7,8-TCDD injected
Qis  =  quantity of 13Cl2-2,3,7,8-TCDD injected
                    13
 rs
        quantity of   C12-1,2,3,4-TCDD
     Calculate the mean RRF and the percent relative standard deviation for the
triplicate runs of each calibration solution.
                   SD
          %RSD  =  — x   100
                   X
                                      B -  15

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Where:.
     SD
 TN (xt - x)2

* 1=1  N - 1
     X  =  mean of each of the three Response Factors respectively

     From the 4 mean, native response factors and 4 mean internal standard
     response factors:  calculate the mean of means for each respective RRF's.
                                      B  -  16

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Laboratory:
Case/Batch No.:
           FORM B-3

 ROUTINE  CALIBRATION  SUMMARY

____	    CC Solution Alternative:

                     Instrument ID:
                   (PCS) PERFORMANCE CHECK SOL.
                                         (CC1)
                                 CON.  CALIB.  SOL.  #1
Date
Time
Response
259
320
322
328
332IS
334IS
332RS
334RS
Ratios
320/322
332/334IS
332/334RS
RRFn
RRF<

Z Valley















	
	

















• 	
	

















	
	

















	
	

















	
	

















	
	



























































                                      B  -  17
                                                  9/86

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C.   Routine Calibration Summary (Form B-3)

     Complete the header information including the laboratory,  instrument ID
     Case/Batch number and EPA CC Solution Alternative.

     For each performance check solution analyzed complete the  date and time
     and 13C17-l,2,3,4-fCDD.
           , the response for ra/z 259, 320, and 322 for unlabeled 2,3,7,8-
           or 37Cl4-2,3,7,8-TCDD, and 332 and 334 for 13Cl2-2,3,7,8-TCDD
           ,2,3,4-TCDD.

Ion ratios for m/z 320/322, ra/z 332/334 for 13C12-2,3,7,8-TCDD and m/2
332/334 for 13C12-1,2,3,4-TCDD are to be calculated and recorded.
of analysis
TCDD,,328 for
      '•12
     Response factors are to be calculated as in the Initial Calibration Summary
     (Section B).

     For calculation of valley percent see Section D, Section 9.2.6.1.

     For each Concentration Calibration Solution #1 used In Routine  Calibration,
     complete all  the above information.
                                     B - 18

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                                    FORM B-4
                            QUALITY CONTROL SUMMARY
Laboratory Name
Case/Batch No.
Instrument ID
Accuracy, Fortified?
Spike Field Blank:
Relative Difference (Z),
Duplicate Analysis:  	
                                      SOIL
                                     WATER
EPA Sample Number:

EPA Sample Number:
Accuracy, Fortified/
Spike Field Blank:
Relative Difference (Z),
Duplicate Analysis:  	
EPA Sample Number:
EPA Sample Number:
                                      B  -  19
                             9/86

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D.   QC Summary

     Complete all the header Information.

     Report the sample number for the fortified field blank and the % accuracy
of the fortified/spike field blank by using the following equation:

                    amount measured
     2 accuracy  =  	  x 100
                          1.0

     Record the sample used for duplicate and the Relative Percent Difference
which is calculated as follows:
     RPD  =  	  x 100
              Si - S2
     Where:

     Si and 82 represent sample and duplicate sample results.
                                      B  -  20

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        EXHIBIT C




SAMPLE RERUN REQUIREMENTS

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                  Exhibit C - Sample Rerun Requirements


1.   Scope and Application

     The Contractor shall be required to reextract and reanalyze certain sam-
     ples or batches of samples In a variety of situations that may occur In
     the process of contract performance.  (For purposes of this contract, the
     term "rerun" shall Indicate sample reextraction,  cleanup and reanalysis.)

     In situations where the rerun is required due to  matrix effects,  inter-
     ferences or other problems encountered because of difficult samples, the
     Government will pay the Contractor for the reruns.  Such reruns shall be
     billable and accountable under the specified contract allotment of auto-
    • matic reruns.

     In situations where the rerun is required due to  Contractor materials,
     equipment or~lnstrumentation problems, or lack of contractor's adherence
     to specified contract procedures, the rerun shall not be billable nor
     accountable under the terms of the contract.

     Contractor's failure to perform any of the sample reruns specified herein,
     either billable or non-btllable, shall be construed as Contractor non-
     performance and may result in termination of the  contract for default by
     Contractor.

     NOTE:  The only circumstance that may require more than one rerun per
            sample is a contaminated method blank.

2.   Required Sample Reruns

     2.1  Automatic sample reruns, billable as such under the contract.

          2.1.1   If the calculated unlabeled TCDD amount was outside the upper
                  initial calibration range, the Contractor shall reextract
                  the sample using a smaller sample aliquot, and reanalyze the
                  sample.  (See Section  12.1.2, Exhibit D.)

          2.1.2   If the internal standard was not found to be present with at
                  least 10/1 signal  to noise ratio at mass 332 and 334, the
                  Contractor shall reextract and reanalyze the sample.
                  NOTE: This rerun is billable only if the Contractor can
                  demonstrate that the internal standard was added to the
                  sample in accordance with contract  specifications.  (See
                  Sections 3.11 and  11.6.3, Exhibit D.)
                                      C  -  1

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     2.1.3  If the internal standard 332/334 ratio was outside of the
            contract specified control limits of 0.67-0.90,  the Contractor
            shall reextract and reanalyze the sample.  (See  Section
            11.6.5, Exhibit D.)  This reanalysis is billable, only if
            the internal standard 332/334 ratio is still outside the
            0.67-0.90 control limits.

     2.1.4  If the isotope abundance ratio for m/z 320/322 is less than
            0.67 or greater than 0.90 and all other criteria contained in
            Section 11.6.1 through 11.6.5 of Exhibit D are met, then the
            sample must be rerun unless the MFC is _<0.3 ug/Kg for soil or
            0.003 ug/L.  (See Section 6.2, Exhibit E.)  NOTE:  This
            reanalysis is billable only if the isotope abundance ratio of
            m/z 320/322 on the rerun is still outside the criteria.

     2.1.5  If the estimated maximum possible concentration  is greater
            than 1 ug/kg (soil) or 10 ng/L (water), the Contractor
            shall reextract and reanalyze the sample.  This  reanalysis
            is billable only if the maximum possible concentration is
            still greater than 1 ug/kg or 10 ng/L.

2.2  Sample reruns to be performed at Contractor's expense (i.e., not
     billable under terms of contract).

     2.2.1  Acceptable laboratory method blanks must not contain any
            signal at 320, 322 or 259 which is greater than  2* of the
            m/z 332 response within +5 scans of the m/z 332  peak maximum.
            The Contractor shall reanalyze the affected positive samples
            associated with a contaminated blank (see Section 4.1.5,
            Exhibit E).

     2.2.2  If the performance check (PC) solution does not  meet specified
            criteria, the Contractor shall reanalyze all positive samples
            run during the time period between the last acceptable PC run
            and the unacceptable PC run (see Section 2.4, Exhibit E).

     2.2.3  If a false positive is reported for an uncontaminated soil or
            water (blind QC) sample, upon notification by the Sample
            Management Office the Contractor shall reextract and reanalyze
            all positive samples in the associated batch of  samples
            (see Section 7.1.1, Exhibit E).

     2.2.4  If the analytical results for a performance evaluation blind QC
            sample fall outside of EPA-established acceptance windows,
            upon notification by the Sample Management Office the Contrac-
            tor shall reextract and reanalyze the entire associated batch
            of samples (see Section 7.4.1, Exhibit E).
                                C - 2

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          2.2.5  If the accuracy of the measured concentration of native
                 2,3,7,8-TCDD In the spiked (fortified) field blank Is not
                 between 60-140%, the contractor shall reextract and reanalyze
                 a second aliquot of the fortified field blank sample.

3.    Sample Rerun QC

     3.1  A native spike and duplicate shall be performed for each batch of
          samples reanalyzed as specified In Section 2.

          3.1.1  If a concurrent Dloxln Case Is being processed, the native
                 spike and duplicate from that case may be shared with the
                 rerun samples If the total number of samples does not exceed
                 24.  If the total number of samples exceeds 24 an additional
                 native spike and duplicate must be analyzed as In Section
                 3.1.2 below.  The native spike and duplicate data shall be
                 reported In each Case Data Package.  (Note:  The QC samples
                 are to be billed only under the Case number In which the QC
                 sample was received.)

          3.1.2  If no other Dloxln Case Is being processed at the time of
                 reanalysls, the native spike and duplicate shall be chosen
                 from the Case and batch In which the rerun sample belongs.
                 The QC samples are to be billed only If the rerun samples
                 are blllable according to Section 2.
                                     C - 3

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    EXHIBIT D




ANALYTICAL METHODS

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                                  INDEX
Section
 Number                          Subject
   1.         Scope and Application
   2.         Summary of Method
   3.         Definitions
   A.         Interferences
   5.         Safety
   6.         Apparatus and Equipment
   7.         Reagents and Consumable Materials
   8.         Sample Preservation and Handling (Ref. Exhibit G)
   9.         Calibration
  10.         Quality Control (Ref. Exhibit E)
  11.         Analysis Procedures
  11.1        Soil Sample Extraction
  11.2        Water Sample Extraction
  11.3        Column Chromatography
  11.4        Carbopack Column Chromatography Procedure
  11.5        GC/MS Analysis
  11.6        Identification Criteria
  12.         Calculations
                                       D - 1

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                         Exhibit D - Analytical Methods

                  2,3,7,8-Tetrachlorodlbenzo-p-dioxin in Soil,
           Sediment and Water by High Resolution Gas Chromatography/
                        Low Resolution Mass Spectrometry
1.  SCOPE AND APPLICATION

     1.1  This method provides procedures for detection and measurement of
          2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD; CAS Registry Num-
          ber 1746-01-6; STORET Number 34675) at concentrations of 1 ug/kg to
          100 ug/kg in 10-g aliquots of wet soil/sediment and 10 ng/L to 1000
          ng/L in 1 L aliquots of water.  The use of 1 g aliquots permits
          measurement of concentration up to 1000 ug/kg In soil/sediment.  The
          use of a 100 mL aliquot volume permits measurement of concentrations
          up to IQ^ug/L in water.

     1.2  CAUTION: The analysis of water samples includes whatever particulates
                   may be present.  The estimated solubility of 2,3,7,8-TCDD in
                   water is less than 50 ng/L', therefore positive values ibove
                   this level should be considered to be a function of the TCDD
                   associated with the particulates rather than the water.

     1.3  The minimum measurable concentration is estimated to be 0.3 ug/kg or
          3 ng/L, but is dependent on interfering compounds present in the
          sample matrix.

     1.4  This method is designed for use by analysts who are experienced in
          the use of a gas chromatograph/mass spectrometer.
     1.5  CAUTION:
Because 2,3,7,8-TCDD is extremely toxic, safety procedures
described In Section 5 of this method should be followed to
prevent exposure of laboratory personnel to materials
containing this compound.    .
2.  SUMMARY OF METHOD

    2.1  Soil/Sediment Extraction;  For purposes of this contract a soil/sedi-
         ment sample is defined as a portion of wet soil or sediment which may
         contain other solids such as stones, vegetation etc., but should not
         contain an obvious liquid phase (See Exhibit D, Section 8.3.2);  •
         Fifty (50) ng of  13C12-labeled 2,3,7,8-TCDD and 1.4 ng of 3 C14~
         labeled 2,3,7,8TCDD are added to a 10 g aliquot of wet soil or
         sediment  sample,  the sample aliquot is mixed with 20 g of anhyt'.r^us
         sodium sulfate and is extracted with a mixture of hexane and metharol
         by agitating the  sample aliquot and solvent continually in a glaas-
         jar.
                                      D  -  2

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2.2  Water Extraction:  For the purpose of this contract a water sample Is
     defined as a single phase system that Is primarily water but may contain
     small amounts of floating, suspended, and settled partlculate matter.
     Multiple phases should not be present (See Exhibit D, Section 8.3.2.).
     Fifty (50) ng of 13C12-labeled 2,3,7,8-TCDD and 1.4 ng of 37Cl4~labeled
     2,3,7,8TCDD are added to approximately 1 L of water and extracted with
     methylene chloride using a separatory funnel.  The methylene chloride
     extract Is exchanged to hexane during concentration.

2.3  Cleanup and Analysis;  Column chroma tographic procedures are used to help
     eliminate sample components that may interfere with detection and measure-
     ment of 2,3,7,8-TCDD.  The extract Is concentrated to 50 uL, 50 ng
     13C12-1,2,3,4-TCDD are ad*ied, and a 2 uL aliquot is injected into a fused
     silica capillary column in a gas chromatograph (GC) interfaced to a mass
     spectrometer (MS) that has at least unit resolution at m/z 334.  Identifi-
     cation of 2,3,7,8-TCDD is based on detection of three ions, measurement of
     the appropriate relative abundances of two characteristic ions in the
     molecular ion cluster, and determination of the retention time of the
     sample analyte relative to the internal standard, ^C^-^.S^S-TCDD,
     contained in the sample extract.   The 2,3,7,8-TCDD concentration is
     determined by measuring the MS response to the sample component relative
     to the MS response to  3C12-2,3,7,8-TCDD (the internal standard).  The
     labeled internal standard method presumes that internal standard losses
     during method procedures are equal to unlabeled TCDD losses.  Therefore,
     the calculated sample 2,3 ,7 ,8, -TCDD concentration is corrected for losses
     during sample preparation.

     The 37C1 ^-2,3,7,8-TCDD is a surrogate compound that is added to each
     sample and is analyzed exactly the same as unlabeled TCDD.  The surrogate
     compound is used to determine that the detection criteria for unlabeled
     2,3,7,8-TCDD in the same sample have been met.

     The 13C12~1,2,3,4-TCDD is a recovery standard that is added to each sample
     and blank.  The recovery of the internal standard (13C12-2,3,7,8-TCDD) atld
     the surrogate compound (  Cl. -2,3,7,8-TCDD) are related to the precision
     and sensitivity of the analysis for unlabeled 2,3,7,8-TCDD in the sample.

3.   DEFINITIONS
     3.1  Concentration calibration solution — a solution containing known
          amounts of the analyte (unlabeled 2,3,7,8-TCDD), the surrogate
          compound (37C14~2,3,7 ,8-TCDD) , the recovery standard (13C12~1, 2,3,4-
          TCDD) and the internal standard (13C12~2,3,7,8-TCDD); it is uced
          to determine the Instrument response of the analyte compound relative
          to the internal standard and the recovery of the internal standard.

     3.2  Field blank — a portion of soil/sediment or water uncontamlnated.
          with 2,3,7,8-TCDD submitted with the samples.
                                     D  -  3

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 3.3  Rinsate  — a portion of trichloroethylene used to rinse sampling
      equipment and analyzed to demonstrate that samples were not contami-
      nated during sampling.

 3.4  Internal standard — 13C12-2,3,7,8-TCDD, which Is added to every
      sample and Is present at the same concentration In every blank,
      quality control sample, and concentration calibration solution.  It
      Is added to the samples before extraction and Is used to measure the
      concentration of the analyte.

 3.5  Recovery standard — 13C12-1,2,3,4-TCDD is added to every extract and
      Is present In all standards.  It Is added to every extract just
      before analysis and Is used to measure the recovery of the Internal
      standard.
 3,6
 3.7
 3.8
 3.9
3.10
3.11
Surrogate compound — A known concentration of 3'Cl^-2,3,7,8-TCDD,
which Is added to all samples before analysis.  Its signal to noise
ratio Is measured In each sample, and Is used to Indicate that
unlabeled 2,3,7,8-TCDD Is detectable at less than 1.0 ug/kg or
10 ng/L.

Laboratory method blank — a blank prepared In the laboratory by
performing all analytical procedures except addition of a sample
aliquot to the extraction vessel.

Performance check mixture — a mixture of known amounts of selected
standard compounds; It Is used to demonstrate continued acceptable
performance of the GC/MS/DS system.

Performance evaluation sample — a soil/sediment or water sample
containing a known amount of unlabeled 2,3,7,8-TCDD.  It Is distri-
buted by EPA to potential contractor laboratories who must analyze It
and obtain acceptable results before being awarded a contract for
sample analyses (see IFB Pre-Award Bid Confirmations).  It may also
be Included as an unspecified QC sample In any sample batch submitted
to the laboratory for analysis.

Response factor — response of the mass spectrometer to a known
amount of an analyte relative to a known amount of an Internal
standard.
Signal-to-nolse (for the purpose of this contract)
ratio of analyte signal to random background signal
characteristic ion using a window 20 scans wide and
the elutlon time of 2,3,7,8-TCDD.  Draw a base line
point In the 20 scan window.  The noise Is defined
the largest signal (excluding signal due to TCDD or
on either side of the 2,3,7,8-TCDD peak, within the
The signal Is defined as the height of 2,3,7,8-TCDD
noise Is left to the judgement of the analyst.
is defined as the
   Display eazh
 centered around
 from the lowest
as the helj-.h-i, .of
 other chem*. ca J s )
 20 scan wtuJcv.
 peak.  Chemical
                                 D - A

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     3.12  Abbreviations

          TCDD - Tetrachlorodibenzo-p-dioxln
          GC   - Gas Chromatograph
          MS   - Mass Spectrometer
          DS   - Data System
          SIM  - Selected Ion Monitoring
          SMO  - Sample Management Office
          SICP - Selected Ion Current Profile
          S/N  - Signal to Noise
          PC   - Performance Check Standard
          CC   - Calibration Check Standard
          RRF  - Relative Response Factor
          IS   - Internal Standard
          RS   - Recovery Standard
          K-D  - Kudema-Danish Apparatus
          OD   - Outside Diameter
          m/z  - Mass to Charge Ratio
          MPC  - Maximum Possible Concentration
          VTSR - Verified Time of Sample Receipt

4.   INTERFERENCES

     Any compound that yields ions at m/z 259, 320, 322, or 328 and also
     elutes within 10 scans of the internal standard is a potential interfer-
     ence.  Most frequently encountered interferences are other sample compo-
     nents that are extracted along with TCDD.  Because very low levels of TCDD
     must be measured, elimination of Interference is essential.  High purity
     reagents and solvents must be used and all equipment must be scrupulously
     cleaned.  Laboratory method blanks (Exhibit E, Quality Control, Section A)
     must be analyzed to demonstrate lack of contamination that would Interfere
     with TCDD measurement.  Column chromatographic procedures are used to
     remove some coextracted sample components; these procedures must be per-
     formed carefully to minimize loss of TCDD during attempts to enrich its
     concentration relative to other sample components.

5.   SAFETY

     5.1  The toxicity or carclnogenicity of each reagent used in this method
          has not been precisely defined; therefore, each chemical compound
          should be treated as a potential health hazard.  From this viewpoint,
          exposure to these chemicals must be reduced to the lowest possible
          level by whatever means available.  The laboratory is responsible, "cor
          maintaining a file of current OSHA regulations regarding the safe
          handling of the chemicals specified in this method.  A reference file
          of material data handling sheets should also be made available to all
          personnel involved in the chemical analysis.  Additional references
          to laboratory safety are identified.(l~3)  2,3,7,8-TCDD has been '
          identified as a suspected human or mammalian carcinogen.
                                     D - 5

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5.2  Each laboratory must develop a strict safety program for handling
     2,3,7,8-TCDD.  The following laboratory practices are recommended:

     5.2.1  Contamination of the laboratory will be minimized by con-
            ducting all manipulations in a hood.

     5.2.2  The effluents of sample splitters for the gas chromatograph
            and roughing pumps on the GC/MS should pass through either a
            column of activated charcoal or through a trap containing oil
            or hlghboillng alcohols.

5.3  The following precautions for safe handling of 2,3,7,8-TCDD in the
     laboratory are presented as guidelines only, and are based on safe
     handling practices included in USEPA Method 613.(^)  The precautions
     for safe handling and use are necessarily general in nature because
     detailed, specific recommendations can be made only for the par-
     ticular ^exposure and circumstances of each individual usage.
     Assistance In evaluating the health hazards of particular laboratory
     conditions may be obtained from certain consulting laboratories and
     from State Departments of Health or of Labor, many of which have an
     industrial health service.  Although 2,3,7,8TCDD is extremely toxic
     to laboratory animals, it has been handled for years without injury
     in analytical and biological laboratories.   Techniques used In
     handling radioactive and infectious materials are applicable to
     2,3,7,8-TCDD.

     5.3.1  Protective Equipment:  Throw-away plastic gloves, apron or lab
            coat,  safety glasses and lab hood adequate for radioactive
            work.

     5.3.2  Training:  Workers must be trained in the proper method of
            removing of contaminated gloves and clothing without
            contacting the exterior surfaces.

     5.3.3  Personal Hygiene:  Thorough washing of hands and forearms
            after each manipulation and before breaks (coffee, lunch, and
            shift) with any mild soap and plenty of scrubbing action.

     5.3.4  Confinement:  Isolated work area, posted with signs;
            segregated glassware and tools; and plastic-backed absorbent
            paper on benchtops.

     5.3.5  Waste:  Good technique includes minimizing contaminated waste.
            Plastic bag liners should be used in waste cans.  Janitucs
            should not handle wastes.

     5.3.6  Disposal of Wastes:  2,3,7,8-TCDD decomposes above 800°.C. .Low
            level waste, such as the absorbent paper and plastic glovcc,
            may be burned in a good Incinerator.  Waste containing gtoss
            quantities (milligrams) of 2,3,7,8-TCDD should be packaged
            securely and disposed through commercial or governmental
                                D - 6

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        channels that are capable of handling high-level or extremely
        toxic wastes.  Liquids should be allowed to evaporate In a
        good hood and In a disposable container; residues may then be
        handled as above.

 5.3.7  Glassware, Tools, and Surfaces:  Satisfactory cleaning may be
        accomplished by rinsing with 1,1,1-trlchloroethane, then
        washing with any detergent and water.  Dishwater may be
        disposed to the sewer.  (Also see Section 6.5.)

 5.3.8  Laundry:  Clothing known to be contaminated should be disposed
        with the precautions described under Section 5.3.6.  Lab coats
        or other clothing worn In 2,3,7,8-TCDD work may be laundered.
        Clothing should be collected In plastic bags.  Persons who
        convey the bags and launder the clothing should be advised of
        the hazard and trained In proper handling.  The clothing may
        be put Into a washer without contact If the launderer knows
        the problem.  The washer should be run through a cycle before
        being used again for other clothing.  Disposable garments may
        be used to avoid a laundry problem, but they must be properly
        disposed or Incinerated.

 5.3.9  Wipe Tests:  A useful method to determine cleanliness of work
        surfaces and tools Is to wipe the surface with a piece of
        filter paper, which Is extracted and analyzed by gas chromato-
        graphy (limit of sensitivity of approximately 0.1 ug per
        wipe).  Less than 4 pg/cm^ 2,3,7,8-TCDD indicates acceptable
        cleanliness; anything higher warrants further cleaning.  More
        than 400 pg/cm^ Indicates an acute hazard that requires prompt
        cleaning before further use of the equipment or work space and
        Indicates that unacceptable work practices have been employed
        In the past.

5.3.10  Inhalation:  Any procedure that may produce airborne contami-
        nation should be performed with good ventilation.  Gross
        losses to a ventilation system should not be allowed.  Han-
        dling of the dilute solutions normally used in analytical and
        animal work presents no inhalation hazards except in case of
        an accident.  Finely divided soils contaminated with 2,3,7,8-
        TCDD are hazardous because of the potential for inhalation.
        Such samples should be handled in a confined environment, such
        as a hood or glove box, or laboratory personnel should wear
        masks fitted with a particulate filter and charcoal sorbent.

5.3.11  Accidents:  Remove contaminated clothing Immediately, taking
        precautions not to contaminate skin or other articles.;  Wat,h
        exposed skin vigorously and repeatedly until medical attention
        is obtained.
                            D - 7

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6.  APPARATUS AND EQUIPMENT

    6.1  Gas Chromatograph/Mass Spectrometer/Data System (GC/MS/DS)

          6.1.1  The GC must be capable of temperature programming and be
                 equipped with all required accessories, such as syringes,
                 gases, and a capillary column.  The GC injection port must be
                 designed for capillary columns.  Splitless or on-column injec-
                 tion technique is recommended.  With this method, a 2 uL
                 injection volume is used consistently.  However, with some GC
                 injection ports other volumes may be more appropriate.  Any
                 volume that produces adequate precision sensitivity, and
                 chromatographic separation may be used.  A 1 uL injection
                 volume may be used If adequate sensitivity and precision can
                 be achieved.  CAUTION:  The Injection volume for all extracts,
                 blanks, calibration solutions and the performance check samples
                 must be the same.

          6.1.2  Mass spectral data are obtained with electron ionizatlon at a
                 nominal electron energy of 70 eV.  To ensure sufficient pre-
                 cision of mass spectral data, the required MS scan rate must
                 allow acquisition of at least five data points for each of six
                 ions while a sample component elutes from the GC.

          6.1.3  An Interfaced data system (DS) is required to acquire, store,
                 reduce and output mass spectral data.  The DS must be equipped
                 with a selected ion monitoring (SIM) program to acquire data
                 for at least six ions that are characteristic of labeled and
                 unlabeled 2,3,7,8-TCDD.  (The mass spectrum of unlabeled
                 2,3,7,8-TCDD Is shown In Figure 1 at the end of this Exhibit.)
                 The same integration time must be used for each ion monitored,
                 and the Integration time used for sample analyses must be the
                 same as the time used to analyze concentration calibration
                 solutions and the performance check solution.  Total data
                 acquisition time per cycle (six ions) must not exceed 1.5
                 seconds.

          6.1.4  The Contractor shall use a magnetic media storage device
                 capable of recording data suitable for long-term off-line
                 storage.  The Contractor shall record all raw GC/MS data
                 acquired during the entire contract period on magnetic media
                 in appropriate instrument manufacturer format.  The Contractor
                 shall provide the data on 9-track magnetic tape In appropriate
                 instrument manufacturers format to the US EPA within sever. (7)
                 days of request by the Project Office or SMO.  The tapes .uust
                 be retained by the contractor for 180 days after data package
                 submission unless requested by EPA.

    6.2  GC Column — Two fused silica capillary columns are  recommended; cne
         is a 60-m SP-2330 and the other is a 50-m CP-SIL 88.  Any capillary
         column that separates 2,3,7,8-TCDD from all other TCDDs may be uce-i,
         but this separation must be demonstrated.  Minimum acceptance criteria
         must be determined per Section 9.2.6.1.  At the beg inn ing-and er.a of

                                     D - 8

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     each 12-hour period during which sample or concentration calibration
     solutions will be analyzed, column operating conditions must be
     demonstrated to achieve the required separation on the column to be
     used for samples.  Operating conditions known to produce acceptable
     results with the recommended columns are shown In Table 1 at the end
     of this Exhibit.  It Is the Contractor's responsibility to verify
     whether the Information In Table 1 Is suitable for the laboratory's
     Instrument(s).

6.3  Miscellaneous Equipment

     6.3.1  Nitrogen evaporation apparatus with variable flow rate.

     6.3.2  Mechanical shaker — A magnetic stirrer or a wrist-action or
            platform-type shaker that produces vigorous agitation.

     6.3.3  Analytical balance capable of accurately weighing 0.01 g.

     6.3.4  Centrifuge capable of operating at 400 x G.

     6.3.5  Water bath — equipped  with concentric ring cover and
            temperature controlled within +2*C.

     6.3.6  Stainless steel spatulas or spoons.

     6.3.7  Stainless steel (or glass) pan large enough to hold contents
            of 1-pint sample containers.

     6.3.8  Glove box.

6.4  Glassware

     6.4.1  Extraction jars —  amber glass with Teflon-lined screw cap;
            minimum  capacity of approximately  500  mL; must be compatible
            with mechanical shaker to  be used.

     6.4.2  Kuderna-Danish apparatus — 500-raL evaporating flask,  10-mL
            graduated concentrator tubes with  ground-glass stoppers,
            3-ball macro-Snyder column, and  2-ball micro-Snyder  column.

     6.4.3  Culture  tubes — 8-mL glass.

     6.4.4  Mini-vials  — 1-mL,amber borosilicate  glass with conlccl-
             shaped reservoir and  screw caps lined  with Teflon-faced  • •
             silicone disks.

     6.4.5   Funnels  —  glass;  appropriate size to  accommodate filter p*per
             used to  filter  jar extract (volume of  approximately  170  .nt,,'.

     6.4.6   Chromatography  columns  — 1 cm ID x 20 cm long and 1 cm II)
             x 30 cm long.
                               D - 9

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          6.4.7  Separatory  funnels —  2 L with Teflon  stopcock.

          6.4.8  Drying column  19 mm  ID glass chromatographic column with a
                 coarse frit (a small pad of pyrex  glass wool may be
                 substituted for the  frit to avoid  cross contamination).

          6.4.9  Boiling chips  — Approximately 10/40 mesh.  Silicon carbide
                 or Teflon may  be used.  Heat to 400°C  for 30 mln or Soxhlet
                 extract with methylene chloride as appropriate.

     6.5  NOTE:  Reuse of glassware should be minimized to avoid the risk of
                 using contaminated glassware.  All glassware that is reused
                 must be scrupulously cleaned as soon as possible after use,
                 applying the following procedure.  Rinse glassware with the
                 last solvent used in it.  Wash with hot water containing
                 detergent.  Rinse with copious amounts of tap water and
                 several portions of distilled water.  Drain dry and heat In a
                 muffle furnace at 400°C for 15 to 30 rain.  Volumetric glass-
                 ware should not be heated In a muffle furnace, and some
                 thermally stable materials (such as PCBs) may not be removed
                 by heating  in a muffle furnace.  In these cases, rinsing with
                 high-purity acetone and hexane may be substituted for muffle
                 furnace heating.   After glassware is dry and cool, store
                 inverted or capped with aluminum foil in a clean environment.

       CAUTION:  The analysis for 2,3,7,8-TCDD in water is for much lower con-
                 centrations than in soil/sediment.  Extreme care must be
                 taken to prevent cross-contamination between soil and water
                 samples.   It is strongly recommended that separate glassware
                 be reserved for analyzing water samples.   It is recommended
                 that all glassware be  rinsed with solvent immediately before
                 use and that the pooled solvent for a set of extractions be
                 concentrated and analyzed as a method of demonstrating that
                 the glassware was free of contamination.

7.  REAGENTS AND CONSUMABLE MATERIALS

    7.1  Column Chromatography Reagents

          7.1.1  Alumina,  acidic AG4, Bio Rad Laboratories (catalog #132-1240
                 or equivalent) — Soxhlet extract with methylene chloride for
                 21 hours and activate by heating in a foil covered glass
                 container for 24 hours at 190°C.

          7.1.2  Silica gel — high purity grade,  type 60, 70-230 mesh; C-Jxhlet
                 extract with methylene chloride for 21 hours and activate by
                 heating in a foil-covered glass container for 24 hours: at
                 130°C.

          7.1.3  Silica gel  Impregnated with sodium hydroxide — Add one part
                 of 1 M NaOH solution to two parts of silica gel'(extracted and
                 activated)  in a screw-cap bottle and mix with a glass rod
                 until free of lumps.                            	.

                                     D  - LO

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     7.1.4  Silica gel Impregnated with 40Z (by weight) sulfurlc acid —
            Add two parts (by weight) concentrated sulfurlc acid to three
            parts (by weight) silica gel (extracted and activated), mix
            with a glass rod until free of lumps, and store In a screw-
            capped glass bottle.

     7.1.5  Sulfurlc acid, concentrated — ACS grade, specific gravity
            1.84.

     7.1.6  Graphitlzed carbon black (Carbopack C or equivalent), surface
            area of approximately 12 m2/g, 80/100 mesh.

     7.1.7  Cellte 545, reagent grade, or equivalent.

7.2  Filter paper — Whatman No. 1 or equivalent; rinse with hexane
     before use.

7.3  Glass wool, silanlzed — Extract with methylene chloride and then
     hexane before use.

7.4  Sodium sulfate — Granular, anhydrous; before use, extract with
     methylene chloride and dry for >4 h In a shallow tray placed in an
     oven operated at 120°C.

7.5  Solvents — High purity, dlstilled-ln-glass; hexane, methanol,
     raethylene chloride, toluene, and isooctane.

7.6  Concentration Calibration Solutions (Table 2) — EMSL-LV will provide
     the concentration calibration solutions in either of two formulations
     depending on the availability of standard materials.  Alternative one
     (Section 7.6.1) includes the 13C,o-l,2,3,4-TCDD recoi
                                     •12
     the concentration calibration solutions.  Alternative two (Section
                                                          13/»  _i t t /._
                                                recovery standard in
                                                     ^1
7.6.2 requires the addition of a specified amount of  '^^2~i»x
TCDD to 1 mL of each concentration calibration solution.  The
solutions obtained will be clearly labeled to identify which
formulation Is supplied.
                                     containing unlabeled 2,3,7,8-TCDD at
                                     d   ^272,3,7,8-TCDD (the internal
7.6.1  Alternative One

       Four isooctane solutions
       varying concentrations and
       standard, CASRN 80494-19-5) anriJC12-l,2,3,4-TCDD (the
       recovery standard) at a constant concentration.  Two of these
       solutions also contain   Cl^-2,3,7,8-TCDD  (the surrogate com-
       pound, CASRN 85508-50-5) at a constant concentration.  Concen-
       tration calibration solutions are to be obtained from  the
       Quality Assurance Division, US EPA Environmental Monit«»cit.K
       Systems Laboratory (EMSL-LV), Las Vegas, Nevada.  However, if
       not available from EMSL-LV, standards may  be obtained  from
       commercial sources, and solutions may be prepared in the
       contractor laboratory.  Traceabillty of standards must te
                                 D -  11

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       verified against EPA-supplied standard solutions, by labora-
       tory SOP's as required In IFB Pre-Award Bid Confirmations,
       part 2.f.(4).
       7.6.1.1  Each of solutions #1-04 contains 13C12-2, 3,7,8-
                TCDD at a concentration of 1 ng/uL which is
                equivalent to a 50-uL extract of a 10-g sample to
                which that compound (the internal standard) was
                added at a concentration of 5 ug/kg or a 50 uL
                extract of a 1 L water sample to which the
                internal standard was added at a concentration of
                50 ng/L.

       7.6.1.2  Solutions #1-04 contain unlabeled 2,3,7,8-TCDD
                at concentrations of 0.2, 1, 5, and 20 ng/uL
                respectively; those concentrations are equivalent
                to 50-uL extracts of 10-g samples containing
                1, 5, 25, and 100 ppb, respectively, or of 1 L
                water samples containing 0.01, 0.05, 0.25, and
                1.0 ppb, respectively.

       7.6.1.3  Solutions #l-#4 contain 13C12-1,2,3,4-TCDD at a
                concentration of 0.6 ng/uL.
7.6.1.4
                Solutions 01-#2 contain 37C14~2,3,7 ,8-TCDD at a
                concentration of 0.028 ng/uL, this concentration
                is equivalent to an extract of a sample containing
                0.14 ug/kg or 1.4 ng/L the amount of -''d^-TCDD (the
                surrogate compound) added to each sample before
                extraction.
7.6.2  Alternative Two

       Four isooctane solutions containing unlabeled 2,3,7,8-TCDD at
       varying concentrations and   C12-2,3,7,8-TCDD (the Internal
       standard (CASRN 80494-19-5) at a constant concentration.
       Three of these solutions also contain 37C1^2,3,7,8~TCDD (the
       surrogate compound, CASRN 85508-50-5) at varying concentra-
       tions.  Concentration calibration solutions are to be obtained
       from the Quality Assurance Division, US EPA Environmental
       Monitoring Systems Laboratory (EMSL-LV), Las Vegas, Nevada.
       However, if not available from EMSL-LV, standards may be
       obtained from commercial sources, and solutions may be pre-
       pared in the contractor laboratory.  Traceability of standards
       must be verified against EPA-supplied standard solutions,
       by laboratory SOP's as required in  IFB Pre-Award Bid
       Confirmations, part 2.f.(4).                          '.'.'.
       7.6.2.1  A solution of 13C12~1,2,3,4-TCDD at a concentra-
                tion of 10 ng/uL in  tsooctane  is provided to be
                added to each of the concentration calibration
                           D -  12

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                     (CC) solutions.   The amount to be added to each CC
                     solution Is given below.   This will result In all
                     compounds being  In the same ratios as Alternative
                     One but the concentrations are 9 percent lower.

                      10 ng/uL 13C,2-1,2,3,4,-TCDD Solution
         CC1
         CC2
         CC3
         CCA
                                13
1 mL CCl  + 60 uL
1 mL CC2  + 60 uL
1 mL CC3  + 60 uL l:>Cj2-l ,2,3,4-TCDD + 40  uL Isooctane
1 mL CC4  + 60 uL 13C12~i ,2,3,4-TCDD •*• 40  uL Isooctane
  C12~1'2'3'/*~TCDD
13C12-1,2,3,4-TCDD + 40 uL Isooctane
            7.6.2.2  The final CC#1-CC#4 solutions contain   C12~
                     2,3,7,8-TCDD at 0.909 ng/uL which Is equivalent
                     to a 50-uL extract of a 10 g or 1 L sample to
                     which that compound (the Internal standard)
            ^        was added at a concentration of 4.5 ug/Kg or
                     45 ng/L.                        :

            7.6.2.3  The final CCtfl-CC#4 solutions contain unlabeled
                     2,3,7,8-TCDD at concentrations of 0.182, 0.909,
                     4.545,  and 18.18 ng/uL, respectively.

            7.6.2.4  Solutions #1-04 contain 13C12-1,2,3,4-TCDD at
                     a concentration of 0.54 ng/uL.

            7.6.2.5  Solutions #1-03 contain 37Cl4-2,3,7,8-TCDD
                     at concentrations of 0.054, 0.109 and 0.182
                     ng/uL,  respectively.

                     NOTE:  The  surrogate concentrations do not
                            correspond to Alternative One and are not
                            at the level used for the confirmation
                            of the 1.0 ug/kg or 10 ng/L detection
                            criteria.

     7.6.3  Store concentration calibration solutions in 1-raL amber mini-
            vials at room temperature.

7.7  Performance Check Solution — A mixture containing at a minimum:
     unlabeled 2,3,7,8-TCDD (CASRN 1746-01-6); 1,2,3,4-TCDD (CASRN
     30746-58-8); 1,4,7,8-TCDD (CASRN 40581-94-0); 1,2,3,7-TCDD (CASRN
     67028-18-6); 1,2,3,8-TCDD (CASRN 53555-02-5); 1,2,7,8-TCDD (CASRN
     34816-53-0) and 1,2,6,7-TCDD (CASRN 40581-90-6) must be obtained from
     the Quality Assurance Division, Environmental Monitoring Systems
     Laboratory, Las Vegas, Nevada.  Note:  This solution may vary between
     lots.                                                        :'. '
     To this dry mixture add 500 uL of the sample fortification solution
     (Section 7.8) containing   C12-2,3,7,8-TCDD at a concentration cf 0.
     ng/uL and 37C1.-2,3,7,8-TCDD at a concentration of 0.014 ng/uL aud 5
                                         5
                                        50
                                D -  13
                                8/87 Rev.

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          uL of the 10 ng/uL 13C12~1,2,3,4-TCDD recovery standard solution.
          Store in 1-raL amber mini-vial at 4°C.

     7.8  Sample Fortification Solution — An isooctane solution containing the
          internal standard at a concentration of 0.5 ng/uL and the surrogate
          compound at a concentration of 0,014 ng/uL.  Mix 100 uL with 1.5 mL of
          acetone before adding to each sample and blank.

     7.9  Field Blank Fortification Solution — An isooctane solution con-
          taining the internal standard at a concentration of 0.5 ng/uL, the
          surrogate compound at a concentration of 0.014 ng/uL, and the unlabeled
          2,3,7,8-TCDD at a concentration of 0.1 ng/uL.  Mix 100 uL with 1.5 raL
          of acetone before adding to each field blank.

   • 7.10  Recovery Standard Solution — An isooctane solution containing the
          recovery standard  ^Ci2-l,2,3,4-TCDD at a concentration of 10 ng/uL.

          7.10.1 ""For samples to be analyzed using Alternative One CC Solu-
                  tions, the recovery standard   Ci2-l,2,3,4-TCDD is used at a
                  concentration of 10 ng/uL.

          7.10.2  For samples to be analyzed using Alternative Two CC solutions
                  as standards, the recovery standard   C^2~1,2,3,4-TCDD must:
                  be diluted before use; this is done by adding 100 uL of
                  isooctane to a measured 1.0 mL of the 10 ng/uL   Cj2-l,2,3,4-
                  TCDD solution.

8.  SAMPLE PRESERVATION AND HANDLING

    8.1  Chaln-of-custody Procedures (see Exhibit G)

     8.2  Sample Preservation

          8.2.1  Soil Samples;  When received, each sample will be contained in
                 a 1-pint glass jar surrounded by vermiculite in a sealed metal
                 paint can.  Until a portion is to be removed for analysis,
                 store the sealed paint cans in a locked limited-access area
                 where ambient temperature is maintained above freezing.  After
                 a portion is removed for analysis, return the unused portion
                 of sample to its original containers and store as stated
                 above.  Do not freeze samples; they may contain sufficient
                 water to break the sample jar  If frozen.

          8.2.2  Water Samples;  Each water sample received will consist of
                 two  (2) 1 liter (or quart) amber glass  bottles.  Samples..-
                 may  be  iced or refrigerated at 4°C  from the time of
                 collection until extraction.   Do not  freeze.  Samples ;.«ust. be
                 extracted within 10 days of VTSR.

         8.2.3   All  samples must be protected  from  light from the  time of
                 collection until extraction to prevent  photodecompositicn.


                                     D  -  14

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8.3  Sample Handling

     8.3.1  CAUTION:  Finely divided soils contaminated with 2,3,7,8-TCDD
                      are hazardous because of the potential for Inha-
                      lation or Ingestlon of particles containing 2,3,7,8-
                      TCDD.  Such samples should be handled In a confined
                      environment (i.e., a closed hood or a glove box).

     8.3.2  Pre-extraction Sample Treatment

            8.3.2.1 For the purpose of this contract a water sample Is
                    defined as a single phase system, the primary
                    component of which Is water.  This may Include
                    floating, suspended, and settled partlculate matter
                    In quantities that do not cause severe problems with
                    the extraction.   If sufficient partlculate matter Is
                    present to be considered a separate phase or It
                    causes severe extraction problems precede to Section
                    8.3.2.A.

            8.3.2.2 For the purpose of this contract a soil/sediment
                    sample Is defined as a single phase solid system
                    composed of soil or sediment.  It may contain
                    particulates such as stones, vegetation, etc. but
                    should not contain an obvious liquid phase.  If a
                    liquid phase Is  present, precede to Section 8.3.2.A.
            8.3.2.3 Homogenization — Although sampling personnel will
                    attempt to collect homogeneous samples, the contractor
                    shall examine each sample and judge if It needs fur-
                    ther mixing.   NOTE:  Contractor personnel have the
                    responsibility to take a representative sample
                   . aliquot this  responsibility entails efforts to make
                    the sample as homogeneous as possible.  Stirring is
                    recommended when possible.

            8.3.2,A Centrifugation — If a soil or water sample contains
                    more than one phase, contact your DPO to determine
                    which phase(s) should be analyzed.  If the sample
                    contains obvious aqueous/solid phases, centrifuge It
                    to separate liquid and solid phases (an organic
                    phase is beyond the scope of this method, contact
                    your DPO for instructions).  Place the entire sample
                    In suitable centrifuge bottle(s) and centrifuge'.for
                    30 minutes at AGO x G.  Remove bottle(s) from
                    centrifuge and decant the aqueous phase to be :  . '.
                    analyzed as a water sample.  Mix solid layer
                    with stainless steel spatula and remove a portion co
                    be weighed and analyzed as a soil/sediment sample.
                                D - 15

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                          Return the remaining solid portion to original sample
                          bottle and store.
                          CAUTION:  A phase not analyzed may contain TCDD and
                                    should be handled and disposed of
                                    appropriately.
9.   CALIBRATION
     9.1  Two types of calibration procedures are required.  One type, initial
          calibration, is required before any samples are analyzed for TCDD,
          and is required intermittently throughout sample analyses as dictated
          by results of routine calibration procedures described below.  The
          other type, routine calibration, consists of analyzing the column
          performance check solution and concentration calibration solution #1
          (Section 7.6).  No samples are to be analyzed until acceptable cali-
          bration as described in Section 9.2 and 9.3 is demonstrated and
          documenFed.

     9.2  Initial Calibration

          9.2.1  Concentration calibration solutions — the four solutions
                 described in Section 7.6 are required.

          9.2.2  Inject an appropriate aliquot of the performance check
                 solution (CAUTION:  See Section 6.1.1) and acquire selected-
                 ionmonitoring (SIM) mass spectral data using the MS operating
                 conditions specified in Section 9.2.4.  Determine GC operating
                 conditions necessary to achieve separation described in
                 Section 9.2.6.1.

          9.2.3  Determine valley percent as described in Section 9.2.6.1 and
                 the m/z ratio according to the criteria in Section 9.2.6.2.
                 If the valley percent and/or m/z ratios are outside require-
                 ments, corrective action to meet the criteria must be taken
                 (as described in Section 6.1.1) before further sample analyses
                 are performed.

          9.2.4  Using the same GC conditions that produced acceptable results
                 with the performance check solution, analyze a 2-uL or other
                 appropriate aliquot (as described in Section 6.1.1) of each of
                 the four concentration calibration solutions with the
                 following MS operating parameters.

                 9-2.4..1  Acquire selected-ion-monitoring data for m/z 2:3S -
                          320, 322, 328, 332 and 334.

                 9.2.4.2  Total cycle time for data acquisition must be'
-------
       9.2.4.4  Use the same data acquisition time for each of the
                six Ions being monitored.

9.2.5  Repeat Section 9.2.4 two times to produce triplicate data sets
       for each solution.  NOTE: CC solutions should be analyzed In
       either random order or in order of Increasing concentration to
       avoid biasing the calibration.

9.2.6  The Laboratory must not proceed with analysis before deter-
       mining and documenting acceptable calibration with the
       following criteria:

       9.2.6.1 GC Column Performance

               9.2.6.1.1  The valley between 2,3,7,8-TCDD and the
                          peaks representing all other TCDD isomers
                          must be resolved with a valley £25%.
                          Valley (Z) = x/y X 100, when y is peak
                          height of 2,3,7,8TCDD, x is measured as
                          shown in Figures 2 and 3 at the end of this
                          Exhibit.  The peak representing 2,3,7,8-
                          TCDU shall be labeled and identified as
                          such on the chromatograms.

               9.2.6.1.2  Ratio of integrated ion current for m/z 320
                          to m/z 322 for 2,3,7,8-TCDD must be X).67
                          and £0.90.

               9.2.6.1.3  Ratio of integrated ion current for m/z 332
                          to m/z 334 for l3C12-2,3,7,8-TCDD must be
                          X).67 and £0.90.

       9.2.6.2  Calibration solutions must meet the following
                criteria:
                9.2.6.2.1 MS sensitivity — signal-to-noise (S/N)
                          ratio (Section 3.10) of >2.5 for m/z
                          259, 320,and 322
                          TCDD and 328 for
                          >10 for m/z 332 and
                          TCDD.
,1V/  OJL  /t..J  XUL  III/ f,
 for  unlabeled  2,3,7,8-
 37Cl4-2,3,7.8-TCDD and
md 334  for I3C12-2,3,7,8-
                9.2.6.2.2 The  ratio of  integrated  ion current  for m/z
                          320  to m/z  322  for 2,3,7,8-TCDD must be
                          X).67 and <0.90.

                9,2.6.2.3 The  ratio of  integrated  ion current  foe. m/z
                          332  to ra/z  334  for 13C12-2,3,7,8-TCDD'must
                          be >0.67 and  <0.90.
                            D -  17

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 9.2.6.3  Calculate the response factor for unlabeled 2,3,7,8-TCDD
          relative to 13C122,3,7,8-TCDD:
                                 V" *
                      RRFn  =  	
        Where  Ax  -  the sura of integrated ion abundances of m/z
                      320 and m/z 322 for unlabeled 2,3,7,8-TCDD,

              A*s  =  the sura of integrated abundances of m/z
                      332 and m/z 334 for 13C12-2,3,7,8-TCDD,

              Qlg  =  quantity of 13C12-2,3,7,8-TCDD, and

               Qx  =  quantity of unlabeled 2,3,7,8-TCDD
                      injected.

              RRF is a diraenstonless number; units used to
              express quantities must be consistent.

9.2.6.A  Calculate the response factor for 13C12-2,3,7,8-TCDD
         relative to 13C12-1,2,3,4-TCDD:

                 Ais - Qrs
        Where Ars
The sum of the integrated ion abundance of
m/z 332 and m/z 334 for 13C12-1,2,3,4-TCDD
              Qrs  =  Quantity of 13C12-1,2,3,4-TCDD Injected
                      Als and QIS are as in Section 9.2.6.3.

 9.2.6.5  Response Factor Criteria:

          9.2.6.5.1  Calculate the mean RRF and  its percent relative
                     standard deviation (%RSD) from.triplicate
                     analysis of each of 4 concentration solutions
                     for unlabeled 2,3,7,8-TCDD  and 1JC12-TCDD.

                            Standard  Deviation
                  %RSD  =   	  x 100
                               Mean  RRF
                      D - 18

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                     9.2.6.5.2  The variation of the RRF calculated for
                                unlabeled 2,3,7,8-TCDD at each
                                concentration level must not exceed 10%
                                RSD.

                     9.2.6.5.3  Calculate the mean and ZRSD of the 4 mean
                                 IPs for unlabeled 2,3,7,8-TCDD and for
                                  C12-TCDD.
                                                                13,
                     9.2.6.5.4  The %RSD of the 4 mean RRFs for   C12~
                                2,3,7,8TCDD should not exceed 10Z RSD.

                     9.2.6.5.5  The ZRSD of the 4 mean RRFs for unlabeled
                                TCDD must not exceed 10Z RSD.

                     9.2.6.5.6  The mean of the mean RRFs for each com-
                                pound must be used for concentration
                                calculations.
                     9.2.6.5.7
The concentration curves must be plotted
(RRF vs concentration) for enclosure in
the deliverables package.
9.3  Routine Calibration
     9.3.1  Inject an appropriate aliquot (CAUTION:  See Section 6.1.1)
            of the performance check solution (Section 7.7) and acquire
            selected ion monitoring mass spectral data for m/z 259, 320,
            322, 328, 332, and 334 within a total cycle time of <1.5
            seconds.  Acquire at least five data points for each GC peak
            and use the same data acquisition time for each of the six
            ions being monitored.  NOTE:  The same data acquisition para-
            meters previously used to analyze concentration calibration
            solutions during initial calibration must be used for the
            performance check solution.  The column performance check
            solution must be run at the beginning and end of each 12-hour
            period, if the contractor laboratory operates during consecu-
            tive 12-hour periods (shifts), analysis of the performance
            check solution at the beginning of each 12-hour period and at
            the end of the final 12-hour period is sufficient,

     9.3.2  Determine and document acceptable column performance as
            described in Section 9.2.6.1.

     9.3.3  Inject 2 uL of concentration calibration solution #1 which
            contains 0.2 ng/uL of unlabeled 2,3,7,8-TCDD once at the
            begininning of each  12-hour period.  Using the same GC'tfS/DS
            conditions as used in Section 9.3.1, acquire data for m/z
            259, 320, 322, 328,  332 and 334.  Determine and document
            acceptable calibration as described below.
                                 D - 19

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                 9.3.3.1  MS sensitivity — signal-to-noise (S/N) ratio (Sec-
                          tion 3.8) of >2;5 for tn/z 259, 320, 322,and 328 for
                          unlabeled 2,3,7,8-TCDD and 37Cl4-2,3,7,8-TCDD and >10
                          for ra/z 332 and 334 for UC^-2,3,7,8-TCDO is
                          required.  The ratio of integrated ion current for
                          m/z 320/322 must be XJ.67 and <0.90.

                 9.3.3.2  Measured response factor for unlabeled 2,3,7,8-TCDD
                          relative to 13Cl2-2,3,7,8-TCDD must be within .+10% of
                          the mean value established (Section 9.2.6.5.3) by
                          initial analyses of the concentration calibration
                          solutions.

         9.3.4  Further sample analyses must not be performed if the criteria
                in Section 9.3.2 and 9.3.3 are not met.  Possible remedies are
                listed in Section 9.3.5.  Following corrective action,  a
                'routine calibration must be performed and criteria listed in
                Section 9.3.3 must be met before further analysis of samples is
                performed; if the routine calibration does not meet criteria
                a new initial calibration must be performed.

         9.3.5  Remedial actions shall be taken by Contractor if criteria are
                not met.  Possible remedies are:

                9.3.5.1  Check and adjust GC and/or MS  operating conditions.

                9.3.5.2  Replace GC column (performance of initial calibration
                         procedures are required if acceptance criteria for
                         continuing calibration are not met).

                9.3.5.3  Tune MS for greater or lesser resolution.

                9.3.5.4  Calibrate MS mass scale.

                9.3.5.5  Prepare and analyze new performance  check solution.

10.  QUALITY CONTROL

     See Exhibit E for QA/QC Requirements.

11.  PROCEDURES

     11.1 Soil Sample Extraction

         11.1.1  CAUTION:  See Section 5 for safety guidelines and recommendations.

         11.1.2  Jar extraction.  NOTE: Extremely wet samples may require
                 centrifuging to remove water before addition of sodium
                 sulfate (see Section 8.3.2.2).
                                     D - 20
Rev. 8/87

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11.1,2.1  Accurately weigh to three significant figures a
          10 g (+0.5 g) portion of the wet soil or sediment
          sample, and transfer It to the extraction jar.

11.1.2.2  Note:   Additional QC samples are required as speci-
          fied In exhibit E.  These are processed as described
          In this section with the following exceptions:

               a.  Laboratory Method Blank - Perform all steps
                   In the analytical procedure but substitute
                   an aliquot of sodium sulfate for the soil/
                   sediment sample.

               b.  Fortified Field Blank - Perform all steps
                   In the analytical procedure, but spike the
                   designated sample with 1.5 mL of the acetone
                   dilution of the field blank fortification
                   solution (Section 7.9) rather than the sample
                   fortification solution.

11.1.2.3  Add 1.5 mL of the acetone dilution of the sample
          fortification solution (Section 7.8) to the soil or
          sediment in the extraction jar.  Add small portions
          of the solution at several sites on the surface of
          the soil or sediment.

11.1.2.4  Add 20 g of purified anhydrous sodium sulfate, and
          mix thoroughly using a stainless steel spoon or
          spatula.

11.1.2.5  Allow the mixture of soil and sodium sulfate to set
          for 2 hours at ambient temperature; mix again,
          break all visible lumps, and allow to set for at
          least A more hours.

11.1.2.6  Mix again and add 20 mL of methanol; mix again and
          add 150 mL of hexane.

11.1.2.7  Place the extraction jajr containing the soil,
          sodium sulfate and solvents in  the shaker and shake
          for at least 3 hours.

11.1.2.8  Remove the jar from the  shaker  and allow all  solids to
          settle.  Decant the solvent through a glass funnel
          containing hexane-rinsed filter paper into a  clean
          Kuderna-Danish apparatus.  Rinse  the jar, solid
          sample residue, and  filter residue with four :>-ml.
          portions of hexane.
                      D  -  21

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           11.1.2.9  Concentrate the extract volume to approximately 2
                     to 3 mL with a Kuderna-Danlsh apparatus.   NOTE:
                     Glassware used for more than one sample must be
                     carefully cleaned between samples to prevent cross
                     contamination (see Section 6.5).

           11.1.2.10  Rinse the evaporator flask with 3 mL portions of
                      hexane; transfer each rinse to the  concentrator
                      tube.  Between additions of hexane rinse, reduce the
                      extract volume in the concentrator tube enough to
                      allow addition of another 5 mL volume of rinse.  To
                      reduce the volume, place the concentrator tube in a
                      water bath adjusted to operate at 50°C and position
                      the tube so that the surfaces of the extract and the
                      water are at about the same level.  Evaporate the
                      solvent with a stream of nitrogen with the tip of the
                      nitrogen delivery tube 2 cm above the solution.

           1111.2.11  After the final rinse has been added, reduce the
                      extract volume to approximately 1 mL.  Proceed to
                      section 11.3.2.  If further processing will be
                      delayed, quantitatively transfer the extract to a
                      Teflon sealed screw-cap vial and store refrigerated
                      and protected from light.

11.2  Water Sample Extraction

      Caution:  When using this method to analyze for 2,3,7,8-TCDD, all
                of the following operations'should be performed in a
                limited access laboratory with the analyst wearing full
                protective covering for all exposed skin surfaces.  See
                Section 5.

    11.2.1  Mark  the water meniscus on the side of the sample bottle for
            later determination of the sample volume.  Pour the entire
            sample into a 2 L separatory funnel.  Note: a continuous
            liquid-liquid extractor may also be used.

            11.2.1.1.  NOTE:  Additional QC samples are required
                       as specified in exhibit E.  These are
                       processed as described  in  this section with
                       the following exceptions:

                           a.  Laboratory Method  Blank  - Perform all  steps
                               In  the analytical  procedure  but  substitute
                               an  aliquot of  reagent  water  for  the .«?r».ple.

                           b.  Fortified  Field Blank -  Perform all'steps
                                in  the analytical  procedure,  but spike
                               the designated  sample  with  1.5  mL of. th-»
                               acetone  dilution  of  the  field blank forti-
                               fication solution  (Section  7.9) rat^tc than
                               the sample fortification

                                 D  - 22

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 11.2.2  Add 1.5 mL of the acetone dilution of the sample fortification
         solution containing 50 ng of the internal standard and 1.4 ng
         of the surrogate compound to the sample In the separatory
         funnel.

 11.2.3  Add 60 mL of raethylene chloride to the sample bottle, seal,
         and shake 30 seconds to rinse the Inner surface.  Transfer the
         solvent to the separatory funnel and extract the sample by
         shaking the funnel for 2 minutes with periodic venting to
         release excess pressure.  Allow the organic layer to separate
         from the water phase for a minimum of 10 minutes.  If the
         emulsion Interface between layers Is more than one-third the
         volume of the solvent layer, the analyst must employ mechan-
         ical techniques to complete the phase separation.  The optimum
         technique depends upon the sample, but may include stirring,
         filtration of the emulsion through glass wool, centrifugation,
         or other physical methods.  Collect the methylene chloride
         extract in a 250 mL Erlenmeyer flask.

11.2.4   Add a second 60 mL volume of methylene chloride to the sample
         bottle and repeat the extraction procedure a second time,
         combining the extracts in the Erlenmeyer flask.  Perform a
         third extraction in the same manner.

11.2.5   Assemble a Kudema-Danlsh (K-D) concentrator by attaching a 10
         mL concentrator tube to a 500 mL evaporative flask.  Pour the
         combined extracts into the K-D concentrator through a drying
         column containing about 6 cm of sodium sulfate.  Rinse the
         Erlenmeyer flask with 25-30 mL methylene chloride and pour it
         through the drying column, rinse the drying column with an
         additional 10 ml methylene chloride.  All rinses are added to
         the concentrator.

11.2.6   Add one or two clean boiling chips to the evaporative flask
         and attach a three-ball Snyder column.  Prewet the Snyder
         column by adding about 1 mL of methylene chloride to the top.
         Place the K-D apparatus on a hot water bath (60 to 65°C) so
         that the concentrator tube is-partially immersed in the hot
         water, and the entire lower rounded surface of the flask Is
         bathed with hot vapor.  Adjust the vertical position of the
         apparatus and the water temperature as required to complete
         the concentration in 15-20 minutes.  At the proper rate of
         distillation, the balls in the column will actively chatter
         but the chambers will not flood with condensed solvent,  .When
         the apparent volume of liquid reaches 1 mL, remove the -K-D
         apparatus and allow it to drain and cool for at least 10-
         minutes.

11.2.7   Momentarily remove the Snyder column, add 50 mL of hexark mnd
         a new boiling chip, and reattach  the Snyder column.  Raise the
                             D - 23

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              temperature of the water bath to 85 to 90°C.  Concentrate the
              extract as in section 11.2.6 except use hexane to prewet the
              column.  Remove the Snyder column and rinse the flask and Its
              lower joint Into the concentrator tube with 1 to 2 mL of
              hexane.

     11.2.8   Add a clean boiling chip to the concentrator tube and attach a
              two-ball micro-Snyder column.   Prewet the column by adding
              about 1 mL of hexane to the top.  Place the micro-K-D
              apparatus on the water bath so that the concentrator tube Is
              partially immersed In the hot water.  Adjust the vertical
              position of the apparatus and the water temperature as
              required to complete the concentration In 5 to 10 minutes.
              At the proper rate of distillation the balls of the column
              will actively chatter but the chambers will not flood.  When
              the apparent volume of the liquid reaches about 0.5 mL,
              remove the K-D apparatus and allow It to drain and cool for
             ~at least 10 minutes.  Remove the mlcro-Snyder column and
              rinse its lower joint into the concentrator tube with 0.2 mL
              hexane.  Proceed to section 11.3.2.  If further processing
              Is to be delayed, the extract should be quantitatively
              transfered to a Teflon sealed screw-cap vial and store
              refrigerated and protected from light.

     11.2.9  Fill the sample bottle with water to the mark and measure the
             volume to the nearest 10 mL in a 1 L graduated cylinder.
                                                     1
11.3  Column Chromatograph

     11.3.1 Column Preparation

            11.3.1.1  Column 1:  Place 1.0 g of silica gel into a 1 cm x
                      20 ,cm column and tap the column gently to settle
                      the silica gel.  Add 2 g sodium hydroxide-impregnated
                      silica gel, 1 g silica gel, 4.0 g of sulfuric acid-
                      impregnated silica gel, and 2 g silica gel.  Tap
                      column gently after each addition.

            11.3.1.2  Column 2:  Place 6.0 g of alumina into a 1 cm x 30
                      cm column and tap the column gently to settle the
                      alumina.  Add a 1-cra layer of purified sodium
                      sulfate  to the top of the alumina.

            11.3.1.3  Add hexane to each column until the packing 1<3 free
                      of channels and air bubbles.  A small positive
                      pressure (5 psi) of clean nitrogen  can be used if
                      needed.

     11.3.2  Quantitatively  transfer  the hexane  sample extract from.rli°
             concentrator tube to  the top of  the  silica gel  in Column  1.
             Rinse  the  concentrator  tube with two  0.5 mL  portions cL
             hexane;  transfer  rinses  to Column 1.             	

                                  D -  24

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     11.3.3  With 90 mL of hexane, elute the extract from Column 1 directly
             Into Column 2 containing alumina and sodium sulfate.

     11.3.4  Add 20 mL of hexane to Column 2 and elute until the hexane
             level Is just below the top of the sodium sulfate; discard the
             eluted hexane.

     11.3.5  Add 20 mL of 20% methylene chloride/80% hexane (volume/volume)
             to Column 2 and collect the eluate.

     11.3.6  Reduce the volume of the eluate with a gentle stream of
             filtered dry nitrogen.  When the volume of the eluate Is about
             1 to 2 mL, transfer the eluate to the Carbopack column
             (Section 11.4.A).  Rinse the eluate container with two 0.5
             mL portions of hexane; transfer the rinses to the Carbopack
             column.   CAUTION:  Do not evaporate the sample extract to
             dryness.  NOTE:  The Carbopack cleanup is not required for
             water samples unless needed to meet detection sensitivity
             criteria.

11.4  Carbopack Column Chromatography Procedure

     11.4.1  Thoroughly mix 3.6 g of Carbopack C (or equivalent) with
             16.4 g of Celite 545 (or equivalent) in a 40 mL vial and
             activate by heating in an oven at 130°C for 6 hours.
             Store in a desiccator.  CAUTION:  Check each new batch of
             mixed Carbopack/Celite to ensure TCDD recovery of >50%.
             Subject the low level concentration calibration solution to
             this procedure and measure the quantity of labeled and
             unlabeled 2,3,7,8-TCDD.

     11.4.2  Insert a small plug of glass wool into a disposable
             pipet approximately 15 cm long by 7 mm O.D.  Apply
             suction with a vacuum aspirator attached to the pointed
             end of the pipet, and add the Carbopack/Celite mixture
             until a 2 cm packing is obtained.

     11.4.3  Pre-elute the column with:

             11.4.3.1  2 mL toluene

             11.4.3.2  1 mL of mixture of 75% (by volume) methylene
                        chloride, 20% methanol and 5% benzene

             11.4.3.3  1 mL of 50% (by volume) cyclohexane and 50%
                        methylene chloride

             11.4.3.4  2 mL of hexane

     11.4.4  While the column  is still wet with hexane add the sample
             extract  from  section  11.2.6.  Elute the column with  the
             following sequence of solvents and discard the elaates.

                                 D - 25

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             11.4.4.1   2 mL hexane

             11.4.4.2   1 mL of 50Z (by volume)  cyclohexane  and  50Z  tnethylene
                       chloride

             11.4.4.3   1 mL of 75% (by volume)  methylene chloride,  20Z
                       methanol and 5Z benzene

     11.4.5  Elute with 2 mL of toluene and collect the elutate,  which
             contains  the TCDD.  Transfer the rinses to a 1-mL  amber mini-
             vial with conical reservoir with further concentration as
             necessary.  CAUTION:  Do not evaporate the sample  extract to
             dryness.

     11.3.6  Store the sample extract in the dark at 4°C until  just before
             GC/MS analysis.

11.5  GC/MS Analysis

     11.5.1  Remove the sample extract or blank from storage and allow it
             to warm to ambient laboratory temperature.  With a stream of
             dry, filtered nitrogen, reduce the extract/blank volume to
             near dryness.  Immediately before  GC/MS analysis,  add  5 uL of
             the 10 ng/uL recovery standard solution and adjust the extract
             or blank volume to 50 uL with isooctane.

     11.5.2  Inject a 2-uL aliquot of the extract into the GC,  operated
             under conditions previously used (Section. 9) to.produce
             acceptable results with the performance check solution.

     11.5.3  Acquire mass spectral data for the following selected
             characteristic ions:  m/z 259, 320, and 322 for unlabeled
             2,3,7,8-TCDD: m/z 328 for 37Cl4-2,3.7,8-TCDD;  and  m/z  332
             and 334 for 13C12~2,3,7,8-TCDD and I3C12~1,2,3,4-
             TCDD.  Use the same data acquisition time and MS operating
             conditions previously used (Section 9.2.6) to determine
             response factors.

11.6  Identification Criteria.  NOTE: Refer to Exhibit E, Section 7,  for
      application of identification criteria.

     11.6.1  Retention  time (at maximum peak height) of the sample  com-
             ponent must be within 3 seconds of the retention time  of
             the 13C12-2,3,7,8-TCDD.  Retention times are required  for
             all chromatograms,  but  scan  numbers  are optional.  These
             parameters should be printed next to  the appropriate peak.

     11.6.2  The integrated ion  currents  detected  for m/z 259, 320, ana
             322 must maximize simultaneously.  If there are peaks  ths.t
             will affect  the  maximization or quantitation of peaks  of
             Interest,  attempts  should be made to  narrow the scan window
             to  eliminate the Interfering peaks.   This  should  be reported
             on  a separate chroma tog rain.                               ' •

                                  D  - 26

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         11.6.3  The integrated ion current for each analyte ion (m/z 259,
                 320 and 322) must be at least 2.5 times background noise and
                 must not have saturated the detector; internal standard ions
                 (m/z 332 and 334) must be at least 10 times background noise
                 and must not have saturated the detector.

         11.6.4  Abundance of integrated ion counts detected for m/z 320 must
                 be >67% and <90% of integrated ion counts detected for m/z
                 322.

         11.6.5  Abundance of integrated ion counts detected for m/z 332 must
                 be >b7% and <90% of integrated ion counts detected for ra/z
                 334.

         11.6.6  The recovery of the internal standard 13C12-2,3,7,8-TCDD should
                 be within a 40 percent to 120 percent recovery window.  This
                -is an advisory limit only, an action window may be set when
                 sufficient data is available.

12. CALCULATIONS

    12.1 Concentration

         12.1.1  Calculate the concentration of 2,3,7,8-TCDD using the formula:

                                    Ax • Qis
                           Q  =   ~""~     ————
                                  Ais . RFn . W

                where      Cx  -  2,3,7,8-TCDD concentration in ug/kg or ug/L

                           AX  -  the sum of integrated ion abundance
                                  detected for m/z  320 and 322

                          Ais  =  the sum of integrated ion abundances
                                  detected for m/z  332 and 334
                                  (characteristic ions of
                                    C12-2,3,7,8-TCDD,  the internal
                                  standard)

                          QZS  =  quantity (in ng)  of  13C12-2,3,7,8-TCDD added
                                  to the sample before extraction

                               =  calculated mean response factor for
                                  unlabeled 2,3,7,8-TCDD relative to
                                    C12-2,3,7,8-TCDD

                            W  =  weight (in g) of  wet soil or sediment sample
                                  or volume of water extracted (in mL).
                                     D - 27                            Rev. a/87

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     12.1.2  If the calculated concentration of unlabeled 2,3,7,8-TCDD
             exceeds 100 ug/kg for soil/sediment or 1  ug/L for water,  which
             Is the maximum concentration of the concentration calibration
             solutions, the linear range may have been exceeded,  and a
             smaller aliquot of that sample must be analyzed.   Accurately
             weigh to three significant figures a 1-g  aliquot  of  the wet
             soil/sediment or measure a 100 mL aliquot of water.   Add the
             1.5 raL acetone dilution of 100 uL of the  sample fortification
             solution (Section 7.8), just as for the larger sample aliquot.
             Extract and analyze.

             12.1.3  Calculate the concentration of the internal  standard
                     i Cj2~2>3,7,8-TCDD using the formula:
                             Ars
             where
                     C,   -  concentration of 13C12-2,3,7,8-TCDD in ug/kg
                      is          ,               **•
                             or ug/L

                     Ais  =  sum of  integrated Ion abundances for m/z
                             332 and 334 for 13C12-2,3,7,8-TCDD
                             sum of integrated ion abundanc
                             332 and 334 for 13C12-1,2,3,4-
abundances for m/z
        TCDD
                     Qrs  =  quantity (in ng) of 13C12-l,2,3,4-rTCDD added
                             to the sample before injection

                     RF                                          13
                       i  -  calculated mean response factor for   ^12"
                             1,2,3,4-TCDD

                       W  =  weight (in g) of wet soil or sediment
                             sample or volume of water extracted (in
                             mL).

12.2 Estimated Maximum Possible Concentration — For samples in which no
     unlabeled 2,3,7,8-TCDD was detected, calculate the estimated
     maximum possible concentration, which is the concentration required
     to produce a signal with peak height of 2.5 times the backgrot-nrf  .
     signal level.  The background level is determined by measuring tne
     range of the noise (minimum to maximum) for either m/z 320 or.322
     in the appropriate region of the SICP (as defined in section !'
     3.11), multiplying that noise height by 2.5, and relating the.
     product height to an estimated concentration that would produce
     that product height.

     Use the formula:
                                  D - 28

-------
                          2.5  •  Hx
                  MPC =
                           "is  -  RFn -  W
     where  MPC  =  estimated maximum possible concentration of  unlabeled
                    2,3,7,8-TCDD required to produce Ux in ug/kg or  ug/L

             Hx  =  peak height for either ra/z 320 or 322 within +_ 5 scans
                    of the internal standard peak used to measure Hls

            His  =  peak height of the appropriate ion characteristic of
                    the internal standard m/z 332 when m/z 320 is used
                    to determine Hx, and m/z 334 when ra/z 322 is used
                    to determine Hx

            -Qis, RF and W retain the definitions previously stated in
            Section 12.1.1

12.4  The relative percent difference (RPD) is calculated as follows:
      (See Section 5.1.1, Exhibit E.)

      RPD  - |  Si _ S2 |  x 100 .  -        |sl   S2 |  x 100

             Mean Concentration             Sl + S2

                                               2

      **1 and S2 represent sample and duplicate sample results.

12.6  Percent Recovery of 2,3,7,8-TCDD in spiked field blanks =

      concentration found
      	x 100
      concentration added

12.7 . Percent Recovery of internal standard, 13C12-2,3,7,8-TCDD   =

   ... concentration found
      	  x 10Q
      concentration added
12.8  Standard deviation  =  S  =
J* <*i.:.*>!
 Vi=l  N - 1
12.9  Percent relative standard deviation  =

      Standard Deviation              S
      	   x 100  =   -  x 100
            Mean                      X
                                 D - 29                           Rev. 8/87

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                    TABLE 1.  OPERATING CONDITION GUIDELINES
Column coating

Film thickness

Column dimensions

Helium* linear velocity


Initial temperature

Initial time

Temperature program
2,3,7,8-TCDD retention
 time
SP-2330

0.2  urn

60 m x 0.24 mm

28-29 cm/sec
at 240°C

70°C

4 min

Rapid increase to 200°C
200°C to 240°C
at 4°C/min

24 min
CP-SIL 88

0.22 urn

50 m x 0.22 mm

28-29 cm/sec
at 240°C

45°C

3 min

Rapid increase to 190°C
190°C to 240°C
at 5°C/min

26 min
*Hydrogen is an acceptable carrier gas.
                                     D -  30

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          TABLE 2.  COMPOSITION OF CONGENTRATION CALIBRATION SOLUTIONS



                                Alternative One

                                     (TCDD)
Solution #
CC1
CC2
CC3
CC4
Unlabeled
2,3,7,8 37ClA-2,3,7,8
0.2 ng/uL 0.028 ng/uL
1.0 0.028
5.0 	
20.0 	
13C12-2,3,7,8
1.0 ng/uL
1.0
1.0
1.0
13C12-1,2,3,4
0.6 ng/uL
0.6
0.6
0.6
                                Alternative Two

These are the final concentrations obtained.  All compounds except   Cl^-
2,3,7,8-TCDD, are in the same ratios as Alternative One but are 9% lower.

                                     (TCDD)
Solution if
CC1
CC2
CC3
r>f/.
Unlabeled
2,3,7,8
0.182 ng/uL
0.909
4.545
37C142,3,7,8
0.054 ng/uL
0.109
0.182
13C12-2,3,7,8
0.909 ng/uL
0.909
'0.909
13r _,
c12-i,
0.545
0.545
0.545
,2,3,4
ng/uL


                                      D  - 31

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D-34

-------
REFERENCES

1.  "Carcinogens-Working with Carcinogens," Department of Health, Education,
    and Welfare, Public Health Service, Centers for Disease Control, National
    Institute for Occupational Safety and Health, Publication No. 77-206, Aug.
    1977.

2.  "OSHA Safety and Health Standards, General Industry," (29CFR1910), Occupa-
    tional Safety and Health Administration, OSHA 2206 (Revised, January
    1976).

3.  "Safety in Academic Chemistry Laboratories," American Chemical Society
    Publication, Committee on Chemical Safety, 3rd Edition, 1979.

4.  Method 613, "2,3,7,8-Tetrachlorodibenzo-p-dioxin," Federal Register, 44
    (233) 69529, December 3, 1979.

5.  "Quality Assurance Plan for 2,3,7,8-TCDD Monitoring Project," R. D. Kleopfer
    and C. J. Kirchmer, presented by the Division of Environmental Chemistry,
    American Chemical Society, Washington, D.C., September 1983.

6.  "Determination of 2,3,7,8-TCDD in Soil," R. D. Kleopfer, K. Yue, and W. W.
    Bunn, presented before the Division of Environmental Chemistry, American
    Chemical Society, Washington, D.C., September 1983.

7.  "Water Solubility of 2,3,7,8-Tetrachlorodibenzo-p-dioxin," Leland Marple,
    Robert Brunck, and Lewis Throop, Environmental Science and Technology,
    Vol. 20, No. 2, 180-182, 1986
                                      D -  35

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    EXHIBIT  E




QA./QC REQUIREMENTS

-------
                      Exhibit E - QA/QC Requirements


SUMMARY OF QC ANALYSES

1.  Initial and periodic calibration and instrument performance checks.

2.  Laboratory method blank analyses (Section 4.1 of QUALITY CONTROL); minimum
    of one blank per matrix shall be analyzed with each sample batch; an
    additional blank shall be analyzed when new reagents are used and with each
    set of samples rerun.

3.  Analysis of a batch of samples with accompanying QC analyses:

   .  3.1  Sample Batch — <24 samples, including field blank(s), rinsate
          sample(s) and any reruns generated by prior batch analyses.

          NOTE:  see Exhibit C, Section 3, if total samples exceed 24,
                 additional QC analyses are required.
     3.2  Additional QC Analyses Per Batch:
          Laboratory method blank for each matrix
          Duplicate sample analysis for each matrix

          TOTAL
1-2
1-2

2-4
4.  "Blind" QC samples may be submitted to contractor as an ordinary soil or
    sediment or water sample included among the batch of samples.  Blind
    samples include:

     4.1  uncontaminated soil or water,

     4.2  split samples,

     4.3  unlabeled duplicates, and

     4.4  performance evaluation samples.


QUALITY CONTROL

1.  Performance Evaluation Samples — Included among samples in some batches
    will be samples containing known amounts of unlabeled 2,3,7,8-TCDD.

2.  Performance Check Solution and Concentration Calibration Solutions

     2.1  At the beginning of each 12-hour period during which samples ire to
          be analyzed, an aliquot of the performance check solution and an
          aliquot of concentration calibration solution #1 shall be analyzed to
          demonstrate adequate GC and MS resolution and sensitivity, r.»st.ouse
          factor reproducibility, and mass range calibration.
                                     E - 1

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 2.2
These procedures are described in Section 9 o£ Exhibit D.  If any
required criteria are not met, remedial action must be taken
before any samples are analyzed.

To validate sample data, the performance check solution must be analyzed
at the end of each 12-hour period during which samples are analyzed.
      2.2.1  If the contractor laboratory operates only during one 12-hour
             period (shift) each day, the performance check solution must
             be analyzed twice (at the beginning and end of the 12-hour
             period) to validate .data acquired during the interim period.

      2.2.2  If the contractor laboratory operates during consecutive 12-hour
             periods (shifts), analysis of the performance check solution at
             the beginning of each 12-hour period and at the end of the
             final 12-hour period is sufficient.

 2.3  Results 'of at least two analyses of the performance check solution
      must be reported with sample data collected during a 12-hour period.

 2.4  Deviations from criteria specified for the performance check solution
      (Section 9.2.6.1, Exhibit D) invalidate all sample data collected
      between analyses of. the performance check solution, and samples shall
      be rerun (see Exhibit C).

The performance check mixture, concentration calibration solutions, and the
sample and field blank fortification solutions are to be obtained from
EMSL-LV.  However, if not available from EMSL-LV, standards can be obtained
from other sources, and solutions can be prepared in the contractor labora-
tory.  Concentrations of all solutions containing unlabeled 2,3,7,8-TCDD and
not obtained from EMSL-LV must be verified by comparison to the unlabeled
2,3,7,8-TCDD standard solution (concentration of 7.87 ug/roL) that is avail-
able from EMSL-LV.

Blanks

 4.1  Laboratory method blank — Perform all steps in the analytical
      procedure (Section 11, Exhibit D) using all reagents, standards,
      equipment, apparatus, glassware, and solvents that would be used
      for a sample analysis, using an aliquot of reagent water for the
      water blank and an aliquot of sodium sulfate for the soil blank.

      4.1.1  Except in the case noted below in Section 4.1 3, a laboratory
             method blank must contain the same amount of ^7Cl^-2,3,7,
             and ^C^^.S^.S-TCDD that is added to samples before
             extraction.

      4.1.2  Extract and analyze a laboratory method blank before any
             are extracted and analyzed.
                                 E - 2

-------
     4.1.3  Extract and analyze two laboratory method blanks before new
            solvents or reagents are used for sample extraction or for
            column chromatographic procedures.  Do not add any "Cl« —
            2,3,7,8-TCDD or 13C12-2,3,7,8-TCDD to one blank, to demon-
            strate that reagents contain no Impurities producing an ion
            current above the level of background noise for m/z 328, 332
            and 334.

     4.1.4  In addition to the specification in preceding section 4.1.2,
            extract and analyze a laboratory method blank for each matrix
            along with each batch of samples.

     4.1.5  Acceptable laboratory method blanks must not contain any
            signal at 320, 322, or 259 which is greater than 22 of the m/z
            332 response within +5 scans of the m/z 332 peak maximum.
            If the method blank that was extracted along with a batch of
            samples Is contaminated, the associated positive samples must
            be rerun.  (See Exhibit C.)

            4.1.5.1  If the above criterion is not met, check solvents,  .
                     reagents, apparatus, and glassware to locate and
                     eliminate the source of contamination before any
                     samples are extracted and analyzed.

            4.1.5.2  If new batches of reagents or solvents contain
                     interfering contaminants, purify or discard them.

4.2*  Field Blanks— Each.batch of samples contains a sample of uncontami-
            riated soil/sediment and/or water that is to be fortified with
            unlabeled 2,3,7,8-TCDD at a concentration of 1 ug/kg for soil
            or 10 ng/L for water before analysis.  In addition to that
            field blank, a batch of samples may Include a rinsate sample,
            that is a portion of solvent (usually trichloroethylene) that
            was used to rinse sampling equipment.  The rinsate is analyzed
            to assure that samples have not been contaminated by sampling
            equipment.

     4.2.1  Unfortified field blank •— Analyze with procedures used for
            environmental samples (Section 11, Exhibit D).  This blank may
            or may not be labeled as such (i.e., it may be a "blind" QC
            sample).

     4.2.2  Fortified (Spiked) Field Blank                                ••

            4.2.2.1  Weigh a 10-g or measure a 1 L aliquot of the specified
                    .field blank sample and add 1.5 mL of th1, acetone
                     dilution of the 100 uL of field blank fortification
                     solution which contains 0.1 ng/uL of unlabeled
                     2,3,7,8-TCDD, 0.5 ng/uL of 13C12-2,3,7,8TCDD, and
                     0.014 ng/uL of 37Cl4-2,3,7,8-TCDD.
                                E - 3

-------
                 4.2.2.2  Extract with the appropriate method from Exhibit D
                          and analyze a 2-uL aliquot.

                 4.2.2.3  Calculate the concentration (Section 12.1, Exhibit
                          D) of unlabeled 2,3,7,8-TCDD, and the Internal
                          standard recovery (Section 12.1.3, Exhibit D) of
                          the measured concentration.

          4.2.3  Rlnsate Sample
                 4.2.3.1
                 4.2.3.2
                 4.2.3.3
                 4.2.3.4
                 4.2.3.5
                 4.2.3.6
5.  Duplicate Analyses
To a 100-mL aliquot (or entire sample if less than
100 mL Is provided) of equipment rinse solvent
(trichloroethylene-rlnsate sample), add 1.5 mL of the
acetone dilution of 100 uL of the sample fortification
solution which contains 0.5 ng/uL of 13C12-2,3,7,8-TCDD
and 0.014 ng/uL of 37Cl4-2,3,7,8-tCDD.

Using a Kuderna-Danish apparatus, concentrate the
volume to approximately 5 mL.

Transfer the total 5-mL concentrate in 1-mL portions to
a 1 mL-amber mini-vial, reducing volume as necessary
with a gentle stream of dry nitrogen.

Rinse container with two 0.5 mL portions of hexane and
transfer rinses to the 1-mL amber mini-vial.

Just before analysis, reduce volume to near dryness,
add 5 uL of the recovery standard solution and make
to a final volume of SO uL with isooctane.  (Column
chromatography is not required.)

Analyze an aliquot with the same procedures used to
analyze samples (Section 11.5, Exhibit D).
    5.1  Laboratory Duplicates — In each batch of samples, locate the sample
         specified for duplicate analyses and analyze a second sample aliquot.
         If no .sample is specified for duplicate analysis the laboratory shall
         select one and analyze it in duplicate.  The sample chosen must not be
         the field blank.

         5.1.1  Results of laboratory duplicates must agree within 50% relative
                difference (difference expressed as percentage of the mean).,
                If the RPD is >50Z, Contractor shall immediately contact th*- '..'
                Sample Management Office for resolution of the problem.  Report;
                all results,                                                 • •  '
                                      E - 4

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                   RPD
      - S2[ x 100

Mean Concentration
- S2| x 100

sl + S2
            Where S^ and S2 represent sample and duplicate sample results.

     5.1.2  Recommended actions to help locate problem:

            S.I.2.1  Analyze an aliquot of the performance check standard to
                     verify satisfactory instrument performance (Section 9,
                     Exhibit D),

            5.1.2.2  If possible, determine that no error was made while
                     weighing or measuring sample aliquots.

            5.1.2.3  Review analytical procedures with performing laboratory
                     personnel.
Identification criteria

6.1  If any of the four Initial identification criteria (Sections 11.6.1-
     11.6.4, Exhibit D) are not met, the sample is reported not to contain
     unlabeled 2,3,7,8-TCDD at the maximum possible concentration limit
     (Section 12.2, Exhibit D).

6.2  When the' four initial identification criteria are met, but the fifth
     criteria, the isotopic abundance ratio for m/z 320 and 322 (Section
     11.6.4, Exhibit D) is not met, that sample is presumed to contain
     interfering contaminants.  Contractor shall, reextract, clean-up, and
     reanalyze the sample.

6.3  The recovery of the internal standard 13C12-2,3,7,8-TCDD should be
     within a 40 percent to 120 percent recovery window.  This is an
     advisory limit only, an action window may be set when sufficient data
     Is available.

Blind QC Samples — Included among soil and sediment or water samples may
be QC samples that are not specified as such to the performing laboratory.
Types that may be included are:

7.1  Uncontaminated Soil or Water.                                    .   ..

     7.1.1  If a false positive Is reported for this sample, the Contractor
            shall be required  to rerun the entire associated batch of cauples
            (see Exhibit C).                                          '.  " .

7.2  Split Samples — composited sample aliquots sent to more than one
     laboratory.

7.3  Unlabeled Field Duplicates — two aliquots of a composited sample.   ' '.

                                E - 5

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     7.4  Performance Evaluation Sample — soil/sediment or water sample
          containing a known amount of unlabeled 2,3,7,8-TCDD.

          7.4.1   If the performance evaluation sample result falls outside the
                  acceptance windows established by EPA, the Contractor shall be
                  required to rerun the entire associated batch of samples (see
                  Exhibit C).  NOTE:  EPA acceptance windows are based on
                  historical data results.
LABORATORY EVALUATION PROCEDURES

1.  On a continuing basis, the EPA Project Officer and/or designated represen-
    tatives may conduct an evaluation of the laboratory to ascertain that the
    laboratory is meeting contract requirements.  This section outlines the
    procedures which may be used by the Project Officer or his authorized
    representative in order to conduct a successful evaluation of laboratories
    conducting dibxin analyses according to this protocol.  The evaluation
    process consists of the following steps:  1} analysis of a performance
    evaluation (PE) sample, and 2) on-site evaluation of the laboratory to
    verify continuity of personnel, instrumentation, and quality assurance/
    quality control functions.  The following is a description of these two
    steps.

2.  Performance Evaluation Sample Analysis

    The PE samples are supplied by EMSL-LV to the EPA Regions who include them
    with the cases submitted to the laboratories.  The PE samples are sent
    in this manner to assure that they are processed and reported in a routine
    manner by laboratory personnel.  The EPA Region client will evaluate the
    results to verify that the laboratory is continuing to produce acceptable
    analytical results.  The acceptance windows provided by EMSL-LV are based
    on PE sample performance data and may be updated periodically as the size
    of the database increases.  The PE samples will be representative of the
    types of samples that will be subject to analysis under this contract.

3.   On-Site Laboratory Evaluation

     3.1  An on-site laboratory evaluation is performed to verify that the
          laboratory is maintaining the necessary minimum level In instru-
          mentation and levels of experience in personnel committed to the
          contract and that the necessary quality control/assurance activities
          are being carried out.  It also serves as a mechanism for discussing
          laboratory weaknesses Identified through routine data audits, PE  "
          sample analyses results, and prior on-site evaluation.

     3.2  The sequence of events  for the on-site evaluations  Is shown in
          Figure  I.  The Site Evaluation Sheet  (SES) (Figure 2) is used to  '••'
          document the results of the evaluation.
                                      E  -  6

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                              Figure 1                             E X A M P  L E

                  EVENT SEQUENCE FOR  SITE  EVALUATION


I.  HEETING WITH LABORATORY MANAGER AND PROJECT MANAGER

General discussion of purpose of site visit, purpose of analyses and current
contract award status.

II.  VERIFICATION OF PERSONNEL

Review qualifications of contractor personnel tn place and committed to
project (Section I, SES).

III.  VERIFICATION OF INSTRUMENTATION

Review equipment in place and committed to project (Section II, SES).  The
bidder must demonstrate adequate equipment redundancy to ensure capability to
perform required analyses In the required time.

IV.  QUALITY CONTROL PROCEDURES

    Walk through laboratory to review:

    1.   Sample reception and logging procedures
    2.   Sample and extract storage area,
    3.   Procedures to prevent sample contamination,
    4.   Security.procedures for laboratory and samples,
    5.   Safety procedures,
    6.   Conformance to written Standard Operating Procedures,
    7.   Instrument records and logbooks,
    8.   Sample and data control systems,
    9.   Procedures for handling and disposing of hazardous materials,
    10.  Glassware cleaning procedures,
    11.  Status of.equipment and its availability,
    12.  Procedures for data handling, analysis, reporting, and case file
         preparation and
 ;   13.  Chain-of-custody procedures.

V.  REVIEW OF STANDARD OPERATING PROCEDURES (SOPs)

Review SOPs with project manager to assure that the  laboratory understands
the dimensions and requirements of this program.                          ;•,  •.

VI.  IDENTIFICATION OF NEEDED CORRECTIVE ACTIONS                          -\ •  ";

Discuss with project manager, the actions needed to correct weaknesses identifled
during site inspection, PE sample analysis or production 'of reports  (hard •
copies and magnetic tapes) and documentation.  Determine how and when corrective
actions will be documented, how and when improvements will be demonstrated, and
the contractor employee responsible for corrective actions.
                                     E-7

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                                 Figure 2                        _E X A M P  L E


                     LABORATORY SITE EVALUATION SHEET (SES)
Laboratory:


Date:
Type of Evaluation:


Contract Number:


Contract Title:
Personnel Contacted:
                 Name                                      Title
Laboratory Evaluation Team:
                 Name                                      Ti tie
                                                       j
                                          E-8

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I.   Organization and Personnel  (Page 1  of 2)
                                                               EXAMPLE
ITEM
Laboratory or Project Manager (individual
responsible for overall technical effort):
Name:

GC/MS Operator:
Name:
Experience: 1 year minimum requirement per
appropriate ins eminent
GC/MS Spectral Interpretation Expert:
Name:
Experience: 2 years minimum requirement
Extraction Concentration Expert:
Name:
Experience: 6 months minimum requirement
Do personnel assigned to this project have the
appropriate educational background to success-
fully accomplish the objectives of the program?
Do personnel assigned to this project have the
appropriate level and type of experience to
successfully accomplish the objectives of this
program?
Is the organization adequately staffed to
meet project commitments in a timely manner?
YES







NO







COMMENT







                                      E-9

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                                                               EXAMPLE
I.   Organization and Personnel  (Page 2 of 2)
ITEM
Does the laboratory Quality Assurance
Supervisor report to senior management levels?
Has the Project Manager available during the
evaluation?
Was the Quality Assurance Supervisor available
during the evaluation?
YES



NO



COMMENT



                                  E-10

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-  General Fac11ities  (Page .1 of  6)
                                                                EXAMPLE
Does the laboratory appear to have adequate
workspace (120 sq. feet, 6 linear feet of
unencumbered bench space per analytst)?
Are voltage control devices used on major
instrumentation?
Does the laboratory have a source of distilled/
demineralized water?
I,s the conductivity of distilled/demineralized
water routinely checked and recorded?
Is the analytical balance located away from
draft and areas subject to rapid temperature
changes?
Has the balance been calibrated within one year
by a certified technician?
Is the balance routinely checked with class S
weights before each use and the results recorded
In a logbook?





















                                 E-ll

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                                                          EXAMPLE
A.  General Facilittes  (Page 2 of 6)
ITEM
Are properly filtered exhaust hoods provided to
allow efficient work with hazardous/ toxic
materials?
Is the laboratory maintained in a clean and
organized maner?
Ts a glove box available to allow efficient
work with hazardous/toxic materials?
Are contamination-free work areas provided for
the handling of toxic materials?
Are the toxic chemical handling areas either a
stainless steel bench or an impervious material
covered with absorbent material?
Are adequate facilities provided for storage of
samples , ext racts , and cal ibrat ion s tandards ,
including temperature controlled storage?
Is the temperature of the cold storage units
recorded daily in logbooks?
Are chemical waste disposal policies/procedures
adequate?
Are contamination-free areas provided for trace
level analytical work?
Can the laboratory supervisor document that
trace-free water is available for preparation
of standards and blanks?
YES










NO










COMMENT








'
•
                                  E-12

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                                                          EXAMPLE
A.  General Facilities  (Page 3 of 6)
ITEM
Is the laboratory secure?
Can the laboratory supervisor document that
organic solvents .used are free of trace
contaminants?
YES


NO

-
COMMENT
-

Comments on Laboratory Facilities
                                     E-13

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                                                          EXAMPLE
B.  Equipment  (Page 4 of 6)




    1.  GC/MS/DS Instrumentation






                   Manufacturer
Model
Installation Date
HRGC/MS HRMS
ID #
GC/MS
ID I
Peak Matching
Unit ID 9
GC (interfaced
with MS) ID#
Data System
ID#
Data System
ID t


















Comments on GC/MS/DS Instrumentation:
                                   E-14

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                                                           EXAMPLE
B.  Equipment  (Page 5 of 6)
ITEM
Are manufacturer's operating manuals readily
available to the operator?
Is there a calibration protocol available to
the operator?
Are calibration results kept in a permanent
record? /
Is service maintenance by contract?
Is preventatlve maintenance applied?
Is a permanent service record maintained In a
logbook?
Has the instrument been modified in any way?
Is the instrument properly vented?
Is a 9-track mag- tape available?
Is a split/splitless capillary injector
in place?
Is the column direct to the source?
Are sufficient in-house replacement parts
available?
YES












NO








'-



COMMENT











; -
                                   E-15

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                                                         E  X A M P L.E
B.  Equipment  (Page 6 of 6)
Comments on GC/HS Instrumentation
                                  E-16

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                                                             EXAMPLE
III.  Documentatton  (Page 1 of 2)

      When reviewing documentation, give special attention to:

           a) traceabllity
           b) neatness and completion

A.  DocumentatJon/Tracking
ITEM
Is a sample custodian designated? If yes,
name of sample custodian.
Name:

Are the sample custodian's procedures and
responsibilities documented? If yes, where
are these documented?
Are written Standard Operating Procedures (SOP)
developed for receipt of samples? If yes,
where are the SOP documented (laboratory manual,
written instructions, etc.)?
Are quality assurance procedures documented
and available to the analysts? If yes, where
are these documented?
Are written Standard Operating Procedures (SOP)
developed for compiling and maintaining sample
document files? If yes, where are the SOP
documented (laboratory manual, written
instructions, etc.)?
Are the magnetic tapes stored in a secure area?
Is a permanently-bound notebook with preprinted,
consecutively-numbered pages being used?
YES







NO







COMMENT





:
•
                                    E-17

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                                                         EXAMPLE
B.  Documentation/Notebooks  (Page 2 of 2)
ITEM
Is the type of work clearly displayed on the
notebook (i.e., EPA Extraction)?
Is the notebook maintained In a legible manner?
Are entries noting anomalies routinely
recorded?
Has the analyst avoided obliterating entries?
Are inserts (i.e., chroma tograms, computer
printout, etc.) permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual maintaining
the notebook personally examined and reviewed
the notebook periodically, and signed his/her
name therein, together with the date and appro-
priate comments as to whether or not the
notebook is being maintained in an appropriate
manner?
Where .applicable, is the notebook holder
referencing reports or memoranda pertinent
to the contents of an entry?
YES







NO







COMMENT







                                  E-18

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                                                          EXAMPLE
IV.   Analytical Methodology  (Page 1  of 2)
ITEM
Are the required methods used?
Is there any unauthorized deviation from
contract methodology?
Are written analytical procedures provided to
the analyst?
Are distilled-in-glass grade or other. high
purity chemicals used to prepare standards?
Are fresh analytical standards prepared at a
frequency consistent with good QA?
Are reference materials properly labeled with
concentrations, date of preparation, and the
identity of the person preparing the sample?
Is a standards preparation and tracking logbook
maintained?
Do* the analysts record bench data in a neat and
accurate manner?
Is the appropriate instrumentation used in .
accordance with the required protocol(s)?
YES









NO









COMMENT









                                  E-19

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                                                          EXAMPLE
Comments on Analytical Methods and Practices  (Page 2 of 2)
                                  E-20

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                                                             EXAMPLE
V.  Quality Control Manual Checklist  (Page 1 of 2)
ITEM
Does the laboratory maintain a Quality Control
Manual?
Does the manual address the Important elements
of a QC program, including the following:
a. Personnel?
b. Facilities and equipment?
c. Operation of instruments?
d. Documentation of procedures?
e. Procurement and inventory practices?
£. Preventive maintenance?
g. Reliability of data?
h. Data validation?
i. Feedback and corrective action?
j. Instrument calibration?
k, Recordkeeping?
1. Internal audits?
YES














NO














COMMENT


f







.



                                     E-21

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                                                         EXAMPLE
V.  Quality Control Manual Checklist  (Page 2 of 2)
ITEM
Are QC responsibilities and reporting relation-
ships clearly defined?
Have standard curves been adequately documented?
Are laboratory standards traceable?
Are quality control charts maintained for each
routine analysis?
Do QC records show corrective action when
analytical results fall to meet QC criteria?
Do supervisory personnel review the data and
QC results?
YES






NO






COMMENT






                                E-22

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VII.  Summary




A.  Summary Checksheet (Page 1 of 2)
                                                        EXAMPLE
ITEM
Do responses to the evaluation indicate that
project and supervisory personnel are aware of
QA and its application to the project?
Do project and supervisory personnel place
positive emphasis on QA/QC?
Have responses with respect to QA/QC aspects of
the project been open and direct?
Has a cooperative attitude been displayed by all
project and. supervisory personnel?
Does the organization place the proper emphasis
on quality assurance?
Have any QA/QC deficiencies been discussed
before leaving?
Is the overall quality assurance adequate to
accomplish the objectives of the project?
Have .corrective actions recommended during
previous evaluations been implemented?
Are any corrective actions required? If so,
list the necessary actions below.
YES









NO









COMMENT








,
                                E-24

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                                                        E X A M P  L.E
VI.  Data Handling Checklist   (Page  1 of 1)
ITEM
Are data calculations checked by a second
person?
Are data calculations documented?
Do records Indicate corrective action that has
been taken on rejected data?
Are limits of detection determined and reported
properly?
Are all data and records retained for the
required amount of time?
Are quality control data (e.g. , standard curve,
results of duplication and spikes) accessible
for all analytical results?
YES






NO






COMMENT






                                 E-23

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                                                          EXAMPLE



B.  Summary Comments and Corrective Actions  (Page 2 of 2)
                                     E-25

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                          EXHIBIT F
                     SPECIFICATIONS FOR
             CHAIN-OF-CUSTODY,  DOCUMENT  CONTROL,
              AND STANDARD OPERATING  PROCEDURES
NOTE:  The Contractor shall not deviate from the procedures
       described herein without the prior written approval
       of the Contracting Officer:  Provided, that the
       Contracting Officer may ratify in writing such
       deviation and such ratification shall constitute the
       approval required herein.

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     SPECIFICATIONS FOR CHAIN-OF-CUSTODY,  DOCUMENT CONTROL
         PROCEDURES,  AND STANDARD OPERATING PROCEDURES
1.   SAMPLE CHAIN-OF-CUSTODY

          A sample is physical evidence collected from a
     facility or from the environment.   An essential part of
     the hazardous, waste investigation effort is that the
     evidence gathered be controlled.  To accomplish this, the
     following chain-of-custody procedures have been
     established.

     1.1  Sample Identification

          To assure the traceability of samples through the
          •laboratory, a method for sample identification shall
          be developed and documented in the laboratory SOPs
          (see Section 3).  Each sample or sample preparation
          container shall be labelled with a unique number
          identifier (or the EPA sample number). This identifier
          shall be cross-referenced to the sample tag number
          and the EPA sample number.   There shall be a written
          description of the method of assigning this
          identifier and attaching it to the sample bottle,
          included in the laboratory SOPs.

     1.2  Chain-of-Custody Procedures

          Because of the nature of the data being collected,
          the possession of samples must be traceable from the
          time the samples are collected until they are
          introduced as evidence in legal proceedings.  To
          maintain and document sample custody, the chain-of-
          custody procedures described below shall be
          followed.

          1.2.1  A sample is under custody if:

                 1.2.1.1  It is in your actual possession,

                 1.2.1.2  It is in your view after being in
                          your physical possession,

                 1.2.1.3  It was in your possession and then
                          you locked or sealed it up to
                          prevent tampering, or

                 1.2.1.4  It is In a secure area.

          1.2.2  Upon receipt of the samples in custody, the
                 contractor shall inspect the shipping
                 container and sample bottles, and shall
                 document receiving  information as specified
                          F-l

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in Section 3.2.  The sample custodian or a
designated representative shall sign and date
all appropriate receiving documents at the
time of receipt (i.e., EPA chain-of-custody
forms, traffic reports, airbills, etc.).  The
contractor shall contact SMO if documents are
absent, information on receiving documents
does not agree, custody seals are not intact,
or the sample is not in good condition.  The
contractor shall document resolution of any
discrepancies.

        F-2

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2.  DOCUMENT CONTROL PROCEDURES

          The goal  of the  laboratory document control program
    is to assure that all  documents for a specified case will
    be accounted for when  the project is completed.
    Accountable documents  used by contract laboratories shall
    include,  but not be limited to, logbooks, chain-of-
    custody records,  sample work sheets, bench sheets, and
    other documents relating to the sample or sample
    analyses.  The  following document control procedures have
    been established to assure that all laboratory records
    are assembled and stored for delivery to EPA or are
    available upon  request form EPA prior to the delivery
    schedule.

    2.1  Preprinted Data Sheets and Logbooks

         Preprinted data sheets shall contain the'name of the
         laboratory and be dated and signed by the analyst  or
         individual performing the work.  All documents
         produced by the laboratory which are directly
         related to the preparation and analysis of EPA
         samples shall become the property of the EPA and
         shall be placed in the case file.  For that  reason,
         all observations  and results recorded by the
         laboratory but not on preprinted data sheets are
         entered into permanent laboratorey logbooks.  The
         person responsible for the work shall sign and date
         each entry and/or page in the logbook.  When all
         data from  a case  is compiled, copies of all  EPA
         case-related logbook entries shall be included in
        'the documentation package.  Analysts' logbook
         entries must be in chronological order and shall
         include only one  case per page.  Instrument  run  logs
         shall be maintained so as to enable a reconstruction
         of the run sequences of individual instruments.

         Because the laboratory must provide copies of  the
         instrument run logs to EPA, the laboratory may
         exercise the option of using only laboratory or  SKO
         sample identification numbers in the  logs  for  sample
         ID rather  than government agency or commercial
         client names.

         Using laboratory  or SMO  sample  IDs  only  in  the run
         sequences  will assist the  laboratory  in  preserving
         the confidentiality of  commercial clients.

    2 .2  Error Correction  Procedure

         All documentation in logbooks  and other documents
         shall be in ink.   If an error  is  madeT corrections
         shall be made by  crossing  a line  through the error
                       F-3

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     and entering the correct information.   Changes shall
     be dated and initialed.  No information shall be
     obliterated or rendered unreadable.

2.3  Consistency of Documentation

     Before releasing analytical results, the laboratory
     shall assemble and cross-check the information on
     sample tags/ custody records, lab bench sheets,
     personal and instrument logs, and other relevant
     data to ensure that data pertaining to each
     particular sample or case is consistent throughout
     the case file.

2.4  Document Numbering and Inventory Procedure

    —-In order to provide document accountability of the
     completed analysis records, each item in a case
     shall be inventoried and assigned a serialized
     number and identifier associating it to the case and
     Region.

     Case # - Region - Serialized number (For example:
     75-2-0240)

     The number of pages of each item must be accounted
     for if each page is not individually numbered.  All
     documents relevant to each case, including logbook
     pages, bench sheets, mass spectra, chromatograms,
     custody records, library search results, etc., shall
     be inventoried.  The laboratory shall be responsible
   „ for ensuring that all documents generated are placed
     in the file for inventory and are delivered to EPA.
     Figure 1 is an example of a document inventory.

2.5  Shipping Data Packages and Case Files

     The contractor shall have written procedures to
     document shipment of deliverables packages to the
     recipients.  These shipments require custody seals
     on the containers placed such that it cannot be
     opened without damaging or breaking the seal.  The
     contractor shall also document what was sent, to
     whom,  the date, and the method (carrier) used.
                    F-4

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  SPECIFICATIONS FOILJLIMPARD OPERATING PROCEDURES

        The  contractor must have written standard operating
   procedures  (SOPS) for receipt of samples,  maintenance of
   custody,  sample storage,  tracking the analysis of samples
   and assembly of completed data.


       An SOP is defined  as a written narrative  step-wise
  description of laboratory operating procedures including
  examples of laboratory  documentation.  The SOPs must
  accurately describe the actual procedures used in the
  laboratory,  and copies of the written SOPs shall be
 available  to the appropriate laboratory personnel.   These
 procedures are necessary to ensure that analytical  data
 produced under this contract are  acceptable for use in
 EPA enforcement case preparation  and  litigation.  The
 contractor's SOPs  shall  provide mechanisms and
 documentation to meet each of the  following
 specifications  and  shall be used by EPA as the basis for
 laboratory  evidence audits.


3.1  The contractor shall have a designated sample
     custodian responsible  for receipt  of samples  and
     have written SOPs describing his/her duties and
     responsibilities.


 . 2  The contractor shall have written SOPs for receiving
    and logging in of the samples.   The procedures shall
    include but not be limited to  documenting the
    following information:


    3.2.1  Presence  or absence of EPA chain-of-custody
          forms


   3.2.2  Presence or absence of airbills

   3.2.3  Presence  or absence of traffic reports or SAS
         packing lists


   3.2.4  Presence or absence of custody  seals on
         shipping and/or sample containers and  their
         condition

  3.2.5  Presence or absence of sample tags

  3.2.6   Sample tag ID numbers if  not  recorded on the
         chain-of-custody record(s)  or packing list(s)

 3.2.7  Condition of the shipping  container

 3.2.8  Condition of the sample bottles

 3.2.9  Verification of agreement  or non-agreemejjt  of.
        information on receiving documents
               F-5'

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                                                   with
                      	_-!"-««^m- v-'LJLXCe

3-3  The contractor cv, = n i	
                                      SOPS

     and shaU-^onitraS™"^?.* S**^*s after
          n                 ct- sops  *«
       and shall demons t»£ s££i?v o?""?^5  *fter
       areas and laboratory?  The  soL  K^e Sample
       include .descriptions Of a?i  2f«  hal1 sPecif
       samples in the labo?a?orv    ?h~ So areas fo
       to--^^
   •4   ...,. v,«xn.tacT;or snall havo ^.^^	
                                                 tracking
               SOP shall              oowng


                           °f                        to
             transfers,             ron,
             analyses.               raions,  and sample
      3.4.2



      3.4.3
3.5
          A description of the documentation used to
          record calibration and QA/QC laboratory work.

          Examples  of the  document  formats  and
          laboratory  documentation  used  in  the sample
          receipt,  sample  storage,  sample transfer, and
          sample analyses.
                                      /'
  The contractor shall have written SOPs for
  organization and assembly of all documents relating
  to each EPA case.  Documents shall be filed on a
  case-specific basis.  The procedures must ensure
  that all documents  including logbook pages,  sample
  tracking records, chromatographic charts,  computer
  printouts,  raw data summaries,  correspondence,  and
  any  other written documents  having reference to the
  case are compiled in one location for  submission to
  EPA.  The system  must include a document  numbering
  and inventory procedure.
                 F-6

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4.  HANDLING OF CONFIDENTIAL INFORMATION

         A contractor conducting work under this contract may
    receive EPA-designated confidential information from the
    agency.  Confidential information must be handled
    separately from other documentation developed under this
    contract.  To accomplish this, the following procedures
    for the handling of confidential information have been
    established.

    4.1  All confidential documents shall be under the
         supervision of a designated document control officer
         (DCO).

    4.2  Confidential Information

        -Any samples or information received with a request
         of confidentiality shall be handled as
         "confidential."  A separate locked file shall be
         maintained to store this information and shall be
         segregated frow other nonconfidential information.
         Data generated from confidential samples shall be
         treated as confidential.  Upon receipt of
         confidential irformatinr,  W!?.P JCO lo^fe these
         documents vat'-a-wbnfidential Inventory Log.   The
         infonrLlon is then made available to authorized
         peuonnel but only after it has been signed out to
         the person by the DCO.   The documents shall be
         r^urned to the  locked file at the conclusion of
         yach working day.  Confidential information may not
         be reproduced except upon approval by the 1PA
         contracting officer.   The DCO will enter all copies
         into the document control system.  In addition, this
         information may  not be disposed of except upon
         approval by the  EPA contracting officer.  The DCO
         shall remove and retain the cover page of any
         confidential information disposed of for one year
         and shall keep a record of the disposition in the
         confidential Inventory Log.
                        F-7

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                              Figure 1
                                             232-2-0001

                                             Case No. 232
                               Example
Document Control J.*

232-2-0001
232-2-0002
232-2-0003   	
232-2-0004
232-2-0005
232-2-0006
232-2-0007
232-2-0008
232-2-0009
232-2-0010
232-2-0011
232-2-0012
   etc.
     DOCUMENT INVENTORY

       Document Type

Case File Document Inventory Sheet
Chain-of-Custody Records
Shipping Manifests
Sample Tags
SMO Organics Traffic Reports
GC/MS spectra for sample B0310
GC/MS spectra for sample BO^ll
GC/MS spectra for sample B0319
Analyst's logbook pages
GC/MS library search worksheets
GC instrument log pages
GC/MS QC data sheets
        etc.
# Pages

   1
   2
   2
  50
  10
  20
  20
  20
   6
  15
   5
   4
 etc.
* This number is to be recorded on each set of documents.

                           F-8

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