United States
             Environmental Protection
             Agency
       Region 5
       Eastern District Office
       25089 Center Ridge Road
       Westlake, Ohio 44145
EPA-905/4-88-004
March 1987
vvEPA      Michigan  Dioxin  Studies

             Dow Chemical
             Building 703 Incinerator Exhaust
             and  Ambient Air Study
                              I Ml
                                      X
                                      Air Monitoring Locations
Dow Chsmieal
  Company
                              Bunding 703
                              Incinerator

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DOW CHEMICAL BUILDING 703  INCINERATOR  EXHAUST

            AND AMBIENT AIR  STUDY
                  MARCH  1987
              MARTIN  G.  TREMBLY
               GARY A. AMENDOLA
     U.S. ENVIRONMENTAL  PROTECTION AGENCY
                    REGION V
       ENVIRONMENTAL  SERVICES DIVISION
            EASTERN  DISTRICT OFFICE
                 WESTLAKE, OHIO
                          U.S.  Envircnra-^rital Protection Agency
                          Rsffion  5, Library ("5FL-16)
                          230 S.  Dearborn St-eet, Boom 1670
                          Chicago,  IL   60604

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                                ACKNOWLEDGMENTS
     The authors would  like  to express their appreciation to several individuals
who provided valuable assistance leading  toward  the  completion of this study:

     Derivation of study and sample analysis  plan - Marcia  A.  Kuehl , Charles T.
         Elly -U.S.  Environmental  Protection  Agency, Region V, Central Regional
         Laboratory.   Dr. Robert G.  Lewis,  Dr. Thomas  R.  Mauser,  Dr.  John B.
         Clements, Dr.  Joseph F. Walling- Environmental Monitoring and  Support
         Laboratory,  U.S. Environmental  Protection Agency.

     Background information  about facility and study  area  -  Robert  Teoh,  Jim
         Sygo - Michigan Department of Natural Resources.

     Conduct of field work and compilation of data -  Mark  del and, Mark  Conti,
         Brian Buckham,  Kenneth Radtke,  Eric  Burneson,  David  Perko  -  U.S.
         Environmental  Protection  Agency,  Region V,  Eastern  District  Office.
         Edward Peduto, John Podlenski, Mark Gollands, Patrick Ford  -  GCA/Tech-
         nol ogy Division.  Ronald  Agin,  Richard  Johnson,  Jackie Anderson  - Dow
         Chemical Company.

     Laboratory analyses -  Dr.  Michael  Taylor,   Dr.  Thomas  Tiernan  -  Wright
         State University.  Bennett Tyson -  EAL Corporation.   Dr. John Stanley -
         Midwest Research Institute.   Al  Tordini -  U.S.  Testing Laboratories.
         Robert L. Harless,  Environmental  Monitoring  and  Support  Laboratory,
         U.S. Environmental  Protection Agency.

     Laboratory data review - Francis Thomas, Thomas Bauer - U.S. Environmental
         Protection Agency,  Region V, Central Regional Laboratory.

     Draft  report revi-ew - Donald  Barnes, Chlorinated  Dioxins  Work  Group,  U.S.
         Environmental  Protection  Agency.  Edward Lillis,  William  Kuykendal  -
         Office of  Air  Quality  Planning  and  Standards,  U.S.  Environmental
         Protection Agency.   David Kee,  Larry  Fink  -  U.S.  Environmental  Pro-
         tection Agency, Region V.

     Finally, the invaluable assistance of Carol  Kopcak, Ellen Harrison, Minnie
Brantley, and  Terence  Griffin  in  typing   and  proofreading this  report   is
acknowledged.
                                   DISCLAIMER


      This document  has  been  reviewed  in  accordance  with  U.S.  Environmental
 Protection Agency policy  and  approved for publication.  Mention of trade  names
 or commercial  products does  not  constitute endorsement  or recommendation  for
 use.

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                                 TABLE  OF  CONTENTS
  ACKNOWLEDGMENTS  .................   .      ii

  LIST OF  TABLES    ..................      1v

  LIST OF  FIGURES  .................   .     vi i

  I.   INTRODUCTION  ..................       1

 II.   OBJECTIVES    .........   .   ........       3

III.   SCOPE  OF WORK   ......   .   ..........       4

 IV.   FINDINGS AND  CONCLUSIONS ..........   ....       5

  V.   DOW  CHEMICAL  MIDLAND PLANT
      BUILDING 703  INCINERATOR EMISSIONS STUDY    ........       8

      A.  Facility  Description                                               8
      B.  Sampling  Strategy                                                 12
      C.  Conduct of Study                                                  19
      D.  Analytical  Procedures and  Quality Assurance  Reviews                20
      E.  Incinerator Operations During  Tests                                21
      F.  Results and Discussion                                            21

 VI.   AMBIENT AIR STUDY IN VICINITY  OF
      DOW  CHEMICAL  COMPANY MIDLAND PLANT ...........      58

      A.  Monitoring Network Description                                    59
      B.  Monitor Descriptions and Sampling Methods                          67
      C.  Conduct of Study                                                  67
      D.  Analytical  Procedures and  Quality Assurance                        69
      E.  Results of Study and Discussion                                    69


      REFERENCES    ..................      93

      APPENDICES

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                                 LIST OF TABLES
Table 1-1      Tier 4 Dioxin Sampling and Analysis Strategy -    ...    2
               June 1984 Draft

Table V-l      Dow Chemical  Company Building 703 Incinerator  ....   13
               Target Compounds in Air

Table V-2      Dow Chemical  Company Building 703 Incinerator  ....   14
               Target Compounds in Water and Solids Discharges

Table V-3      Sampling and Analysis Summary   .........   22
               Oow Chemical  Company Building 703 Incinerator
               Emissions Study 8/28, 8/30, 9/5/84

Table V-4      Volatile Compounds - Precombustion Air   ......   24
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, 9/5/84

Table V-5      Semi-Volatile Compounds - Precombustion Air .....   25
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, 9/5/84

Table V-6      Incinerator Precombustion Air - PCDD/PCDF Analyses.  .  .   25
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, 9/5/84

Table V-7      Quantitated Volatile Compounds - Liquid Waste Inputs .  .   27
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, 9/5/84

Table V-8      Quantitated Semi-Vol atile Compounds - Liquid Waste Inputs   29
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, 9/5/84

Table V-9      Liquid Waste Inputs - Quantitated Pesticide/PCB Compounds   30
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, 9/5/84

Table V-10     Liquid Waste Inputs - Quantitated PCDD/PCDF 	   31
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, 9/5/84

Table V-ll     Low-BTU Liquid Waste - Volatile Compounds   	   32
               Dow Chemical  Company Building 703 Incinerator
               8/28 and 9/5/84
                                       IV

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                           LIST OF TABLES (continued)
                                                                          Page

Table V-12     Low-BTU Liquid Waste - Semi-Volatil e Compounds ....   33
               Dow Chemical  Company Building 703 Incinerator
               8/28 and 9/5/84

Table V-13     Low-BTU Liquid Waste - PCDD/PCDF Analyses   ......   34
               Dow Chemical  Company Building 703 Incinerator
               8/28 and 9/5/84

Table V-14     Approximate Concentrations of Volatile Compounds  ...   35
               in Incinerator Exhaust 8/28, 8/30, 9/5/84

Table V-15     Approximate Concentration of Semi-Volatile Compounds .  .   35
               in Incinerator Exhaust 8/30/84

Table V-16     Incinerator Exhaust - PCDD/PCDF Analyses 	   37
               Expressed in Terms of Concentration in Air
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, 9/5/84

Table V-16A    Incinerator Exhaust - PCDD/PCDF Analyses 	   38
               Concentration Expressed in ng/dscm, Adjusted
               to Standard Temperature and Pressure (68°F, 29.92 in.Hg),
               and Normalized to 3% Oxygen Content

Table V-17     Results of Sampling for Vinylidene Chloride	39
               Dow Chemical  Company Building 703 Incinerator

Table V-18     Incinerator Ash Semi-Vol atil es	40
               Dow Chemical  Company Building 703 Incinerator

Table V-19     Incinerator Ash - PCDD/PCDF Analyses	41
               Dow Chemical  Company Building 703 Incinerator
               8/28, 8/30, and 9/5/84

Table V-20     Aqueous Influents and Effluents - PCDD/PCDF Analyses .  .   43
               Dow Chemical  Company Building 703 Incinerator
               8/28/84

Table V-21     Aqueous Influents and Effluents - PCDD/PCDF Analyses .  .   44
               Dow Chemical  Company Building 703 Incinerator
               8/30/84

Table V-22     Aqueous Influents and Effluents - PCDD/PCDF Analyses .  .   45
               Dow Chemical  Company Building 703 Incinerator
               9/5/84

Table V-23     Overall Data Completeness	46
               Based Upon Analytical Accuracy Criteria
               Dow Chemical  Company Building 703 Incinerator

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                           LIST OF TABLES (continued)
Table V-24     Adherence to Desired Detection Limits
               Dow Chemical  Company Building 703 Incinerator

Table VI-1     Midland, Michigan, Ambient Air Sampling Study,
               Summary of Sample Types and Sampling Times
Table VI-2     Results of Ambient Air PCDD/PCDF Sampling .......
               In Vicinity of Dow Chemical  Company, Midland, Michigan
               September 1984

Table VI-3     Comparative Analyses for Total  and 2378 Isomer of TCDD and TCDF
               Midwest Research Institute and EMSL-RTP, EPA

Table VI-4     Comparative Values for Total  and 2378 Isomer of TCDD and TCDF
               Midwest Research Institute and EMSL-RTP, EPA

Table VI-5     Wind Data - Ambient Air Sampling Program - Midland, Michigan.
               September 7-27, 1984

Table VI-6     Results of Ambient Air Sampling for PCDD/PCDF   .  .  .  .  .
               In Vicinity of Dow Chemical,  Midland, Michigan
               September 1984

Table VI-7     Results of Ambient Air Sampling for Semi-Vol atile Compounds .
               in Vicinity of Dow Chemical  Company, Midland, Michigan,
               September 1984

Table VI-8     Tentatively Identified Semi-Vol atile Compounds Detected In  .
               Ambient Air Sampling In Vicinity of Dow Chemical  Company,
               Midland, Michigan, September  1984

Table VI-9     Ranges of Concentrations of Quantitated Semi-Volatile Compounds
               In Ambient Air on Nine Sampling Days - Midland, Michigan
               9/7/84 - 9/25/84

Table VI-10    Comparative Results of Carbon Molecular Sieve Tube ....
               Validation Study

Table VI-11    Results of Ambient Air Sampling for Volatile Compounds.  .  .
               In Vicinity of Dow Chemical  Company, Midland, Michigan
               September 1984
Table VI-12    Results of Ambient Air Sampling for Formaldehyde.
               In Vicinity of Dow Chemical  Company, Midland, Michigan
               September 1984

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                LIST OF FIGURES
Figure V-l
Figure V-2
Figure V-3
Figure V-4
Figure V-5
Figure V-6
Figure V-7
Figure V-8
Figure VI-1
Figure VI-2
Figure VI-3
Figure VI-4
Figure VI-5
Figure VI-6

Dow Chemical Company Building 703 Incinerator
Dow Chemical Company Building 703 Incinerator.
Exhaust Gas Sampling Points
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company - Midland Plant - Building 703. .
Incinerator Distribution of PCDDs and PCDFs Among
Incinerator Ash, Air, and Water Outputs
Dow Chemical Company - Midland Plant - Building 703. .
Incinerator Comparison of PCDD and PCDF Inputs and
Outputs
Midland, Michigan, Ambient Air Monitoring Network . .
Location of Ambient Air Monitoring Site 1 ....
Location of Ambient Air Monitoring Site 2 ....
Location of Ambient Air Monitoring Site 3 ....
Location of Ambient Air Monitoring Site 4 ....
Location of Ambient Air Monitoring Site 7 ....
Page
9
17
50
51
52
53
55
57
60
61
63
64
65
66
(wind monitoring  site)

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                                   APPENDICES
Appendix A     Detailed Description  of  Conduct  of  Study  -  Michigan Dioxin
               Study -  Dow  Chemical Building  703  Incinerator  Emissions Study

Appendix B     Extraction Procedure for  "High Hazard"  Liquid Waste Samples   -
               Fred C. Hart Associates, Inc.

Appendix C     Analytical Procedures for PCDD/PCDF - Brehm  Laboratory - Wright
               State University

Appendix D     Incinerator Exhaust Study Sampling Results

Appendix E     Detailed Descriptions of Ambient  Air  Monitoring  Equipment and
               Sampling Methods -  Michigan  Oioxin  Studies - Midland, Michigan,
               Ambient Air Sampling Study

Appendix F     Detailed Description  of  Conduct  of  Study  -  Michigan Dioxin
               Studies - Midland, Michigan, Ambient Air Sampling Study

Appendix G     Raw Analytical Data - Ambient Air PCDD/PCDF Sampling in Vicinity
               of Dow Chemical Company, Midland, Michigan

Appendix H     Results of Reanalysis of Selected  PCDD/PCDF  Samples  by USEPA-
               EMSL-RTP and Explanatory Information

Appendix J     Detailed Discussion  of  Air  Dispersion   Modeling  to Determine
               Point of Maximum Ground-Level Impact
                                       vm

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I.  INTRODUCTION

    The U.S. Environmental Protection  Agency  (USEPA)  Region V has  conducted  a
series of comprehensive  multi-media  studies  of dioxins and other  toxic  pollu-
tants at the Dow  Chemical  Company Midland  Plant,  in the Tittabawassee  River,
and in and  near the  city of Midland,  Michigan.  The  purposes  of these  studies
were to determine  current emissions  and  ambient  levels  of toxic  pollutants and
whether those levels  warrant  remedial  action  to  minimize or  eliminate  public
exposure and environmental risks.   Soil  sampling was conducted in  Midland,  at
Dow Chemical ,  and  at  comparison  and  background  sites during 1983 and  1984.
Results from the soil study were released in April  1985.1   Screening studies  of
surface water supplies,  potable ground water,  and  brine operations at the Dow
facility was completed  in 1984  and  1985; the results  of  these   studies  were
released in  December 1985.2   During  1984,  samples  were  collected  from  Dow
Chemical's waste  incinerator;  ambient air;  Dow Chemical's  industrial   waste-
waters; and Tittabawassee River sediments.   In  July 1986, Region V  also  released
the results  of  comprehensive  testing  of Dow  Chemical  in-plant  and effluent
wastewaters, sludges,  and  Tittabawassee  River  sediments  and  native  fish.2a
This report presents  the  results  of the hazardous waste  incinerator  emissions
testing and ambient air monitoring.

    On December 1,  1983, EPA  published  a Dioxin  Strategy,3  which provides  a
framework under which the Agency is to

    -  study the nature  and  extent of contamination  of 2,3,7,8-tetrachlorodi-
       benzo-p-dioxin (2378-TCDD)   and  the  associated risks  to humans and the
       environment;

    -  implement or compel  necessary cleanup actions at  contaminated sites; and

    -  further evaluate regulatory  alternatives to prevent future contamination,
       as well  as  disposal  alternatives to alleviate current problems.

    The Dioxin Strategy focuses on  seven  tiers of sources,  ordered  by decreasing
potential for 2378-TCDD  contamination.  Combustion sources, including the Dow
Chemical waste  incinerator,  comprise Tier 4.   EPA  published  sampling  and
analysis plans  in  February 1985.4   Facilities studied  as  part  of the  Tier  4
strategy were sampled at specific fuel  and  air  input points; air,  solid, and
water effluent points; and selected surrounding sites for  soils.   This  sampling
and analysis model is reproduced  as  Table 1-1.  The  Dow  Chemical  facility was
studied consistent with  the Tier 4 model, but  on a separate schedule and  with
different field sampling and analytical teams.

    In March 1983, the Michigan Department of Natural Resources (MDNR) requested
that EPA  conduct  studies  of  the  presence  of dioxins  and  other  compounds  in
various media in the Midland  area.  Responding to this  request,  the range  of
compounds selected  for  study   in  the incinerator  emissions  and   ambient  air
studies was expanded  from that shown in Table 1-1 to include several which  have
estimated risks associated with  respiratory exposure  (see Tables  V-l  and V-2).

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                                                                      TABLE 1-1

Sample
Inputs
Preconfcustion Air
Quench Water
Feed/Fuel
TIER 4 DIOXIN
Method
XAD-2
Grab
Grab (every 4 hours)
SAMPLING AND ANALYSIS STRATEGY
Recommended
(Samples/Day)
0-1
0
Dally Composite
- JUNE 1984 DRAFT
Recommended Analyses
2,3,7,8-TCDD. Homologs. PCBs. TOC1
Cl -phenols. Cl -Benzenes
PCDO scan. Cl -phenols, Cl -benzenes

Total Samples*
for Analysis
1
0.
3b
Outputs

 Stack (before control)
MM5T
 Stack (after control)
MH5T
2 trains
 -Gaseous dally composite
  -Condenser rinse
  -Adsorbent resin
 -Partlculate dally composite
  -cyclone catch
  -filter
  -probe rinse

2 trains
 -Gaseous dally composite
  -Condenser rinse
  -Adsorbent resin
 -Partlculate daily composite
  -filter catch
  -probe rinse
                                                                                           PCBs,  TOC1
2,3,7,8-TCDD, Homologs
2,3,7,8-TCDD, Homologs
. Bottom Ash
Ash from Control Device
Quench Mater Effluent
Environmental
Ambient Air
Surface Water
Soil

Grab
Grab
Grab

every 4 hours)
every 4 hours)
every 4 hours)

XAD-2
Grab
Boring


Daily Composite
Daily Composite
Daily Composite

0
0
1

2,3.7,8-TCDD, Homologs 1
2.3.7,8-TCDD, Homologs 1
2,3.7.8-TCOP /

2,3,7,8-TCDD

3-6c
3

0
0
I
TOTAL 23-26
?flased on 3 sampling days.
IT Analysis by contractor.
 Hay be combined daily composite.

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II.   OBJECTIVES

     A.   Incinerator  Exhaust  Study

     The purposes  of  the  incinerator emissions study were to

         -  determine  concentrations   and   mass  loadings  of  polychlorinated
            dibenzo-p-dioxins  (PCDDs),   polychlorinated  dibenzofurans  (PCDFs),
            chlorobenzenes, chlorophenols,  and  other  chemicals in  the exhaust
            gas, wastewater,   and  solid  matter  (ash  and  waterborne  suspended
            solids) discharges from  the  incinerator,  under  normal  operating
            conditions; and

         -  relate the  compounds  found   in  the  discharged  streams  to  the
            characteristics of liquid  and  solid  wastes  incinerated  at  those
            times.

     B.   Ambient Air  Study

     A companion  study of the  ambient  air  around  the  Dow  Chemical  facility was
 designed to determine the presence of  PCDDs,  PCDFs, and other semi-volatile and
 volatile compounds;  to relate these findings  to air emissions from the Building
 703 incinerator;  and to  detect other  compounds that  may  be emitted from other
 point sources or  fugitive   sources  at the Midland  Plant.   It was  originally
 intended that ambient air  samples  would be obtained on the same days as incin-
 erator  exhaust sampling.  However,  resource requirements  of this work dictated
 that the monitoring  programs be conducted  separately.

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III.   SCOPE  OF  WORK

      A.   Incinerator  Exhaust  Study

      Numerous  process  vents other than the Building 703 incinerator exist at the
  Dow Chemical  Company Midland  Plant.   However, based  upon  the results  of Dow
  Chemical  self-monitoring   of  principal  process  vents  in  organic  chemical
  production areas,  the incinerator  was determined to  be  the dominant potential
  source  of  PCDO and PCDF emissions in the plant.  Therefore,  sampling was limited
  to  the  incinerator.

      Sampling  occurred on  August  28, August  30, and  September 5,  1984.   The
  conduct of this  work is described  in Section  V  and  Appendix  A of this report.
  A total  of 267 samples were collected  and  analyzed in  this portion of the study.

      B.   Ambient  Air  Study

      For the purposes  of the  ambient  air  study, the  range of compounds selected
  for sampling  was expanded beyond  PCDOs and PCDFs, to include  other compounds
  which have demonstrated  risks through  respiratory  exposure;  compounds  with
  chemical  structures  similar  to these; and  other compounds  which  may have been
  traceable  to  emissions  from  the  Dow  Chemical  Company  incinerator.   This
  selection  was based  upon an  evaluation of information available in files of the
  MDNR and USEPA,  concerning plant processes, products, intermediates, and wastes
  generated.  The  target  compounds included the  following:

       acryl onitril e             chlorinated  phenols     methyl  chloroform
       benzene                   chloroform              methylene chloride
       biphenyl                  ethyl ene dibromide      perchloroethylene
       chl orobenzenes            ethyl ene dichloride     phenylphenol s
       carbon tetrachloride      ethyl ene oxide          vinyl idene chloride
       chlorinated biphenyl s     formaldehyde

      Constituents such as metals  (arsenic, beryllium, etc.)  were not included as
  the above-referenced  file  information indicated they were not involved in  plant
  processes, while others,  such as  vinyl  chloride,  were not  among  the target
  compounds  as  no available  sampling methods were  applicable to them.  However,
  compounds  not appearing in the above list were reported when they were detected,
  subject to quality  assurance limitations, as shown in the discussion to follow.

      Ambient air was sampled at  four  locations near the Dow Chemical Midland  Plant
  on  18 days between September 7 and  27,  1984.   The  conduct  of this study  and  a
  discussion of results  appears  as  Section  VI  of this  report;  a  total  of 353
  samples were gathered and  analyzed.

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IV.   FINDINGS  AND  CONCLUSIONS

     A.   Incinerator  Exhaust Study

     1.   Tetra-  through  octa-CDDs  and tetra- through  octa-CDFs were detected in
 Building 703  incinerator exhaust  on two of  the  three  sampling  days.   On the
 third day,  only TCDDs,  OCDD,  TCDFs, and PeCOFs were  found  in the incinerator
 exhaust.  TCDDs were detected  in  the  5 to  45  ng/m3  range,  while  TCDFs  were
 found at 80 to  125 ng/m3.  Other PCDDs  and  PCDFs were  found at levels typically
 lower than  10  ng/m3.   2378-TCDD  was not detected in  Building 703 incinerator
 exhaust  at  detection levels  of approximately  1  ng/m3.  A  single  finding  of
 2378-TCDD in  combustion air drawn  into  the  incinerator is reported.

     2.   The Modified Method  5 train  chosen as the sampling apparatus for PCDDs
 and PCDFs and semi-volatile compounds trapped these compounds, frequently at or
 near the low detection  limits desired  in  this  study.   However,  the collection
 and retention efficiency of the Modified Method 5 sampler for  PCDDs, PCDFs, and
 other semi-volatile  compounds has not been  validated.   Therefore,  the analytical
 results  stated    for PCDDs,   PCDFs,  and   semi-volatile  compounds  should  be
 considered  minimum  values.   Analytical  accuracy was acceptable  for  79% of the
 samples  obtained  for the measurement  of tetra-  and  penta-CDDs,  which  are of
 greatest concern  with respect to possible health effects.

     3.   Comparisons  were made of mass  inputs of PCDDs and PCDFs  in incinerator
 feed streams, scrubber  and quench  waters, and combustion air,  with mass outputs
 in  stack emissions,  scrubber  and  quench waters,  and  collected  ash.   A clear
 relation between  the mass of  PCDDs  and PCDFs in input  streams  and discharges
 was not  discernible; however, higher concentrations of  PCDDs  and  PCDFs in liquid
 wastes consumed in  the  incinerator appeared to translate into higher levels of
 PCDDs and PCDFs  in  incinerator discharge  streams.   The data  suggest  limited
 destruction in  the incinerator  of  TCDDs and HpCDDs, somewhat higher destruction
 of  PeCDDs,  and  mass transfer of HxCDDs  and  OCDDs  from input streams to output
 streams.  For PCDFs, the data  suggest  destruction  of  nearly  90% of the input
 TCDFs, and  formation of other  PCDFs, primarily HxCDFs  and OCDF.

     4.   Analyses  for suspected PCDD and  PCDF precursors in the  influent streams,
 such as   PCBs  and chlorinated  benzenes and  phenols,   were  not  conclusive  in
 establishing  a  relationship  between these  compounds  and  emitted  PCDDs  and
 PCDFs.   However,  the concentrations  of  certain semi-volatile  compounds such as
 chlorobenzenes  and   chlorophenol s  in the  incinerator   exhaust,  did appear  to
 relate directly with emissions  of  PCDDs and PCDFs.

     5.   While extensive data on incinerator  operating temperatures, pressures,
 air pollution control  device  water,  and flow rates  were obtained, there was no
 discernible relationship between  any   of  these  characteristics  and  exhausted
 PCDD and PCDF  concentrations  within   the  ranges  encountered  in this  study.

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    6.  Quality assurance  results  for  semi-volatile  and  volatile  compounds
indicated analytical  accuracy and precision problems, such that data for these
compounds were of  limited quantitative  use.

    7.  On two of  three sampling  days,  emissions  of  particulate matter from the
incinerator exhaust were within the  standard of 0.08 grain/dscf established for
incinerators burning hazardous  waste (40 CFR Part 264.343(c)).  Values ranging
from 0.0615 to  0.0842  grain/dscf were measured   with  a mean  value  of 0.0747
grain/dscf.

    8.  Wastes from a nearby Dow Corning Corporation facility were incinerated
on all three sampling days; these  wastes contained  PCDDs and PCDFs (primarily the
1368 and  1379 TCDD isomers).  Ash discharged from the Building 703 incinerator
included silane and siloxane compounds  most  likely attributable to Dow Corning.

    B.  Ambient Air Study

    1.  No 2378-TCDD was detected on a  first analysis of ambient air  samples by
a contract laboratory.   However,  reanalysis of two  of  the 15 sets of sampling
media by  the  EPA  Environmental  Monitoring and   Support  Laboratory, Research
Triangle Park, North Carolina,  resulted in  detection of  2378-TCDD  at  an ambient
site near the Dow Chemical Company plant fenceline  at a concentration of about
5 pg/m3.  Ambient  air monitoring by Dow Chemical in 1983 and 1984 showed positive
results for 2378-TCDD  up to 0.2  pg/m^.  The Dow Chemical  data  were obtained
with a glass fiber filter in the  sampler.

    2.  Other homologues of PCDD and  PCDF were detected with generally  acceptable
accuracy in the range of 0.1 to approximately  400 pg/m^.  These homologues were
present in proportions  similar to those found in previous  studies   of ambient
air near  incineration  processes,  and  in soils sampled  by EPA in the Midland,
Michigan, area in 1984.

    3.  The modified high-volume  sampler used for  PCDD and PCDF sampling trapped
the full  range of PCDD  and  PCDF  homologues.   However,  the  collection  and
retention efficiency of  the  Modified Method  5 sampler  for PCDDs  and  PCDFs has
not been  validated.   Therefore,  the analytical  results  stated  for  PCDDs and
PCDFs should be considered minimum values.

    It was  found  that  lower-chlorinated homologues  generally were  trapped in
the second-stage XAD-2 resin trap incorporated into  the samplers,  while higher-
chlorinated homologues  remained  in  or   on the  first-stage glass  fiber filter.
While no  particle size data were  obtained at this time,  these findings  strongly
suggest that both  sampling media  should be  exposed  in  series to  ambient  air to
sample for  the  full  range  of  PCDD  and PCDF homologues.  Also,  it   is implied
that lower-chlorinated  homologues may  either  attach to finer, more  respirable
particulate matter, or  may  be  air-stripped  from  larger  particles  caught  in the
glass fiber filter.  No  particle  sizing data were gathered at this time to test
this  possibil ity.

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    4.  A sampler similar to that  employed  for  PCDDs  and  PCDFs was  effective in
sampling for semi-vol atile compounds in ambient  air.   While  analytical  precision
was remarkably   good in  many samples  for  semi-volatil e  compounds,  accuracy
problems were frequently encountered.

    5.  Sources within the  Dow Chemical  facility,  other than the  Building 703
incinerator exhaust stack, such as process  vents  or  fugitive  emissions  sources,
may be  responsible  for  the levels and  diversity  of  semi-vol atile  compounds
detected in  ambient  air around  the plant.  Principal  semi-vol atile  compounds
found in this  study  were trichlorobenzene  (three isomers);  tetrachlorobenzene
(two isomers);  2,4-dichlorophenol ;  and  2,4,6-trichl orophenol , in  ranges  from
approximately 10 to 1000 ng/m3.

    6.  Sampling for volatile compounds in  ambient  air  did  not yield  valid  data
due to  failure  of a contract laboratory to  prepare  and analyze  field  samples
within acceptable sample holding times.   However, the results obtained have  been
reported and  interpreted  within   the  limits  dictated  by  quality  assurance
results.

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V.  DOW  CHEMICAL  MIDLAND  PLANT  BUILDING  703  INCINERATOR  EMISSIONS  STUDY

    A.  Facility Description

    The Dow Chemical  Company  operates  a  hazardous  waste  incinerator  at  the
Midland Plant  identified  as Building 703.   The incinerator is located in  the
southwest quadrant of the facility (see  Figure VI-1).   Liquid wastes,  tars,  and
containerized  and loose  solid wastes  are incinerated  at  this site.   Company
records indicate about 200  tons  per  day of solid and  liquid combustible  trash
and waste are  burned on a typical day.  Built as a rotary  kiln burner in  1957,
the incinerator  has been  augmented in succeeding years  by  addition  of  an after-
burner section and  air  pollution control   equipment  including   a quench tower,
venturi scrubber, demister,  and a wet electrostatic precipitator.   The level  of
complexity and expected efficiency of  this air pollution control  equipment  is
generally greater than typically  found  at other  municipal  or  hazardous  waste
incinerators in  the United  States.   A schematic drawing of  the incinerator  and
associated air pollution   control  equipment  as  currently configured appears  as
Figure V-l.

    1.  Waste  Feeds and  Incinerator Operational  Characteristics

    Waste feeds  to the incinerator are  as  follows:

    a.  Liquid Wastes

    Liquid wastes are delivered to the incinerator from an  adjacent tank  farm,
or via direct  burn systems in which individual  truck or trailer loads  of wastes
are consumed.    Three  wastes  may be  burned  simultaneously in  separate  feed
nozzles.  Two  of these nozzles, identified as "BA" and  "BB", are located at  the
head end of the  rotary kiln, and  each feeds wastes longitudinally at  an  average
rate of three to four gallons per  minute,  atomized   with  steam.   Waste feed
nozzle "C"  is placed  in the afterburner  section.    The   nozzle  is directed
approximately  at a right  angle to exhaust  gas  flow to  induce turbulence in  the
firing zone.  These wastes  are air-atomized,  and typically flow at an  average
rate of five to  six  gallons per minute.   Combustion  may be supplemented with
natural gas at all  three  nozzles.

    b.  Low-BTU  Liquid Wastes

    Collected  rainwater  or  surface  runoff  from within the liquid waste tank
farm and handling area,  and  other contaminated  water such as carbon  adsorption
bed condensates  and  runoffs from reaction vessel cleaning, may be fed to  the
incinerator as needed to  modulate temperature fluctuations.   This water  flow is
not continuous.   As  allowed by the MDNR24,  surface  runoff is  directed to  the
plant wastewater treatment  system  if the  total  organic carbon  content  is less
than 100 parts per million.

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WASTE FEED-
NOZZLES "8A"
AND  BB
LOW BTU
WASTE
                QUENCH/SERVICE
    AFTERBURNER     WATER
                                                                         VENTURI
                                                                          WATER
    COMBUSTION/
    ATOMIZATION
      AIR FAN
                                                         QUENCH
                                                         TOWER
                                             AFTER-
                                             BURNER
                                        VENTURI
                                        SCRUBBER
 RUBBISH
   AND
   BULK
  SOLIDS
                                             1000-
                                             IIOO'C
                               ASH   /
                             TROUGH f-*	SERVICE
                                    I	1    WATER
                                          (ASH TROUGH
                                            WATER)
                       KILN
                       COMBUSTION
                       AIR
                                                                                                          TO WASTEWATER
                                                                                                          TREATMENT
                                                                                                          PLANT
      CONTAINERIZED
        WASTES
     (PACKS,DRUMS)
ASH TO
CLASS I
LANDFILL
PRETREATMENT PLANT
AND WASTEWATER
TREATMENT  PLANT
                                                FIGURE  V-l

                                            SCHEMATIC  DIAGRAM

                                 DOW CHEMICAL  COMPANY BUILDING 703 INCINERATOR

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    c.  Containerized Bulk Wastes

    Various types of  wastes  in volumes too  small  or viscous to be  handled  in
the liquid waste system, and  solid  wastes  from  laboratory  operations,  facility
demolition and cleanup, are conveyed  to  the head end of the  rotary  kiln.   One
pack or barrel  of  containerized waste,  weighing a  maximum  of 200  pounds,  is
introduced to the kiln every  six minutes  from a staging area  in which  several
packs may be prepared sequentially  for incineration.   In a  typical  feed,  a  pack
is advanced from a  conveyor  to the outside  door of  an  air lock, the  air  lock
door opens, the  pack  is  pushed  into the  lock,  and the  outside door  closes.
Approximately 30 seconds later, the inside  air lock  door opens  and  the pack  is
dumped into the rotary kiln.  At this time, another  pack  is  moved to the outside
air lock door, and  the next pack in line  is conveyed  over a scale for weighing.

    d.  Miscellaneous Containerized Wastes

    On occasion, small quantities,  typically less than a few  liters,  of bottled
liquid or tarry wastes may be introduced directly to the rotary kiln.  A small
air lock, or "bottle drop", is provided for this  purpose, and  company  procedures
provide that a person  representing  the  area of  the  plant  generating the waste
be present during this operation.

    e.  Loose Rubbish

    Loose solid waste generated in  the Midland Plant  is  incinerated  at  Building
703.  These wastes,  consisting chiefly of paper,  plastics,  and wood,  are  dumped
into a  holding  pit  from whence  a  clamshell deposits batch  quantities into  a
shredder.  Shredded  wastes are  conveyed  at  a controlled  rate  of  four to  six
tons per hour through an incline to the incinerator.

    f.  Other Wastes

    Wastewater treatment  plant  solids were  formerly  fed  to the   incinerator
along with  loose rubbish.    However,  according  to  information   provided   by
plant representatives, this waste stream  was redirected  to  landfill  disposal  as
of July 1984.

    Combustion air  is  provided  through two  separate  forced-draft  fans  in  the
rotary kiln  and  afterburner  sections.   Oxygen   concentrations  of  at  least  3
percent, but  typically  over  10 percent,   are  maintained  in the   afterburner
exhaust.  Combustion temperatures within the rotary  kiln are designed to  vary
between 650° and 950°C, and between 1000°  and 1100°C in the  afterburner.   The
temperatures are maintained by  cycling the  combustion  of  wastes at the three
nozzles and by selectively adding low-BTU liquid  wastes  to  reduce high  tempera-
tures.  Thus, temperatures within  the  rotary kiln may  vary   over a  relatively
large range within  short time  periods.   However,  temperatures  within  the  after-
burner fluctuate much  more narrowly.   Although rotary kiln and   afterburner
pressures are held  slightly  negative, usually  between  -0.1  and -0.3  inch  of
water, violent  ignition  of waste  packs  can cause momentary  periods in which
positive pressures  are experienced.
                                     10

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    Gas residence  times within  the  incinerator  have  been  calculated  by Dow
Chemical as  one 'to  three  seconds  in  the rotary  kiln, and  approximately 1.5
seconds in the afterburner.21,22

    2.  Air Pollution Control  Equipment

    As indicated previously,  the  air pollution control  system  associated  with
the Building 703 incinerator consists of several components shown in Figure  V-l.
That figure  also  contains  a  schematic  of water  sources through  each  control
device.

    a.  Quench Tower

    Exhaust gases from  the  afterburner  pass  to the quench tower,  in  which gas
temperature is reduced  from about  1000°C  to below 100°C.  To accomplish this,
a normal  water  application  rate  of 650 to  750  gpm  is  maintained.   Secondary
treated wastewater from the  plant  wastewater  treatment system  is  the  primary
water supply.  Water  pumped  from  the company's Tittabawassee River  intake may
be used to  supplement  the  primary  supply.   Water effluents  from the  quench
tower split  into two  discharges   to the  plant  wastewater  treatment  system.

    b.  Venturi  Scrubber

    Cooled exhaust gases from  the quench tower are directed to a  variable-throat
venturi scrubber which  operates at  a pressure differential  of  15 to  30  inches
of water.   Water  application  rates are  typically between  200 and  275  gpm,
composed of secondary treated wastewater.  Venturi effluents combine with  the
discharge of the demister tower.  This heated water is directed  to  a portion of
the plant wastewater  system  in which  phenolic wastes are pretreated prior to
mixing with general  plant wastewaters.

    c.  Demister Tower

    A water flow of 700.  to 1000 gpm of secondary treated wastewater is maintained
through the 12-foot-diameter demister.

    d.  Wet Electrostatic Precipitator

    Exhaust gases from  the  demister  are  routed through an  induced-draft  fan
into a single-field  wet electrostatic precipitator.   The  emitting anodes  and
collection plates are arranged concentrically,  and  are cleaned with  a continuous
stream of water taken from  the  company's river intake,  at  a volume of  160 to
200 gpm.   Effluent  waters   are  directed  to  the  general  wastewater  treatment
system.

    e.  Stack

    A 200-foot-tall ,   12-foot-diameter  brick  stack vents  emissions  from   the
incinerator.  As  the  gas discharge  is  usually  saturated with water, the stack
has a drain to the general  wastewater treatment system,  for which Dow Chemical
estimates  a flow of 1 gpm.
                                     11

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    3.  .Other Haste Discharges

    The types and volumes  of  effluent wastewaters from the air pollution control
devices associated  with  the  incinerator  were described  above.   In  addition,
bulk solids  falling  from  the  rotary  kiln  are  quenched and  cooled  in  an  ash
trough through which  a  flow of  40  to  60 gpm of  water drawn from the plant's
Tittabawassee River  intake  is  maintained.    In  addition,   a  small  stream  of
untreated river water, estimated at 10 gpm,  flows  in  a  sluice under  the  rotary
kiln's head  end   to   receive  and convey  spills  of  heavy  particulate  matter
falling from  gaps  in the  seal.   The  effluent  waters  from  the  ash  trough
are routed to  the general  plant wastewater  treatment system.  About  15  to  20
cubic yards per day of solids are cleaned from the ash trough, and deposited in
Oow Chemical's landfill  located on Salzburg Road.

    B.  Sampling Strategy

    1.  Background

    As indicated  previously,  the draft  project  plan  for  the  National  Dioxin
Study Tier 4 - Combustion Sources formed  the basis for selecting the input and
discharge streams to  be sampled  in  this study.   However, that  sampling  scheme
was formulated for  a  comparatively  simple  facility  with  a  single waste input
and a  single  air  pollution  control  device.  To  adapt the  model  to the  Dow
Chemical incinerator, with  two  precombustion  air intakes,  four liquid  waste
feeds, and water  effluent  discharges  from four air  pollution control  devices,
required the collection  of a significant number of samples  to assess  conditions
during the emissions tests,  and to evaluate compounds  present in  exhaust gases as
they related to wastes incinerated on  the test days.

    2.  Target Compounds

    Table 1-1  presents  a  list of samples  and analyses  required for  a  Tier 4
sampling program.  The lists  of target compounds  presented in  Tables V-l  and
V-2 for air  components, water,  and  solid samples  build upon  the primary list.
In the  case  of the latter, the  compounds added  include  several which  may  be
precursors to  formation of  polychlorinated  dibenzo-p-dioxins (PCDDs)  and poly-
chlorinated dibenzofurans  (PCDFs)   when  subjected to  elevated  temperatures.
These compounds  were  also  selected based upon information  about  Dow Chemical
manufacturing  processes  and liquid wastes consumed at the incinerator.  For air
components, compounds with  known or suspected health  effects when  respired in
ambient air, such as carbon tetrachloride and trichloroethylene, were added for
the purpose  of determining  whether significant  air  emissions, from  a  public
health standpoint, were occurring from the incinerator.

    The compounds listed  in Tables  V-l  and  V-2 are  arranged by analysis type
(PCDD/PCDF, semi-volatile  organic   (semi-VOA), and volatile  organic  (VOA))  to
enable association with  the sampling methods  presented in the  following section.

    The Tier 4 sampling  and  analysis matrix shown in Table 1-1 includes analyses
for total organic chlorine  in  the two  classes of  input streams, and for PCDDs.
It was determined that available methods for sampling for total  organic chlorine
                                      12

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                                   TABLE V-l

                 DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                            TARGET COMPOUNDS IN AIR
Analysis Type

  PCDD/PCDF
Semi-volatile
  Volatile
2378-TCDD
21 TCDD isomers
Total PeCDD
Total HxCDD
Total HpCDD
OCOD
2378-TCDF
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
OCDF

Polychlorinated biphenyls (as positional isomer classes)
Other chlorinated biphenyls
Chlorinated phenols
Chlorinated benzenes
Diphenyl oxide
Chlorinated diphenyl oxides
Phenol
Phenyl phenol
Biphenyl

Carbon tetrachloride
Ethylene dichloride
Perchloroethylene
Trichloroethylene
Vinylidene chloride
                                     13

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                               TABLE V-2

             DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
            TARGET COMPOUNDS IN WATER AND SOLIDS DISCHARGES
Analysis Type

  PCDD/PCDF
  Vol
Semi -
Semi -
Semi -
  Vol
Semi -
Semi -
Semi -
Semi-
Semi-
Semi-
  Vol
Semi-
Semi-
  Vol
Semi-
Semi-
  Vol
Semi-
  Vol
Semi-
  Vol
  Vol
atile
volatile
volatile
volatile
atile
volatile
volatile
volatile
volatile
volatile
volatile
atile
volatile
volatile
atile
volatile
volatile
atile
volatile
atile
volatile
atile
atile
2378-TCDD
21 TCDD isomers
Total  PeCDD
Total  HxCDD
Total  HpCDD
OCDD
2378-TCDF
Total  TCOF
Total  PeCDF
Total  HxCDF
Total  HpCDF
OCDF
Benzene
Biphenyl
Chlorinated biphenyls (as positional isomer classes)
Biphenyl phenyl ether
Carbon tetrachloride
Chlorinated benzenes
Chlorinated phenols
Diphenyl oxide
Chlorinated diphenyl oxides
Di vinyl  benzene
Ethyl benzene
Ethylene dichloride
Hydroxybenzaldehyde
Hydroxybenzoic acid (ortho and para)
Perchloroethylene
Phenol
Phenyl phenols (ortho and para)
Styrene
2,4,5-T and esters
Trichloroethylene
Vinyl  toluene (ethenyl methyl benzene)
Vinylidene chloride
Xylene
                                  14

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in liquid streams would not distinguish between organic and inorganic  chlorine;
also, the analytical methods  were  not of  sufficient  accuracy to be of use  in
this study.  For this  study,  analyses for PCDDs and  PCDFs  were  limited to the
tetra-CDO isomers, total tetra- through hepta-CDD and  CDF  homologues, and OCDD
and OCDF.

    In addition  to  the  above  analytical  work,  incinerator emissions  were
evaluated with   respect  to  requirements  for  hazardous   waste  incinerators
developed pursuant to  the Resource  Conservation and  Recovery Act (RCRA) and
listed at  40   CFR  Part  264.343(c).   Specifically,  particulate  emissions for
incinerators consuming  hazardous  waste  are limited  to 0.08 grain/dscf.   In
accordance with the regulation, the weight  of  particulate  matter caught in the
filter and probe wash  portion  of the  Modified  Method   5 train on   each sampling
day was  reported  and   compared  against  the   standard.    Consistent  with the
requirements of  EPA Method  5,  this   analysis did  not consider any  of the
particulate matter trapped in  the "back half"  (impinger catch) of the  train;  in
any event, such an analysis would have disrupted the determination of  PCDDs and
PCDFs in this  portion  of the  train,  and would  likely  have added little to the
total  catch of particulate matter.

    3.  Sampling Locations

    The following  streams  and  locations  were  selected for  sampling based upon
the unique characteristics  of  the Building 703 incinerator.  These  locations
are also described in the quality assurance  project plan written by the sampling
contractor, GCA  Corporation,  in  preparation   for  conducting  sampling  work.5

    a.  Precombustion Air

    The Tier  4  project  plan  requires  sampling of   precombustion  air  if  a
significant source of  suspected PCDD precursors  is   in the vicinity  of the
sampling site.   It was  known  that  2,4,5-trichl orophenoxyacetic  acid  and  other
precursor chemicals were  manufactured or handled at  several locations  within
the Dow  Chemical   facility.   Also,  previous   work  by EPA  and   Dow  Chemical
established that surficial soils in the plant   were contaminated  with  2378-TCDD
and other PCDDs, notably  in the  immediate area of the  incinerator.   For  these
reasons, precombustion  air was  sampled.

    As indicated earlier,  the  rotary  kiln  and afterburner  sections  each have
combustion air  intakes.   Given the   proximity  of  these air intakes,  it was
estimated that ambient  air  quality would be similar at  either intake; therefore,
only one  of  the  intakes was  sampled.  Owing  to  greater  accessibility, the
rotary kiln air intake  was selected.

    b.  Liquid Waste Feeds

    Each of the  three  liquid waste feed  nozzles, and   the  low-BTU liquid  waste
nozzle, was fitted  with an existing  valve  and  spigot  for  sample collection.
Samples were  taken  directly   into  holding containers  from these  spigots.
                                     15

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    c.  Incinerator Exhaust

    Because a variety  of sampling  equipment  was  employed  in  collecting and
analyzing exhaust gas samples, three separate locations were selected.  As  shown
in Figure  V-2,  the  sampling  locations  were  between  the  outlet  of  the wet
electrostatic precipitator and  the  stack  breeching.

       (1)  PCDDs, PCDFs, and  Semi-Volatile  Compounds

        An existing pair  of four-inch sampling ports spaced 90° apart was used to
    operate two  Modified Method 5 trains, one  dedicated to  PCDDs and  PCDFs and
    the other to  semi-volatile pollutants.  The  trains  were  operated simul-
    taneously in the two ports, such that the probes did not interfere or  cause
    turbulence with respect  to each other.   As Figure  V-2  indicates,  the  ports
    were sufficiently  separated  from  upstream  and  downstream  bends  in the
    three-foot-diameter exhaust duct,  to comply  with  the  requirements  of EPA
    test Method  1.

       (2)  Volatile Compounds

        A single  four-inch-diameter  sample  port  located  about  six feet  down-
    stream of a  90° duct bend was employed for gas sampling  utilizing a Volatile
    Organic Sampling Train (VOST),  described later in  this  report.

       (3)  Continuous Emissions Monitoring  and Sampling for Vinyl idene Chloride

        Continuous emissions monitor (CEM) probes for  oxygen, carbon  monoxide,
    and carbon  dioxide  were inserted  into  the exhaust duct  at  a point  about
    five feet downstream  of the  VOST, and  three  feet upstream of  the  stack
    breeching.  In addition, several samples for direct analysis of vinylidene
    chloride were  drawn   through  a  separate  probe   inserted  at  this point.

        The exhaust  of  a carbon-bed  adsorbing column is  located  between the
    first and second sampling  locations described above.   The column is  used to
    filter airborne hydrocarbon emissions displaced from the loading  of liquid
    wastes into  the  incinerator  tank  farm.  These   emissions  were   formerly
    vented to the atmosphere.  The  adsorber  was  installed  in  July  1984 and
    operates only  when  liquid  transfer to the tank farm  occurs.  As  no  other
    appropriate sampling locations were available for  the  VOST,  CEM, and Tedlar
    bag samplers, it was decided to use those ports.   The  compounds detected  in
    the exhaust  gas  were to be evaluated  with respect to  the likelihood they
    may have arisen from carbon bed operation, as well  as  combustion within the
    incinerator.

        (4)  Sampling Incinerator Emissions Before Control  Devices

        The Tier 4 sampling  and analysis protocol  (see  Table 1-1) prescribes that
    samples be  taken  for PCDDs and PCDFs  at  a  point preceding air  pollution
    control devices.  The feasibility  of obtaining these  samples was  evaluated
    early  in the  test planning process; no access  to exhaust  gases was  available
    prior  to  the quench  tower, other  than  a  single   port  at  the  rear of the
                                      16

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MMS 	
SAMPLING
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SAMPLING
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                                WET
                                ESP
-10'
                          VOSTone
                            amp ling Port
                      CEM
                      Sample
                      Port
                                               200'
                              FIGURE V-2
           DOW CHEMICAL  COMPANY  BUILDING 703 INCINERATOR
                      EXHAUST GAS SArirLING POINTS
                                17

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    incinerator afterburner which formerly held temperature  monitoring  probes.
    Because this location did not satisfy the  requirements  of EPA Method 1  in
    terms of separation from flow disturbances,  it  was  rejected.

        A second possible test location  at  the  outlet  of the quench tower was
    considered and rejected as only a single port  was  provided in a duct bend.
    Samples of exhaust  gases prior to air pollution  control devices were thus not
    taken as appropriate test locations  were  not available.

    d.  Incinerator Ash

    Heavy solids are removed from the incinerator  ash trough  by a  dragout chain
which is operated  for  about  ten  minutes per hour.  Grab samples  were taken  of
material conveyed  out  of the trough by  the  scraper mechanism associated with
the dragout chain.

    e.  Influent and Effluent Water  and  Control  Device  Ash

       (1)  Influent Service Water

        Samples of the secondary  treatment water returned to  the  incinerator  to
    serve the quench tower,  venturi,  and demister were drawn from a one-inch-
    diameter spigot at the influent  side of  the  quench  tower.  Suspended solids
    are filtered  from  this influent  water  immediately  prior  to  the sampling
    point; therefore,  separate  samples  or  analyses of  the  solids  portion  of
    this stream  were  not specified.  Samples  of   influent water  from  the Dow
    Chemical Tittabawassee River  intake, which is  directed  to the ash  trough
    and electrostatic  precipitator,  were not obtained.   Previous sampling  by
    EPA in  1981  showed  PCDDs  and  PCDFs  in  this  stream were  not  present  at
    detection levels of 7 to 60 parts per quadrillion.

        (2)  Quench Tower Effluent

        As described previously,  waters  leave the quench tower through two dis-
    charges.  The  composition  of both discharges  was  expected  to be similar;
    therefore, one discharge point,  referred to as  the west discharge, was chosen
    for sampl ing.

        Advance  inspections of the facility  indicated the effluent streams from
    the quench tower were heavily laden with suspended  solids from contact with
    incinerator  exhaust gases.  As the draft Tier 4 project  plan  specified that
    air pollution control device  ash was to  be analyzed separately,  analyses  of
    the aqueous  and filterable solids portions of these samples  were performed.

        (3)  Venturi Scrubber/Demister Effluent

        Effluent streams from these  devices combine  prior to  discharge to a sump
    located beneath the venturi scrubber, and samples were taken here.   Analyses
    of  aqueous and filterable solids portions were specified.
                                     18

-------
       (4)  Electrostatic Precipitator Effluent

        These samples were obtained  from  a discharge  sump  beneath the electro-
    static precipitator, and  separate analyses of aqueous and filterable solids
    portions were requested.

       (5)  Ash Trough Water  Effluent

        About 50 gpm  of water  overflows  the  ash  trough for  discharge  to  the
    general  wastewater  treatment  system.   Samples  were taken  of this  stream
    from a short open discharge flume located near the rotary kiln incinerator.
    The aqueous  and  filterable solids  portions  of  each sample  were  analyzed
    separately.

    C.  Conduct of Study

    Incinerator sampling   was  planned  to  include  three  separate  days   of
operation, with each day's sampling spanning  eight hours.  This sampling period
was chosen  to  assure that sufficient  materials  would  be  collected  to  enable
compound detection,  possible  replicate  analyses,  and  splitting  of  sample
extracts between analytical  laboratories.

    The following influent and effluent streams of the Building 703 incinerator
were sampled, when applicable, during the  three-day study period:

        Influent Streams

            Precombustion Air (incinerator makeup)
            Liquid Waste Feeds (maximum of four inlet nozzles)
            Influent (service) Water

        Effluent Streams

            Incinerator Exhaust
            Incinerator Ash
            Effluent Water (from incinerator  and  air pollution control devices)
            Air Pollution Control  Device Ash

Each stream was sampled  for the presence of PCDDs  and  PCDFs and the semi-volatile
and volatile  compounds  referenced  in Tables  V-l and  V-2.    In  addition,  the
incinerator exhaust was sampled using  a  specialized analytical  method specific
to vinylidene  chloride.   Detailed  information with  respect  to the  conduct  of
the study,  including  sample   handling  and custody,  analytical  procedures,  and
incinerator operations  while  samples were obtained,  appears  in  Appendix A  of
this report.

    Sample collection and other field work were documented by the USEPA's field
contractor (GCA Corporation)  and USEPA  personnel.  Sample documentation included
unique identification numbers and  tags or labels;  field workbooks;  USEPA  and
GCA-generated sample custody  records; and  USEPA Sample Management Office Traffic
Reports and Packing Lists.
                                      19

-------
    Samples were gathered  and  handled according  to  the  protocols outlined  in
the USEPA draft study plan? with minor revisions  prompted by  field conditions.
Generally, the samples were composited over time to represent the entire  sampling
period on each day.  However, for volatile compounds in aqueous streams (influent
and effluent water) and  in  liquid  waste  feeds, single grab samples were  taken
as no  reliable  method  was available to  composite such samples.   In addition,
as discussed  in  the  "Analytical  Procedures"  section  of  Appendix A,  separate
analyses were provided of the  concentrations  of  the above constituents in  the
liquid and  in  the  suspended or  settleable solids  (filtrate)  portions of  the
influent and   effluent  waters.    For  volatile   compound   analyses,   however,
unfiltered grab  samples  of  influent  and  effluent  waters  were  analyzed  as  a
whol e.

    The samples collected during this study were  identified,  packed (cooled  as
appropriate), and either  shipped via  commercial   services for  next-day  arrival
at contract laboratories, or, in the case  of  certain samples  for which holding
times prior  to  analysis  were  not   of  concern, delivered  by  USEPA personnel.

    D.  Analytical  Procedures and Quality Assurance  Reviews

    1.  Analytical  Procedures

    Selection of contract laboratories  was coordinated by  the USEPA   Region  V
Central Regional Laboratory.   Individual   contracts  were  prepared for  various
groups of compound analyses, and sent  to candidate laboratories  for bid.   The
laboratories ultimately selected  were the  EAL Corporation, Richmond, California,
for volatile  compounds,  semi-volatile compounds,  pesticides,  and PCBs;  and  the
Brehm Laboratory, Wright  State  University, Dayton,  Ohio, for  PCODs and PCOFs.
For the former,  analytical  methods  are detailed  in  Appendix A,  Section III  of
this report.   Analytical   procedures  for  PCODs   and  PCDFs   are  described   in
References 7 and 8, and Appendix C.

    Several samples  were  taken  of  liquid  wastes   fed  to  the  Building  703
incinerator.  It was  known  in advance that  these wastes were highly concentrated
in single  compounds, making  them hazardous for analysis without  prior extrac-
tion.  Procedures  for  separating   and   all quoting   these   waste  samples  are
presented in  Appendix B  to  this  report.   This  work  was carried out by  Fred  C.
Hart Associates,  Inc.,  Denver,  Colorado.  The  extracts  were  shipped to  EAL
Corporation for analysis.

    2.  Quality Assurance Reviews

    Data returned from the  contract laboratories  were  reviewed for consistency
with contract  requirements  by the USEPA  Sample Management  Office  (Viar  and
Company, Alexandria, Virginia), and for adherence to quality assurance  criteria
contained in  the Quality Assurance Project  Plan  developed  for  the study (see
Reference 7) by the USEPA Region V Central Regional  Laboratory.  The  results of
these  reviews  are  referenced  in  the discussion of  general  analytical  findings
which  follows as Section V.F of this report.
                                      20

-------
    E.  Incinerator Operations During Tests

    Extensive data concerning the operation of the Building 703 incinerator  and
the wastes burned during emissions  testing were recorded by Dow  Chemical ,  GCA
Corporation, and USEPA personnel.  This information is  compiled  in  Appendix A,
Section IV.

    F.  Results and Discussion

    1.  General  Findings

    Detailed results  of  sample  analyses   associated   with  the  Building  703
incinerator emissions study are presented  in  Appendix D.   Table  V-3  summarizes
the streams that were sampled  and the compound groups  analyzed.  As  indicated
previously, no samples of loose or  containerized  solid  wastes  were  taken  owing
to the unavailability of suitable sampling  methods.

    Detailed operating  and  sample  analytical  data were  gathered during this
study to  enable  association  of  emissions  with  such  phenomena  as  incinerator
temperatures, air pollution control  device  operations,  wastes incinerated, and,
if possible, to derive pollutant mass balances around the incinerator.   However,
as discussed in  Section  III.A.  of Appendix D to  this  report,  some  limitations
were placed  on  the acceptability of  some  of the  data.  For PCDOs  and  PCDFs,
specifically, the recoveries  of surrogate  compounds used to assess the accuracy
of analysis for  certain homologue groups were not always  within  the relatively
narrow ranges of acceptability  established  initially for this study.   The ranges
established in the  study  plan7 were also  revised  to  be consistent  with  those
normally used by USEPA and others in the conduct of studies of  PCDDs and PCDFs.
In any event, overall completeness  of  PCDD and PCDF analytical  data  tended to
be best for  the tetra- through hexa-CDD  homologues,  for  which  health-related
concerns are greatest.

    For volatile  and  semi-volatile  compounds,  individual  analyses  were con-
sidered fully acceptable  only  if the  recoveries  of  all   introduced  surrogate
compounds were  within  prescribed  ranges.   There  is  no  generally  accepted
protocol  which would  permit  selective acceptance, compound  by compound,  based
upon the  recovery  of specific  single  surrogates.  However, for  semi-volatile
compound data, analytical  results for an acid compound  were considered valid if
the recoveries of  all  acid surrogates  were  acceptable; the same was  done  for
base-neutral compounds.   Overall data  completeness  for  semi-vol atil e' compounds
was based upon acceptable recoveries of all six surrogate compounds.

    a.  Influent Streams

       (1)  Precombustion Air

        As described previously,  this  stream was  sampled at the  air  intake of
    the rotary  kiln  portion  of the  Building 703 incinerator, but  is  taken to
    represent the  characteristics of  all  air  drawn  into the incinerator  and
    afterburner at any  point  preceding the combustion  process.  These data  may
    also be  used to  assess the  characteristics  of ambient air in the immediate
    vicinity of the incinerator.


                                     21

-------
                                                       TABLE V-3
ro
ro
Influent Streams

   Precombustion Air

   Liquid Waste Feeds

   Influent (service) Water



Effluent Streams

   Incinerator Exhaust

   Incinerator Ash

   Effluent Water

   Air Pollution Control Device Ash3
SAMPLING AND ANALYSIS SUMMARY
iL COMPANY

Volatile
Compounds-
X
X
X
X

X

BUILDING 703 INCINERATOR EMISSIONS STUDY
8/28, 8/30, 9/5/84
Semi -Volatile Pesticides
1 Compounds2 and PCB PCDDs
X
X X
X
X
X
X
X


Vinylidene
and PCDFs Chloride
X
X
X
X X
X
X
X
    foiling  points  less  than  100°C.
    ^Boiling  points  greater  than  100°C.
    3Analysis of  filterable  solids  from effluent
     wastewater streams  from individual air
     pollution devices associated with the
     incinerator.

-------
    Data for  volatile  pollutants   (see  Table  V-4)  showed  the  possible
presence of the following compounds  in the 1 to 100 parts-per-bill ion range:

            carbon tetrachloride,
            monochlorobenzene,
            trichloroethylene, and
            ethyl benzene.

However, the stringent quality assurance criteria (see discussion in Section
III.A. of  Appendix  D)  established  for accuracy were  such that only  three
of eight  (38%)  of  the  precombustion  air  volatile  compound analyses  were
considered acceptable.  Also,   field  duplicate  sample  analyses,  limited
to one  of the  three  sampling  days,  suggested  the  quantitation  of  only
monochl orobenzene to  have  been  reliably  established.   The  semi-volatile
compound 1,4-dichlorobenzene was  detected  with good  precision, and  these
data are included in  Table  V-4  for informational  purposes; however,  as  no
calibration standard for dichl orobenzene was  run  in the  volatile  compound
analysis, the analytical method  for semi-volatile  compounds is more appro-
priate for this compound.  Reference is made to Table V-5, where the detected
semi-vol atile compounds are listed.

    Of the semi-vol atile compounds  (Table  V-5), the  following  were present
in concentrations of approximately  1 ug/m^:

            1,2-dichlorobenzene,
            1,3-di chl orobenzene,
            1,4-dichlorobenzene,
            1,2,4-trichlorobenzene, and
            naphthalene.

In addition, monochlorobenzene was  detected at  levels apparently lower than
those indicated by the  sampling method  for volatile  compounds.4   However,
this is not  considered  a  reliable  quantitation, as a calibration  standard
was not  run  for this analyte.  Tentative findings  of low levels  of  other
benzene-ring compounds are detailed in Appendix 0,  Table D-3.  All of  the
eight samples  taken  over  the three-day  period  were  found  to be  accurate
within acceptable limits;  however,  precision  criteria  were met  only  for
1,2-dichlorobenzene and 1,2,4-trichlorobenzene.

    Levels of PCDD and  PCOF (Table V-6) ranging from approximately 10 to over
800 pg/m3 of various homologues  were  found on  all three  sampling  days,  and
about 5 pg/m^  of  2378-TCDO was detected on the second sampling  day.   The
data appear to  show the consistent  presence of TCDD,  OCDD,  TCDF,  and  OCDF,
along with  scattered  findings  of   other  homologues.  More detailed  data
concerning TCDD isomers appear in Appendix  D.

   (2)  Liquid Waste Feeds

    The concentrated liquid wastes  incinerated  on the three  sampling  days
contained a wide variety of volatile  compounds, fully shown in Appendix D,
Table D-10 (and summarized  in  Table V-7), including  several  chlorinated  and
                                 23

-------
                            TABLE V-4

             VOLATILE COMPOUNDS - PRE-COM8USTION AIR
          DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                        8/28, 8/30, 9/5/84

                 COMPOUND CONCENTRATION (ug/m3)l
                                  COMPOUNDS DETECTED















SAMPLING DATE
8/28/84
8/28/84
(Field Duplicate)
8/30/84
9/5/84
Precision (RPD)
8/28/84
Samples
























-o
c_
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o
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c_
+J

M
C
cu

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jr
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10.63
29.26

--
—
93

1  Sample Concentration Less Field Blank Concentration
2  Compound Tentatively Identified
                              24

-------
                                                           TABLE V-5



                                          SEMI-VOLATILE COMPOUNDS - PRE-COMBUSTION AIR

                                         DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR

                                                       8/28, 8/30, 9/5/84



                                                 COMPOUND CONCENTRATION (ug/m3)!
                              TARGETED COMPOUNDS
OTHER COMPOUNDS DETECTED
ro
en




















SAMPLING DATE
8/28/84
8/30/84
8/30/84
(Field
Duplicate)
9/5/84
Precision (RPD)
8/30/84
Sampl es


01
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1.42
0.84
1.03

3.73

21



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1.58
0.86
1.19

2.59

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               Sample  Concentration Less Field Blank Concentration

               Compound Tentatively Identified

-------
                                                              TABLE  V-6

                                         INCINERATOR  PRECOMBUSTION AIR -  PCDD/PCDF ANALYSES
                                            DOW CHEMICAL  COMPANY  BUILDING 703 INCINERATOR
                                                         8/28,  8/30,  9/5/84
SAMPLE IDENTIFICATION
8-28-84
MODIFIED METHOD 5 TRAIN
FIELD DUPLICATE
FIELD BLANK
8-30-84
MODIFIED METHOD 5 TRAIN
FIELD BLANK
9-5-84
MODIFIED METHOD 5 TRAIN
FIELD BLANK
2378-
TCDD
ND
(7.86)
ND
(11.32)
Total
TCDD
58.21
ND
(53.4)
Total
PeCDD
ND
(11.01)
ND
(131)
Total
HxCDD
ND
(6.62)
ND
(125)
Total
HpCDD
ND
(12.02)
ND
(5.43)
OCDD
216.60
335.14
2378-
TCDF
ND
(7.89)
ND
(29.2)
Total
TCDF
391.22
628.02
Total
PeCDF
ND
(6.07)
ND
(6.01)
Total
HxCDF
ND
(16.2)
ND
(4.20)
Total
HpCDF
ND
(27.50)
ND
(8.45)
OCDF
21.18
ND
(30.2)
(Sample analysis not returned from laboratory.)
5.16
ND
(0.77)
ND
(1.48)
ND
(0.55)
17.99
ND
(0.41)
38.90
ND
(0.35)
ND
(2.30)
ND
(2.17)
ND
(0.94)
ND
(0.40)
10.39
ND
(3.67)
ND
(1.46)
ND
(0.85)
235.10
ND
(4.51)
98.14
ND
(2.15)
802.08
ND
(11.85)
306.51
ND
(4.83)
12.93
ND
(1.11)
ND
(1.74)
ND
(0.39)
12.93
ND
(1.20)
206.60
ND
(0.29)
12.50
ND
(1.96)
ND
(1.45)
ND
(0.37)
14.23
ND
(3.28)
ND
1.42
ND
(0.33)
108.48
ND
(5.20)
37.43
ND
(3.08)
113.67
ND
(13.93)
30.95
ND
(4.21)
ro
en
          Note:   Data expressed  In  pg/m^.
                 Detection  level  indicated  in parentheses.

-------
                                                             TABLE  V-7
                                       QUANTITATED VOLATILE  COMPOUNDS -  LIQUID WASTE  INPUTS
                                           DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                        8/28. 8/30. 9/5/84
                                    TARGET
                                   COMPOUNDS
   OTHER
CHLORINATED
 COMPOUNDS
BENZENE RING
 COMPOUNDS
  OTHER
COMPOUNDS

REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA Dilution
Nozzle BB fl
Nozzle BB It
Nozzle BB *2 Dilution
Nozzle C
Nozzle C RERUN
Field Blank
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB 11
Nozzle BB 11 Field Duplicate
Nozzle BB 12
Nozzle BB 12 Field Duplicate
Nozzle BB ft Meld Duplicate RERUN
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Duplicate RERUN
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA Dilution
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C Dilution
Nozzle C Field Blank
Monochl orobenzene




15300













17700


(St


749C
4340





Carbon tetrachloride





















Chloroform





















1 BELOW)






446.270
283.000







2970
3260

01
•o
l_
o
J=
0

C_
0
.c
o

144
















77200





128.500
137,200
1804
173
2838
2900

Tetrachl oroethyl ene




//UO












04b
«4bO





9180
4400





Benzene
131
192





3ll























Ethyl benzene



1494
2050
35600











2890
2850


44700


1290

1540


96320

IV
c
Ol
i.
>>
4J





350
15900






35500








42400




1573


230,400

Toluene





1700
260

2370
2110


1950





43400

210
2440



9920


4620
4340

V)
o>
c
o>
*>,
X
'n
*J
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2700






1850




2920


1600







176,405


Acetone
393


1478



1700
990
950






65
14


260








2-Butanone
1U5/























1




(SEE 1


2-Hexanone












J4UU







9b3U
9bUO







3tLUW

Bromomethane






4/0
























NOTES:
        1.  Sample extracts were diluted, prior to analysis, five times or more.
            were  therefore  out of acceptable ranges.
        2.  Data expressed  In  mg/kg.
                           Surrogate  recoveries

-------
benzene-ring compounds.   A  complete  listing  of  tentatively   identified
volatile compounds appears in Appendix D,  Table 0-11.   However,  nine  of  the
28 individual • analyses for volatile compounds were judged  to  be unacceptable
in terms of  accuracy (see Appendix  D, Table  0-10),  as  recoveries for  all
surrogate compounds  were  not  within  the  ranges established for  the  study.
For semi-volatile  compounds  (Table  V-8),  15  of  the  29 samples  submitted
were analyzed with  satisfactory  accuracy  for all six surrogate  compounds.
(see Appendix 0,  Table  D-12);  some chlorinated phenols and other benzene-
ring compounds were qualitatively detected on  the first  and  second sampling
day.  A discussion of possible limitations  on  the use of these semi-vol atile
data may be found in Appendix D,  Section  III.0.2.

    Pesticides in the low ppm  range  were tentatively  found  (see  Table V-9)
on scattered  occasions,  but  accuracy data   were  not  submitted  by  the
analytical  laboratory,  and  available precision data appear poor.  No PCBs
were found  in any liquid  waste;  however,  the detection limit requested  of
the analytical laboratory, 5 ppb, was  not met,  by at  least  three  orders  of
magnitude.

    When found,  PCDDs  and  PCDFs  appeared  in  liquid  wastes   fed  to  the
incinerator through nozzles BB and C.   The data  in Table V-10 show generally
good precision between  duplicate  samples  from these  nozzles on  the  second
sampling day; accuracy  goals  were   generally  met  for surrogate  compounds
(see Appendix D,  Table 0-17).  Of the  TCDD  isomers, the  1368 and 1379 were
most prevalent.

   (3)  Low-BTU Liquid Waste

    A comparison  of volatile  compounds detected (Table  V-ll)   reveals,  as
expected, concentrations  significantly  lower  in  1 ow-BTU  liquid   wastes
than in the liquid  wastes  described  above.   Concentrations  in the  range of
10 to  100  ug/L  were  established on  the  third  sampling day  for vinyl idene
chloride, ethyl ene  dichloride,  and  chloroform,  within  satisfactory  limits
for precision  and accuracy.   Of  the  semi-volatile compounds (Table  V-12)
only 1,2-dichlorobenzene  was  found,  within  acceptable  quality  assurance
1imits.

    Analyses  for  PCDDs and  PCDFs  were  generally successful  in achieving
accuracy goals  for  PCDD surrogates  but not for PCDF  (see Appendix D, Table
D-17).  Therefore,  the  TCDF data contained  in Table  V-13 may  be suspect.
However, homologue-by-homologue precision on  the third sampling day met  the
goal established  for the study (<50%  relative  percent difference).  Dioxin
homologues  were  limited  to  tetra,  hepta,  and  octa, and  low-ppq  concen-
trations of TCDF  were indicated.   As with  the  liquid wastes described
previously, most  TCDD was composed of the 1368 and 1379 isomers; no 2378-TCDD
was  found.
                                  28

-------
                                    TABLE  V-8
            QUANTITATED  SEMI-VOLATILE  COMPOUNDS  -  LIQUID  WASTE  INPUTS
                  DOW  CHEMICAL  COMPANY BUILDING  703  INCINERATOR
                                8/28,  8/30,  9/5/84
                                              TARGET
                                             COMPOUNDS
BENZENE RING
 COMPOUNDS
OTHER

REAGENT BLANK 1
REAGENT BLANK 2

8/28/84
Nozzle BA
Nozzle BA, 5X Dilution
Nozzle BA, 20X Dilution
Nozzle BB #1
Nozzle BB #1, 10X Dilution
Nozzle BB #1, 20X Dilution
Nozzle BB #2
Nozzle BB #2, 10X Dilution
Nozzle C
Field Blank (Nozzles BA & BB)

8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #1 Field Duplicate
Nozzle BB #1 Field Duplicate, 5X Dilution
Nozzle BB #2
Nozzle BB #2 Field Duplicate
Nozzle BB #2 Field Duplicate, 10X Dilution
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Duplicate, 10X Dilution
Nozzle C Field Blank

9/5/84
Nozzle BA
Nozzle BA, 10X Dilution
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C, 10X Dilution
Nozzle C Field Blank








































1,2-dichlorobenzene



















1406
1570



1240













o
c
(U
-C
a.






































2,4,5-trichlorophenol







4690
1900















4450













2,4,6-trichlorophenol

















110

8320
5570



4490













Naphthalene







144











680




34b
fc>2












2-methyl naphthal ene







77








33


2320
1950




27












Anthracene




















bbU



41)













Fluorene



















190




14b




















































Diethylphthalate








10500
60800






1390
1130



5930
110



270











NOTE:   Data expressed in mg/kg.
                                       29

-------
                                                        TABLE V-9
                                LIQUID WASTE INPUTS - QUANTITATED PESTICIDE/PCB COMPOUNDS
                                      DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                  8/28, 8/30, and 9/5/84
                                                          PESTICIDES
                                                       PCB (AROCLORS)

REAGENT BLANK 1
REAGENT BLANK 2

8/28/84
Nozzle BA
Nozzle BB #1
Nozzle BB #2
Nozzle C
Nozzles BA & BB Field Blank
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #1 Field Duplicate
Nozzle BB #2
Nozzle BB #2 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C Field Blank

c
•1—
c_
~o
<










1.4






3.1








o
:r
CO
i

-------
                                                 TABLE  V-10
                                LIQUID  WASTE  INPUTS  - QUANTITATED  PCDD/PCDF
                               DOW  CHEMICAL COMPANY  BUILDING  703  INCINERATOR
                                          8/28,  8/30,  and 9/5/84

REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #2
Nozzle C
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #1 Field Duplicate
Nozzle BB #2
Nozzle BB #2 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BB
Nozzle BA Field Blank
Nozzle C
Nozzle C Field Blank

























0
O
O
I—
1
00
r--
co
evi
























o
Q
0
i—
(O
4->
o
I—





5.8
0.5




33.0
30.7


60.3
21.8



5.9

0.8

o
Q
O
0)
Q_
*
o
i—





11.8





6.3
4.9


3.5
6.1



0.8
(SAM


Q
Q
O
X
in

o
1—





1.2





0.9
0.4


2.6
4.2




>LE AN/


Q
Q
O
Q.
3C
r—
(O
4-J
O





2.8





3.0
2.6


3.8
5.7




Q
Q
0
O





22.0





11.5
12.1


19.8
19.8



1.2
U.YSIS NOT RE1




u_
Q
0
1—
1
oo
r^
oo
CVJ











0.3
1.4



2.1



0.2
Li-
CS
O
I—
fO
4J
0
1—





9.2
0.4




37.0
32.3


36.6
18.0



6.5
LL_
0
{_>

0
1 —





0.8





1.8
5.3


1.5
4.3



0.2
u_
Q
0
X
nr
(O
4->
O
t—











0.7



3.5
7.1




fURNED FROM LABORATORY)


0.2





u_
Q
C_3
Q.
rc
(C
-M
o
1—











0.6



8.1
8.2







Ll_
Q
<_>
O





1.2





0.6



7.4
7.7







NOTES:    Data expressed in ng/g.
Where data are not stated, homologue was not detected,

-------
                                                TABLE  V-ll

                                 LOW-BTU  LIQUID WASTE  -  VOLATILE  COMPOUNDS
                               DOW CHEMICAL  COMPANY  BUILDING  703  INCINERATOR
                                              8/28 AND 9/5/84
                                                                                               TENTATIVELY
                                                                                               IDENTIFIED
                                                                                                COMPOUNDS










>













8/28/84
COMPOSITE SAMPLE
FIELD BLANK

9/5/84
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK



|

r-H
*
i— 1
*
t-H







24

























4












O)
C
O)
N
C
0)
_o
^—
>»
_c
+J
0)







14

















O)
c
Ol
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4J
to







12






O)
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(_
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0

Ol
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6
170


112?
1241


















O)
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^_
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127
137






0)
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t_
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u
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T3

0)
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86
93















p
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t_
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12
13








O)
c
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378













O)
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0)
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(_
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260














(U
c
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429
7659





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c_
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C-
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2916










(U
c
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J=
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8









i
o
r—
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>> a
o c
• — «
>> >
^ c
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QJ ••-
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(O ••-
x t-
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200
ai
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2791
6222












a>
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N
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(U
JD

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1160


NOTE:  Data expressed in ug/L.

-------
                                                    TABLE V-12
                                   LOW-BTU LIQUID WASTE-SEMI-VOLATILE COMPOUNDS
                                  DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                 8/28 AND 9/5/84
CO
co




























8/28/84
Composite Sample
Field Blank

9/5/84
Composite Sample
Field Duplicate
leld Blank


QUANTITATED COMPOUNDS








CO
c
Q)
Nl
C
0)
JO
o
c.
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1 —
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•^
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1
CM

i— i





121
9b











CU
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JC
•M
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Ol
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1/4
809




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49
96











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313









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167









































TENTATIVELY - IDENTIFIED COMPOUNDS

c
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1807









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0
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-------
                                                            TABLE V-13
                                             LOW-BTU LIQUID WASTE - PCDD/PCDF ANALYSES
                                           DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                          8/28 AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
8/30/84
(NO SAMPLE TAKEN - Low-BTU Ik
9/5/84
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
PRECISION (RPD) -
SAMPLE AND FIELD DUPLICATE
2378-
TCDD


|uid wasl




Total
TCDD


;e was nc
29.3
22.8

25
Total
PeCDD


)t incint




Total
HxCDD
10.4

jrated or




Total
HpCDD


i this d<
181
132

31
OCDD


y)
753
570

28
2378-
TCDF







Total
TCDF



33.9
46.4

31
Total
PeCDF







Total
HxCDF







Total
HpCDF







OCDF







CO
                 NOTES:   1.   All  data expressed  in  pg/g.
                         2.   Blank spaces  denote homologue  not  detected.
                             Detection limits  ranged  from 0.2 to  10.2 ppt  for
                             TCDD and TCDF,  to 8.9  to 162 ppt for OCDD and OCDF.

-------
b.  Effluent Streams
   (1)  Incinerator Exhaust

    Analyses for volatile  compounds  presented in Appendix  D,  Tables  D-30,
0-31, and D-32, should be  evaluated in  light of previous comments concerning
the stringency of the  accuracy  criteria  established  for  this  study.  Among
the compounds  appearing  in incinerator  exhaust  gases  were carbon  tetra-
chloride, monochlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, per-
chloroethylene, and trichloroethylene.   These data  are  summarized  below:

                               Table  V-14

            Approximate Concentrations of Volatile Compounds
               in Incinerator Exhaust 8/28, 8/30, 9/5/84
                                      Concentration, ug/m^
                              8/28/84
       8/30/84
   carbon tetrachloride
   monochlorobenzene
   1,2-dichlorobenzene
   1,4-dichlorobenzene
   perchloroethylene
   trichloroethylene
ND
0.09-0.13
ND
ND
ND
ND
0.03-0.59
0.01-0.47
0.04-3.81
ND-0.52
0.01-0.07
0.001-0.01
 9/5/84

    ND
0.06-0.09
    ND
    ND
0.01-0.04
    ND
   ND =  not  detected  in  concentration  higher  than  in  field  blanks.

Note that  the  two   dichlorobenzenes  detected  by  the  volatile  compound
sampling method  are  considered  semi-volatile  compounds under  the  boiling
point definition  established  previously in  this  report.  With  respect to
semi-volatile compounds,  only the  following  were detected  on the  second
sampling day, August  30,  1984.   No  semi-volatile compounds  were  found on
the other sampling days.

                               Table V-15

          Approximate Concentration of Semi-Volatile Compounds
                     in Incinerator Exhaust 8/30/84
               Compound

          1,2-di chlorobenzene
          1,4-di chlorobenzene
          tetrachlorobenzene
          naphthalene
Concentration, ug/m3
        115
        102
         25
         33
                                  35

-------
However, as shown in  Appendix  0,  Table D-36, these  compounds  were detected
in the XAD-2  cartridge  portion of the Modified  Method  5 train,  for  which
the recoveries of the three acid  surrogates did  not meet  the  accuracy  goal
of 20 to  180%  established  for  the study (see Appendix 0,  Section  III.A.).
The above data should be evaluated in this  context.

    Table V-16 is  a presentation of PCDD and PCDF emissions from the Building
703 incinerator, expressed in  ng/m3.  These data were developed by  summing
the amounts of  PCDD  and PCDF found  in each  of  the  four components of  the
Modified Method 5 train.   No  2378-TCDD was  found,  at detection limits  of
0.02 to 2 ng/m3.

    The data presented  in  Table  V-16A are expressed  in  units of  ng/dscm,
adjusted to standard  temperature and  pressure, and normalized to a 3% oxygen
content in exhaust gas.  This was done to render the data directly comparable
to information presented  in  the  draft  Project   Summary  Report -  National
Dioxin Study Tier 4 - Combustion  Sources  (document  EPA-450/4-84-014g,  April
1986), in which emissions  data for a wide range of sources  are  presented.

    Vinylidene chloride   was  detected in  exhaust  gas  at  concentrations
ranging between 28.1  and 279.8  ppb, as shown  in  Table  V-17.

    Prior to  analysis,  the Modified Method  5  trains used to  sample  for
PCDDs and PCDFs were  disassembled and the filter  and probe  wash  portions
were dried  and weighed  in  a   manner conforming  to  EPA Method  5.    The
particulate emissions of the incinerator on the three test days were  found
to be 0.0842,  0.0615, and 0.0784 grain/dscf.    The  arithmetic  average  of
these data  is  0.0747  grain/dscf.  The Resource  Conservation and  Recovery
Act standard  for  hazardous waste  incinerators,  appearing at  40  CFR  Part
264.343(c), is  0.08   grain/dscf.    That   standard   does   not   provide   for
arithmetic averaging  to  determine  compliance.

    To obtain  the weights of filter and probe wash residues, these  fractions
were desiccated  to   constant   weight.  Because  of  possible  losses   from
volatilization of PCDDs  and  PCDFs from the  filters  and  probe washes,  the
data presented in Tables  V-16  and V-16A may be  biased low.   However,  low
volatilities of PCDDs and  PCDFs suggest any losses would not be significant.

   (2)  Incinerator Ash

    Table V-18 includes  the results of analyses  for  semi-volatile  compounds
present in incinerator ash sampled on the  three  test days.

    Table V-19 shows  the concentrations of PCDD  and  PCDF  found in  this  ash.
Among the  PCDDs,  the higher-chlorinated  homo! ogues  were predominant,  at
low parts per  billion levels.   No 2378-TCDD  was detected  at  the  low  parts
per trillion  range;   other isomers,  primarily   the  1368, 1379,  1237  and
1238, were  present at levels of  about 0.1 to 1.2 ng/g.   Of  the  PCDFs, the
tetra, hepta,   and octa homo! ogues  were  found   at  low  parts per  billion
concentrations.
                                  36

-------
                   TABLE V-16
    INCINERATOR EXHAUST - PCOD/PCDF ANALYSES
EXPRESSED IN TERMS OF CONCENTRATION IN AIR (ng/m3)
  DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
               8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
Modified Method 5 Train
Catches
8/28/84
8/30/84
9/5/84









2378-
TCDD





Total
TCDD


[45.95]
43.75
- 4.92
Total
PeCDD


6.49
1.94

Total
HxCDD


(p. 88)
0.37

Total
HpCDD


0.21
0.84

NOTES -
OCDD


0.93
2.52
0.47








2378-
TCDF


1.51
1.67


Total
TCDF


[81.22]
76.98
124.8

Total
PeCDF


[12.95]
4.28
0.07

Total
HxCDF


[2.47]
1.95


Total
HpCDF


0.26
0.55


OCDF


0.06
0.17


(^) - Data out of control with respect to precision criteria (+50% RPD)
["] - Bracketed data denote homologues detected in filter and probe wash portion
of Modified Method 5 train were deleted owing to unacceptable duplicate
analysis results. Only a small fraction of total concentration detected
was affected (see data in Appendix D, Table D-38).
- Matrix spike analyses indicated recoveries out of control for the following:
Filter and probe wash - PeCDD and HxCDF
XAD-2 cartridge - HpCDD and HpCDF

(
)ther mec
lia in tt
le sampl
ng train showed c
icceptab'
e matri>
, spike r
ecoverie
s.

-------
                                                           TABLE V-16A
                                             INCINERATOR EXHAUST - PCDD/PCDF ANALYSES
                                     CONCENTRATION  EXPRESSED  IN ng/dscw. ADJUSTED TO STANDARD
                         TEMPERATURE AND PRESSURE (68°F, 29.92 in.Hg). AND NORMALIZED TO  3* OXYGEN CONTENT
                                                       8/28. 8/30. 9/5/84
SAMPLE IDENTIFICATION
Modified Method 5 Train
Catches
8/28/84
8/30/84
9/5/84











2378-
TCDD





Total
TCDD


[116.8]
123.8
11.37
Total
PeCDD


16.49
5.49

Total
HxCDD


v'2y
1.05

Total
HpCDD


0.53
2.38

NOTES -
OCDD


2.36
7.13
1.09

2378-
TCDF


3.84
4.72


Total
TCDF


[206.4]
217.8
288.5

Total
PeCDF


[32.91]
12.11
0.17

Total
HxCDF


[6.28]
5.52


Total
HpCDF


0.66
1.56


OCDF


0.15
0.48


O - Data out of control with respect to precision criteria (^50t RPO)
[ ] - Bracketed data denote homologues detected In filter and probe wash portion
of Modified Method 5 train Mere deleted owing to unacceptable duplicate
analysis results. Only a small fraction of total concentration detected
was affected (see data In Appendix 0, Table D-38).
- Matrix spike analyses indicated recoveries out of control for the following:
Filter and probe wash - PeCDD and HxCDF
XAD-2 cartridge - HpCDD and HpCDF
Other media in the sampling train showed acceptable matrix spike recoveries.
1 I 1
I II ! 1 1 I 1
00

-------
                                      TABLE V-17
                     RESULTS OF SAMPLING FOR VINYLIDENE CHLORIDE
                    DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
DATE
8/28/84






8/30/84





9/5/84






SAMPLE RUN
1
2
3
4
5
6
7
1
2
3
4
5
6
1
2
2 DUPLICATE
3
4
5
6
SAMPLE
COLLECTION TIME (EOT)
1230-1330
1405-1510
1525-1625
1640-1735
1750-1845
1850-1930
1935-2015
1000-1050
1100-1200
1210-1250
1300-1350
1400-1450
1500-1550
1000-1045
1100-1150
1100-1150
1200-1245
1400-1445
1500-1545
1600-1630
VINYLIDENE CHLORIDE
CONCENTRATION (ppbv)
88.6 (83.1, 88.0, 94.7)
68.3 (72.1, 72.3, 60.2)
64.3 (113.0*, 67.5, 61.1)
74.5 (73.9, 74.7, 74.8)
88.9 (94.2, 88.4, 84.1)
112.4 (113.6, 111.2, 138.6*)
104.4 (102.1, 107.8, 103.3)
149.7 (150.0, 154.9, 144.3)
187.6 (180.9, 189.3, 192.7)
241.6 (263.7, 219.5, 402.7*)
279.8 (275.3, 285.9, 278.3)
218.0 (219.6, 216.3)
28.1 (28.9, 27.9, 27.6)
88.7 (94.3, 93.3, 78.5)
70.3 (69.4, 68.9, 72.6)
79.3 (76.7, 81.9, 79.3)
157.8 (156.4, 152.5, 164.4)
154.3 (162.2, 143.5, 157.2)
156.0 (154.7, 161.6, 151.8)
143.5 (146.6, 143.3, 140.6)
STANDARD
DEVIATION
5.8
6.9
4.5
0.5
5.1
1.7
3.0
5.3
6.1
31.3
5.5
2.3
0.7
8.8
2.0
2.6
6.1
9.7
5.0
3.0
* Rejected as greater than one standard deviation from mean of three analyses.
                                         39

-------
                 TABLE V-18
       INCINERATOR ASH SEMI-VOLATILES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
          (Results in uy/kg)















8/28/84
8/28/84
Field Blank
8/30/84
8/30/84
Field Pup.
8/30/84
Field Blank
9/5/84
9/5/84
Field Blank




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41


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11,243
9965



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(SAMPLE ANALYSIS NOT RETURNED FROM LABORATORY)







363
1110
423
530

170
435

321











1069
(SAMPLE ANALYSIS NOT RETURNED FROM LABORATORY)


-------
                              TABLE  V-19
                 INCINERATOR  ASH  - PCDD/PCDF  ANALYSES
            DOW CHEMICAL  COMPANY  BUILDING  703 INCINERATOR
                       8/28,  8/30,  AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
8/30/84
COMPOSITE SAMPLE
FIELD DUPLICATE
PRECISION (RPD)
FIELD BLANK
9/5/84
COMPOSITE SAMPLE
FIELD BLANK
2378-
TCDD
ND
(27.7)
ND
(8.2)
ND
(23.1)
ND
(11.8)

ND
(7.1)
ND
(6.9)

Total
TCDD
1170
ND
(9.6)
131
107
20
ND
(3.1)
71
(An<
Total
PeCDD
ND
(19.1)
ND
(35.8)
ND
(13.6)
ND
(15.6)

ND
(15.5)
ND
(16.2)
ilytical
Total
HxCDD
793
ND
(17.5)
129
111
15
ND
(6.1)
ND
(10.9)
data no1
Total
HpCDD
6060
ND
(12.7)
806
498
47
ND
(15.5)
76
; returns
OCDD
32,700
ND
(25.8)
3180
2370
29
ND
(25.8)
266
id from








i
2378-
TCDF
66
ND
(12.6)
17
ND
(11.3)

ND
(4.2)
ND
(6.5)
iborator
Total
TCDF
9160
ND
(12.8)
594
263
77
ND
(5.4)
540
')
Total
PeCDF
68
ND
(21.2)
ND
(5.4)
ND
(7.3)

ND
(7.4)
ND
(7.8)

Total
HxCDF
455
ND
(19.6)
44
37
17
ND
(8.6)
ND
(19.5)

Total
HpCDF
1520
ND
(15.9)
449
248
58
ND
(21.7)
ND
(20.2)

OCDF
2570
ND
(23.4)
573
399
36
ND
(11.3)
78

NOTE:   Data expressed  in  pg/g.

-------
       (3)  Aqueous Influents and Effluents

        Chloroform and carbon tetrachloride were found at low parts per trillion
    levels in  service  water supplied to the  incinerator  air  pollution  control
    devices.  Otherwise, there were no consistent  findings of any other volatile
    compounds (see  Appendix  D,   Tables  D-50,  D-51,  and  0-52).   Other  than
    scattered detection  of  phthalate compounds,  few  semi-volatile  compounds
    were found in effluent wastewaters.  On the second and third sampling days,
    various chlorophenols  and chlorobenzenes  were  found  in   influent  service
    water, and biphenyls and  terphenyls  appeared  in  effluent  wastewaters.   Any
    association between these compounds is speculative.

        Tables V-20, V-21, and V-22 are detailed presentations of PCDO and  PCDF
    data for  influent   and  effluent  waters.    Of particular  interest   is  the
    apparent strong affinity of PCDO and PCDF for the filterable solids  present
    in these waters.   Also,  some  TCOD, TCDF, HpCDF, and  OCDF  were detected  in
    influent service waters.  No  2378-TCOD was  found at any time, at  detection
    limits of approximately  1 ng/L  for aqueous samples and 10  ng/g for  solids
    samples.  Detailed   information  with  respect  to  the TCOO  isomers  detected
    appears in Appendix D, Tables D-60, D-61, and 0-62.

    2.  Quality Assurance Review

    As indicated  in  the  Quality Assurance  Project Plan  for  the  incinerator
exhaust study (Reference 7), a goal  of 90% was  established  with respect  to the
completeness of the  analytical  data.  This measure  was devised to assess the
overall suitability of  groups of data; individual  data points  were judged to  be
complete if precision and accuracy  criteria  applicable to a particular type  of
sample were met.   In retrospect,  given the complexity of this  study this  goal
was overly optimistic.

    Field duplicate samples  were obtained  on  one of the three  study days for
each sample type.  Where calculable,  precision  data  are presented in the  data
tables and discussion  included  in  Section V  and Appendix  D  of  this  report.
Owing to the wide  range of  compounds sought  for  analysis in  each sample, and
the number of field duplicate samples  taken, there were few cases  in  which the
same compounds  were found in both actual  samples  and  the field  duplicates.   The
quality assurance objective was  +_ 50% or +_ the detection limit.   Because  of the
wide variety of compounds detected and the few opportunities to  assess precision,
the following discussion centers  on  completeness  based  solely  on data  accuracy,
as measured by  analysis of  surrogate compounds  introduced  to each sample  by the
laboratories during analysis.  These data are presented in the  raw data summary
tables in Appendix D, and,  where  appropriate, in  the data tables in Section  V.
Several cases  surfaced  in  which  surrogate  compounds were  not  detected  or
recovered less  than  10%.   Laboratory  personnel  indicated  these samples  were
generally diluted during analysis  such that some  of  the  surrogate peaks  were
lost.                                  .                          •   •

    Table V-23   is  a   summary  of  data  completeness  for  the  categories  of
samples and compound groups  other than PCDDs  and  PCDFs  analyzed in this  study.
Generally, the completeness  goal of 90%, established in the plan for the study7,
                                      42

-------
                                                                                TABLE V-20
                                                          AQUEOUS  INFLUENTS AND EFFLUENTS  - PCDD/PCOF ANALYSES
                                                              DOW  CHEMICAL COMPANY BUILDING 703  INCINERATOR
                                                                                 8/28/84
CO
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturi/Demister Water
(Water)
Venturi/Demister Hater
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water Backup
Field Blank
2378-
TCDD
ND
(.0021)
ND
(.0013)
ND
(15.6)
ND
(.0011)
ND
(2.98)


ND
(.0003)
ND
(19.8)
ND
(.0003)
ND
(.0002)
Total
TCDD
0.0384
NO
(.0010)
432
NO
(.0010)
238


NO
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
Total
PeCDD
ND
(.0043)
ND
(.0010)
54.9
ND
(.0027)
82.0


ND
(.0010)
ND
(171)
ND
(.0016)
ND
(.0054)
Total
HxCDD
ND
(.0086)
ND
(.0042)
43.7
ND
(.0026)
55.1
Total
HpCDD
ND
(.0073)
ND
(.0079)
274
ND
(.0059)
265
OCDD
0.198
ND
( .0206)
1437
NO
(.0147)
1113
2378-
TCDF
ND
(.0011)
ND
(.0005)
11.0
ND
(.0002)
8.52
Total
TCDF
1.26
0.0025
170
0.0393
137
Total
PeCOF
ND
(.0026)
ND
(.0015)
66.4
ND
(.0022)
100
SAMPLE ANALYSIS DATA NOT RETURNED FROM LABORATORY
SAMPLE ANALYSIS DATA NOT RETURNED FROM LABORATORY
ND
(.0027)
ND
(94.3)
ND
(.0026)
ND
(.0115)
ND
(.0058)
ND
(126)
ND
j.0083)
ND
(.0275)
ND
(.0289)
323
ND
(.0130)
NO
(.0447)
ND
(.0003)
ND
(27.4)
ND
(.0002)
ND
(.0003)
ND
(.0010)
189
ND
(.0010)
ND
(.0010)
ND
(.0031)
NO
(45.1)
ND
(.0039)
ND
(.0037)
Total
HxCDF
ND
(.0057)
ND
(.0029)
117
NO
(.0018)
130


ND
(.0012)
ND
(42.5)
ND
(.0014)
NO
(.0075)
Total
HpCDF
0.0558
ND
(.0055)
427
ND
(.0030)
337


ND
(.0066)
ND
(91.5)
ND
(.0055)
NO
(.0167)
Total
OCDF
ND
(.0130)
NO
(.0118)
379
ND
(.0139)
284


ND
(.0121)
NO
(118)
NO
(.0098)
ND
(.0284)
                                  Note - Date expressed in ng/g for solids samples,  ng/L for aqueous  samples.

-------
                                             TABLE V-21
                        AQUEOUS INFLUENTS AND EFFLUENTS  - PCDD/PCOF ANALYSES
                            DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                               8/30/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
ESP Water (Water)
Field
ESP Water (Water) Duplicate
ESP Water (Solids)
Field
ESP Water (Solids) Duplicate
Venturi/Demister Water
(Water)
Venturi/Demister Water
(Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water Backup
Field Blank
2378-
TCDD
NO
(.0027)
ND
(.0007)
ND
(11.1)
ND
(.0009)
ND
( .0028)
ND
(35.3)
ND
(65.5)
ND
(.0006)
ND
(2.08)
ND
(.0010)
NO
(1.08)
ND
(.0005)
ND
(.0005)
Total
TCOD
0.0464
ND
(.0010)
707
.0062
.0189
4212
1864
ND
(.0010)
307
NO
(.0025)
15.9
ND
(.0010)
ND
(.0010)
Total
PeCDO
ND
(.0019)
ND
(.0024)
99.3
NO
(.0011)
NO
(.0019)
885
393
NO
(.0012)
49.2
ND
(.0240)
ND
(3.09)
NO
(.0011)
ND
( .0080)
Total
HxCOD
NO
(.0021)
ND
( .0042)
75.3
NO
( .0028)
ND
( .0029)
147
205
ND
(.0021)
27.6
ND
(.0227)
ND
(3.14)
ND
(.0021)
ND
(.0063)
Total
HpCOD
0.0179
ND
(.0115)
460
ND
(.0057)
NO
( .0044)
417
515
ND
( .0089)
162
NO
(.0292)
21.5
ND
(.0031)
NO
(.0083)
OCDD
0.187
ND
(.0301)
2358
ND .
(.0192)
NO
(.0077)
2199
2530
ND
(.0075)
707
ND
(.0453)
94.9
ND
( .0053)
ND
(.0104)
2378-
TCDF
ND
(.0012)
ND
(.0001)
15.4
ND
(.0004)
NO
(.0004)
45.3
47.7
ND
(.0005)
3.22
ND
(.0022)
ND
(1.71)
ND
(.0006)
NO
(.0014)
Total
TCDF
1.42
0.0223
182
0.287
0.607
539
6574
0.0682
168
ND
( .0038)
114
NO
(.0010)
ND
(.0025)
Total
PeCDF
0.0088
NO
(.0037)
ND
87.5
NO
(.0051)
ND
(.0039)
405
345
ND
(.0021)
64.6
ND
(.0120)
ND
(3.15)
ND
(.0024)
ND
(.0077)
Total
HxCDF
NO
(.0067)
ND
(.0028)
124
ND
(.0037)
ND
(.0017)
75.7
58.6
ND
(.0033)
82.9
ND
(.0110)
ND
(2.93)
NO
(.0017)
NO
(.0128)
Total
HpCDF
0.0167
ND
(.0131)
785
ND
(.0055)
ND
(.0070)
150
161
ND
(.0056)
199
NO
(.0232)
10.0
ND
(.0052)
ND
(.0046)
OCDF
0.0477
NO
(.0168)
641
NO
(.0182)
ND
( .0099)
200
226
ND
j.0164)
283
ND
( .0269)
12.5
NO
(.0037)
NO
(.0127)
Note - Data expressed  in ng/g for solids samples, ng/L for aqueous samples.

-------
                                                        TABLE V-22
                                   AQUEOUS INFLUENTS AND EFFLUENTS - PCDD/PCDF ANALYSES
                                       DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                          9/5/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturi/Demister Water
(Water)
Venturi/Demister Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water Backup
Field Blank
2378-
TCOD
ND
(0.341)
ND
(.0004)
ND
(1.10)
NO
( .0008)
ND
(1.29)
ND
(.0014)
ND
(28.2)
ND
(.0003)

ND
(.0013)
ND
(.0003)
Total
TCOD
ND
(0.229)
ND
(.0010)
73.9
ND
(.0010)
56.3
0.0052
247
ND
(.0010)

ND
( .0010]
ND
(.0010)
Total
PeCDD
ND
(0.556)
ND
(.0024)
ND
(7.43)
ND
(.0021)
17.5
ND
(.0104)
61.5
ND
(.0012)

ND
(.0016)
ND
( .0048)
Total
HxCDD
ND
(0.720)
ND
(.0027)
ND
(3.19)
ND
(.0031)
7.35
ND
(.0039)
20.3
ND
(.0017)
Total
HpCDD
ND
(0.318)
ND
(.0018)
69.0
ND
(.0036)
44.3
ND
(.0087)
96.0
ND
( .0029)
OCDD
ND
(0.520)
ND
( .0020)
236
ND
(.0064)
261
ND
(.0051)
423
ND
( .0025)
(SAMPLE ANALYSIS DATA NOT
ND
(.0071)
ND
(.0027)
ND
(.0067)
ND
(.0039)
ND
(.0088)
ND
( .0058)
2378-
TCDF
ND
(0.192)
ND
(.0001)
ND
(1.93)
ND
(.0001)
2.05
ND
(.0015)
9.70
ND
(.0001)
Total
TCOF
ND
(0.517)
0.0058
830
0.0157
723
0.0995
90.0
ND
(.0010)
Total
PeCDF
ND
(0.299)
ND
(.0015)
7.09
ND
(.0010)
22.3
ND
(.0041)
47.0
ND
(.0010)
RETURNED FROM LABORATORY)
ND
(.0023)
ND
( .0002)
ND
(.0022)
ND
(.0010)
ND
( .0080)
NO
(.0025)
Total
HxCDF
ND
(0.351)
ND
(.0015)
16.1
ND
(.0024)
19.7
ND
( .0030)
14.7
ND
(.0010)

ND
(.0025)
ND
( .0027]
Total
HpCDF
ND
(0.627)
ND
(.0012)
125
ND
(.0017)
69.1
ND
(.0026)
68.2
ND
(.0021)

ND
(.0049)
ND
LSS^L
OCDF
ND
(0.396)
ND
(.0011)
103
ND
(.0035)
84.8
ND
(.0061)
82.1
ND
(.0037)

ND
(.0057)
ND
iiOp_39J.
Note - Data expressed in ng/g  for  solids samples,  ng/L  for aqueous  samples.

-------
                                                           TABLE V-23
                                                   OVERALL DATA COMPLETENESS
                                            BASED UPON ANALYTICAL ACCURACY CRITERIA
                                  DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR EMISSIONS STUDY
                                       Analysis Type
Type of Sample
Precombustlon Air
Liquid Wastes
Low-BTU Liquid Haste
Incinerator Exhaust
-P» Incinerator Ash
CT>
Aqueous Influents
Volatile
Compounds
38% (3/8)
68t (19/28)
100% (5/5)
13* (2/16)
95% (21/22)
Semi -Volatile
Compounds
88% (7/8)
52% (15/29)
SOX (4/5)
57% (16/28)
71% (5/7)
89% (31/35)
Pesticides/PCB
0% (0/19)1
—
—
—
PCDD/PCDF Internal  Standards
   and Effluents
"W
71% (5/7)
84% (16/19)
80% (4/5)
79% (19/24)
86% (6/7)
74% (26/35)
37C1 4-2378-
TCDD
86% (6/7)
95% (18/19)
100% (5/5)
83% (20/24)
86% (6/7)
91% (32/35)
13C12-OCDD
29% (2/7)
74% (14/19)
100% (5/5)
75% (18/24)
86% (6/7)
74% (26/35)
37CI4-2378-
TCDF
71% (5/7)
84% (16/19)
20% (1/5)
67% (16/24)
86% (6/7)
60% (21/35)
lowing to dilution effects  during  analysis, the target detection limit was not met.

-------
was not met,  but  in many  cases  was nearly met.  In any event, this performance
should be evaluated with respect to comments made previously about the stringency
of the accuracy criteria  used to judge the  acceptability  of  volatile and semi-
volatile compound analyses.

    Similar data  for  PCDDs  and  PCDFs  may be  found  in  the tables  in Appendix D
in which analytical  results are presented.   As  indicated previously, accuracy
with respect to the TCDD surrogates deemed most important in evaluating potential
health risks,  was generally near  80%;  for OCDD  and  PCDFs,   accuracy  was  less
reliable, but  these  compounds   are   of   less   concern  regarding  health  risk
assessment.

    The above-referenced study plan also describes desired detection limits for
the types of  samples  and  analytical  procedures employed  in  this  study.   These
data (Table V-24) indicate detection limits were met or nearly met for volatile
and semi-volatile   analyses  except  those  of  liquid  wastes,  where  sample
extraction and dilution was necessary.  For  PCDDs and PCDFs, requested detection
limits were very  low, but were met in  several  cases.  Of particular interest is
the demonstrated  detection  of PCDDs  and PCDFs  in  incinerator exhaust  in the
XAD-2 sorbent  portion of  the Modified  Method  5  train,  where a  significant
portion of PCDDs  and PCDFs was trapped.

    3.  Discussion of Results

    The concentrations  of  PCDDs  and   PCDFs  entering  and discharged  from the
Building 703 incinerator on the three  sampling days, are presented in detail in
Appendix D, Tables D-64 through D-66;  Tables D-67 through D-69 of that appendix
show similar data for TCDD isomers.  Detailed  summaries of incoming and outgoing
loadings of  PCDDs and PCDFs,  and  TCDD  isomers,  are  presented in  Appendix D,
Tables D-70 through D-75.

    It must be  remembered in interpreting these data that a  major  waste  stream
introduced to the incinerator, the loose and  containerized solid  wastes, could
not be representatively sampled in this study.   While no samples of Tittabawassee
River water  were  taken (this  being  a component  of some waters  taken  in  and
circulated through air pollution control  devices),  concentrations  of PCDDs and
PCDFs were expected to be either not  present or not significant in  this stream.
Samples obtained  by EPA as  part  of a  1981  water sampling study9  support  this
conclusion.  At that time, 2378-TCDD and other dioxin  homologues were not found
in the Tittabawassee River  water intake  to  the  Dow  Chemical  plant  at detection
levels in the parts per quadrillion range.

    Total  suspended  solids  (TSS) concentrations  used  to calculate  discharged
PCDD and PCDF  loadings in  the  solid  portions  of  the  wastewater  streams  were
taken from data   developed  by the  analytical  laboratory during  analysis  of
PCDDs and PCDFs.  These data are stated below, and compared with data for those
streams gathered  on four  separate days in  1984  by  Dow  Chemical20,  and during a
sampling program conducted on August 28-29, 1984, by the USEPA Region V Eastern
District Office:
                                      47

-------
                                                                                 TABLE V-24
                                                              COMPARISON OF ACTUAL AND DESIRED DETECTION LIMITS
                                                        DOM CHEMICAL COMPANY BUILDING 703  INCINERATOR EMISSIONS STUDY
Type of Sample
Precombustion Air
Liquid Wastes
Low-BTU Liquid Wastes
Incinerator Exhaust
Incinerator Ash
Aqueous Influents
and Effluents
Volatile Compounds
Detection Limit
Desired Actual
1 ppb 0.3-0.8 ppb
1 ppb 1 ppm
1 ppb 3 ppt
1 ppb 0.25-
0.50 ppb
...
1 ppb 5 ppb
Semi-Volatile Compounds
Detection Limit
Desired Actual
5 ppb 0.05 ppb
5 ppb 1-10 ppm
5 ppb 6 ppt
5 ppb 1-2 ppb
5 ppb 0.5 ppb
5 ppb 10 ppb
Pestlcldes/PCB
Detection Limit
Desired Actual

5 ppb 100 ppb
...
...
...
...
2378-TCDD
2378-TCOF
Total TCDO
Total TCOF
C15-C18 CDD
C15-C18 CDF
TCDO/TCDF
OCDU/OCDF
TCUD/TCDF
OCDD/OCDF
Impingers
XAD-2 sorbent
TCOO/TCDF
Cl5-C)fj PCDD/PCDF
Water
Solids
PCDD/PCDF
Detection Limit
Desired Actual
2 ny 4.7-94 ny
2 ng 3.3-242 ng
2 ng 3-433 ng
2 ng 2.4-9.3 ng
6 ny 3.4-1038 ny
6 ng 2.8-250 ny
30 ppq 0.25-10.6 ppt
90 ppq 0.77-40.6 ppt
30 ppq 14-714 ppq
90 ppq 230-7940 ppq
30-90 ppq "5-100 ppt
2-6 ny 0.52-126 ny
5 ppt 0.5-1.9 ppt
15 ppt ~0. 3-2.0 ppt
30-90 ppq ->20-1600 ppq
5-15 ppt ~60-6000 ppt
00

-------
                            TOTAL SUSPENDED SOLIDS (mg/L)

                         EPA Incinerator Study      Dow Chemical       EPA
   Water Stream       8/28/84   8/30/84   9/5/84      (1984)      8/28-29/84

   Quench Tower         71        111      127       106- 488        840
   Venturi/Demister     77        132      169        72-1144        276
   ESP                  --         16      240        42- 444         34
   Ash Pit               3        132      156        46- 393         82

These data illustrate the  variability  of TSS concentrations  in  the wastewater
streams.  Effluent loadings of  PCDDs and PCDFs in incinerator ash were calculated
based upon a density of 0.66 ton per cubic yard, as supplied by Dow Chemical 20,
and a disposal rate, as described previously, of 15  to  20 cubic yards per day.
Loadings of  discharged  PCDDs  and  PCDFs  stated  in  the  tables  correspond  to
the range  of 15  to 20  cubic  yards  of  incinerator ash  disposed  daily  (see
Section V.A. of this report).

    Three of  the  loadings tables  (Appendix  D,   Tables  D-70 through  D-72)  are
averaged over the three  days  of  sampling and summarized in  Figure V-3 through V-6
for total  TCDD,   OCDD,  TCDF,  and   OCDF.   In general,  the  data  presented  in
these figures indicate   loadings  in streams  discharged  from the  Building  703
incinerator were comparable to or  higher than  in  those fed to it.   There appears
to be  a  strong  tendency  for  the  higher  chlorinated  homologues   (penta-  and
higher) to reside  in the  solid discharges,  such as  the effluent  water  solids
portions and incinerator ash.

    An objective of this  study was  to  relate air, water,  and  solids emissions
of PCDDs and PCDFs and  other compounds  from the  Building 703 incinerator to  the
operational characteristics  and waste  materials consumed  in  the  facility.   As
the operational  characteristics (incinerator temperatures, air pollution control
device water flows, exhaust gas oxygen  content,  etc.) appeared similar over  the
three sampling days, with the exception of an electrostatic precipitator arcing
phenomenon described  in  Section  IV.B.7  of  Appendix   A,   it  is  thought  the
differences in PCDD and PCDF emissions  appearing in Tables V-16,  V-19, and  V-20
through V-22 may have been attributable to waste content.

    In exhaust  gas, in  general,  the  highest   concentrations  of  penta-  and
hexa-CDD and CDF were found  on  the  first  sampling  day,  and of hepta- and octa-
CDD and CDF  on  the second day.   Similar  concentrations  of TCDO and  TCDF were
detected on the first and second days,  with the  lower concentration of TCDD  and
similar concentration   of  TCDF  on  the  third day.  In  effluent  wastewaters,
highest concentrations  of most  homologues  appeared on the second  day.

    Incinerated  loose  and  containerized solid  wastes were not defined  suffi-
ciently to discern  any  correlations in  this area,  and  the liquid  waste  feed
from nozzle  "BA"  was  similar  on  all  three  days.    It was  established  in  the
analytical  results that  the relative concentrations of most compounds in low-BTU
liquid waste  were lower than in any of the concentrated liquid wastes.   While
extensive data on incinerator  operating temperatures, pressures,  air pollution
control  device water, and  flow  rates were  obtained  (see  Appendix  A,  Table A-3),
                                      49

-------
                                                     FIGURE V-3
                                                     TCDD LOADINGS
                                      DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
    tour-
en
O
                               AM HT M4TVA

                                   SOU ft
                                                                                             AMTB4.
                                                                                         Ji
                                                                                          si
NOTE -
                                    S»«pfc
                                         Loadings stated  in grams per year,
                                         and calculated as averages of

                                                       days
                                                     TOTAL LOADINGS OF TCDD
                                                                                        In
                                                                      Out
2 IS
                                                                      87.3

-------
            e

            1
                                  r
                                                         .L3T/W
                                                                                                                             QO
                                                                                                                             Cvl
            in
            ro
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                                                                                                                  i-
                                                                                                                     •
    9) CO
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    )
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 O  C .C  C   J   •
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 i             .9 £

-------
                  FIGURE  v-5

                  TCDF LOADINGS
  DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                       M
                                                       fc *
                                                         £
                                                       !!
NOTE - Loadings stated in grams per year,
      and calculated as averages of
      three sampling days  (8/28, 8/30,
      and 9/5/84).
TOTAL LOADINGS OF  TCDF

 In               Out
                                                     1 872
                 238

-------
                FIGURE  V-6
                OCDF LOADINGS
DOW CHEMICAL  COMPANY BUILDING 703 INCINERATOR
                                                   *•»** AMTiet
                                                    II
NOTE -
   Loadings stated in grams  per year,
   and calculated as averages of

                            8/3°'
                        of
                                                     TOTAL LOADINGS OF OCDF

                                                      In              Out
                                                    45.6
                                                                   72

-------
the ranges of these data frequently overlapped during the three sampling periods,
and no consistent  relationship  appeared between  any  of these  characteristics
and the PCDD  and  PCDF concentrations  appearing  in exhaust  air or  discharged
wastewaters or solids.

    The waste  feeds  from nozzles  "BB"  and "C"  varied  widely  over the  three
days, and there was no discernible  characteristic  in  any waste which  appeared
to have direct  bearing on the exhaust gas  and wastewater PCDD and PCDF  concen-
trations in Tables V-16 and V-20 through V-22.   Referring to  data appearing  in
Tables D-70 through D-72 in Appendix  D, however, higher loadings of  PCDDs and
PCDFs in liquid wastes appear to  translate into  higher loadings in  discharged
streams.  In particular, on  the third  day,  loadings  of  discharged PCDDs and
PCDFs were markedly lower,  corresponding with lower  loadings of  PCDDs  and  PCDFs
(and semi-volatile compounds and pesticides; see Tables V-8 and V-9)  in liquid
wastes.  As  indicated  above,   incinerator operational  characteristics  were
similar on  all  three  sampling days.  For  incinerator ash, there  is no  clear
relation (see Table V-19), as considerably higher concentrations  of all  PCDD and
PCDF homologues were found  on  the  first  day.

    Figures V-3 to V-6 present  a  summary  of annualized  inputs  and  outputs  of
TCDD, OCDD, TCDF,  and OCDF for the  Building  703 incinerator.  Figures  D-l  through
D-10 in Appendix D show these loadings  for all PCDD and PCDF  homologue  groups.
These estimates were  calculated  by  averaging   the  mass  inputs   and  outputs
determined from the  three  test dates  and  converting  the  averages  to annual
discharges.  Because not  all input streams could be sampled  (e.g., containerized
waste, and loose refuse), the mass estimates are rough  approximations.  Nonethe-
less, the data may provide  some  interesting insights into the  fate of PCDDs and
PCDFs in the incinerator.

    Figure V-7  compares  the mass  inputs  and  mass  outputs.   Negative values
imply destruction  of  PCDOs  and  PCDFs; positive  values  imply  formation in the
incinerator.  Values close  to 0% change  imply mass transfer from input  streams
to output  streams.   Those  data  suggest  only  limited  destruction  of TCDDs,
somewhat higher destruction of  PeCDDs  (66%),  and transfer  of HxCDDs and OCDD
from input  streams to output streams.   For PCDFs, the data  suggest  destruction
of TCDFs (86%)  and formation of HxCDFs and OCDF, and  possibly PeCDFs  and  HpCDFs.
However, a significant  portion of some PCDD and  PCDF  homologue  groups  discharged
from the  incinerator  appeared  to  have  entered the  incinerator  system  via the
air pollution  control  device  service  water  supplied  from  the  Dow  Chemical
wastewater treatment facility.   These  PCDDs and PCDFs would not likely have been
destroyed or altered in the once-through water systems  serving  the quench tower,
venturi-demister,  and ESP, or transferred to the incinerator exhaust gas stream.
Within the bounds  of this study, the extent to which PCDDs and PCDFs  present  in
service water  could have  been  destroyed,  transferred  to  other  streams,   or
increased with  their passage  through  the incinerator  system  could  not   be
evaluated.  However, it  is acknowledged  that  a  portion  of the  PCDDs  and  PCDFs
entering the  incinerator  air  pollution  devices  may  have  returned  largely
unaltered to the Dow Chemical  wastewater treatment  system.
                                     54

-------
           +200%-i
                                                              FIGURE V-7
                                            DOW Chemical Company - Midland Plant
                                                     Building 703 Incinerator
                                      Comparison  of PCDD and PCDF Inputs and Outputs
                                                                                          +187%
en
en
           -100%-^
                                                                       -87V.
                           Note. (1) Defined as percent change from estimated mass inputs to estimated mass outputs.
                                   Negative values imply destruction of PCOOs and PCOFs: positive values imply formation.
                                   Values near zero imnlv mass transfer of PCODs and PCDFs from input streams to output streams.

-------
    Figure V-8 shows the relative distribution  of  PCDO and PCDF homo!ogues  in
air, water, and ash outputs  from  the  incinerator.   In  all  cases, most  PCDDs and
PCOFs were discharged in wastewaters;  as  indicated  above,  a  significant loading
of many  PCDO  and  PCDF  homologue  groups  entered  the incinerator  system via
inlet water  supplied to  the  air  pollution  control   devices.   Previous data
tables appearing in this report show  most  of the PCDDs  and  PCDFs in wastewaters
were found  in  filterable  solids.  For  each homologue group,  if  the loadings
found in  wastewaters  (primarily  residing  in filterable  solids)  are combined
with those  in discharged ash,  it  may be concluded  that most, in terms of mass,
are discharged along with  solid  effluents.  Lower chlorinated homologues tend
to appear in greater proportion  in  incinerator  air exhausts; however, in this
study, no more than  18% of  any homologue  group  appeared  in  incinerator exhaust
on a total loading basis.
                                      56

-------
                                                         FIGURE V-8
                                        DOW Chemical Company - Midland Plant
                                                 Building 703 Incinerator
                             Distribution of PCDD's and PCDF's Among Incinerator Ash, Air,
                                                    And Water Outputs
                                 PCDO's
                                                                             PCDF's
          100%-
           75% -
en
c
u>
o
k_
a>
O_
V)
t/>
CO
           50%-
           25%-
            TCDD
|    ASH  2%
f     AIR  17%
5  WATER  81%
                         PeCDD
                         0%
                         9%
                         91%
                             HxCOD
                             19%
                             2%
                             79%
AIR,
"W^iMv^-^."
HpCDD
15%
0.3%
85%


•;H
OCDD
16%
0%
B4%
TCDF
6%
17%
77%
PeCDF
1%
18%
81%
HxCDF
5%
6%
89%
AIR.




AIR,

HpCDF OCDF
3% 6%
0.1% 0.1%
97% 94%
                         Note: Ash-lncmerator Ash Output
                             Air^lncmerator Exhaust Output
                             Water=Ash Pit. Quench Tower, Venturi Scrubber. Oemister and Electrostatic Precipitatar Water Outputs

-------
VI.   AMBIENT AIR SAMPLING STUDY  IN VICINITY OF DOW CHEMICAL COMPANY MIDLAND  PLANT

     The Dioxin Strategy referenced  in Section  I  of  this  report  focused  on  seven
 types, or tiers, of locations and sources, ordered  by decreasing  potential  for
 2378-TCDD contamination.    Combustion sources were grouped  into  Tier 4,  for
 which sampling  and  analysis  plans  were  formulated by  EPA and  published  in
 February 1985 in a comprehensive project  plan.4  That  plan called  for limited
 ambient air monitoring,  only  of  precombustion  air drawn  into the  combustion
 source.  The ambient  air  sampling  study  in  the vicinity  of the Dow  Chemical
 Company Midland Plant  encompassed four sites  at  which monitors  were operated to
 collect specific target compounds;  the scope  of  the study thus  went beyond that
 specified in the Tier  4 project plan.  This  was  the only study  conducted  under
 Tier 4 program  guidance  at  which  extensive  ambient air monitoring was  done.

     The sites  were  constructed  and  operated by  a contractor,  GCA/Technology
 Division, and arranged such  that at  least one of three  sites  would  frequently
 be downwind of  the Dow Chemical  facility  under  typical   summer  wind  conditions
 in the study area.   Two of the downwind monitoring  sites were selected  as  close
 as possible to  the  fenceline  of  the Dow Chemical  plant.  The  third  downwind
 site was placed in  a  residential  and  recreation  area to  assess  compound concen-
 trations to which  the local population may  be  exposed.   The  fourth  site  was
 selected to be  upwind of  Dow  Chemical  under these  conditions and  would thus
 indicate background concentrations   of  the  above  compounds.   Wind  data  were
 obtained at two sites near  the  monitoring  network.   Additional   weather  data
 were taken  as  needed  from  facilities  maintained  locally  by  Dow  Chemical
 and from  public sources  operated  by  the  National  Oceanic  and  Atmospheric
 Administration (NOAA).

     Monitoring was  conducted between  September  7  and  27, 1984,  and  included
 18 days of  sampling.   Analyses  of  various types of samples were  keyed to wind
 directions under which  appropriate  upwind-downwind relationships  were experi-
 enced between   monitoring  stations.   The   site   descriptions  below   include
 distances and  directions  with respect  to the  Building   703 liquid/solid  waste
 incinerator as  well  as references  to  the  Dow  plant  fenceline as  it existed
 at the  time of  the   study.   While  the primary focus  of this  study   was  the
 incinerator, which  was  in operation  throughout the study period,  the results
 are also  indicative of numerous point  source and  fugitive emissions  from the
 Dow Chemical plant.

     The sampling network  was designed to  assess air quality  impacts of the Dow
 Chemical plant, and was not intended  to  evaluate or  determine the exact  location
 of maximum effect.   Also, the purpose of the network was to monitor the effects
 of the entire  Midland Plant,  rather  than  the  Building  703 incinerator  plume in
 particular.  The frequency  of  plume  impaction or  fumigation at  the monitoring
 sites was not evaluated, and the possible effects  of phenomena such as  downwash
 were not  considered.   However, two downwind monitoring  sites  were placed near
 the plant fenceline, where dispersion or dilution  of plant emissions was likely
 to be lowest.
                                      58

-------
    No dispersion modeling work was done prior to establishing the network, and
the monitoring   sites  were,  to  a  large  extent,   selected   based  upon  the
practicality of locating them on existing structures where physical obstructions
to air flow were  absent and adequate deliverable electrical power was available.
These limitations,  as  well  as  the short  duration of  the ambient  air  study,
should be borne in mind as the study results are evaluated.

    Several months  after   the  ambient  air  study  was  completed,  ground-level
exposure to  PCDOs  and  PCDFs  emitted  from  the  stack  of  the  Building  703
incinerator was  estimated  using the Human  Exposure  Model developed  by  USEPA.
This model employed meteorological  and population distribution data to determine
the location of  maximum impact  to  the  surrounding  population  of a single point
source.  This analysis  revealed  the point   of  maximum plume  impact to be  1  km
northeast to east-northeast, downwind  of the  facility, close to  sites  2 and 4
described below.   A full   discussion  of this  analysis,  authored by David  Hc
Cleverly of  the   Pollutant  Assessment  Branch,  Strategies  and  Air  Standards
Division, U.S. Environmental  Protection Agency, Research  Triangle  Park,  North
Carolina, appears in Appendix J.

    A.  Monitoring Network Description

    Figure VI-1 shows the  locations of each  of the monitoring stations described
below.

    1.  Site 1

    As historical data from the Midland area indicated predominant summer winds
to be from the south and southwest, this monitoring site was  intended to be the
upwind reference  for the  three stations  located generally  downwind  the  Dow
facility.  A two-meter-high equipment  scaffold  was placed on  a low hill  at the
west end  of Dow  property, overlooking a  series of  Dow brine  and  wastewater
treatment lagoons.  The intersection of Ashby and Poseyville  Roads was approxi-
mately 100  meters to the   southwest;  the Dow  Chemical  incinerator  was  located
about 1.1  miles  from the  site  at   a  heading  of  about  80°.   Looking from the
site, the Dow facility was visible in a sector  extending  between  0°  and 105°;
thus, winds  blowing  from   any direction between  110°  and 360°  were  considered
not to  have contacted  any portion  of the Dow Midland  Plant  prior to  being
sampled.

    Site 1  included  monitoring  equipment  for  the following distinct  groups  of
compounds:

             PCDDs and PCDFs
             Chlorobenzenes (principally Cl2 through Cls)
             Semi-volatile  and volatile compounds (VOC)
             Formaldehyde

Detailed descriptions of each of  the above samplers appear later in this  report.
In addition  to the above,  site  1 was  equipped with a  wind speed and direction
monitor; the sensors were  placed at a height of 10 meters above ground.   Figure
VI-2 includes a site sketch and information concerning the inlet heights of the
four samplers shown above.


                                        59

-------
                                                       Park did* Scb
                                    ^ -SLS ITE 7
            ,
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  ASHBY RD.
                                     uj x
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                    •77 mcttrt
                                   BLOG
                                    ft,
                            79 mtttrs
i      \
                                                 DOW CHEMICAL CO.
                    BRINE  POND
            W
                                                    -*—X-
                                        •X—X—
 1.   Location - atop scaffolding adjacent to Dow Building No. 1071.
 2.   Nearest intersection - Poseyville and Ashby Roads, 110 meters to SW.
 3.   Pollutants monitored at this site - PCDD/PCDF, chlorobenzenes, VOCs, and
     formaldehyde.
 4.   Additional parameters monitored at this site - wind direction and wind
     speed.
 5.   Hi-Vol  inlet height - 3.1 meters (PCDD/PCDF, chlorobenzenes).
 6.   CMS tube inlet height - 3.4 meters (VOCs).
 7.   Impinger inlet height - 2.6 meters (formaldehyde).
 8.   Meteorological equipment height - 10 meters (wind speed, wind direction).
 9.   Obstructions to samplers - none.
10.   Orientation to Dow Chemical facility - Dow occupies the sector NE of the
     site,  0° N to 100° SE.
11.   UTM coordinates - Zone 16; 4,829.9 km N; 722.1 km E.
12.   Latitude/longitude - 43°35'25" N, 84°14'48" W.


                                 Figure VI-2

                  Location of Ambient Air Monitoring Site 1
                                    61

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    2.  Site 2

    This site was  near the northern fence!ine  of the Dow facility,  such  that
winds between 95°  and 285° would  pass through  the  plant  before  reaching  it.
The incinerator was  about  0.8 mile  from the  site,  at a  bearing  of  195°.   A
major east-west road,  Bay  City  Road,  passed  about 16.5 meters  to  the  north  of
the site.

    Equipment was placed on the  flat  rooftop of Dow Building 911,  a  structure
approximately 3.5 meters in height, to  monitor the full range of compound groups
as described  for  site  1.   Sampler  inlet heights  are shown  in  Figure  VI-3.
In general,  there  were no  significant obstructions  to  free  air  flow to  the
site; Dow  Building  566,  located about  45 meters  southwest,  was  judged to  be
sufficiently distant to preclude significant  wind eddying  effects.

    3.  Site 3

    To assess  concentrations  of target  compounds in  a  population center  and
recreation area, site 3 was assembled atop the Midland Community Center, a  flat-
roofed multistory building about 0.9 mile north of the Dow  Chemical  fence!ine
and 1.8 miles from the plant  incinerator.  The  incinerator was  at  a heading  of
170° from site  3; however, winds between  135° and 225° were  considered upwind
with respect to the  entire Dow  facility.   The site was configured as  shown  in
Figure VI-4.  An airflow obstruction cited  in  the figure was judged  to  be minor;
in any event, this  low wall was northwest of the monitoring equipment, not in the
direction of emissions from the Dow facility.

    4.  Site 4

    A second site at the fenceline of  the  Dow plant  was established to receive
impacts from the facility under ambient wind  conditions between 180°  and  285°.
The Building 703 incinerator  was located 1.1  miles from the monitoring station,
at a heading of 230°.  Monitoring equipment was placed atop a mobile laboratory
trailer parked  in  a  lot  located  at   the  east  boundary  of  the  Dow  Chemical
facility.  Sampler inlet heights are shown in  Figure VI-5.   The site was selected
to deploy  field duplicate and  field  blank   samples  because  of   the  ease  of
servicing this  site  with  equipment  stored in  the trailer.   Periodic  weather
data (temperature, relative  humidity,  and barometric  pressure) were  obtained
manually at this site.

    5.  Other Sites

    A fifth site, designated  as site  7  (Figure VI-6), consisted  of  a monitoring
trailer operated continuously by the Michigan Department of  Natural  Resources,
and included wind  speed and direction  measurement equipment.   The  Dow Chemical
north fenceline was about 0.3 mile south of this  location.  Wind  data gathered at
the site were considered equivalent to those  at  sites  2 and  4 and  were used as
a check on similar data at site 1.

    Sites 5 and 6 were planned  as meteorological  stations, but were  not used and
are not shown in Figure VI-1.
                                     62

-------
I
I
1
1
1
1
^p*

1




1
1
1








BAY CITY Rn
DMI ^ 1 l • r\ \j.

>
<
5
UJ
5
o

MM \f w V

fe "w"
_J
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CD



1
BLOG. '6.5 mttirt
# 911 1
-1
X
~T
11.5 m«ttr»
i DOW FENCELINE

DOW CHEMICAL FACILITY


1. Location - atop Dow Building No. 911.
2. Nearest intersection - Bay City Road and Ball Street, adjacent to site.
3. Pollutants monitored at this site - PCDD/PCDF, chlorobenzenes, VOCs, and
formaldehyde.

4. Additional parameters monitored at this site —none.
5. Hi-Vol inlet height - 4.9 meters (PCDD/PCDF, chlorobenzenes).
6. CMS tube inlet height - 4.9 meters (VOCs).
1

7. Impinger inlet height - 4.1 meters (formaldehyde).
8. Obstructions to samplers - possible obstruction is building approximately
45 meters SW of sample.

•9. Orientation to Dow Chemical facility - Dow occupies the sector from

95° SE to 285° NW.

10. UTM coordinates - Zone 16; 4,831.4 km N; 724.2 km E.
_~^B
11. Latitude/longitude - 43°36'17"
N, 84°13'14" W.
                                           Figure VI-3


                            Location of Ambient Air Monitoring  Site 2


                                              63

-------
 I
 I
 i
 *
 *
*
m
                                       MIDLAND
                                       COMMUNITY
                                       CENTER

 X X
                                                                       UJ
                                                                       UJ
                                                                       e
                          
-------
  I
  I
  I
 I
 I
 I
 I
 I
 I
I
                     AUSTIN  ROAD
                                  BAY CITY ROAD
                                        I
                                   GCA
                                   MOBILE
                                   LABORATORY

                                       PARKING
                                         LOT
                                          '—X—X—X	X	X—X—
 1.   Location - located atop GCA Mobile Laboratory  in NE  parking  lot.
 2.   Nearest intersection - Bay City Road and S. Saginaw  Road.
 3.   Pollutants monitored at this site - PCDD/PCDF, chlorobenzenes,  VOCs,
     and formaldehyde.
 4.   Additional parameters monitored at this site - temperature,  barometric
     pressure, and relative humidity.
 5.   Hi-Vol inlet height - 5.1 meters (PCDD/PCDF and chlorobenzenes).
 6.   CMS tube inlet height - 5.4 meters (VOCs).
 7.   Impinger inlet height - 4.6 meters (formaldehyde).
 8.   Obstructions to samplers - none.
 9.   Orientation to Dow Chemical facility - Dow occupies  the  sector  180°  S to
     285° NW.
10.   UTM coordinates - Zone 16; 4,831.2 km N; 725.2 km E.
11.   Latitude/longitude - 43°36'09" N,  84°12'28" W.




                                  Figure VI-5

                   Location of  Ambient  Air Monitoring  Site 4

                                     65

-------
       •\	1	1	1	1
                           UJ
                           UJ
                           V)
                           o
                           z

                           i
                           to
                                JAMES SAVAGE ROAD
*   D
                                 PARKING
                                   LOT
           CONSUMERS
           POWER  BLDG.


            r- STATE MET.  TRAILER
                                             •SITE 7
         PENN  CENTRAL R.R.
-i—i—i—i—i—i—i—»—i—H
           BARTH  STREET
1.    Location  - Michigan DNR trailer in parking  lot  of Consumecs Power on

     Washington Street.

2.    Nearest intersection - James Savage Road and  Washington Street.

3.    Parameters at  this site - wind direction and  wind speed.

4.    UTM coordinates - Zone 16; 4,832.0 km N; 724.6  km E.
                            Figure VI-6



  Location of Ambient  Air Monitoring Site 7 (Wind  Monitoring Site)
                                66

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    B.  Monitor Descriptions and Sampling Methods

    All four of the monitoring  sites  included  equipment  to monitor  four  groups
of compounds:  PCDDs and  PCOFs;  higher-substituted chlorobenzenes (Cl2 through
015); a general  range of semi-volatile and volatile compounds; and formaldehyde.
The samplers specific to each group are described  in detail in Appendix E to this
report.

    C.  Conduct of Study

    1.  Sampling Procedures

    Field methods for the four types of 24-hour samplers employed in this study
(modified high-volume sampler for PCDDs and PCDFs, and chlorobenzenes and other
semi-volatile compounds; carbon molecular sieve sampler for volatile compounds;
and impinger-type sampler  for  formaldehyde)  were taken from the literature and
modified as  necessary  according to meteorological  conditions  encountered, and
the limitations of  the  selected analytical  laboratories.  While  it  would have
been preferable to  operate all  four  sampler types at each  site  on  every day,
practical and resource limitations  led  to decisions under which  some samplers
were run  only during  periods  when  meteorology  was  favorable  (good  upwind-
downwind relationships  existed),  or a limited number  of exposed samples  were
designated for  analysis.   These  decisions  are  described  in  the  detailed
discussion of sampling methods  appearing  in  Appendix E,  and a summary of samples
obtained is  presented  in  Table  VI-1.   Preparation  and assembly  of  sampler
materials were for  the most  part coordinated in the  GCA sampling trailer also
used as monitoring site 4.

    Detailed descriptions  of  sampling  procedures  for all  of  the  ambient  air
monitors used  in  this  study  may  be  found  in  Appendix  E  of  this  report.

    2.  Custody, Sample Handling, and Shipping

    Samples were  obtained  and  identified  using  chain-of-custody   procedures
described in  the  Quality  Assurance  Project  Plan  developed  for the  study,I5
and EPA  custody  forms  and  GCA  data  record  forms  shown  in  Appendix  D  of
Reference 16 of this report.  In short, standard  EPA chain-of-custody protocols
were followed in the conduct of work.

    Cleaned and prepared sampling media, with the exception of  ONPH  reagent for
formaldehyde sampling,  were held  in  a secured  trailer (site 4)  until  use.   As
indicated in Appendix E,  DNPH  reagent was prepared  immediately  before  use and
shipped to the study area  for placement in sampling equipment.  Exposed sampling
media were kept in  secured  (locked  or sealed)  chests, separated from unexposed
media, in the site 4 monitoring  trailer before shipping.  Subject to  appropriate
holding times, samples were  shipped  under EPA  custody procedures and documents
specific to  the  EPA  Special  Analytical  Services  program,  to  the  contract
laboratories selected to  perform analyses  for various compound  classes.   For
volatile and  semi-volatile compounds,  and  formaldehyde, analytical  services
were provided by United States  Testing  Company,  Hoboken,  New Jersey.  For PCDD
and PCDF, analyses  were  conducted by Midwest Research  Institute, Kansas  City,
Missouri.
                                    67

-------
                              TABLE VI-1

             MIDLAND, MICHIGAN AMBIENT AIR SAMPLING STUDY
              SUMMARY OF SAMPLE TYPES AND SAMPLING TIMES
Run Start                 Chlorobenzenes
   Date      PCDD/PCDF    Semi-Volatlies    Volatlies    Formaldehyde

  9/7/84                        X               XX
  9/8            X              X               XX
  9/9
  9/10
  9/11                          X
  9/12           XX               XX
  9/13                          X
  9/14                          X
  9/15                          X
  9/16                          X
  9/17                          X               X
  9/18                          X               XX
  9/19                          X               XX
  9/20                          X
  9/21                          X
  9/22           XXX
  9/23                          X               X
  9/24                          X               X
  9/25                          X
  9/26                          X
      NOTE:  X denotes sample taken and submitted for analysis
                                 68

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    D.  Analytical Procedures and Quality Assurance
    Analytical methods specified  for  this  study  appear in References 17 (PCDD/
PCDF) and 18  (semi-volatile  compounds, volatile  compounds,  and formaldehyde),
and are summarized briefly below:
    PCDD/PCDF and
    Semi-Volatile
    Compounds

    Volatile Compounds -
          Extraction followed by solvent partitioning and liquid
          chromatography,  analysis  by  gas  chromatography/mass
          spectrometry.
          Collection on carbon  molecular  sieves
          desorption and analysis by GC/MS.
                       then thermal
    Formaldehyde
        - Reverse phase high performance liquid chromatography.
    Samples collected  during  this  study  were  identified,  packed  (cooled  as
appropriate), and  shipped  via  commercial  services  for  next-day  arrival  at
contract laboratories.  Selection  of contract laboratories referenced in Section
VI.C was  coordinated  by  the  USEPA   Region  V  Central  Regional  Laboratory.
Analytical  data  returned  from  the  contract laboratories  were   reviewed  for
consistency with contract  requirements by the  USEPA Sample  Management  Office
(Viar and Company,  Alexandria, Virginia), and for adherence to quality assurance
criteria contained  in  the Quality Assurance Project Plan for this  study (see
Reference 15) by the  USEPA Region V Central Regional  Laboratory.   The results
of these reviews are referenced  in the  discussion of  general analytical  findings
which follows as Section VI.E of this report.

    E.  Results of Study and Discussion

    1.  PCDD/PCDF

    Consistent with the evaluation of incinerator exhausts, a range of  recovery
of analytical  surrogate or  internal   standard  compounds  of  50%  to  150%  was
considered acceptable  with  respect to the  suitability  of PCDD and  PCDF  data.
Recoveries of internal  standards for PCDDs and PCDFs ranged between  22% and 220%,
with no reportable recovery in a small  number of cases.

    Four internal standards were used:  13C12 2378-TCDD, 13C12 2378-TCOF,  37C14
1,2,3,4,6,7,8-HpCDD, and    Cj?  OCDD.    Overall  performance  with  respect  to
recoveries within the  acceptable  range of 50% to  150% was as follows  for the
45 samples included in these analyses:
             13

             13

             37

             13
C12-2378-TCDD

C12-2378-TCDF

Cl4-1,2,3,4,6,7,8-HpCOD

C12-OCDD
  Percent of Samples
Within Acceptable Range

      82% (37/45)

      89% (40/45)

      71% (32/45)

      80% (36/45).
                                       69

-------
The standard   C^p  2378-TCDO is of primary importance as the accuracy determinant
for tetra- through  hexa-CDD;  those homologue groups are  of greatest priority  in
assessing potential    risks  to  health.    In  the  above   table,   satisfactory
recoveries were experienced in 82% of the samples.

    Recoveries of  the  other  three  standards  serve   to  measure  analytical
accuracies for PCDD and PCDF  homologues which are of lesser concern with  respect
to health risk assessment.  In summary,  considering the  low levels  of detection
specified for  this  study  (parts  per  quadrillion  in  air),  the data  presented
below are reasonably complete in terms of accuracy.

    Complete results  of  sampling  for PCDD  and  PCDF  for  the  three selected
sampling days are presented in Table VI-2; these  were derived  from  the raw  data
shown in  Appendix  G,  Table  G-l,  which  are  as  received  from the  analytical
laboratory.  Two of the glass filter (polyurethane  foam  plug sample pairs  (from
sites 2 and 3 on  September 8 and 9,  1984) analyzed by  Midwest Research Institute
(MRI) were  reanalyzed for  verification  by  the  Environmental  Monitoring and
Support Laboratory   (EMSL)  of EPA  in  Research Triangle  Park,  North  Carolina.
The following  findings  were  stated in the  EMSL  reanalysis and review  report:

            Standards values  were in reasonable agreement,
            Quantification of PCDD and PCDF appeared  generally  accurate,
            Most of the TCDF  detected in  the samples  were  1238,  1467, 2468, and
            1236 isomers,   which  were indicated   by  the  EMSL  as  having  been
            detected previously  in  incineration  process  samples  from  other
            studies,
            Similar isomer groups were found in samples   of soils   which   were
            analyzed as  part  of   a   previous  EPA  Region  V  sampling  program
            conducted in Midland, Michigan, in  1984,
            Between 20 and 50% of the concentration of   PeCDFs  reported   in the
            samples was attributable to chlorinated diphenylethers  (CDEs)  which
            el ute simultaneously  from the  capillary  column used  in analysis
            (co-el ution of other CDEs  with other PCDFs was  not  investigated, and
            The analytical results  should  be considered  minimum  values  as
            the air  sampling  method  employed  in  this   study  was   not  formally
            validated as of the time the study occurred.

    Note  in Table VI-2 that 2378-TCDD and 2378-TCDF were not detected by MRI  in
any sample.   In the EMSL reanalyses, however, both  isomers were found, as  shown
in the raw data in  Appendix H.  In two of three cases in which  the EMSL reported
values where MRI did not, the levels of 2378-TCDO and 2378-TCDF detected by the
EMSL were  above  the detection limits stated by MRI.  These data  are presented
in Table  VI-3.   The  single finding of 2378-TCDD, in  the sample from  site  2  on
9/8-9/84, would result in  an  ambient  air  concentration of about 4.8 pg/m3 (ppq).

     In Table  VI-4, the comparative results of analyses  for TCDD and TCDF by MRI
and the  EMSL  are presented in terms  of  concentration in  air.   These data  show
generally close agreement.  The full text of the EMSL's description of reanalysis
of these  samples is presented in Appendix H.
                                     70

-------
                             TABLE VI-2

              RESULTS OF AMBIENT AIR PCOD/PCOF SAMPLING
IN VICINITY OF DOW CHEMICAL COMPANY, MIDLAND, MICHIGAN, SEPTEMBER 1984

        (All data stated  In picograms per cubic meter.)
Sample Identification
9/8-9/84
Site 1
Average wind Site 2
199°, 6 mph
Site 3
Site 4*
Site 4 duplicate
Precision (RPD)
9/12-13/84
Site 1
Average wind Site 2
191°, 6 mph
Site 3
Site 4
Site 4 duplicate
Precision (RPD)
9/22-23/84
Site 1
Average wind Site 2
212°, 5 mph
Site 3
Site 4
Site 4 duplicate*
Precision (RPD)







2378-
TCDD
NDl
ND(0.85)

N0(0.22)
ND(0.09)
ND(0.15)
—

N0(0.19)
ND(0.24)

ND(1.07)
ND(0.15)
ND(0.17)
—

N0(0.06)
ND(0.05)

ND(0.08)
N0(1.63)
*ND(0.59)
--
•Denotes
Total
TCDD
0.99
44.80

2.40
0.86
0.48
56.7

0.13
NO?

3.27
0.38
NO?
—

NO2
22.35

0.59
74.07
24.28
101.3
analysis o
Total
PeCDD
NDl
9.28

N0(0.46)
ND(0.09)
NDJ0.31)
—

N0(0.38)
ND(0.43)

ND(0.80)
ND(0.15)
NDJ0.64)
—

ND(0.24)
ND(0.32)

N0(0.48)
1.37
ND(1.17)
—
f polyuret
Total
HxCDD
0.95
N0(0.84)

N0(0.32)
0.86
NO(l.ll)
—

ND(1.02)
ND(2.55)

ND(1.19)
2.93
ND(1.39)
—

ND(0.18)
0.55

ND(0.39)
0.28
0.96
109.7
lane foam
Total
HpCDD
0.81
2.08

2.07
1.00
1.54
42.5

0.69
ND{3.51)

0.65
1.48
0.48
102.0

ND(0.69)
2.69

0.55
1.14
1.41
21.2
>lug was n
OCDD
1.15
7.70

7.92
2.69
4.10
41.5

1.66
ND(6.71)

5.10
6.75
5.60
18.6

0.30
14.29

2.73
4.01
4.37
8.6
3t provldec
2378-
TCDF
NO1
ND(0.84)

ND(0.34)
ND(0.12)
ND(0.17)
--

ND(0.18)
NDJ0.24)

ND(0.24)
ND(0.20)
ND(0.17)
—

ND(O.ll)
NOJ0.99)

ND(0.12)
ND(1.63)
ND(1.41)
--
by analyt
Total
TCDF
0.86
249.80

14.72
1.53
2.70
55.3

14.52
14.53

44.95
13.88
11.21
21.2
o
NO'
155.69

2.14
375.37
122.70
101.5
ical labor
Total
PeCDF
ND1
29.80

4.44
1.16
1.41
19.5

ND(2.93)
ND(1.07)

2.22
1.06
3.01
95.8

N0(0.13)
7.45

ND(0.23)
36.73
15.42
81.7
atory.
Calculation of analytical precision should therefore be considered tentative.
"NO" symbol Indicates Isomer or homologue was not detected at method detection limit.
The higher of the two detection limits (for glass fiber filter or PUF plug) is stated.
lOetectlon limit not determined.
^Exposed sample concentration lower than that In field blank. Consider equivalent to
nondetectable.
Total
HxCDF
NDl
4.15

N0(0.37)
ND(0.65)
0.73
•""

ND(0.62)
ND(1.02)

ND(1.31)
ND(1.27)
ND(0.80)
_ —

ND(0.26)
4.52

ND(0.15)
3.00
4.37
37.2







Total
HpCOF
NO1
5.01

ND(0.79)
NOJ0.52)
ND(1.15)
""""

ND(2.16)
ND(1.92)

ND(1.24)
N0(0.90)
ND(5.43)
--

ND(0.83)
2.93

ND(0.80)
3.00
2.70
10.5







OCDF
ND
3.42

1.36
1.66
0.84
65.6

0.99
ND(3.35)

0.81
2.67
ND(3.40)
—

0.13
1.60

0.70
4.64
6.55
34.1








-------
                           TABLE VI-3

COMPARATIVE ANALYSES FOR TOTAL AND 2378 ISOMER OF TCDD AND TCDF
          MIDWEST RESEARCH INSTITUTE AND EMSL-RTP, EPA
   Sample Identification
                                       Amount Detected (ng/sample)
MR I
     Note:   (  )  Detection limit expressed in nanograms.
EMSL
9/8-9/84



9/8-9/84



9/8-9/84



9/8-9/84



, Site 2 Filter 2378-TCDD
Total TCDD
2378-TCDF
Total TCOF
Site 2 PUF 2378-TCDD
Total TCDD
2378-TCDF
Total TCDF
Site 3 Filter 2378-TCDD
Total TCDD
2378-TCDF
Total TCDF
Site 3 PUF 2378-TCDD
Total TCDD
2378-TCDF
Total TCDF
ND (0.10)
3.7
ND (0.69)
36
ND (0.70)
33
ND (0.40)
180
ND (0.18)
1.6
ND (0.20)
7.5
ND (0.12)
1.7
ND (0.28)
3.9
0.4
9.0
0.2
28.0
ND
29.0
ND
131.0
ND
0.8
ND
2.2
ND
1.4
0.4
26.0
                             72

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                                               TABLE VI-4
COMPARATIVE VALUES FOR 2378-TCDD, TOTAL TCDDs, 2378-TCDF, and TOTAL
MIDWEST RESEARCH INSTITUTE AND EMSL-RTP, EPA
EMSL-EPA
Filter
PUF
Total
MRI*
Total
9/8-9/84,
2378-TCDD Total TCDDs
0.49 11.00
ND 35.43
0.49 46.43
ND 44.80
Site 2
2378-TCDF
0.24
ND
0.24
ND

Total TCDFs
34.21
160.06
194.27
249.80



2378-TCDD
ND
ND
ND
ND
9/8-9/84
Total TCDDs
0.97
1.71
2.68
2.40
TCDFs
, Site 3
2378-TCDF
ND
0.49
0.49
ND


Total TCDFs
2.68
31.66
34.34
14.72
*Taken from Table VI-2.  Data stated in pg/m3.

-------
    Along with the above reanalysis, the data provided by MRI were  reviewed  by
the EPA  Region  V  Central  Regional  Laboratory.   Following  are the  principal
findings of that review, as they relate to the quality of these  data:

        The surrogate compound ^'Cl4-2378-TCDD was not added  to  any  sample,  as
        required by the  analytical  specifications  for  this  study.   With  this
        lacking, MRI provided internal  standard recovery data  by  quantitating
        one internal standard against another.  The recoveries  of the  surrogate
        13C12-TCDF were considered  as  indication  of bias for tetra- and penta-
        CDD and CDF; an overall  bias of -13% was found.

        Based on  recoveries  of  the surrogate  37Cl4-HpCDD,  the  bias  for  hexa-
        through octa-CDO and  CDF  was  calculated  to  be  +11%.   Both   of  these
        biases were  considered   small  with  respect to  the  errors  introduced
        by taking  the  recovery  of a  particular  homologue  to   represent  that
        of a different homologue.

        Field blank samples were spiked to calculate recoveries   and precision,
        and five  of the 42  analyses  showed  spike  recoveries  out  of control.
        However, precision criteria were met in the duplicate blanks.

        Since all field blank samples were spiked by MRI, it was  not possible  to
        estimate possible  field  contamination   as  planned  in  the  analytical
        protocol.  However,  in   the  spiked  blanks, the  levels detected  were
        close to  the  spiking levels,  suggesting  field  contamination  was  not
        significant.

        While the analytical  request called for a laboratory  matrix  spike for
        every ten  samples  analyzed, this was  not provided.   This  was  judged  to
        be a minor  shortfall, and  available matrix  spike data  showed  generally
        satisfactory performance.

        Resolution  of 2378-TCDD  from neighboring TCDDs  ranged  between  40 and
        60%; the  analytical  request specified  that samples  were  to  have  been
        rerun if resolution was  25% or greater.  As MRI did not detect 2378-TCDD
        in any sample, but  the EMSL did, this  implies  that some of  that reported
        by MRI as total TCDDs may in fact have been 2378-TCDD.

        Response  factors calculated by MRI for some calibration  standards were
        not substantiated  by verifiable data.  Most were provided, however, and
        indicated  satisfactory performance.

 In  summary,  the  Central  Regional   Laboratory  review  of  the MRI  data package
 indicated the data  were generally suitable for project use, as qualified above.
                                        74

-------
    Wind data for the duration of the  ambient air  sampling  study are presented
in Table  VI-5.   As  indicated  previously,  three  of  the periods  having  most
favorable upwind-downwind alignment  of monitoring sites with respect  to  the Dow
Chemical  facility were chosen for PCOD and PCOF sample analyses.  Wind  conditions
averaged over each of these three periods are stated in Table VI-2; Figure  VI-1
may be used  to  relate  these wind directions to  the findings of PCDD and  PCOF
shown in Table VI-2.

    From these data, it is apparent  that site 1  was upwind  of the Dow Chemical
facility on all  three days; correspondingly,  the  lowest concentrations of nearly
all PCDD and PCDF homologues were detected at this  site.   Higher  concentrations
were consistently found at  those  sites downwind  of the Dow  facility.   For the
first two  sampling  periods  analyzed, these  were  sites 2 and  3, while  on  the
third sampling day, sites 2 and 4 were highest  in most  homologues.

    On the  first  sampling  day,  highest  concentrations  were  detected   at  the
north fence! ine  of  the  Dow  facility,  with  considerably  less  found  at  the
comparatively distant Midland  Community  Center  site.   Under very similar  wind
conditions in the second  sampling period,  however,  this pattern  reversed,  with
concentrations of most  PCDD and  PCDF  homologues  in the  same range  (1 to  10
pg/m3) on both days.  With  winds  shifted 15  to 20  degrees toward the  southwest
on the third sampling day, highest concentrations were  found exclusively at the
two Dow  Chemical  fenceline  sites.   Precision between  duplicate  samples  on  all
three days  was  frequently  within the  target range  of  +_ 50%  (relative  percent
difference).

    Overall, these  data  establish  that  point  and   fugitive  emissions  of  PCDD
and PCDF  from  the Dow  Chemical  plant may be  detected at downwind  monitoring
locations.  Downwind concentrations  were consistently  higher than those  upwind
of Dow Chemical .

    In Table VI-6, the concentration data  in Table  VI-2  are presented in terms
of the portions of the PCDD and PCDF homologues  found  in  the glass fiber  filter
and polyurethane foam plug of the samplers.  These  data suggest that  the  lower-
chlorinated homologues,  chiefly the tetra- through penta-, tend to reside in the
polyurethane foam plug,  while the hexa- through octa- homologues are principally
found on the first-stage  glass  fiber filter, where more particulate matter  is
likely to be caught.  These findings imply that

        higher-chlorinated homologues of PCDD  and   PCDF   may bind selectively
        to particulate matter,  while the  tetra-  and  penta- homologues  remain
        in the  gaseous  state  or  bound  to  finer  particul ates.   These  lower-
        chlorinated homologues  may not  be trapped efficiently by the glass fiber
        filter portion of the high-volume sampler,  or may be air-stripped  from
        the filter catch by the  action of air moving through the sampler;  and

        both components  of the  high-volume sampler  should  be used in series  to
        determine the  concentration  of  the  full   range   of  PCDD  and  PCDF
        homo!ogues.
                                     75

-------
    TABLE  VI-5
WIND DATA - AMBIENT AIR SAMPLING PROGRAM
MIDLAND, MICHIGAN - SEPTEMBER 7-27, 1984
Run
29
191
309
331
296
257
212
235
250
334
12
212
197
195
284
293
Oirtction
Std.
deviation
12
14
91
40
32
25
62
38
9
30
44
41
134
15
42
25
25
31
Wind
Mean,
•oh
5.9
6.2
3.8
5.6
3.8
6.6
4.9
3.3
4.1
4.0
4.1
3.7
4.1
4.9
2.6
4.9
6.1
2.7
Sp««d
Std.
deviation
1.5
2.1
0.9
1.3
1.3
1.6
2.8
2.4
1.5
2.0
1.5
2.0
1.7
2.1
l.l
1.4
1.9
1.4
76

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                          TABLE  VI-6

        RESULTS  OF  AMBIENT AIR SAMPLING FOR  PCDD/PCDF
IN VICINITY  OF DOW  CHEMICAL,  MIDLAND,  MICHIGAN,  SEPTEMBER  1984

          Stated 1n Terms of  Concentration (pg/m3)  on
       Glass Fiber  Filter/Polyurethane Foam  (PUF) Plug
Date Site
9/8-9/84
Site 1
Average wind Site 2
199°, 6 mph
Site 3
Site 4
Site 4 duplicate
9-12-13/84
Site 1
Average wind Site 2
191°, 6 roph
Site 3
Site 4
Site 4 duplicate
9/22-23/84
Site.l
Average wind Site 2
212°, 5 mph
Site 3
Site 4
Site 4 duplicate






2378-
TCDD

ND/ND
ND/ND

NO/ NO
NO/ND
NO/ND

NO/ND
ND/ND

ND/ND
ND/ND
ND/ND

ND/ND
ND/ND

ND/ND
ND/ND
ND/M
Keys to
Total
TCDD

0.30/ 0.69
4.82/39.98

0.67/ 1.73
0.14/ 0.72
0.06/ 0.42

0.13/*
*r

*/ 3.27
0.38/*
*/*

*/*
0.49/21.86

*/ 0.59
10.28/63.79
24.28/M
Symbols
Total
PeCDO

ND/ND
1.95/7.33

ND/ND
ND/ND
NO/ND

ND/ND
ND/ND

ND/ND
ND/ND
ND/ND

ND/ND
ND/ND

ND/ND
ND/1.37
ND/ND

Total
HxCDD

0.95/ND
ND/ND

ND/ND
0.86/ND
ND/ND

ND/ND
ND/ND

ND/ND
NO/ 2. 93
ND/ND

ND/ND
0.55/NO

ND/ND
0.28/ND
0.96/ND

Total
HpCDD

0.81/NO
2.08/ND

2.07/ND
1.00/ND
1.54/ND

0.69/ND
NO/ND

0.65/ND
0.22/1.26
0.48/ND

NO/ NO
2.69/ND

0.55/ND
1.14/ND
1.41/NO

OCOO

1.15/*
6.23/1.47

7.31/0.61
2.69/ND
4.10/ND

1.66/ND
ND/ND

5.10/ND
2.67/4.08
5.60/ND

ND/0.30
7.57/6.72

2.73/ND
4.01/ND
4.37/NO

2378-
TCDF

ND/ND
ND/ND

ND/ND
ND/ND
ND/M

ND/ND
ND/ND

ND/ND
ND/ND
ND/ND

ND/ND
ND/ND

ND/ND
ND/ND
ND/ND

Total
TCDF

ND/0.86
59.87/219.93

9.98/ 4.74
1.53/M
1.18/ 1.52

7.13/ 7.39
3.51/ 11.02

7.06/ 37.89
2.80/ 11.08
2.55/ 8.66

2.22/ 0.22
65. 33/ 90.36

4.35/ 7.25
84.60/290.77
122. 70/*

Total
PeCDF

ND/ND
10.75/18.33

0.54/ 3.90
1.16/ND
NO/ 1.41

ND/ND
ND/ND

NO/ 2.22
0.74/ 0.32
1.69/ 1.32

ND/ND
2.69/ 4.76

ND/ND
7.90/28.83
15.42/NO

ND-Not found at detection limit (example detection limit ranges: 0.05-0.62 pg/m3 for
2378-TCDF, 0.03-1.62 pg/m3 for 2378-TCDD)
M-Data not provided by analytical laboratory.
*-Exposed sample concentration lower than that of field blank-consider equivalent to
nondetectable.
Total
HxCDF

ND/ND
2.81/1.34

ND/ND
ND/ND
0.73/ND

NO/ND
ND/ND

ND/ND
NO/ND
NO/ND

ND/ND
4.52/ND

ND/ND
3.00/ND
4.37/ND






Total
HpCDF

ND/ND
5.01/ND

ND/ND
ND/ND
ND/ND

NO/NO
NO/ND

ND/ND
ND/ND
ND/ND

NO/ND
2.93/ND

ND/ND
3.00/ND
2.70/ND






OCDF

ND/ND
3.42/ND

0.57/0.79
1.66/ND
0.84/ND

0.99/ND
ND/ND

0.81/ND
ND/2.67
ND/ND

ND/0.13
1.34/0.26

ND/0.70
4.64/ND
6.55/NO







-------
    2.  Semi-Volatile Compounds

    Because of the large number of individual  samples and compounds  detected in
sampling for semi-volatile compounds,  it  was  decided to limit the  full  review
of these data to those sampling periods in  which consistently favorable relation-
ships existed between  monitoring  sites upwind  and  downwind  of Dow  Chemical.
Nine of the  18  sampling days were  evaluated,  with  southerly to  southwesterly
winds having been  present  in eight of those nine days.  These data  are presented
in Table VI-7.

    Review of these data by the EPA  Region V Central Regional  Laboratory yielded
the following principal findings:

    1.  Limited sampling  media blank  samples  were analyzed.  A  polyurethane
        foam blank was  found free of  contamination.  However, method  blanks of
        XAD-2 resin contained measurable  phenol;  biphenyl;  2,4-dichlorophenol ;
        1,2,4-trichlorobenzene; tetrachlorobenzene,  and  2-hydroxybenzaldehyde.

    2.  Field bias  blanks  frequently  contained phenol,  biphenyl, and diphenyl
        ether.  These  were subtracted  from  the  quantities  detected in  field
        samples, as a correction.

    3.  Problems were  observed with interferences  or mass  spectrum assignment
        criteria in  some  analyses  for phenol  and  biphenyl.   These data  are
        labeled appropriately in Table VI-7.

    4.  Recoveries of acid and base-neutral  surrogate compounds were generally
        not within acceptable limits.   According  to  current  guidance available
        concerning the interpretation  of data  affected in this way (see Section
        V.O. of this report), there is  no  agreed  method to  judge  acceptability
        of compound-by-compound  analytical   data   based  on  the   recovery  of
        specific surrogates.  The semi-volatile compound  data presented herein
        should be used in that  context.

    Nonetheless, positive  identifications of many  semi-volatile compounds  were
achieved, and higher  concentrations  of  several  semi-volatile  compounds  were
found at  sites  downwind of  Dow Chemical.  For the data reviewed,  precision,
compound-by-compound (sample and field duplicate sample from site  4) was within
target criteria for  all detected  compounds ( +  50%  RPD)  on four days  and the
goal was  nearly  met on  a fifth day.   Significantly higher  concentrations of
most compounds including

        1,2,3-trichlorobenzene
        1,2,4-trichlorobenzene
        1,3,5-trichlorobenzene
        1,2,3,4-tetrachlorobenzene
        1,2,4,5-tetrachlorobenzene
        phenol
        2,4-dichlorophenol
        2,4,6-trichlorophenol
        biphenyl, and
        diphenyl ether  (1,1-oxybisbenzene)


                                      78

-------
                              TABLE  VI-7

      HESULTS  Of  AMBIENT  AID  SAMPLING FOH  SEMI-VOLATILE COMPOUNDS
IN VICINITY  OF DOM  CHEMICAL COMPANf, MIDLAND. MICHIGAN. SEPTEMBER  1984
                         (Concentration noVa*)

Sampling Period
9/7-8/84
9/8-9/84
9/12-13/84
Site
1
2
3
4
4FD
1
2
3
4
4FO
2
3
4
4FO
Merage
Mind Direction
and Speed
184*. 5.9 «ph
Precision
Detected In blank
199*. 6.2 niph
Precision
Detected In blank
191*. 5.6 «ph
Precision
Detected In blan
j
f,
t.
102
SO. 3
NO
14.8)

NO


ND
(23.0)
41.0
30.2
ND
(17.1)
(17.1)


ND
(17.0
(17.9
37.3
108
NO
(27.4


|
u
(VJ
699
402
26.6

29.2


ND
(23.0)
312
146
23.9
NO
117.1)


5.09*
250
258
855
HO
(27.4


j
U
"I
ND
21.2)
ND
16.8)
'NO
(14.8)
achloro-
S.
i »
296
184
16.2
achloro-
£ »
^
97.4
62.0
ND
(14.8)
1
Pentachl
NO
(21.2)
1S.1*
NO
(14.8)
Hexachlorobenzene
NO
(21.2)
ND
(16.8)
ND
(14.8)
"o
ND
(21.2)
1546
181
(SaMple not analyzed.)
ND
(16.2)
11.4*'
4.86'
ND
(16.2)
ND
(16.2)
492'
2-Chl oroplwnol
ND
(21.2)
ND
(16.8)
ND
(14.8)

ND
(16.2)
o
NO
(21.2)
ND
(16.8)
ND
(14.8)

ND
(34.1)
2.4-Olchloropbeiwl
1693
3S.2
ND
(14.8)

ND
(Site 4 sample not analyzed - precision not calculated.

NO
(23.0)
O**)
fl!%
(17.1)
HlBi
(17.1)


ND
(17.0)
1.79*
ND
(31.1)
(37.2)
TBT
(27.4)



NO
(23.0)
246
70.0
13.7*
ND
(17.1)


ND
(5.1)'
ND
(17.9)
115
409
ND
(27.4)



ND
(23.0)
67.3
49.4
ND
(17.1)
NO
(17.1)


ND
(17.0)
55.5
46.6
141
ND
(27.4)



ND
(23.0)
11. S*
ND
(15.9)
ND
(17.1)
ND
(17.1)


ND
(17.0)
NO
(17.9)
NO
(31.1)
14.9*
ND
(27.4)



NO
(23.0)
ND
(16.4)
ND
(15.9)
ND
(17.1)
ND
(17.1)


ND
(17.0)
NO
' NO '
(31.1)
ND
(37.2)
NO
(27.4)


*
NO
(115)
128
1000
389
I2!

.
84.9
NO
(17.9)

770
35.6
182.3
*

NO
(23.0)
4.92'
ND
(15.9)
ND
(17.1)
ND
(17.1)


ND
(17.0)
ND
(17.9)
NO
(31.1)
ND
(37.2)
ND
(27.4



NO
(23.0)
NO
(16.4)
ND
(15.9)
ND
(17.1)
ND
(17.1)


NO
(17.0)
ND
(17.9)
ND
(31.1)
NO
(37.2)
(27.4)



ND
(23.0)
ND
(16.4)
28.7'
(17.1)
ND
(17.1)


ND
(17.0)
4114
1398
2232
ND
(27.4)


u
"I
NO
(21.2)
ND
(16.8)
ND
(14.8)

ND
(16.2)
e
u
t/i
ND
(21.2)
41.9
ND
(14.8)

ND
(16.2)


NO
(23.0)
NO
(16.4)
ND
(15.9)
(17.1)
NO
(17.1)


NO
(17.0)
ND
(17.9)
ND
(31.1)
ND
(37.2)
ND
(27.4)



NO
(23.0)
123
23.9'
ND
(17.1)
ND
(17.1)


ND
(17.0)
172
ND
(31.1)
ND
(37.2)
ND
(27.4)


Ichlorophenol
IN*
78.3
ND
(16.8)
ND
(14.8)

ND
(16.2)


NO
(23.0)
ND
(72.2)
ND
(15.9)
ND
(17.1)
HD
(17.1)


NO
(17.0)
ND
(17.9)
ND
(31.1)
ND
(37.2)
ND
(27.4)


oroplwnol
Pentachl
ND
(42.3)
ND
(33.5)
ND
(29.5)

ND
(32.5)


ND
(46.0)
ND
(32.8)
ND
(31.8)
ND
(34.1)
NO
(34.1)


ND
(34.0)
ND
(35.8)
ND
(62.1)
ND
(74.4)
ND
(54.8)


1
f
NO
(55.0)
117
NO
(14.8)

ND
(16.2)


ND
(23.0)
NO
(16.4)
191
ND
(17.1)
NO
(17.1)


3.40-
136
ND
(31.1)
78.1
(27.4)


1
|
ND
(21.2)
NO
(16.8)
ND
(14.8)

1.6"


NO
(23.0)
ND
(16.4)
ND
(15.9)
NO
(17.11
NO
(17.1)


6.79*
(17.9)
ND
(31.1)
(37.2)
(27.4)



I
NO
(21.2)
109
249

ND
(16.2)

*
36.8
93.5
97.1
35.8
1.71*
181.8
*
35.7
94.8
ND
(31.1)
338
27.4
172.8
•
ybenzal dehyde
e
I
NO
(21.2)
ND
(16.8)
19.2

ND
(40.6)


NO
(23.0)
(16.4)
ND
(15.9)
ND
(17.1)
ND
(17.1)


NO
(17.0)
(17.9)
ND
(31.1)
(37.2)
(27.4)


4-Hydroxybenzt 1 dehyde
NO
(275)
ND
(16.8)
ND
(14.8)

ND
(16.2)


ND
(23.0)
(16.4)
(15.9)
ND
(17.1)
ND
(17.1)


ND
(17.0)
37.6
74.5
(37.2)
(27.4)


Diphenyl ether
1204
1120
161

117'

*
(')
745
627
17.1
ND
(17.1)
—
•
NO
(17.0)
1789
1025
2194
16.4*
197.0


-------
                                                                                             TABLE VI-;  (continued)
                                                                                              (Concentration ng/m*)
CO
O



9/14-15/84






9/17- 18/84






9/18-19/84







Site

1
2
3
4
4FO


,
2
3
4
4FD


1
2
3
4
4FO



Average
and Speed
331*. 6.6 «ph




Precision
Detected In blank
212*. 4.1 mph




Precision
Detected In blank
235*, 4.0 mph




Precision
Detected In blank
1
u
iT
".
-
ND
(15.9)
ND
(21.0)
NO
(14.6)
NO
ND
(37.6)


ND
(16.0)
43.0
10.1*
41.7
31.1
29.1

NO
(22.5)
130
ND
(17.2)
62.6
54.4
14.0

Trtchlorobenzene
•*.
~
20.6
No
(21.0)
NO
(14.6)
ND
(13.8)
ND
(37.6)


NO
(16.0)
362
37.4
233
173
29.6

NO
(22.5)
566
NO
(17.2)
457
429
6.3

Tnchlorobenzene
"I
-
ND
(15.9)
NO
(21.0)
NO
(14.6)
NO
ND
(37.6)


ND
(16.0)
10.3'
ND
(14.4)
NO
<'£,•/>
ND
(17.3)


NO
(22.5)
ND
(17.1)
NO
(17.2)
10.2-
10.0*


4-Tetrachloro-
zene
™.%
-'
7.94*
NO
(21.0)
NO
(14.6)
NO
(13.8)
ND
(37.6)


NO
(16.0)
327
NO*
(21.6)
167
91.5
56.1

NO
(22.5)
823
ND
(17.2)
237
215
9.7

5-Tetrachloro-
zene
-.8
-
NO
(15.9)
NO
(21.0)
NO
(14.6)
NO
(13.8)
NO
(37.6)


NO
(16.0)
126
12.9*
60.0
32.8
52.1

NO
(22.5)
326
ND
(17.2)
110
97.3
12.3

til orobenzene
a
£
NO
(15.9)
ND
(21.0)
NO
(14.6)
ND
(13.8)
ND
(37.6)


ND
(16.0)
NO
NO
(14.4)
5.0*
3.45"
36.7

NO
(22.5)
NO
(17.1)
NO
(17.2)
8.5*
NO
(14.3)
._

1 orobenzene
S
*
ND
(15.9)
ND
(21.0)
NO
(14.6)
NO
(13.8)
NO
(37.6)


NO
(16.0)
NO
C'-2)
ND
NO
('6-')
ND
(17.3)


NO
(22.5)
NO
(17.1)
141
ND
(16.9)
ND
(14.3)



O
ft-
38.1
162
33.6
83.0
NO
(37.6)
84.7

NO
(16.0)
671
NO
(14.4)
112
259
79.2

405
1715
ND
(17.2)
812
601
29.9

*o
c
5
CXI
ND
(15.9)
ND
(21.0)
ND
(14.6)
ND
(13.8)
NO
(37.6)


ND
(16.0)
NO
(»,•*!
NO
(14.4)
ND
NO
(17.3)


NO
(22.5)
No
(17.1)
ND
(17.2)
ND
(16.9)
NO
(14.3)


rophcnol
§
«*>
NO
(15.9)
NO
(21.0)
NO
(14.6)
ND
(13.8)
NO
(37.6)


NO
(16.0)
NO
(17.2)
NO
(14.4)
NO
(16.7)
ND
(17.3)


NO
(22.5)
NO
(17.1)
ND
(17.2)
NO
(16.9)
NO
(14.3)


|
?
CM
ND
(15.9)
NO
(21.0)
ND
(H.6)
ND
(13.8)
NO
(37.6)


NO
(16.0)
112
ND
(14.4)
23.3
NO
(17.3)


NO
(22.5)
NO
(17.1)
NO
117.2)
2538
2003
23.6

Tncnlorophenol
"1
ri
NO
(15.9)
NO
(21.0)
NO
(14.6)
ND
(13.8)
NO
(37.6)


NO
(16.0)
534
NO
(14.4)
ND
(16.7)
ND
(17.3)


ND
(22.5)
NO
(17.1)
NO
(17.2)
NO
(16.9)
ND
(14.3)


Trlcnlorophenol
u>
CM
NO
(15.9)
ND
(21.0)
ND
(14.6)
NO
(13.8)
ND
(37.6)


NO
(16.0)
NO
(17.2)
NO
(14.4)
NO
(16.7)
(17.3)


ND
(22.5)
ND
(17.1)
NO
(17.2)
ND
(16.9)
ND
(14.3)


Trichlorophenol i
">.
~
NO
(15.9)
NO
(21.0)
ND
(14.6)
ND
NO
(37.6)


ND
(16.0)
189
NO
(14.4)
NO
(16.7)
ND
(17.3)


NO
(22.5)
ND
(17.1)
ND
(17.2)
127
104
19.9

hlorophenol
•
S
ND
(31.7)
ND
(21.0)
ND
(29.2)
NO
(27.7)
ND
(75.1)


NO
(32.0)
ND
(34.4)
ND
(28.8)
ND
(33.3)
ND
(34.5)


NO
(45.0)
NO
(34.2)
ND
(34.5)
NO
(33.8)
ND
(28.6)


ylphenol
«
CM
NO
(15.9)
NO
(21.0)
NO
(14.6)
ND
(13.8)
NO
(37.6)


NO
(16.0)
ND
(17.2)
NO
(24.4)
5.0"
NO
(17.3)


NO
(22.5)
ND
(17.1)
ND
(17.2)
40.6
ND
(14.3)
„

ylpnenol
«
4
NO
(15.9)
NO
(21.0)
HO
CI4.6)
NO
(13.8)
NO
(37.6)


NO
(16.0)
ND
(!'. 2)
NO
(14.4)
ND
(16.7)
NO
(17.3)


ND
(22.5)
NO
(17.1)
ND
(17.2)
3.38*
ND
(14.3)


*x
s
tet
28.6
18.9
17.5
19.4
26.3
30.2

36.8
122
104
53.3
ND
(17.3)

.
67.6
92.6
?2.4*»
112'3
104*1
7.4
.
oxybenzaldenyde

CM
ND
(15.9)
ND
(21.0)
ND
(14.6)
ND
(13.8)
ND
(37.6)


4.8*
NO
(17.2)
7.19*
ND
(16.7)
NO
(1'.3)


22.5
NO
(17.1)
NO
(17.2)
ND
(16.9)
NO
(14.3)


oxybenzaldehyde

4
NO
(15.9)
ND
(14.6)
W
(13.8)
ND
(37.6)


NO
(16.0)
KD
(17.2)
NO
(14.4)
NO
(16.7)
ND
(17.3)


NO
(22.5)
NO
(17.1)
NO
(17.2)
NO
(16.9)
NO



1
o
NO
(15.9)
23.1*
ND
(14.6)
NO
(13.8)
NO
(37.6)


3.2-
ND
(17.2)
575
283
157
57.3

ND
(22.5)
2227
ND
(17-2)
1149
1086
5.6
.

-------
                                                                                               IABLE  VI-7  (continued)
                                                                                                (Concentration  ng/m3)
00

Sampl Ing Period
9/22-23/84
9/23-24/84
9/24-25/84
Site
2
3
4
4FD
1
2
3
4
4FD
1
2
3
4
4FO
Average
Wind Direction
and Speed
212°, 4.9 «ph
Precision
Detected In blank
197'. 2.* niph
Prec Is Ion
Detected In blank
195*. 4.9 inph
Precision
Detected In blank
rrlchlorobenzene
".

57.0
7.16*
61.0
52.8
14.4

3.23*
30.8
10.2*
14.7"
12.3*
17.8

5.57*
38.8
14.2
6.46*
10.8*
50.3

hlorobenzene
~
~:

326
28.6
425
347
20.2

9.71*
199
67.9
101
91.7
9.7

13.0*
254
65.3
51.7
77.1
39.4

hlorobenzene
-
J,
(Incom
NO
(16.3)
NO
(14.3)
3.70*
3.30"
11.4

NO
(16.2)
ND
(18.1)
ND
(17.0)
NO
(18.3)
ND
(17.6)


NO
(18.6)
ND
(18.5)
ND
(14.2)
NO
(16.1)
ND
(17.9)


trachloro-

i*
lete s
151
21.5
296
314
5.9

21.0
181
52.6
75.2
68.8
8.9

24.1
203
75.3
43.6
62.8
36.1

o
o
o
7 £
-"I
mp 1 1 ng
83.0
18.6
107
107
0.0

3.24*
77.8
25.4
25.7
24.7
4.0

NO
(18.6)
83.1
41.2
24.2
37.7
43.6

obenzene
o
1
run --
ND
(16-3)
NO
(14.3)
11. I*
NO
(16.5)


ND
(16.2)
NO
(18.1)
NO
(17.0)
ND
(18.3)
1.76*
__

ND
(18.6)
ND
(18.5)
2.8*
ND
(16.1)
ND
(17.9)


benzene
r_
*J
1
sample
NO
HO
(14.3)
NO
(18.5)
NO
(16.5)


NO
(16.2)
NO
(18.1)
NO
(17.0)
ND
(18.3)
ND
(18.3)


ND
(18.6)
ND
(18.5)
NO
(14.2)
NO
(16.1)
ND
(17.9)


1
not an
6941
1379
956
649
38.3
.
359
6666
1836
224
215
4.1
.
186
1736"
1250
436"
508"
22.4

"o
|
o
<••*
Ijzed.
NO
(1S-3)
Ml
(14.3)
NO
(18.5)
NO
(16.5)


ND
(16.2)
NO
(18.1)
NO
(17.0)
NO
(18.3)
ND
(17.6)


ND
(18.6)
ND
(18.5)
ND
(14.2)
NO
(16.1)
NO
(17.9)



C
o
o

NO
(16.3)
NO
(14.3)
NO
(18.5)
NO
(16.5)


NO
(16.2)
NO
(18.1)
NO
(17.0)
ND
(18.3)
ND
(17.6)


ND
(18.6)
NO
(18.5)
ND
(14.2)
NO
(16.1)
ND
(17.9)


,
|
B

ND
(l«-3)
NO
(14.3)
721
528
30.9

NO
(16.2)
ND
959
ND
(17.0)
NO
(18. J)
NO
(17.6)


NO
(18.6)
ND
(18.5)
ND
(14.2)
ND
(16.1)
ND
(17.9)


1
c
"I

ND
(16.3)
NO
(14.3)
ND
(18.5)
ND
(16.5)


ND
(16.2)
ND
(18.1)
ND
(17.0)
NO
(18.3)
NO
(17.6)


NO
(18.6)
NO
(18.5)
ND
(14.2)
NO
(16.1)
ND
(17.9)


1
1
5
LO

ND
(16.3)
NO
(14.3)
NO
(18.5)
NO
(16.5)


ND
(16.2)
NO
(18.1)
ND
(17.0)
ND
(18.3)
NO
(17.6)


ND
(18.6)
ND
(18.5)
NO
(14.2)
ND
(16.1)
NO
(17.9)


0.
o
u
"I

179
ND
(14.3)
181
162
11.1

ND
(16.2)
ND
(18.1)
30.5
25.7
24.7
4.0

NO
(18.6)
177
31.2
NO
(16.1)
NO
(17.9)


llorophenot
1

ND
(32.6)
NO
(28.6)
ND
(37.0)
ND
(33.0)


NO
(32.4)
NO
(36.2)
ND
(33.9)
NO
(36.7)
ND
(35.3)


ND
(37.1)
ND
(36.9)
NO
(28.4)
ND
(32.3)
NO
(35.9)


1
a.
|

NO
(16.3)
NO
(14.3)
NO
(18.5)
ND
(16.5)


NO
(16.2)
ND
81.5
ND
(17.0)
ND
(18-3)
NO
(17.6)


ND
(18.6)
NO
(18.5)
63.9
NO
(16.1)
ND
(17.9)


"o
I
1

ND
(16.3)
NO
(14.3)
NO
(18.5)
ND
(16.5)


NO
(16.2)
ND
(18.1)
ND
(17.0)
ND
(18.3)
ND
(17.6)


ND
(18.6)
(18.5)
ND
(14.2)
NO
(16.1)
ND
(17.9)



I

111
80.2"
115"3
129*'
11.5
*
64. 7*3
1703
96.7
95. 31
95.2
0.1

16.7
122
115
51.7'
68.2
27.5

i
•

ND
(16.3)
NO
(14.3)
NO
(18.5)
ND
(16.5)


53.4
NO
(18.1)
ND
(17.0)
NO
(18.3)
NO
(17.6)


ND
(18.6)
(18.5)
19.9
ND
(16.1)
ND
(17.9)


4-Hydroxybenzaldehyde

NO
(16.3)
ND
(14.3)
NO
(18.5)
Nb
(16.5)


ND
(16.2)
NO
(18.1)
NO
(17.0)
NO
(18.3)
NO
(17.6)


ND
(18.6)
(18.5)
ND
(14.2)
HO
(16.1)
ND
(17.9)


Diphenylether

1530
286
1128
1090
3.4

ND
(16.2)
1792
594
440
459
4.2

3.7*
720
469
194
251
25.6


-------
                                                                                   TABLE VI-7 (continued)


            NOTES:  ND = Not detected.
                    FO = Field duplicate sample.
                     * = Estimated value.
                       = Identification and quantitation of dichlorophenol  and trichlorophenol  suspect.
                     2 = Concentration in blank higher than in sample.
                       » Quantitation of blphenyl  suspect;  all  mass spectrum
                         assignment criteria were not met.
                     ** » Interferences present In mass spectrum;
                         suspected positive bias.
oo
ro

-------
were detected  principally  at  downwind  monitors,  in  the  following  sampling
periods:

        9/18-19/84
        9/22-23/84
        9/23-24/84, and
        9/24-25/84

with precision achieving the target criterion for many  compounds on 9/17-18/84.
As indicated  above,  southerly  to  southwesterly  wind patterns  were  considered
most appropriate  to  judge  upwind-downwind  relationships.  As  a  control,  one
sampling period in which northerly winds were present,  9/14-15/84, was reviewed
to determine  whether any  of the  compounds were present when little  or  no  wind
contacted the Dow  Chemical  facility prior to  collection  in the  samplers.   As
expected, most  compounds  were  not  detected.    These  data  demonstrate  that
the Dow  Chemical   facility  does   emit  measurable  quantities  of  semi-volatile
compounds.  In  addition,  the  range of  tentatively  identified  compounds  (see
Table VI-8) was generally larger  at downwind monitoring sites.

    Referring to Table V-15 (Section V  of this  report), the identifiable semi-
volatile compounds measured in Building  703 incinerator  exhaust  were few,  and
were in the range of 10 to  100 ppb.  The  complement  of  semi-volatile compounds
presented in  Tables  VI-7  and  VI-9 is much more  extensive;  further,  the single
compound detected  in  both  the incinerator exhaust  and  ambient  air  sampling,
tetrachlorobenzene, was  found  to  be present in  ambient  air  at  a  level  con-
siderably higher than expected if the incinerator exhaust  were the sole source.
Applying an  approximate  dilution  factor of  105 to account  for  the distance
and elevation  difference  of   the   ambient  monitoring   sites   with  respect  to
the incinerator  stack,  to  the  tetrachlorobenzene  concentration  presented  in
Table V-15,  an  approximate  ground  level  concentration  of tetrachlorobenzene
(1,2,3,4 plus 1,2,4,5 isomer)  would  be  in the  range  of 0.1  ppt rather than  the
maximum concentrations between  100  and  1000 ppt  shown  in  Table  VI-9.   These
data suggest  that sources  within  the  Dow  Chemical  facility  other than  the
Building 703  incinerator  exhaust  stack,  such   as  process  vents or fugitive
emissions sources, may be attributable for the  levels of semi-volatile compounds
detected in ambient  air  around the plant.  It  is known that 2,4-dichlorophenol
is currently  produced  at the  Midland  plant.   The finding  of  2,4,5-trichloro-
phenol is surprising in  that Dow  Chemical  has not  produced 2,4,5-trichlorophenol
for some time,  nor does the company report  any  current use  of 2,4,5-trichloro-
phenol to any significant extent.23

    3.  Volatile Compounds

    As described  previously,  these  compounds  were sampled  using traps packed
with carbon molecular sieves (CMS) and a study was conducted to demonstrate  the
validity of  this  sorbent  for  the  compounds  to  be  sampled.   Most  of  the  CMS
tubes used in the validation study were not analyzed by the  contract laboratory
within required times; results  from those tubes analyzed before their expiration
are shown in  Table  VI-10.  Seven of the  eight compounds  spiked  into the tubes
were not  detected.   The  detection  of  perchloroethylene  (tetrachloroethylene),
the remaining spiked compound, was not in consistent  agreement  with the known
levels spiked.
                                      83

-------
                                                                                TABLE VI-8

                                              TENTATIVELY IDENTIFIED SEMI-VOLATILE COMPOUNDS DETECTED IN AMBIENT AIR SAMPLING
                                                   IN VICINITY OF DOW CHEMICAL COMPANY, MIDLAND. MICHIGAN. SEPTEMBER 1984
       Sampling  Period   Site
           9/7-8/84
  1
  2

  3
  4
4FD
4FB
   Average
Wind Direction
  and Speed

 184°. 6 mph
Compounds  Tentatively Identified

Ethylcyclopentane;  methylcyclohexane;  xylene;  methyl ethyl benzene; dlchlorobenzene; methyl naphthalene
Methyl naphthalene;  dlchlorobenzene;  benzole acid;  1.2-dlethyl benzene; ethenylmethylbenzene; ethylmethyl-
benzene; ethylmethyl benzene;  chlorobenzene; toluene
Methylphenanthrene; phenylblcyclohexyl;  terphenyl;  methyl naphthalene; b1s(d1methylethylJphenol; xylene; toluene
(Sample not  analyzed.)
Ethylbenzene; ethylmethylbenzene;  blphenyl
Naphthalene; ethylmethylbenzene; toluene; ethylcyclopentane
          9/8-9/84         1      199°, 6 mph     Ethylmethylbenzene; propylbenzene; toluene; benzene; benzothlazole; xylene
                           2                     01 ethyl benzene; ethenylethyl benzene; propylbenzene; ethylmethylbenzene; ethylbenzene; toluene
                           3                     Dlchlorobenzene; dlethyl benzene; trlmethylnaphthalene; chlorobenzene; dimethyl benzene; styrene; ethylmethyl-
                                                benzene; ethenylethylbenzene; d1ethenylbenzene; methylbenzaldehyde; ethylbenzene
                           4                     Dlethylbenzene; ethylbenzene; ethenylbenzene; ethylmethylbenzene; 2,3-d1hydro1ndene; ethenylethylbenzene;
                                                dlethenylbenzene
                        4FD                     Ethylbenzene; ethenylbenzene; ethylmethylbenzene
                        4FB                     Ethylmethylbenzene; trlmethyl benzene; benzene; ethylbenzene; dlethylbenzene
        9/12-13/84
00
  1     191°. 6 mph


  2

  3
                          4
                        4FD

                        4FB
                 Hexanedlolc acid dloctyl ester; dodecanonltrlle; d1-l,2-benzened1carboxyl1c acid; ethylbenzoic  acid;  2,6-bls
                 (l.l-dlmethyl)phenol;  l,l'-(l,4-phenylene) B ethanone; benzole acid;  1.2,3-trlmethylbenzene,  l-ethyl-2-
                 ntethylbenzene; ethylbenzene; xylene; acetic acid butylester
                 1-Methylethylbenzene;  2,3-dihydro  1 H-1ndene;  1,3-dlethylbenzene,  l-ethenyl-4-ethylbenzene;  l.l'-oxybisbenzene;
                 hexadecanolc acid methyl ester; 2-methylnaphthalene
                 3.7-D1methyl-l,6-octad1en-3-ol; l-ethyl-2-methylbenzene; 1-methylethylbenzene; xylene; 2,2-dimethyloctanol;
                 b1s(2-ethylhexyl) hexanedlolc acid; methyl ethyl benzene; ethylbenzene; 1.2-dlethyl benzene; xylene;  1,4-dihydro-
                 1.4-methanonaphthalene
                 Dlethylbenzene; ethylbenzene; xylene; 2,3-dihydro 1 H-lndene; 1-methylethylbenzene
                 1-Methyl ethyl benzene;  2-ethylhexanolc acid; 2,6-b1s(l,l-d1methylethyl)phenol; 4-methyl-l,3-benzenediamine;
                 5,7-methylundecane; 2-cyclohexen-l-one
                 Olmethylbenzene; blcyclo [4.2.0] octa-l,3,5-tr1ene; 1,3,6-octatrlene; 3,7-d1methyl; 1-ethyl-2-methylbenzene;
                 6,6-d1me blcyclo [3.1.1] heptane; octamethylcyclotetraslloxane; dodecamethylcyclohexaslloxane;  2-methyltrl-
                 decane; d1-l,2-benzene dlcarboxyllc acid; 2.10-methylundecane; 2,6-b1s(l,l-d1methyl) phenol;  5,7-dimethyl-
                 undecane; 2-fluorophenol; ethylbenzene; hexanedlolc add dloctylester; 2,7-dlraethyloctane; 1-nltroethyl-
                 benzene
        9/14-15/84
                          3
                          4
                        4FD
                        4FB
        331", 7 mph      Xylene; 4-methyl-l-(3)-cyclohexen-l-ol; l-ethyl-2-methylbenzene; ethylmethylbenzene; hexadecanolc acid; ethyl-
                        benzene methyl ethyl benzene
                        Xylene; ethylmethylbenzene; 1,2-dlethylbenzene; 1,2,3,4-tetramethylbenzene; 1-ethylnaphthalene; hexadecanoic
                        acid methyl ester; methyl benzene; ethylmethylbenzene; 1,2,4-trlmethylbenzene; l-ethyl-2,3-d1methylbenzene;
                        methyl naphthalene; 1.4-d1hydro-l,4-methanonaphthalene
                        3-Bromodecane; hexadecanolc acid dloctylester; ethylmethylbenzene; xylene
                        3-Bromodecane; ethylbenzene;  1-methylethylbenzene; 2-propylheptanol, xylene
                        l-Acetyl-l,2,3.4-tetrapyr1d1ne; 3-bromodecane; ethyl dimethyl benzene; 2-methylpropylbenzene; ethylmethylbenzene
                        Methylcyclohexane; methyl benzene; d1-l,2-benzened1carboxy!1c acid; 2-propenyl1ndenocyclobutene; methylethyl-
                        benzene

-------
                                                                                TABLE VI-8 (continued)
      Sampling Period   Site
        Average
     Wind  Direction
       and Speed
        9/17-18/84
00
en
1     212°.  4 mph



2


3
                          4

                        4FD


                        4FB
Compounds Tentatively Identified

2-Methylnaphthalene;  1,1-dlmethylethylbenzene;  4-ethyl-l,2-d1methylbenzene;  1,2,3,4-tetramethylbenzene;  ethyl-
benzene;  benzole acid;  l-methyl-4-propylbenzene;  2-methylnaphthalene;  ethylcyclopentane;  Il-n1tro-l-undecane;
dimethyl benzene; 1,3.5-cycloheptatHene;  4-methyl-l,3-cyclohexen-l-ol; ethylmethylbenzene;  trlmethyl benzene;
ethyl dimethyl benzene; 1,3-dlmethyl benzene
2,4-Hexadfyne;  methylbenzene;  xylene;  1,3,5,7-cyclooctatetraene;  1-methylethylbenzene;  diethylbenzene;
undecane; naphthalene;  methyl naphthalene; 3,4,5-trlmethylhexene;  dlmethylpentene;  4-ethenylcyclohexene;  chloro-
benzene;  ethyl benzene
Methyl naphthalene; benzenedlcarbonltrlle; I,l-d1methylethylbenzene; 1-methylpropylbenzene;  1,2.4-trimethyl-
benzene;  1-methylethylbenzene; 1-ethyl-2-methylbenzene;  xylene;  chlorobenzene;  methylcyclohexane;  1,2-dimethyl-
4-ethylbenzene; 2-methyldecahydronaphthalene;  propylbenzene
Ethylbenzene;  4-(6-methyl-2-benz)  benzamlne;  1-undecane. 11-nltro;  o,o-d1ethylphosphoroth1o acid;  2-propyl-l-
heptanol; 1,2-benzenedicarbonltrile;  xylene;  1,3,5,7-cyclooctatetraene
2-Methylphenanthrene; l-(2-bromoethyl)-3-fluorobenzene;  2,4-dinitrobenzeneamine;  2.2,7.7-tetra-4,5-octadien-
3-one;  2-ethyl-2H-benzotriazole; l,r-(l,4-phenylene)  B-ethanone methylsulfonylbenzene; dichlorobenzene;
1-ethyl-4-methylbenzene;  1-methylethenylbenzene;  ethylbenzene;  1,2-diethylbenzene; 1-methylethylbenzene; xylene
1,2,3-Trimethylbenzene; di-l,2-benzenedicarboxyl1c acid; 1-methylethylbenzene;  methyl benzene;  l-ethyl-2-
methylbenzene
9/18-19/84
9/22-23/84
9/23-24/84
1
2
3
4
4FO
4FB
1
2
3
4
4FD
4FB
1
2
3
4
4FO
4FB
235°. 4 mph Dlmethylbenzene; ethylmethylbenzene; methylbropyl benzene, trlmethylbenzene; benzenedicarbonitrile
Chlorobenzene; ethylbenzene; ethenylbenzene; methylethylbenzene; dichlorobenzene; diethylbenzene; methyl benzo-
furan
Pyrene; dlmethylbenzene; ethylbenzene; ethyldlmethylbenzene; methylethylbenzene; propyl benzene; methylpropyl-
benzene
Dlmethylbenzaldehyde; dimethylbenzene; dichlorobenzene; ethylmethylbenzene; ethenylbenzene; methyl benzaldehyde;
dlethenylbenzene
Methyl benzaldehyde; diethylbenzene; ethylmethylbenzene; dimethylbenzene; dichlorobenzene; ethenylbenzene;
ethylbenzene
Dlmethylbenzaldehyde; dlethenylbenzene; ethenyl ethyl benzene; di ethenylbenzene
212°, 5 mph 1, !'-(!, 4-Phenylene)b1s ethanone; benzoic add; ethylmethylbenzene; dlmethylbenzene
Ethylbenzene; dimethylethylbenzene; phenanthrene, diethylbenzene; dichlorobenzene; ethenylbenzene; chlorobenzene
Ethylmethylbenzene; dichlorobenzene; diethylbenzene; ethyldlmethylbenzene; methyl naphthalene; naphthalene;
dlethenylbenzene; methyl propyl benzene; dlmethylbenzene
Methylethylbenzene; diethylbenzene; ethylbenzene
Ethenyl ethyl benzene; diethylbenzene; methylethylbenzene; ethenylbenzene; ethylbenzene; dlethenylbenzene;
dichlorobenzene; dlmethylbenzene
Dlmethylbenzaldehyde; propyl benzene; ethylmethylbenzene
197", 3 mph Methylnaphthalene; naphthalene; dimethylethylbenzene; methyl propyl benzene; methylethylbenzene; dimethylbenzene
Anthracene; methylethylbenzene; ethenylbenzene; dlmethylbenzene; dichlorobenzene; ethylbenzene; diethylbenzene;
1 ,l'-(l,4-phenylene)b1s ethanone; naphthalene; dlethenylbenzene
Diethylbenzene; ethenyl ethyl benzene; ethylbenzene; l,l'-(l,4-phenylene)bis ethanone; methyl naphthalene;
naphthalene; ethenylethylbenzene; dichlorobenzene; ethenylbenzene; dlmethylbenzene
l,l'-(l,4-Phenylene)bis ethanone; dimethylbenzene; ethenylethylbenzene; di ethenyl benzene; ethyldlmethylbenzene;
diethylbenzene; ethylbenzene; I,l'-oxyb1sbenzene; naphthalene; dichlorobenzene
Dimethylnaphthalene; naphthalene; ethylbenzene; methylethylbenzene; propyl benzene; dlethenylbenzene; dimethyl-
ethylbenzene; diethylbenzene; dlmethylbenzene; dichlorobenzene; ethenylethylbenzene
Propyl benzene; trlmethylbenzene; methyl ethyl benzene; dlmethylbenzene

-------
                                                                          TABLE  VI-8  (continued)
Sampling Period   Site
  9/24-25/84
  1
  2

  3
  4

4FD

4FB
   Average
Wind Direction
  and Speed

 195°. 5 mph
Compounds Tentatively  Identified

1.1'-(1,4-Phenylene)b1s  ethanone;  methyl ethyl benzene;  dlmethylbenzene
Ethylbenzene;  methyl ethyl benzene;  dlethyl benzene;  dlethenylbenzene;  naphthalene;  l.l'-oxybisbenzene;  methyl-
benzene;  dlraethylbenzene;  dlchlorobenzene;  methyl naphthalene;  1,l'-(l,4-phenylene)bis ethanone
Methylnaphthalene;  dlethylbenzene; methyl ethyl benzene;  1,l'-(l,4-phenylene)b1s  ethanone;  diethenylbenzene
Dlmethylbenzene;  ethylmethylbenzene;  dlethylbenzene; ethenylethylbenzene;  dlethenylbenzene;  naphthalene;
l.l'-oxyblsbenzene;  tetramethylbenzene
Dlmethylbenzene;  dlethylbenzene; ethenylethylbenzene;  dlmethylbenzene;  dlethenylbenzene;  methylphenylethanone;
l.l'-oxyblsbenzene
Dlethylbenzene; methyl ethyl benzene; dimethylbenzaldehyde
NOTES:  FD = Field duplicate sample.
        FB = Field blank sample.
  00
  cn

-------
                                                                             TABLE VI-9
                                                   RANGES OF CONCENTRATIONS OF QUANTITATED SEMI-VOLATILE COMPOUNDS
                                                        IN AMBIENT AIR ON NINE SAMPLING DAYS - MIDLAND, MICHIGAN
                                                                          9/7/84 - 9/25/84
                                                                      (Data expressed In ng/m3)













Site

1


2


3


4

















Maximum
Minimum
Average
Maximum
Minimum
Average
Maximum
Minimum
Average
Maximum
Minimum
Average
2
Ot
c
£
e
0

o


I—

CO
•l
CM

102
ND
13.8
130
ND
43.4
37.3
ND
12.1
108
ND
26.8
%
01
c
0)
o
o
f
o



1

CM
A

699
ND
95.4
566
ND
297
258
ND
70.0
855
ND
194
8
01
N
C
01
o
o
o
f-
o


I—
1
u->
ro

ND
NO
—
10.3
ND
1.34
ND
ND
—
10.2
NO
1.60

1
O
L.
O
-g
«J

01 O>
H- C
1 41
*r isi
* c
CO Ol
CM
*

296
ND
43.6
327
ND
235
115
ND
39.0
409
NO
118

1
O
L.
O
•g
«0
L.

Q) Q)

| (JJ
l/l N
» C
^ fl,
• .o
CM
*

97.4
ND
12.6
326
ND
97.9
49.4
ND
21.6
141
ND
45.4



01
N
C
01
.0
o

o

JC
o

ND
NO
—
ND
ND
—
ND
ND
~
NO
ND
—



8
01
ex
O
C.
O

f
0

o
1
CM
1693
ND
242
4114
ND
580
1398
ND
158
2538
ND
473

8
0)
.c
ex.
o
i.
o

o


t—
t

ro
CM
ND
ND
--
534
NO
59.3
ND
NO
—
ND
ND
—

8
Ol
.C
Q.
O
t_
O
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u">
«t
CM
ND
NO
—
172
ND
37.4
239
ND
2.65
ND
ND
—

8
Ol
Q.
O
C-
o

u

c_
K-
1

^
CM
78.3
ND
9.79
189
ND
60.6
31.2
NO
6.86
181
ND
36.7



"o
c
Ol
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ex
o
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o


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ND
ND
—
ND
ND
—
ND
ND
—
NO
ND
—




,_
8
OJ
£
CL


C
at
a.
i
CM
3.4
NO
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136
ND
37.2
191
ND
28.3
78.1
NO
7.28




,_
8
01
f~
CL


C
01
ex
1
*
6.79
ND
0.85
NO
ND
—
NO
ND
~
3.38
ND
0.29











C
a>
a.
QO
67.6
NO
35.9
170
18.9
104
249
ND
84.4
358
ND
93.8
01
•a

•o
'a
Nl
c
01
-0

X
o

"O
3:
i
CM
53.4
ND
10.1
ND
ND
--
19.9
NO
5.14
ND
ND
—
01
•a

01
-o
1o
Kl
c
01
.a

X
o

"U
1
"*
ND
ND
—
37.6
ND
4.18
74.5
ND
8.28
NO
NO
—





c_

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ai
ex
Q
1204
ND
151
2227
ND
1105
1025
NO
415
2194
ND
498
00

-------
                                    TABLE  VI-10

                 COMPARATIVE RESULTS OF CARBON MOLECULAR SIEVE TUBE
                                  VALIDATION STUDY


     Tube
Identification           Compound           Amount  Spiked (ng)     Amount  Detected (ng)


     4-E          perchloroethylene              131                  20.0


     5-A          1,1,1-trichloroethane      (not spiked)            1290

                  perchloroethylene               26                  31.8


     5-B          1,1,1-trichloroethane      (not spiked)             537

                  perchloroethylene               26                  56.5


     5-C          (no spiked compounds detected)
                                        88

-------
    Also, because of  difficulties relating  primarily  to sample  holding times
prior to analysis  and possible  blank contamination, most  CMS tubes  were  not
analyzed successfully.  Therefore, the  data  for volatile compounds  in ambient
air presented in Table VI-11 are presented in qualitative terms.

    From these  data  the   following   general  conclusions  appear  supportable:

    1.  On each  sampling  day,  site  1 was considered  upwind of  Dow Chemical.
        A wider range of  compounds  was  usually  detected  at  the downwind sites.

    2.  Two compounds, 1,1,1-trichloroethane  and perchloroethylene,  were found
        in most  samples   on  the  eight  days  for   which  analytical  data  are
        available.  However,  both  compounds  were  frequently found  as  a  blank
        contamination.  Also, 1,1,1-trichloroethane  appeared  at  high levels  in
        the method validation study, though it was  not  spiked.

    3.  Precision between  field duplicate samples was generally poor.

    4.  On each sampling  day, either the low-flow or high-flow set of CMS tubes
        was designated  the  primary  set  for  analysis,  based  upon  ambient
        temperature and humidity  conditions  (see  Appendix  F,  Section  III.A).
        There was no distinct superiority or consistent pattern in the levels of
        compound detection in primary tubes.

    5.  Acrylonitrile and  chloroform, when  detected,  were   found  primarily  at
        monitoring sites  downwind of Dow Chemical.

    In addition to the six compounds appearing in Table VI-11, three compounds:
monochlorobenzene, 1,3-dichlorobenzene,   and  1,4-dichlorobenzene,  were  not  de-
tected in  any  sample.  However,  many of the volatile  compounds  selected  for
analysis (see  Section II  of  this   report)  were  not  included.   Among  these
compounds were  benzene,   ethylene  dibromide,  ethylene  dichloride,  ethylene
oxide, methyl chloroform,  methylene chloride, and vinylidene chloride.  Several
of these  compounds   were  detected  in  Building 703 incinerator  exhaust,   as
described in Section V of  this report.

    Thus, this portion of the ambient air study was  not  successful  in scanning
for the full  range of  desired compounds, either because of sampling or analytical
method unsuitability,  or   insurmountable analytical problems.   The  available
data should be considered  qualitative.

    4.  Formaldehyde

    The analytical  results  appearing  in Table VI-12  show  higher  levels   of
formaldehyde in method and field blanks than in any  of  the 25 exposed  field
samples, with  two  exceptions.   These  data,  evaluated  by   the  EPA  Region   V
Central Regional  Laboratory as  acceptable   in  terms  of  analytical  accuracy,
are not  usable for  quantifying  the  presence  or  absence  of formaldehyde   in
ambient air during the study period.
                                       89

-------
                                           TABLE VI-11
                    RESULTS  OF AMBIENT AIR SAMPLING FOR VOLATILE  COMPOUNDS

            IN VICINITY  OF DOW CHEMICAL COMPANY, MIDLAND, MICHIGAN,  SEPTEMBER 1984
                                                            Ol
                                                                  01
                                                                  0)
                                                                  o
oethane
                                                                        0)
                                                                        t_  Ol
                                                                        o  c
                                                                        i—  01
Dates (1984)
Wind Direction
 and Average
    Speed
Site
  High
   or
Low Flowl
                                                               o

                                                               o
                                                               c_
                                                               o
                                                                     *"""  *O  ^H
                                                                           
-------
                                           TABLE VI-11 (continued)
Dates (1984)
                                                             ,
                       t_
                       o
                                                                O
                                                                C_
                                                                O
                                                 O  O  -M
                                                 f— -i-  OJ
                                                 .Ct-.M
                                                 U -M
                                                 -r-  I   C
                                                 -O r-(  O
                                                                   CVJ
                                                                J=   •
                                                                O  r-4
                                                           O)
                                                           c
                                                           (U
                                                                             0)
                                                                             O
                                                                             C-
                                                                             O
                                                                             O
                                                                         C_>
Comments
9/19-20 250° , 4 mph 1 H
2 L
3 H
4 L
4 H
4 H_

9/22-23 212°, 5 mph 1 H_

2 L
2 H
3 L
3 H
4 L
4 L.

9/23-24 197°, 3 mph 1 L
2 I
2 H
3 L
4 L
4 _L

9/24-25 195°, 5 mph 3 L_

4 j.





X












X









X

X
X




X







X



































X*

X*
X

X


X*



X


X
X
X

X

X







X

X

X

X






X




X





X
X*
X













X











Field duplicate
sample
Field blank not
analyzed





Field duplicate
sample





Field duplicate
sample
Field blank not
analyzed

Notes:  *Denotes compound detected at higher concentration in field blank  sample.

         IPrimary tubes (high  or  low flow) are underlined in this category.

                                              91

-------
                                  TABLE VI-12

                RESULTS OF AMBIENT AIR SAMPLING FOR FORMALDEHYDE
     IN VICINITY OF DOW CHEMICAL COMPANY, MIDLAND,  MICHIGAN,  SEPTEMBER 1984


                 Wind Direction          Sample          Formaldehyde Derivative
Date (1984)      and Speed (mph)     Identification       Detected (ug/sample)

  9/7-8          184°, 6 mph          Method Blank                5.34
                                      Field Blank                4.78
                                      Site 1                     2.04
                                      Site 2                     4.09
                                      Site 3                     2.68
                                      Site 4                     1.89
                                      Site 4 Duplicate           2.15

  9/8-9          199°, 6 mph          Method Blank                5.24
                                      Field Blank                3.91
                                      Site 1                     1.13
                                      Site 2                     1.69
                                      Site 3                     1.00
                                      Site 4                     0.95
                                      Site 4 Duplicate           0.79

  9/12-13        191°, 6 mph          Method Blank                2.52
                                      Field Blank                2.11
                                      Site 1                     1.46
                                      Site 2                     0.14
                                      Site 3                     0.19
                                      Site 4                     0.29
                                      Site 4 Duplicate           0.22

  9/18-19        235°, 4 mph          Method Blank                2.24
                                      Field Blank                1.80
                                      Site 1                     0.51
                                      Site 2                     0.90
                                      Site 3                     0.55
                                      Site 4                     0.36
                                      Site 4 Duplicate           2.91

  9/19-20        250°, 4 mph          Method Blank               1.42
                                      Field Blank                1.64
                                      Site 1                     0.48
                                      Site 2                     0.81
                                      Site 3                     0.76
                                      Site 4                     1.46
                                      Site 4 Duplicate           0.75
                                     92

-------
                                 REFERENCES


 1.  Amendola, Gary A., Soil  Screening Survey at Four Midwestern Sites,  Environ-
     mental  Services Division, Region  V, U.S.  Environmental  Protection  Agency,
     Westlake, Ohio, EPA 905/4-85-005, June 1985.

 2.  Michigan Dioxin Studies   -  Screening  Survey  of  Surface  Water Supplies,
     Potable Ground Water,  and Dow Chemical  Brine Operations, EasternDistrict
     Office, Environmental   Services  Division,   Region  \T,   U.S.  Environmental
     Protection Agency, Westlake, Ohio, December 1985.

2a.  Amendola, Gary A.  and Barna, David R.,   Dow Chemical  Wastewater Characteri-
     zation  Study  -  Tittabawassee  River  Sediments  and  Native Fish,  Eastern
     District Office, Environmental  Services  Division,  Region  V,  U.S.  Environ-
     mental  Protection  Agency, Westlake, Ohio, July 1986.

 3.  Dioxin  Strategy, Office  of Water Regulations and Standards, Office  of Solid
     Waste and Emergency Response,  Dioxin Strategy Task Force, U.S. Environmental
     Protection Agency, Washington, D.C., October 20, 1983.

 4.  National  Dioxin  Strategy  Tier  4  -  Combustion Sources  -  Project Plan,
     EPA 450/4-84-014a, Air  Management  Technology  Branch,Office  of  Air  and
     Radiation, Office  of  Air Quality Planning and Standards, U.S. Environmental
     Protection Agency, Research Triangle Park,   North  Carolina,  Draft,  February
     1985.

 5.  Quality Assurance  Project Plan - Source Testing of the  Dow Chemical  Compact
     Rotary  Kiln Incinerator, Midland, Michigan, Contract  No.  68-02-3168,  Work
     Assignment No.Ill,GCA/TechnologyDivision,  GCA  Corporation,  Bedford,
     Massachusetts, July 19,  1984.

 6.  Riggin, R.M.,  Compendium of Methods for the Determination of Toxic  Organic
     Compounds in Ambient  Air, ContractHo~.68-02-3745(WA-9),Environmental
     Monitoring SystemsLaboratory,  Office  of  Research  and Development,  U.S.
     Environmental  Protection Agency,  Research  Triangle  Park,  North Carolina.

 7.  Dow Chemical  Company, Midland, Michigan, Incinerator  Exhaust Sampling Plan,
     Eastern District  Office,  EnvironmentalServices  Division,  Region  V,  U.S.
     Environmental  Protection Agency, Revision 7, September  24, 1984.

 8.  Report  on Analyses Accomplished Under Special  Analytical  Services Order No.
     1148-E, VolumesI-IV, Brehm Laboratory,Wright  State  University,  Dayton,
     Ohio, March 25, 1985.

 9.  Dow Chemical  Company   -   Midland Plant  Wastewater Characterization  Study   -
     Preliminary Summary  of   Results,  U.S.  Environmental   Protection   Agency,
     Region5,  EnvironmentalServices  Division,    Eastern  District   Office,
     March 28, 1983, page  26.


                                      93

-------
                              REFERENCES (continued)
10.
     Point Sources and Environmental  r	
     benzo-p-dloxin)  on the Midland Plant
                                     Levels  of  2378-TCDD  (2.3,7,8-Tetrachlorodl-
                                                       Dow  Chemical  Company  and
     	.  ,.        '  -••  —  • ••	   • —   Site  of
     in the City of Midland,  Michigan,Sections
     Midland,  Michigan,  November  5,  1984.
              the
                                                   A-D,   Dow  Chemical   Company,
13,
11.
     Lewis, Robert 6.,  and  MacLeod,  Kathryn E.,  Portable Sampler  for  Pesticides
     and Semi-Volatile Industrial  Organic Chemicals  in  Air,  J.  Anal  Chem.,  1982,
     54, 310-315 (February 1982).
12.  Lewis,  Robert,  G.,  Brown,  Alan,  R.,  Jackson,  D.  Merrill,  Evaluation  of
     Polyurethane Foam for Sampling of Pesticides,  Polychlorinated  Biphenyls and
     Polychl orinated Naphthalenes  in Ambient  Air,  Analytical  Chemistry,  Vol
     Page 1668, October 1977.
                                                                             49,
     Lewis,  Robert,  G.
     a High-Volume Air
                        and  Jackson,
                        Sampler   for
Merril 1,0.,
 Pesticides
Modification and Evaluation of
andSemi-VolatileIndustrial
     Organic Chemicals, Analytical  Chemistry, Vol. 54, Pages 592-594, March  1982.
14.  IERL-RTP Procedures Manual;   Level  1  Environmental  Assessment,  2nd  Edition,
     EPA-600/7-78-201, U.S.  Environmental   Protection  Agency, Research  Triangle
     Park, North Carolina, October 1978.

15.  Dow Chemical  Company, Midland,  Michigan,  Ambient  Air  Sampling  Plan, Eastern
     District Office,  EnvironmentalServices  Division,  Region V, U.S.  Environ-
     mental  Protection Agency,  Revision  3, June 15,  1984.
16.  Qua!ity Assurance Project  Plan
     Chemical  Company Complex,  Midland^
     Assignment No.  Ill,   GCA/Technology
     Massachusetts, August 7,  1984.
                                     -   Ambient  Monitoring  in
                                                  Contract  No
                                                              and Around the Dow
                                                               68-02-3168, Work
   Michigan
      Division,
                                                     GCA  Corporation,   Bedford,
17.  Special   Analytical
     Management  Office,
     Virginia.

18.  Special   Analytical
     Management  Office,
     Virginia.
                          Services   Regional   Request   No.   1149-E,   HWI   Sample
                          U.S.   Environmental   Protection   Agency,    Alexandria,
                          Services   Regional   Request   No.   1151-E,
                          U.S.   Environmental   Protection   Agency,
                                                                     HWI   Sample
                                                                     Al exandria,
19.  Ambient Monitoring In and Around  the Dow Chemical  Company  Complex,  Midland,
     Michigan, Contract No.  68-01-6769,  Work  Assignment  No. 84-340, GCA/Tech-
     nology Division,  GCA  Corporation,  Bedford,  Massachusetts, November  1984.

20.  Agin, Ron, Superintendent, Environmental  Operations, Dow  Chemical  Company,
     to (Martin  G.   Trembly,  U.S.  Environmental  Protection Agency,  Region  V,
     Eastern District Office) June  26, 1985,  ALS,  1  p.
                                      94

-------
                              REFERENCES (continued)


21.  Veurink, Gary, Dow Chemical  Company to (Delbert Rector, Michigan Department
     of Natural  Resources) February 10, 1985, ALS, Ip.

22.  703 Incinerator:  State of Michigan  -  Observed  Experiments for Licensing
     Under Michigan Act 64, Dow  Chemical  Company,  Midland, Michigan,  undated.

23.  Personal communication  with Michael  Rio,  Dow  Chemical Company,  April  15,
     1986.

24.  Rector, Delbert,  Chief, Hazardous  Waste  Division,  Michigan Department  of
     Natural Resources,  to   (James  H.   Story,  Technical  Manager,  Environmental
     Services,  Dow Chemical  Company) November 29,  1983, ALS, 2  pp.

25.  Cleverly,  David H.,  Estimation of the Public Health  Risks  Associated with
     Exposure of CDDs/CDFs Emitted from a Waste  Incinerator,  and  from Ambient
     Monitored  Concentrations, Office of Air  and Radiation, Office of Air Quality
     Planning and  Standards,  Strategies and  Air  Standards  Division,  Pollutant
     Assessment Branch, U.S.  Environmental Protection  Agency,  Research Triangle
     Park, North Carolina, Review Draft, March 7,  1986, pp. 26-30.
                                      95

-------
                      APPENDIX A
       DETAILED DESCRIPTION OF CONDUCT OF STUDY
               MICHIGAN DIOXIN STUDIES
DOW CHEMICAL BUILDING 703 INCINERATOR EMISSIONS STUDY

-------
                                   APPENDIX A
I.  SAMPLING METHODS

    The following sections concern the  selection  of  methods employed  to  detect
the compounds of interest from the various media  that  were  sampled.   Reference
is made to Tables V-l and V-2 of  this report,  where the compounds  are  differen-
tiated according  to  the  analytical  procedures   necessary  to  detect   them.

    A.  Precombustion Air

    A high-volume air  sampler modified  for  the  collection of PCDD/PCDF,  and
another similar  sampler  for  semi-volatile  organic  compounds,  were  placed  at
ground level between two  and four meters from  the rotary  kiln combustion  air
intake.  Each sampler  consisted  of  a  glass  fiber filter of the  type commonly
employed in  ambient air  monitoring  for particulate  matter,  followed  by  a
cylindrical trap  containing   25  grams  of 16/50  mesh Amberlite  XAO-2  resin,
configured in a manner based upon that developed by Lewis et.al.12,13

    Design flow  rates  for  the  two   samplers  were  derived  on the  basis  of
calculated resin  breakthrough volumes  for  the  compounds  of  interest.   For
PCDD/PCDF, it was determined  that  a  sampling flow rate  of 1.1 to 1.5 m^/min,
and a total sample volume no greater than 720  scm,  would be appropriate. For the
other semi-volatile  (semi-VOA) compounds  a flow rate of 0.6 to 0.8 m^/min  was
selected, to result  in a final sample volume not  to  exceed  350  scm.   In  actual
practice, however,   both   samplers  operated  at   flow  rates  of  approximately
0.7 m3/min  owing  to the air  flow resistance presented  by the tightly-packed
XAD-2 resin columns.

    Volatile compounds  (for VOA,  or  volatile organics  analysis) were  monitored
utilizing a  low-volume  sampler  patterned  after  that described  by   Riggin.6
Sampling cartridges   containing   1.5  grams  of  Tenax®  GC   [poly  (2,6-diphenyl
phenylene oxide)] were suspended  approximately  two meters  above  ground  and
three to four meters from the rotary kiln air intake.  Air  flow rates of 25 to
35 cm^/min  were maintained  for  eight-hour  sampling  periods,  with  a  target
sampled gas volume of 14.4 standard liters.

    Field blank samples were  procured  for each  of the three  samplers  on every
sampling day.   In addition,  a duplicate  sample  specific  to  each sampler  was
provided on one of the three sampling days.

    B.  Liquid Waste Feeds

    It was  known prior to the sampling  effort that the sources  and  composition
of waste delivered to the incinerator through each nozzle were likely  to  change
every two to four hours  on average.   Also, because  many of the  liquid  wastes
were described  by Dow  personnel  as  containing  more  than 15 percent  of  single
compounds, special  handling  and  extraction  procedures,  involving  intermediate
                                       A-l

-------
preparation of extracts by  an  EPA  contractor laboratory prior to analysis  by a
second contract  laboratory, were   required.   These  procedures   are  described
fully in Appendix B to this report.  As extracts  for  semi-VOA and VOA analysis
were obtainable  from  the   same  samples  utilizing  these procedures,  it  was
necessary only to obtain  single  representative samples of each  distinct  waste
stream for these compound classes.   For  PCDO/PCDF,  a second sample was required.
In summary, each waste stream was to be represented by a time-composited sample
for PCDO/PCDF, held  in a 500-mL hexane-rinsed amber glass bottle, and a pair of
hexane-rinsed 40-mL  clear-glass  VOA vials with  Teflon septa, each  containing
composited aliquots  of wastes.   For VOA,  care was taken to  avoid  agitation  of
sampled wastes and  minimize possible  losses  of the  volatile compounds to  be
analyzed.  In any event, no sampling procedure for compositing VOA  samples  was
available.

    For samples to be  representative over time, it was planned to obtain portions
of liquid waste  every  half-hour,  avoiding periods in  which  waste  changes  were
occurring.  Thus, for  an eight-hour sampling  period,  up to  17  individual  sets
of grab  samples  were projected  to  be composited  manually  on an  equal-volume
basis.  However, in  some cases  few samples were taken where particularly viscous
or fuming wastes were handled.

    Field blank  samples were  obtained  on  all  three test days;  a  single  field
blank represented nozzles  "BA"  and "BB"  as  the  nozzles were   spaced  closely
together, while  another  field  blank  was taken  for  nozzle  "C".  Three  field
duplicate samples were drawn,  all  on  the second  test day,  of  two  wastes  at
nozzle "BB" and a single waste  at nozzle "C".

    The following sections  describe the ways  in which  the liquid  waste sampling
plan was altered at  each nozzle.

    1.  Nozzle "BA"

    On all three  test days, the  origin of  the  liquid wastes  flowing  through
this nozzle  remained  constant  throughout  the  test  periods.   However,   Dow
Chemical  personnel  indicated the waste  originated from  a   chlorosilane manu-
facturing process at  the   adjacent  Dow Corning  Corporation  plant,  and was  a
fuming material which  reacted  violently with  moisture  in  air.  As  the contents
of the tank  truck connected to nozzle  "BA"  were reported to  be  well-mixed  and
manual compositing would have presented a hazard to sampling  personnel, it  was
decided to obtain a  single grab sample for PCDD/PCDF, and a pair of VOA samples,
midway through each  test day.

    2.  Nozzle "BB"
    During the  sampling  periods,  two distinct wastes  were fed through  nozzle
"BB" on the first and second  sampling days,  and a single waste was  burned  on  the
third day.   Composites  for  PCDD/PCDF  were manually  formulated  from the  grab
samples taken  every  half-hour.   For  semi-VOA and  VOA,  compositing was  also
performed on the first sampling day but  was found to  be  laborious,  with  a  high
risk of spillage of liquids.   Therefore, on  the second and third days, PCDD/PCDF
composites continued  to  be  created,  but  to  avoid  the  risks associated  with
                                       A-2

-------
compositing the lower-volume semi-VOA and VOA  samples,  it  was decided  that  the
grab sample (pair of VOA  vials) taken midway in time through  each run  of  waste
would be chosen for analysis to represent that  waste.

    An indicated previously,  field  blank samples  were  obtained  on all  three
days in  the  vicinity  of  nozzles  "BA"   and  "88",  to  apply  to  both  nozzles.
Cleaned 500-mL amber glass bottles and 40-mL clear  glass  VOA  vials  were filled
with methanol  for this purpose.  Field duplicate samples  were taken  of the  two
wastes processed on the second sampling  day.

    3.  Nozzle "C"

    On all three  sampling days,  the  wastes  fed  through  nozzle  "C"  remained
relatively constant throughout the sampling day,  so that only a single  set  of
samples was required to represent each day.  For PCDD/PCDF, these samples were
composited from grabs  taken  every  half-hour on the first day and, to  accommodate
time constraints, every hour on the  third sampling  day.   Semi-VOA  and VOA waste
samples were  taken  at  times  approximating   the   midpoint  of   these  tests.

    On the  second  sampling  day,  nozzle  "C"  waste  was particularly  viscous,
making representative  compositing infeasible.   Thus,  a   single  set  of grab
samples for PCDD/PCDF  and  semi-VOA/VOA  was  obtained  at  the  start of  the test
run; a field duplicate sample  consisted  of  a second complement of  grabs taken
at the  same  time.   Field  blank  samples  for  all  three  days   were  made up  of
methanol-filled sample containers  kept closed  in the vicinity  of the nozzle  "C"
sampling area for the duration of  the test periods.

    C.  Low-BTU Liquid Waste

    A spigot near waste nozzles "BA"  and "BB"  was  drawn  to obtain  samples every
half-hour for PCDD/PCDF and  semi-VOA.  Equal  volumes  of  this  liquid  were taken
and placed directly into composite bottles at these  times.   For volatile organic
analyses (VOA),  grab   samples  were  obtained  every  half-hour; however,  as  no
feasible method of  compositing these samples  was  available,   one sample  taken
midway through  the  sampling period  was  selected  for  analysis.   Field  blank
samples, consisting of deionized water-filled  sample  containers,  were  taken  on
each day.

    D.  Incinerator Exhaust

    1.  Modified Method 5 (MM5) Trains for PCDD/PCDF and Semi-Volatiles

    Two trains were operated  simultaneously  in  sampling ports placed 90° apart
in the exhaust duct downstream of the electrostatic precipitator.   Each  sample
train, constructed  as shown in Figure A-l, and based on  previous designs of  the
MM5 train, consisted of a glass-lined,  heated  probe terminating in  a stainless
steel button-hook nozzle  and  attached  thermocouple  and  pi tot  tubes.  The probe
outlet was attached  to a  glass  filter holder  containing  a tared  glass  fiber
filter (Reeve Angel 934 AH)  maintained  at a temperature of 248°F +_ 25°F in  an
electrically-heated oven.    Following  the  filter,  sample  gas passed  through
                                       A-3

-------
         PROBE
REVERSE-TYPE
 PITOT TUBE
             FLOW
             THERMOSTATIC
              WATER BATH
                               UNGREASED-
                                FITTINGS
     HEATED
     FILTER
                                                XAO  BACKUP
                                                    r-THERMOMETER
         L f     S-VA\
         llr^'
                              CHECK
                              VALVE
                                                   5*?
                                                     I
                                                     l
                                          2    3    4   i
                                                        VACUUM
                                                  	'    LINE
                      THERMOMETER
                                        BY-PASS
                                         VALVE
           ORIFICE^
         MANOMETER
                            TEST\
                         METER
J
           VACUUM
            GAUGE

            P.
                                                MAIN
                                                VALVE
I   \ AIR
^
     TIGHT
     PUMP
                          FIGURE A-l

          MODIFIED METHOD 5 EXHAUST GAS SAMPLING TRAIN
                               A-4

-------
flexible Teflon tubing  to  a  water-cooled module  containing approximately  25
grams of XAD-2 resin.  A thermostatically-controlled water  bath  maintained the
sorbent temperature at 70°F or below.

    Water condensed  from the  gas stream  passing  through  the XAD-2 module  was
retained in an  impinger fitted  with  a  short-stem inlet to  avoid sample  gas
bubbling through  collected  condensate.   The  second and  third  impingers  each
held long-stem inlets; the second impinger was filled  with  100 ml  of  deionized
water at the  start  of sampling,  while the third  impinger was empty.   A  backup
sorbent cartridge  containing  7.5 grams  of  XAD-2  was  placed  between  the  third
and fourth  impinger.   The  fourth  impinger  held  approximately  200  grams  of
indicating silica  gel  to remove  traces   of  water from  the sampled  gas.   All
connections within the trains  were  composed of  nonreactive materials such  as
glass or Teflon,  and no  sealant greases  were employed.   Sampled gas  flowed
through a check valve,  tubing  with  a vacuum pump  connected  in parallel  with a
bypass valve,  a dry  gas  meter,  and  an orifice and manometer  for instantaneous
flow rate measurement.

    As indicated  previously,  two  trains  configured  as  above  were  operated
simultaneously at a location in which two sampling ports were placed 90°  apart.
Initial plans  called for a sampling  period of eight hours, to obtain sufficient
volumes of  sample  extracts  for replicate  analysis,  sample  splitting,  and
archiving.  However,  on  the  first  sampling  day,  air  flow  through  both  trains
could not be maintained for longer than approximately 6 1/2 hours.   Apparently,
the resistance  to  flow  presented  by the sorbents  in the  train  and possibly
collected moisture was too great to be overcome  by the pump powering the sampling
train.  As a  result of this experience, the planned sampling period was reduced
to six hours on the second and third sampling days.

    Uwing to time delays, and the risk of causing leaks in  the sampling  trains
by moving them, both  trains  remained on   the same  traverse  in the  exhaust duct
during all three sampling periods.   Thus, the trains  sampled each point twice on
the same traverse; the traverses were alternated such that one pair of diameters
was employed  on  the  first  sampling day, and  the  other pair of diameters  was
used for the  PCDD/PCDF  and  semi-volatile trains  on  the  second  and third days.
This was done to  avoid  unnecessary  movement of sampling  trains  in the limited
space available on  the  sampling  platform, and was not anticipated to have any
significant effect on analytical  results.

    Two field  blank  trains  were  assembled for  each sampling day and allowed to
remain undisturbed  near  the nn5  sampling area.  Sorbents and impinger contents
of the  sample and blank trains  for PCDD/PCDF  were  removed  from the  trains  by
the analytical laboratory, with the exception of the sampling probe wash, which
was conducted by the  field contractor and placed in an amber glass  bottle.  The
sample and blank trains for semi-volatile compounds were disassembled and  rinsed
by the field contractor, and placed  in containers for shipment to the analytical
laboratory.   Field  duplicate  samples  were not obtained  as  both  sampling ports
were utilized simultaneously.
                                        A-5

-------
    2.  Volatile Organic Sampling Train (VQST)

    The VOST was constructed consistent with configurations developed by Midwest
Research Institute, as shown  in Figure A-2.  The  train was composed of a heated
glass-lined probe  with a  plug  of  glass  wool  placed at  the  tip to  remove
particulate matter.  A  series  of condensers and  organic  resin  traps  followed
the probe; the  first  condenser  cooled the sample gas  stream to  condense  water
vapor.  Sampled gas and condensed water  vapor  then passed through  a  cartridge
containing 1.5 grams of 60/80 mesh Tenax  GC®.  Condensate was  collected in  the

first impinger; the second condenser and  a trap containing approximately 1 gram
of Tenax and  1  gram  of activated charcoal were positioned to  retain  compounds
having low breakthrough volumes.  A  second impinger  and a drying tube followed
the second sorbent trap, for  residual  moisture  removal.

    Sample temperatures were monitored with  thermocouples  at the outlet of  the
probe and the inlet of the first Tenax cartridge.  Gas temperatures within  the
probe were maintained  above  130°C to  avoid premature  condensation  of volatile
compounds; through  the resin   traps,  gases  were cooled to  20°C  or  below.

    All of the VOST sampling runs with the exception  of two  were conducted  for
40 minutes at  sample  gas  flow rates  of  0.5 liter per minute,  resulting in  a
total collected  volume of 20  liters.  For the remaining  two  runs,  a sampling
rate of 1 liter per minute was maintained for 20  minutes;  one of these runs  was
that in which a field duplicate sample was taken.

    Five or six  VOST  runs were completed on each  sampling day.   For each run,
the two sorbent  tubes  were submitted  for analysis as  single  samples.  Between
runs, the  sorbent  cartridges were  changed;  however, the  condensate  impingers
remained in place  for  entire  sampling days and thus  represented  a composite of
all of the runs.   The  sorbent  cartridges  were  transferred to containers packed
with activated  charcoal  for  shipment  to  the analytical   laboratory,  while  the
contents of  the condensate  impingers were  placed  in 40  mL   VGA  vials.   Head
spaces in  these  vials  were eliminated by the  addition of distilled, deionized
water.

     In addition to the  single  field duplicate  sample noted above, field blanks
of the VOST were taken on  each  sampling day.  These unexposed sampling materials
remained in the sampling  area for complete days while all  of the VOSTs for that
day were utilized.   The cartridges  and condensate impingers  were then handled
in the same manner as  regular samples.

     3.  Tedlar  Bag Samples for  Vinylidene Chloride

     Samples were collected for  approximately one hour utilizing  an apparatus as
shown  in  Figure A-3.   The sampling  assembly consisted of a  cleaned, evacuated
Tedlar bag placed  inside  a  rigid container.  Prior  to sampling,  each  bag  was
purged with  prepurified nitrogen.   The Teflon sampling tubing was attached to
the  Tedlar bag  container  by a quick-disconnect coupling.
                                        A-6

-------
    HEATED SAMPLING PROBE
•GLASS WOOL

  THERMOCOUPLE

 ICC WATER
 CONDENSER

  THERMOCOUPLE

      TENAX
     CARTRIDGE
ICE WATER
CONDENSER
TENAX/CHARCOAL
CARTRIDGE
                    VACUUM
                    •GAUGE
                                   VALVE
                                   —CXI—i
                                                ROTAMETER
                                                                                  PUMP
                         MIMET
                        IMPINttCRS
                                  FIGURE  A-2
                        VOLATILE  ORGANIC SAMPLING TRAIN

-------
                                                                         m   M  M  M
                                        FIGURE  A-3

                          TEDLAR BAG SAMPLING SYSTEM FOR VINYLIDENE CHLORIDE
oo
                              STAINLESS STEEL
                                  PROBE
                                             TEFLON LINE
                     GLASS
                     CONDENSER
                     UNIT
                               TO  PUMP
ICE BATH
                                                   TEDLAR  BAG

-------
    Within two hours after  sampling,  filled bags  were transported to a  field
laboratory in which  direct  analyses were  performed  with a gas  chromatograph-
electron capture detector  (GC-ECD).  One  field bias  blank,   consisting  of  a
bag filled with prepurified nitrogen,  was analyzed  daily.  One collocated  field
duplicate sample was obtained  on  the  second day of sampling.   A description of
the GC-ECD and its operating conditions  are described in Table A-l.

    4.  Continuous Emissions Monitoring  System

    Incinerator combustion  conditions   were monitored  utilizing  a  continuous
emissions monitoring system (CEMS) assembled as shown in Figure A-4, consisting
of a gas  conditioning module,  monitors  for  measurement  of  CO, C02, and 03,  and
a data acquisition system.  Samples were extracted  from the exhaust  gas  stream
at a  point  described  previously;  the  effects  of  the  carbon  adsorption  bed
exhaust, described  in   Section  V  of  this  report,  on  the measured   flue  gas
components were expected to be minor.

    Sampled gas passed  through  a glass  fiber  filter for  particulate  removal,
and then  to  a two-stage  drier composed  of a condenser and  permeation  drier.
Conditioned gas  was  analyzed   with  the  instruments  detailed  in Table  A-2.

    Exhaust gas was  to  be  monitored for the duration of each  Modified Method 5
test run.  However, equipment startup problems, and the occasional necessity to
utilize the sampling location  for other measurements, prevented the continuous
use of the CEMS.  To supplement and  check the CEMS, integrated samples were also
obtained and analyzed using an Orsat analyzer.

    E.  Incinerator Ash

    As indicated previously, samples of this material were taken from a dragout
chain serving the  ash  trough.   The chain  was  known  from  prior  inspections of
the facility to be started manually by an operator, approximately every hour on
the hour.   Therefore,   a  representative  of the field  contractor  was present
every hour to  take,  or supervise  Dow  personnel  taking, portions  of  the  solid
material  lifted  out  of the ash  trough  on  an  appropriate  number of flights on
the dragout chain.   Typically, this meant samples were taken from three to five
flights per hour; there was insufficient solid  material  remaining on the dragout
chain to  sample more flights  than this.   On occasion, fewer than three flights
were sampled  when   ash  removal  was  particularly  light.   Large  pieces  of
incompletely-burned  wood or fused metal  were avoided in sampling owing to their
unrepresentativeness when  related to the  full  sample, and  the  impossibility
of providing  representative split  samples to  Dow  Chemical  and  EPA  contract
laboratories.

    Individual grab  samples were  taken from the chain utilizing  a hexane-rinsed
aluminum  scoop  mounted  on  a  pole,  and  placed in  a  hexane-rinsed five-gallon
glass jug to  be held for later  compositing and  sample splitting.  Compositing
was performed by later  emptying the jug contents on a floor or ground area which
was covered  first  with  a  clean  sheet  of cardboard,  in  an area well   separated
from  the  incinerator,   mixing  and  quartering  them,  and  apportioning  quarters
with  a  cleaned  scoop  into separate  washed glass  containers for  Dow and  EPA
analysis.
                                        A-9

-------
 i
                                            TABLE  A-l

                   GC-ECD OPERATING CONDITIONS FOR VINYLIDENE CHLORIDE ANALYSIS

                          DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
m
m
i
Instrument

GC Conditions

   Column



   Temperature program

   Injector temperature

   ECD temperature

   Carrier flow

Loop Conditions

   Volume delivered

   Loop  temperature
Perkin Elmer 3920



20% SP2100/0.1% carbowax
1500 on 100/120 supelcoport
10' x 1/8" SS Column

Isothermal at 50°C

110°C

325°C

25 ml/rain, argon/methane



1 ml

125°C
                                                 A-10

-------
                                                    mmmMMMMM
     INSTACK
     FILTER

     O
  CALIBRATION
GASES (CO, C02,
     °2
                                               t
                                          CONDENSATION/
                                         PUMP ING.SYSTEM
 SAMPLE DISTRIBUTION
SYSTEM:  SAMPLE. LOCAL
CALIBRATIONS, PROBE
CALIBRATIONS
                                       FIGURE   A-4

                                   SCHEMATIC DIAGRAM
                     CONTINUOUS EMISSIONS MONITORING SYSTEM
                                                                            HORIBA PIR 2000
                                                                                 CO
                                                                               MSA 802
                                                                                  °2
                                                                            HORIBA PIR 2000
                                                                                 CO,
                                                                                                 EXHAUST

-------
    M   ft   ft   ft   M   ft   ft   «   B   ft    fi   •   1   1   11
                                          TABLE  A-2

                CONTINUOUS EMISSIONS MONITORING SYSTEM OPERATING CONDITIONS

Operating
sensitivity
ranges

Operating
temperature
ranges
Analysis method
Linearity
Accuracy
Drift
Horiba
PIR 2000
C02 analyzer
0-5% C02, FS
0-15% C02, FS
0-25% C02, FS
24°F - 122°F
Nondispersive infrared
+ 1% FS
•«• 1% of Full Scale
+ 1% of Full Scale
Horiba
PIR 2000
CO analyzer
0-1000 ppm CO, FS
0-3000 ppm CO, FS
0-5000 ppm CO, FS
24°F - 122°F
Nondispersive infrared
+ 1% FS
+ 1% of Full Scale
+ 1% of Full Scale
MSA
02 analyzer
0-5% 02, FS
0-10% 02> FS
0-25% 02, FS
32°F - 109°F
Paramagnetic wind
+ 1% of Full Scale
+ 1% of Full Scale
<5% Full Scale for
Noise level
in 24 hours in both
zero and span

<0.5% of Full Scale
in most sensitive range
in 24 hours in both
zero and span

<0.5% of Full Scale
in most sensitive range
24 hours in both zero
and span

<.25% of Full Scale
in most sensitive range

-------
    Water entrained with sampled ash was allowed to drain, as much as possible,
out of the samples.  Ash trough water was sampled separately.

    F.  Influent and Effluent Water and Control  Device Ash

    1.  Influent Service Water

    Grab samples of influent service water (returned secondary treatment water)
for PCDD/PCDF and  semi-volatiles  were  taken  taken every  half-hour  during  the
first and  second  sampling  days,  and,  to  accommodate time  constraints,  every
hour on the third day.  Individual  samples were obtained in a washed and hexane-

rinsed bottle, the contents  of  which  were placed in a washed and hexane-rinsed
brown glass  one-gallon  bottle for  compositing  on an equal-volume  basis.   For
VOA, a pair  of  single grab samples was  taken directly  into  washed 40-mL vials
with Teflon septa, midway through  each sampling  period.

    2.  Effluent Waters

    Effluents, as  described  previously, arose  from the  quench  tower,  venturi
scrubber and  demister (combined stream),  electrostatic precipitator,  and  ash
trough.  Each of  these  streams was  sampled  utilizing  ISCO  automatic  sampling
devices, for  PCDD/PCDF  and semi-volatiles, and  by taking single  grab  samples
for VOA, as detailed above for influent service  water.

    The automatic samplers  were set  to draw a  volume of  water every half-hour
during the  incinerator  exhaust  sampling  period,  sufficient  to  fill  to  an
appropriate level  a five-gallon clear-glass bottle  (washed with deionized water,
methanol, and methylene  chloride,  and oven-dried) held inside  it.   The bottle
was surrounded with ice  for preservation of the  sample.   At the conclusion  of
sampling, portions of  this  total sample were poured into washed and hexane-rinsed
one-quart brown-glass  bottles  to  be  submitted  to  the  analytical  laboratories
for PCDD/PCDF and for  semi-volatile compounds.

    For VOA, each sampling location was represented by filling a single pair of
40-mL vials at a time  corresponding closely to the midpoint of each sampling run.
At all  four  locations,  this  process  necessitated  transferring  samples  from
direct sampling  containers, such as a large clear glass  bottle, into the vials.
In all cases, care  was  taken to  fill  the vials  in a quiescent manner such that
the head spaces  were devoid of gases.

    3.  Control  Device Ash

    The Tier  4  Dioxin  Strategy  referenced  previously   required  analyses  of
control device ash; the  control devices at the Dow Chemical incinerator collected
solid particles  which were dispersed  in water.   Therefore, PCDD/PCDF and semi-
volatile compounds  in each  of  the  four  effluent  water streams  were  analyzed
separately in the  aqueous   and  filterable solid  phases.   The  latter  analysis
was estimated to be a  reasonable representation  of the presence of the analyzed
compounds in  the  particulate  or  ash  fraction  of  the  control  device  water
discharges.
                                      A-13

-------
II.   SAMPLE  IDENTIFICATION,  HANDLING,  AND  CUSTODY

     Samples were obtained by employees of the field contractor,  GCA/Technology
 Division (GCA),  and labeled according to a predetermined coding  system.   Where
 multiple grab samples were  taken  for compositing  or  transport out of the  Dow
 Chemical  facility,  the samples were  generally  held in closed coolers near  the
 individual  sampling points; these  coolers were inspected periodically to  guard
 against tampering.   Incinerator ash  samples  were  stored  in  closed jars adjacent
 to  the dragout chain  in a location where visual custody was  maintained  by  GCA or
 EPA personnel.  Likewise, automatic  samplers  used  for effluent  water sampling
 were set in areas  in  which  they were  open  to constant  view.

     As sampling  was  performed  on  one day and  generally shipped  to analytical
 laboratories on  the next  day, it was necessary to  hold  samples  overnight prior
 to  packing   and  logging.  Two  lockable  trailers,  one  near  the incinerator  and
 the second  placed  on  Dow Chemical  property  immediately  outside the plant  fence
 line, were  used  for secure  storage.

     Sample  compositing and  splitting were  performed  by  or  under the  direct
 control of  GCA personnel.   After samples were placed into appropriate containers
 for shipment, they were  relabeled  to enable  quick identification by contract
 analytical  laboratories.   A master  cross-referenced  list  of  samples and their
 identifying labels  was formulated  and maintained  by  the EPA  project manager.

     Sample  containers were arranged  as appropriate in  shipping  coolers  and  log
 sheets were  completed to describe  all  of the  samples in each cooler.   On  the
 first sampling day, the log sheets were written manually  on standard EPA manifold
 custody forms; on the second and third sampling days, custody forms were  created
 and reproduced using  a computer and  printer.  Each  individual  cooler was  packed
 with coolant  and shock-absorbing material,  and closed and  sealed  with  custody
 tape imprinted  with   GCA  identification.   The  samples were shipped  to  the
 analytical  laboratories  via Federal  Express.

     Information  on liquid waste feedstocks was obtained from Dow Chemical prior
 to the  start  of sampling.  Dow Chemical  indicated that many or  most of these
 wastes were composed of 15 percent  or more of a single constituent.  Therefore,
 liquid waste samples  and  blanks (made up of methanol)  required special  handling
 as "high-hazard" materials.   These   wastes  were  composited  (where  compositing
 was done)  and placed  into the smallest  appropriate  container,  in  this  case
 40-mL vials.  Specialized  tracking  records were  completed for  each  distinct
 sample, and all  such  samples were packed consistent with Department of  Transpor-
 tation regulations for  flammable  liquids  or flammable-corrosive  liquids,  and
 shipped to an intermediary laboratory for extraction.

     The above discussion applied  to all  samples  with the  exception   of  the
 Modified Method  5  PCDD/PCDF  sampling  trains,  and  the liquid  waste  samples
 analyzed for  PCDD/PCDF.   After  sampling,  these   samples   were  stored   in  the
 contractor trailer outside  Dow Chemical  property  until the  conclusion  of  the
 three days  of sampling;  appropriately labeled, packed, and logged;  and  trans-
 ported by  automobile to the analytical laboratory.
                                         A-14

-------
III.   ANALYTICAL PROCEDURES

      Procedures for  analyzing   samples  for  semi-volatiles  and  volatiles  are
  contained in  Reference 7 to this report, while  PCDD/PCDF  methods are indicated
  in  References  7 and 8.  For convenience,  the specific analytical  procedures  and
  quality assurance aspects  relating  to analyses  of  PCDD/PCDF  by the  contract
  laboratory,  the Brehm Laboratory, Wright  State University, are  excerpted  from
  Reference 8  and presented as Appendix C to  this  report.

      A.   Semi-Volatiles and Volatiles

      Volatile  pollutants,  generally those with  boiling points  lower  than  100°C,
  were analyzed   according   to  EPA  Method  624.   Water   samples,  including  the
  incinerator  influent and  effluents,  and VOST impinger liquids, were concentrated
  and analyzed  directly using this method.  However, solid  sampling  media  (Tenax
  and charcoal)  were desorbed in  a Nutech thermal  desorption unit at  190°C  for 10
  minutes at 30  mL/min with  helium,  directly onto  the   head of the  GC  column,
  which was held at 20°C.

      Semi-volatile pollutants with boiling points above 100°C were analyzed using
  EPA Method 625 for  base/neutrals  and acids.  As with volatile component water
  samples, impinger  washes  were  concentrated  and  analyzed.   In the  Modified
  Method  5  train,  front half samples  (probe washes  and  filter)  samples  were
  analyzed as  a  unit.   To  accomplish  this, the probe  wash  was  concentrated  and
  the filter  extracted  separately,   and  the  fractions   were   combined  before
  analysis.  Results were  typically  reported in ug/L  as  the  relative weight  of
  probe wash was much  greater  than  that of the filter.   The  filter,  XAD-2 resin
  samples, samples   of  incinerator  ash,  and  the  solid  filtrates from  effluent
  waters  were  Soxhlet  extracted with methylene chloride  for 16  hours in preparation
  for analysis.   All  analyses were  performed in  a Finnigan model  4000  GC/MS.

      B.   PCDD/PCDF

      As  indicated   above,  References   7  and  8,  and Appendix  C to  this  report
  contain descriptions of the methods  used to analyze  samples for PCDD/PCDF,  and
  specific TCDD isomers.

      C.   Tedlar Bag Samples for  Vinylidene Chloride

      Whole-air samples  were  analyzed  on   a  Perkin  Elmer  model  3920  GC/ECD
  maintained under  the conditions shown in Table A-l.  The  gas  chromatograph  was
  calibrated prior  to  each  daily  run with  zero gas  and  four typical  upscale
  vinylidene chloride  concentrations:   27,   50,  111,  and   235  ppb.   A   fifth
  upscale concentration, 531  ppb,  was  added when  measured  vinylidene  chloride
  concentrations exceeded  235 ppb.
                                         A-15

-------
    Gas samples  were  taken for  periods of  30  to 65  minutes,  such  that  bags
were filled with a volume sufficient to be analyzed.   As each sample was analyzed
in triplicate, the analytical  process typically required a longer time than did
sample collection,  prompting  concerns  about  the  stability  of samples  while
being held for  analysis.   Therefore,  three bag samples were  reanalyzed  on the
day following the first  and third sampling  days.   The results  of  these tests
indicated good sample  stability over nearly 24 hours'  holding time, and suggested
that reactions, leaks, or other changes occurring in samples being  held for one
to four hours before analysis  were not significant.   Sample bags were used only
once and then discarded, to avoid contamination or  wall effects  from sample to
sample.

    D.  Continuous Emissions Monitoring System (CEMS)

    The arrangement  of  the continuous emissions monitoring system  employed to
analyze incinerator  exhaust gases  has been described previously.  The specifica-
tions (see  Table A-2)  of  the  system  show  goals  for  relative accuracy  and
zero and span  drift.   Results  of Orsat analyses for  oxygen  and carbon dioxide
were compared  with  average  data from  the  CEMS  to  derive  relative  accuracy
comparisons; as  carbon  monoxide  concentrations were below the  range of sensi-
tivity of  the  Orsat,  it  was  not possible to  evaluate relative accuracy  with
respect to  CO.   Zero  and  span  drift were  determined approximately  six weeks
after the  completion   of  the  study,  and  the  results  showed   the  following:

      Instrument                        Zero Drift (%)      Span Drift (%)

      MSA 802 02 analyzer                    0.00                0.52
      Horiba PIR-2000 C02 analyzer           0.00                0.00
      Horiba PIR-2000 CO analyzer            0.00                1.09.

These results   compared  favorably  with  the  criteria  shown  in  Table  A-2.
                                       A-16

-------
IV.   WASTES INCINERATED AND INCINERATOR OPERATIONS

     Dow Chemical  provided  general  information concerning  the types  of  liquid
 and solid waste materials incinerated on  each  sampling  day.   In  addition,  basic
 descriptions of the chemical composition of each of these wastes  were furnished,
 as  every waste was labeled with a  serial  number corresponding to an analytical
 form filed internally by the  company.

     A.   First Sampling Day -  August 28, 1984

     Company information  indicated  the  wastes  burned on  this  day consisted  of
 bulk rubbish; drums  and fiber packs  (containerized  solid  wastes);  and  liquid
 wastes  fed through  all  four  input  nozzles,  including  that for  low-BTU  liquid
 waste.   These wastes are described  below:

     1.   Rubbish

     Bulk rubbish consisting of paper,  cardboard,  plastics, and  wood  was  input
 continuously throughout the sampling  period,  at an  average   rate indicated  by
 Dow Chemical  to be  19.9 cubic  yards per  hour,  or  about 9950 pounds  per  hour.

     2.   Containerized Solid Wastes

     A total  of 84 containers of solid  waste  were  incinerated between  1235  and
 2000 EOT; below are general descriptions  of each.
   Dow ID
   Number

    1425-04
     137-02
    1244-01
    1202-03
    2603-01
 Q8-6039-01
    8793-01
    1552-02
    2603-02
    2521-06
Number
 Fed

   6
  18
   5
   1
  13
   8
  21
  10
   1
   1
   Total
Weight (Ibs)

         267
approx. 3000
         381
         120
         600
        1420
        2954
        1322
          90
          89
approx.
Primary Constituents

Glass, plastic filters
Latex, plastic wastes, rubber
Acrylamide, acrylonitrile
Glass, toluene, ethanol
Plastic and saran wastes
Filter aids, silicones,  hydrocarbons
Miscellaneous Styron wastes
ABS resin
Mineral spirits, methanol, MEK
Glass, PVC, tars
       (Total)    84     approx.  10200

     3.   Nozzle "BA"  Feed

     A single waste, identified  as  number Q8-6011-01 and consisting  of  chloro-
 silanes,  benzene,  chlorobenzene, toluene, and other hydrocarbons, was fed  from
 a tank  truck.   The Dow Corning  facility located  near the Dow Chemical  plant was
 the source of the waste.  The average flow rate of  this  waste  was estimated by
 Dow Chemical  as 900  pounds  per  hour.
                                       A-17

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    4.  Nozzle "BB" Feeds

    Two liquid waste mixtures were  fed.   From 1235 until  1606 EOT,  wastes from
a storage tank  were delivered  at  an  average  rate of  1764 pounds  per  hour.
The components  of  this  mixture  were   reported  by  Dow  Chemical  as  follows:

              Dow ID Number      Primary Constituents

                 8420-01         Sodium acetate, Dowanol, toluene
                 8440-03         Amines, Dowanols
                 8492-06         Polyoxyalkylene ether
                 8531-01         Alkanolamines, ethyl alcohol
                 8585-02         Butylene glycol, butylene oxide

    From 1606 until  the end of  sampling at  2000  EOT, 972  pounds per  hour  of
waste 1450-05 were fed  from  a  direct-burn  trailer.  Dow's  waste  description
showed this waste to be composed of 85% methanol and 15% ammonia.

    5.  Nozzle "C" Feed

    Waste 1546-01 was delivered from a  tank  trailer  at an  average  rate  of 2360
pounds per hour.  This waste was described by Dow as containing ethanol, toluene,
acetone, and about 2% Probucol  in water.

    6.  Low-BTU Liquid Waste

    From 1400 until the end of sampling, approximately eight gallons per minute
(4000 pounds per hour)  of  collected precipitation  were fed to the incinerator.

    7.  Incinerator Operational  Characteristics

    No abnormal  operating  phenomena were cited by  Dow personnel.  A summary of
incinerator operating data recorded  at  15-minute  intervals by  Dow personnel
throughout the  sampling  day appears   in  Table  A-3,  and  in   Table A-4  are
exhaust gas oxygen, carbon dioxide, and  carbon monoxide data as measured by the
previously-described continuous  emissions monitoring  system;  note  that  this
system operated  only  during  the  second  half of the   first  sampling  day.

    B.  Second Sampling Day - August 30, 1984

    Incinerated wastes  included bulk rubbish; drums  and fiber packs;  and liquid
wastes fed through  all  but the low-BTU  liquid waste  nozzle.

    1.  Rubbish

    A continuous  feed of  loose  solid  waste was provided, at an average rate of
 17.1  cubic yards  per hour, or about 8550 pounds  per  hour.

    2.  Containerized Solid Wastes

    Between  1005  and  1630 EOT,  73 containers described below were incinerated.
                                        A-18

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                                   Table A-3

                          Incinerator Operational  Data



                                        8/18/84        8/30/84         9/5/84
                                       1235-2000      1005-1630      1010-1630

Rotary Kiln Temperature (°C)            823-1016       851-1089        877-998

Afterburner Temperature (°C)           1038-1106      1013-1096      1013-1121

Quench Water Flow (gpm)                  703-717        706-724        719-727

Venturi Scrubber Water Flow (gpm)        265-276        252-264        207-223

Venturi Differential  Pressure          26.3-28.7      20.7-25.8      16.6-19.4
    (in. H20)

Demister Water Flow (gpm)                961-989        961-985        968-987

ESP Water Flow (gpm)                      169-177        172-176        160-181
                                        A-19

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                                        Table A-4

                                     Exhaust Gas Data
                       As Measured by Continuous Emissions Monitor
                                Oxygen (%)       Carbon Dioxide (%)   Carbon Monoxide (ppm
Date
8/28/84
8/30/84
9/5/84
Time
Measured
(EOT)
1620-2030
1120-1650
1030-1710
Average*
11.76
12.74
11.28
Std.
Deviation
0.35
0.34
0.82
Average*
6.73
6.00
6.21
Std.
Deviation
0.47
0.49
0.50
Average*
47.5
62.7
32.4
Std.
Deviation
16.7
55.9
22.7
* Arithmetic averages of ten-minute-averaged
  data during measurement period cited.
                                             A-20

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  Dow ID      Number       Total
  Number       Fed      Weight (Ibs)    Primary Constituents

 1202-05        19          1159        Wood fiber
 8793-01         4           647        Miscellaneous Styron wastes
 8893-13        43          4292        Styrene, acrylonitrile, ethylbenzene
 1245-05         3           128        Unspecified polymer
 1136-01      	4         	24_        Miscellaneous laboratory wastes

      (Total)   73          6250

    3.  Nozzle "BA" Feed

    Approximately 1800  pounds  per hour of  Dow Chemical waste  Q8-6011-01,  the
same as burned  on  the first  sampling  day,  was fed to  the  rotary  kiln through
this nozzle.

    4.  Nozzle "BB" Feeds

    From 1000  until  1415  EOT,  wastes  from a  storage tank,  consisting of a
mixture of  the  following,  were  fired  at  a   rate  of 682  pounds  per  hour:

              Dow ID Number      Primary Constituents

                 8420-01         Sodium acetate, Dowanol,  toluene
                 8440-03         Amines, Dowanols
                 8440-05         Brake fluids,  Dowanols, Dowfroth, polyglycols
                 8492-01         Acrylamide/acrylic acid copolymer
                 8492-06         Polyoxyalkylene ether
                 8531-01         Alkanolamines, ethyl alcohol
                 8585-02         Butylene glycol, butylene oxide
                 8769-01         Styrene, benzene, ethylbenzene wastes

    From 1415 until the end of sampling, another tank mixture, described below,
was fed to this nozzle at a rate of 1200 pounds per hour:

              Dow ID Number      Primary Constituents

                 8052-04         Dimethyl  sulfoxide,  sodium chloride
                 8052-07         Dimethyl  sulfoxide,  dimethyl phthalate, tars.

    5.  Nozzle "C" Feed

    Viscous liquids stored  in a  stationary tank  were  fed to  the afterburner
section of the incinerator at  a rate of  1171 pounds per  hour.  The tank contents
were a mixture of the following:

              Dow ID Number      Primary Constituents

                 9018-03         #2 Diesel oil
                 9026-01         Phenolic tars, p-phenylphenol.
                                      A-21

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    6.  Low-BTU Liquid Waste

    No wastes of this kind were incinerated on this date.

    7.  Incinerator Operational Characteristics

    These data appear in Table A-3.  Air pollution control  equipment operations
were normal, with  the exception of  a period  from 1515 EOT  until  the end  of
sampling, in which  occasional  arcing was  noted  in the  electrostatic  precipi-
tator, the result of water bridging between the emitting plate and the  sidewall
retaining bolts.  Facility personnel  indicated  such arcing would ordinarily have
triggered the shutdown of the  incinerator  to allow cleaning  of the  interior  of
the precipitator, had it become more severe.

    In Table  A-4, data  concerning  exhaust  gas   characteristics  appear.   Of
particular interest are the  relatively  high CO concentrations  measured.   This
reflects comparatively high peak CO  values  recorded  at intervals corresponding
to the introduction of containerized  solid wastes to the incinerator, or approxi-
mately every six  minutes.   On several occasions,   CO measurements  exceeded the
scale of the monitor (0 to  1000 ppm);  as a  result  of these  sharp  peaks, the
standard deviation of these measurements is also high.

    C.  Third Sampling Day - September 5, 1984

    Incinerated wastes  included  bulk  rubbish;  drums  and   fiber  packs;  and
liquid wastes from all  four input  nozzles during  the  sampling  period, 1010 to
1630 EOT.

    1.  Rubbish

    Loose rubbish was fed  continuously  at an  average  rate  of 20.8 cubic yards
per hour, or about  10,400 pounds per hour.  Most  of these  wastes  consisted  of
cardboard, wood,  and  plastic;  a small portion  was described as wet,  and some
scrap fiberglass  insulation was incinerated.

    2.  Containerized Solid Wastes

    A total  of  58 containers  of solid waste were  incinerated at a uniform rate
between 1010 and  1630 EOT.  Their contents are described below:

  Dow ID      Number       Total
  Number        Fed      Weight  (Ibs)    Primary Constituents

  358-07          1               166    Demolition wastes
  1586-07        17               812    Dowco  453ME
  1250-02          2               143    Miscellaneous  laboratory wastes
  1223-01          2      approx.  250    Miscellaneous  laboratory wastes
  1156-01          1               111    Miscellaneous  waste solvents
  1145-01          1               174    Organic solvents
  1224-08          8               409    DMSO,  perch!oroethylene
  1224-02          1               177    Miscellaneous  laboratory wastes
                                       A-22

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 1407-07
 1215-04
 1215-02
 8428-03
 1584-02
                10
                 1
                 1
                12
                 1
     (Total)    58

    3.  Nozzle "BA" Feed
1459
  57
  81
3375
 106

7320
Polyethyloxazoline
ABS, ethyl benzene, styrene
Styrene, ethyl benzene
Sodium trichloropyridinate
Dursban, methylene chloride
   solid sorbent
    Dow Corning  wastes  were  incinerated  at an  average rate  of  approximately
1726 pounds per hour.  As  indicated  previously, this  waste,  number Q8-6011-01,
was composed  of  chlorosilane,  benzene,   chlorobenzene,  toluene,  and  other
hydrocarbons.

    4.  Nozzle "BB" Feeds

    A mixture of the following liquid wastes was incinerated at an average rate
of 3002 pounds per hour.
              Dow ID Number

                  688-03
                 8020-01
                 8420-01
                 8440-03
                 8440-05
                 8492-01
                 8492-06
                 8531-01
                 8585-02
                 8769-01

    5.  Nozzle "C" Feed
                                 Primary Constituents

                                 Waste oils, chloroethylene, ethylene glycol
                                 Methyldi ethanolami ne
                                 Sodium acetate,  Dowanol, toluene
                                 Amines, Dowanols
                                 Brake fluids, Dowanols,  Dowfroth
                                 Acrylamide/acrylic acid  copolymer
                                 Polyoxyalkylene  ether
                                 Alkanolamines, ethyl alcohol
                                 Butylene glycol, butylene oxide
                                 Styrene,  benzene, ethyl benzene wastes
    A
truck
Dow Chemical
      mixture of  wastes  referred to  as  "Canada-02"  was delivered  from  a  tank
      at a rate of 1758 pounds per hour.   Chemical  composition data provided by
	 	   indicates  the  waste  consisted  primarily  of  styrene,  with  the
following constituents also present, in descending order:  carbon tetrachloride,
4-vinyl  cyclohexene,  benzene/butadiene,  ethyl benzene,  isopropyl  benzene,  and
n-propylbenzene.

    6.  Low-BTU Liquid Waste

    A mixture of aqueous  wastes described by Dow Chemical  as collected precipi-
tation,  condensate  from tank  storage area  carbon  bed  regeneration,  and  water
from hydroblasting  cleanup,  was  fed  to  this  nozzle  at a  steady rate  of  4754
pounds per hour  between 1130 and 1630.   Before  this, water flow was intermittent.
                                       A-23

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    7.  Incinerator Operational  Characteristics

    No operational  abnormalities  were reported  by  Dow  personnel.   Tables  A-3
and A-4 contain operational data  and  exhaust  gas measurements obtained through
continuous emissions monitoring.
                                        A-24

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                        APPENDIX B

EXTRACTION PROCEDURE FOR "HIGH-HAZARD" LIQUID WASTE SAMPLES

               FRED C.  HART ASSOCIATES, INC.

                  MICHIGAN DIOXIN STUDIES
   DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR EMISSIONS STUDY

-------
                    Method:   RSL-901
                    Page:  1  of 5
                    Date:  June 1984
                    Replaces:   All previous editions
      Separation and Aliquoting High Hazard Waste Samples
1.   Scope and Application

    This is a general purpose method that provides procedures
    for phase separating and aliquoting high hazard waste
    samples taken from drums, lagoons, tanks, landfills,  and
    other uncontrolled hazardous wastes.  The method is appli-
    cable to a wide range of analyses including volatile  organics,
    semi-volatile organics, total metals, spot tests,
    and strong acid anions.


2.   Summary of Method

    2.1  Individual phases are separated by decanting and
         centrifuging.  After separation, phases are weighed to
         a tenth of a gram and recomposited by percent weight
         (except for compositional analysis).  Prior to recom-
         position, liquid phases are tested for water misci-
         bility.

    2.2  Phase separation and recomposition is performed  in
         order to obtain representative aliquots from the
         original sample.


3.   Definitions

    The characteristics of the samples defined below are  the
    only descriptions to be used in describing the physical
    attributes of the sample:

    Phase - A solid (gel or paste), water miscible liquid,
            non-water miscible liquid.

    Paste - Inseparable solid and liquid.

    Viscosity - Non-viscous, similar to water, or viscous.

    Color - Colorless, light of the color, medium of the  color,
            or dark of the color.  Use only primary and second-
            ary colors.

    Texture - Fine grain (powdery), medium grain (sand),  or
              course grain (large crystals).

    Turbidity - Clear, cloudy (transmits light),  or  opaque.


                                B-l

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June 1984                                       Page 2 of 5
Method:  RSL-901


Minor phase - Phases that represent less than or equal to 5% by
              weight for mercury aliquoting.  Phases that
              represent less than or equal to 2% by weight for
              all other aliquoting.


4.  Artifacts

    Artifacts may occur in samples depenoing on the nature of
    the waste and how it is obtained.  Aitifacts are not minor
    phases but are due to extraneous agents not of the waste.
    When excluding a portion of a sample from recompositing
    based on the apparent presence of an artifact, the decision
    should be fully documented on the laboratory bench sheet.


5.  Safety

    High hazard samples are expected to contain concentrations
    of substances of unknown toxicity and carcinogencity up to
    100% by weight.  Thus, each sample is to be treated as a
    potential health hazard and exposure to these samples is to
    be minimized.  Each analyst is responsible for maintaining
    awareness of safe handling procedures used in this method.
    The samples are collected, packaged, and shipped according
    to recommended procedures for hazardous wastes and are to be
    prepared using the following method in a Regulated Substances
    Laboratory prior to analysis.


6.  Apparatus and Equipment

    6.1  Radiation meter with pancake probe

    6.2  Centrifuge, explosion-proof

         6.2.1  large process type for 8 oz. jars

         6.2.2  small type for vials

    6.3  Vials and Jars

         6.3.1  2 dram

         6.3.2  40 mL

         6.3.3  20 mL

         6.3.4  8 oz. jar

         6.3.5  4 oz. jar
                               B-2

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June 1984                                     Page 3 of 5
Method:  RSL 901
    6.4  Pipets, various sizes

    6.5  Balance, four place

    6.6  Spatulas, various types

    6.7  Miscellaneous

         6.7.1  Kimwipes

         6.7.2  Soap and water squir; bottles

         6.7.3  Methanol squirt bottles

         6.7.4  Plastic bags, various sizes

         6.7.5  Stainless steel trays

         6.7.6  Teflon liners, various sizes



7.  Sample Handling

    Samples are removed from shipping cans inside a hood and
    repackaged after phase separation and aliquoting in the same
    manner.  Only dilutions, digestions or extractions of a
    sample may be removed from the RSL; however, upon special
    request small amounts of undiluted samples may be taken from
    the regulated area.


8.  Procedure

    8.1  Traffic Report/Sample Verification

         8.1.1  Verify Traffic Report against sample identifi-
            cation tag.  If custody seal is present, sign and
            date where provided.  Verify the information on the
            sample tag with the phase separation record.  If
            there are any discrepancies, the sample tag is
            checked against the Chain-of-Custody record.  The
            differences are recorded under sample tag information.
            Reconciliation is made bv Sample Control if necessary.

    8.2  Place sample can inside small plastic bag.  Remove lid
         from can and perform radioactivity check.  If positive,
         replace can lid, remove gloves and vacate lab.  Remove
         sample from can and record sample condition on Phase
         Separation Record and Traffic Report.  Wipe down
         sample container with a Kimwipe moistened with soapy
         water.
                                B-3

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June 1984                                    Page 4 of 5
Method: RSL 901
    8.3  Open sample container and again perform radioactivity
         check and record results.  If positive, replace jar
         lid, remove gloves ano vacate the lab area.

    8.4  Complete any other header information on the phase
         separation record.

    8.5  Phase Separation

         8.5.1  If sample is a single phase liquid, test for
            water miscibility by adding several drops of sample
            into a 2 dram vial containing 0.5 mL of deionized
            water.  Record results.  Transfer 35 mL of the
            liquid to a labeled 40 mL vial or 2 oz. bottle.
            Recap original sample.

         8.5.2  If sample is a single phase solid, transfer
            approximately 35g into a labeled 40 mL vial.

         8.5.3  If sample is multi-phase, split sample into
            2 jars, place the jars in plastic bags and centri-
            fuge at 3000 rpm (50%).  Centrifuge sample for not
            less than five minutes but no longer than ten minutes.
            Check for separation completeness.  If incomplete,
            centrifuge for an additional five minutes.

         8.5.4  Transfer each individual phase to appropriate
            tared and labeled vials or jars and record final
            weights on separation  record.  Perform water
            miscibility test as described in Section 8.5.1
            on each liquid phase.

    8.6  Describe and record each  phase using phase
         descriptions in Definitions (Section 3).

    8.7  Remove any material from  outside of vials and jars
         with Kimwipes and soap and water.  (Solvents may be
         necessary but use only on SEALED containers) .  Place
         contained phases  in one plastic bag and store for
         future aliquoting.

    8.8  Aliquot ing

         8.8.1  Ascertain whether  aliquoting is for compositional
            or general charactertization analysis.  For
            compositional  analysis weigh a predetermined amount
            of phase into an appropriate test vial.  For general
            characterization analysis, recomposite each phase
            by percent weight into an appropriate test vial.
            Refer  to extraction and analysis methods  for proper
             aliquot weights.


                               B-4

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June 1984
Method: RSL-901
                              Page 5 of 5
         8.8.2  Unless requested,  minor phases are not aliquoted.
            Minor phases are defined in Section 3.


9.  Waste Disposal

    9.1  All items listed in the following table will be placed
         in the appropriate waste  container.   The containers
         will be either labeled with the DOT  classification
         from the table or be placed in another container which
         will be labeled with the  DOT classification (e.g. plastic
         bags will be placed in a  labeled 55  gallon drum).
   Item

Waste Glass


Waste Solvents

Waste Wood
Waste Paper
Gloves, etc.

Waste Liquids
Soapy H20, DDI
 Container

5 Gallon can
  Reinke

Waste Solvent Can

5 Gallon can
  Reinke

Plastic Bag
Waste Solvent Can
Classification (DOT)

Waste Flammable Solid


Waste Flammable Liquid

Waste Flammable Solid


Waste Flammable Solid


Waste Flammable Liquid
Approved by

Reviewed by
                    Date

                    Date
                               B-5

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                        Method:  RSL-902
                        Page:  1 of 10
                        Date:  June 1984
                        Replaces:  All previous editions
Organic Chemical Extraction and Gas Chromatographic Screening o:
                   High Hazard Waste Samples
1.   SCOPE AND APPLICATION

     This is a general purpose method that provides procedures
     for preparation and screening of organic extracts for
     volatile organic (VOA),  base/neutral/acid (B/N/A),  and
     pesticide/PCB.  High hazard waste samples include all
     chemical wastes both in containers,  such as drums or
     tanks,  and uncontained such as in piles, solid chemical
     or pooled liquids.

     The method is directed to highly contaminated soil  samples
     and waste samples that may be solid,  aqueous liquid, or
     nonaqueous liquid and suspected to contain greater  than
     0.01% of any one organic chemical component.  The method
     is not  designed for waste samples expected to contain less
     than 10 ppm of base/neutral and acid  priority pollutants;
     for example, as in many sediment samples taken from
     leachate streams.  That  type of sample should be analyzed
     using more traditional methods, such  as Soxhlet extraction
     or homogenization,  with  larger sediment/soi1 samples.


2.   SUMMARY OF METHOD

     2.1  One to 1.5 gram aliquots of soil,  solid,  aqueous
          liquid, or nonaqueous liquid are transferred to vials
          and diluted with either methanol,  hexane,  or methylene
          chloride.  Solid phase aliquots  which are not  soluble
          in the extracting solvent are sonicated for two
          minutes.  All  other aliquots are either shaken by hand
          or a mechanical wrist shaker for one minute.
     DEFINITIONS

     B/N/A - Base/Neutral/Acid

     VOA - Volatile Organic analysis

     External standard - a known amount  of a pure  compound that
     is analyzed with the same procedures  and conditions  that
                                 B-6

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June 1984                                        Page 2 o ' 10
Method:  RSL-902

are used to analyze samples containing that compound.  From
measured detector responses to known amounts of the external
standard, a concentration of that same compound can be ca '.-
culated from measured detector response to that compound  .n a
sample analyzed with the same procedures.

Internal standard - a pure compound added to a sample in 'cnown
amounts and used to calibrate concentration measurements of
other compounds that are sample components.  The internal
standard must be a compound that is not a sample component.

NEIC dirt - a loamy soil obtained near the NEIC/Denver wh .ch
has been dried, crushed, and sieved in a #10 sieve.

Laboratory control standard - a solution of analytes prepared
in the laboratory by dissolving known amounts of pure com-
pounds in a known amount of solvent.  In this method, the
laboratory control standard is prepared by adding appropr.ate
volumes of the secondary dilution standard solution and the
internal standard/surrogate compound spiking solution to a
known soil/water/oil matrix.

Laboratory replicates - three aliquots of the same sample that
are treated exactly the same throughout laboratory analytical
procedures.  Analysis of laboratory replicates indicate pre-
cision associated with laboratory procedures but not with
sample collection, preservation or storage procedures.

Laboratory reagent blank - a portion of reagent solvent pro-
cessed in the same manner as the sample.

Secondary dilution standard - a solution of analytes prepared
in the laboratory from stock standard solutions and diluted
as needed to prepare calibration solutions and laboratory con-
trol standards.

Stock standard solution - a concentrated solution containing a
certified standard that is a method analyte,  or a concentrated
solution of an analyte prepared in the laboratory with an
assayed reference compound.  Stock standard solutions are used
to prepare secondary standard solutions.

Surrogate compound - a compound that is not expected to be
found in the sample, is added to the original environmental
sample to monitor performance,  and is measured with the same
procedures used to measure sample components.
4.   LIMITATIONS

     The procedure is designed to allow detection limits as  low
     as 10 ppm for volatile organic priority pollutants.  The
     procedure is designed to detect extracts at  100 ppm for
     base/neutral and acid priority pollutants,  10 ppm for TCDD
     and PCB's,  and 10 ppm for chlorinated pesticides; lower
                                B-7

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June 1984                                          page 3 of 10
Method:  RSL-902

     limits of detection, tenfold below these values, can be
     achieved on relatively clean samples by concentrating the
     extracts to 1 mL.  Some samples, however, may contain high
     concentrations of chemicals that interfere with the analy-
     sis of other components at lower levels; the detection
     limits in those cases may be significantly higher.  These
     extraction and preparation procedures were developed for
     rapid and safe handling of high concentration chemical
     waste samples.  The design of the method thus does not
     stress efficient recoveries or low limits of detection of
     all components.  Rather, the procedures were designed to
     screen, at moderate recovery and sufficient sensitivity, a
     broad spectrum of organic chemicals.  The results of the
     analyses thus may reflect only a minimum of the amount
     actually present in some samples.


5.   SAFETY

     Potentially carcinogenic, mutagenic, toxic, and other
     hazardous materials may be present in these waste samples
     at concentrations up to 100 per cent.  This procedure is
     intended for use in a Regulated Substances Laboratory to
     minimize personnel exposure and other hazards relating to
     the handling of the samples.  In particular, good labora-
     tory practices should be used to minimize exposure and
     contamination throughout the preparation and analysis
     of these types of samples.  Each person is responsible
     for maintaining awareness of safe handling procedures
     used in this method.
6.   REAGENTS

     6.1  Sodium sulfate (anhydrous).  Granular, analytical
          reagent grade, pre-extracted with methylene chloride
          or muffled at 400°c. for 3 hours before use to remove
          interferences.

     6.2  Methylene chloride.  Pesticide residue analysis grade,
          or equivalent.

     6.3  Hexane.  Pesticide residue analysis grade, or
          equivalent.

     6.4  Methanol.  Pesticide residue analysis grade, free of
          purgeable organics.  Check by adding 10 uL to 5 mL of
          organic free water, and analyzing by GC/MS using the
          purge and-trap technique or direct injection by GC/HECD.


7.   APPARATUS AND EQUIPMENT

     7.1  Glass scintillation vials, at least 20 mL, with screw
          cap and aluminum foil liner.


                                B-8

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June 1984                                         Page 4 of 10
Method:  RSL-902

     7.2  Wooden tongue depressors.  Dispose of after using to
          transfer solid samples.

     7.3  Balance capable of weighing 100 gra; is to the nearest
          0.01 gram.

     7.4  Vials and caps, 2 dram for GC autosampler.

     7.5  Disposable pipets, 10 mL.  Pasteur pipets.

     7.6  Gas chromatograph with a flame ionization detector
          and electron capture detector.

     7.7  Ultrasonic probe, Braun-Sonic 1510 with intermediate
          probe attachment, or equivalent.

     7.8  Test tube rack.

     7.9  Glass vials with Teflon-lined screw caps, 12 mL for
          shipment of extracts.

     7.10 VGA bottles, 20 or 40 mL with Teflon-backed septum
          and screw cap, for extraction and shipment of VOA samples

     7.11 Hamilton 10 ul and 250 ul gas tight syringes.

     7.12 Glass wool rinsed with methylene chloride.


8.   CALIBRATION

     8.1  BASE/NEUTRAL/ACID ANALYSIS

          8.1.1   Prepare stock external standard solution
                  by weighing about 0.025 grams of pure
                  phenanthrene-dlO.  Dissolve the material in
                  methylene chloride,  dilute to volume in a 20
                  mL volumetric flask.   Dilute a portion of the
                  stock solution (secondary dilution standard)
                  to achieve a concentration of 25 ug/mL.
                  Prepare stock internal standard solution by
                  weighing about 0.050 grams of pure napthalene-
                  -d8 and phenanthrene-dlO.   Dissolve the
                  material in methylene chloride,  dilute to
                  volume in a 10 mL volumetric flask.   Transfer the
                  stock standard solutions into Teflon sealed screw-
                  cap bottles.  Store at 4°  C.   Stock standards
                  should be checked frequently for signs of
                  degradation or evaporation,  especially just
                  prior to preparing calibration standards from
                  them.
          8.1.2
                  Using an injection of 2 uL of the external
                  standard solution,  standardize the flame
                  ionization detector for half-scale response.


                               B-9

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June 1984                                        Page 5 of 10
Method:  RSL-902
          8.1.3  Reconunended operating conditions for the gas
          chromatograph are:
          Thirty (30) meter X 0.25 mm bended-phase silicone-
          coated fused silica capillary column with helium
          carrier gas at a flow rate of 30 cm/second.  Column
          temperature programmed:  isothermal, 50° C. for four
          minutes,  then programmed at 8r C/minute to 300° C.
          Hold time, 15 minutes.

          8.1.4  Concentrate 10.0 mL of the B/N/A Control and
                 Reagent Blank extracts under a gentle stream
                 of purified nitrogen tc 1.0 mL.

          8.1.5  Transfer the 1.0 mL extract to a 2 dram vial
                 and seal.

          8.1.6  Immediately prior to analysis, add 10 uL of
                 the internal standard solution to the extract.
                 The final concentration of the internal standards
                 in the extract should be 50 ug/mL.

          8.1.7  Surrogate compounds shall be quantified by the
                 internal standard method.  The internal standard
                 used shall be the one nearest the retention time
                 to that of a given surrogate.
                                AT   AT
                                *1 J. O  *»W •%
                                  o    ...

                 AIX = Area of Internal standard in standard
                 AIS = Area of internal standard in sample
                 ACS = Area of surrogate in sample
                 ACX = Area of surrogate in standard
                 Cx  = Concentration of surrogate in standard

          8.1.8  Each chromatogram shall be clearly identified
                 with the following information.

                 (a)  Case or Project Number
                 (b)  Sample Identification
                 (c)  Fraction (BNA, V0£,  Pesticide/PCB)
                 (d)  Standard, Reagent Blank, Control
                 (e)  GC run number
                 (f)  If sample is a reagent blank or control,
                      list GC number of Standard used for
                      quantitation
                 (g)  Date of analysis
                 (h)  Analyst name
                 (i)  Standard Operating Procedure number
                 (j)  Each internal standard and surrogate
                      identified.
                                B-10

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June 1984                                          Page 6 of 10
Method: RSL-902
          8.1.9  Report results on QC Bench Sheet


     8.2  PESTICIDE/PCB PREPARATION
          8.2.1  Prepare stock solution by diluting 1.0 mL
                 of concentrated Aroclor 1254  (5000 ug/mL)
                 to 10 mL in acetone.  Final concentration
                 to be 0.5 mg/mL.

          8.2.2  Transfer the stock solution into Teflon-
                 sealed screw-cap bottles.  Store at 4°c.
                 Stock standards should be checked frequently
                 for signs of degradation or evaporation
                 especially just prior to preparing calibration
                 standards from them.

          8.2.3  Using an injection of 2 uL of the secondary
                 dilution  standard, standardize the electron
                 capture detector for half-scale response.
                 The secondary standard is a lOx dilution of
                 the stock solution.

          8.2.4  Recommended operating conditions for the gas
                 chromatograph are:

                 Supelcoport (100/120 mesh) coated with 1.5%
                 SP-2250/1.95% SP-2401 packed  in a 1.8 m long
                 X 4 mm ID glass column with nitrogen carrier
                 at a flow rate of 40 mL/minute.  Column
                 temperature, isothermal at 200°c.

          8.2.5  Dilute the Pesticide/PCB control and Reagent
                 Blank extracts by adding 100  uL of extract to
                 0.9 mL of hexane.

          8.2.6  Surrogate compounds shall be  quantified by
                 the external standard method.  The integrated
                 area or peak height for the five largest and
                 most resolved peaxs are averaged:

                                AS_  * Cx
                 As  =  Average  area of peaks  in  sample
                 Ax  =  Average  are^ of peaks  in  standard
                 Cx  =  Concentration of surrogate  in  standard

           8.2.7  Reporting  (see paragraph  8.1.8)
                                 B-ll

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June 1984                                              p    ?  f 1Q
Method:  RSL-902
9.  QUALITY CONTROL
    9.1   Two reagent blanks for each fraction (VOA, Pesticide/
          PCB, B/N/A) shall be prepared with each project or
          for every 20 samples within a project.   One is analyzed
          at the RSL while the other is shipped with the sample
          extracts to the analysis laboratory.

    9.2   One sample from each project or for every 20 samples
          within a project is prepared for spiking purposes by
          aliquoting six (extra) additional fractions.  Three
          fractions are spiked at 50 ug/g of sample with PCB
          stock solution (Aroclor 1254),  three more fractions
          are spiked at 100 ug/g of sample with Base,  Neutral and
          Acid standards (See Table 1.)

    9.3   Each B/N/A fraction, blank,  and replicate spike shall
          be spiked with 150 uL of surrogate Spike.
         (see Table 1).

    9.4   With each project or 20 samples within  a project, the
          RSL will prepare two 1.5 gram multi-phase control
          samples by mixing 1.0 gram of NEIC "dirt", 0.1 gram of
          vegetable oil, and 0.4 gram of tap water.  One control
          is spike with 150 uL of B/N/A surrogate mix, the second
          with 150 uL of PCB mix.  The normal extraction procedure
          is followed.  (See Table 1 for concentrations of these
          spike mixes.)
10.   PREPARATION PROCEDURE
    10.1  Transfer 1.5 + .04 g aliquots (1.0 + .04 g for VOA)  to
          appropriate test vials (Method RSL-901,  Section 8.8)

    10.2  Dilute the VOA sample with 10 mL interference-free
          methanol.   Disrupt insoluble solid samples by ultrasonic
          probe for  2 minutes at 100 watts power.

          Cap,  and shake all o.her samples for one minute.   Note:
          vials should be capped and removed from the hood prior
          to working with methylene chloride or any other solvent
          in the hood.  They should also be stored in a solvent-
          free  atmosphere at 4°c.

   10.3   Add 150 uL of B/N/A surrogate mix to each of the sample
          portions to be extracted with methylene chloride.  Add
                                 B-12

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June 1984                                       Page 8 of 10
Method:  RSL-902
        the surrogate 50 that it is distributed as uniformly as
        possible over the sample; shake the sample to achieve
        better mixing Lf appropriate.  In addition dilute 100 uL
        of B/N/A surrogate mix up to 10 mL in methylene chloride.
        This is to be ased as the gc calibration standard for
        analyzing blanks and controls.

  10.4  Add 15 mL of hsxane to the pesticide/PCB fractions
        and 15 mL of mathylene chloride to the B/N/A fractions.
        If the pH of the aliquot is less than or equal to five,
        or greater thai or equal to eight, an additional B/N/A
        extract is prepared with pH adjustment.  The pH ad-
        justment is prepared by adding the equivalent amount
        of acid or bas3 necessary to reach the end point of the
        acidity/alkalility determination.  Add 6N HC1 to aliquots
        whose pH is grsater than or equal to 8.  Add 6N NaOH to
        aliquots whose pH is less than or equal to five.  The
        pH adjusted B/M/A aliquot is not  prepared when the
        addition of acid or base exceeds 2.0 mL.

        Calculations for determining required acid or base
        additions.

        vol. of acid or base   =  1.5 X A X NX x Vj
        required for adj., mL           B X N2


        A  = dilution volume, mL
        B  = volume of aliquot, mL
        NI = normality of titrant
        N2 = 6  (normality of adjusting soln.)
        V^ = volume of titrant required, mL


  10.5  Add approximately 2.5 g of anhydrous sodium sulfate
        to each of the B/N/A and pesticide/PCB extracts to
        absorb any water.  Additional sodium sulfate may be
        required.

  10.6  Disrupt insoluble solid samples for 2 minutes using an
        ultrasonic probe at 100 watts power.  Cap and shake all
        other samples for one minute.

  10.7  Using a disposable 10 mL pipette, transfer 10 mL of the
        extract to a shipping vial.  If the sample contains
        suspended solids that will not pass through glass wool,
        filter enough extract through a pasteur pipet loosely
        packed with 2-3 cm of glass wool to yield 10 mL of
        filtrate.

  10.8  If a pH adjustment extraction was performed, add 5.0 mL


                                B-13

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June 1984                                              Page 9 of 10
Method: RSL-902
     of each methylene chloride extract together in a shipping
     vial; the final volume being 10 mL.

     10.9  For all extract vials that are to be shipped, mark
           the liquid level on the side of the vial.


11.  METHOD PERFORMANCE

     11.1  The results of recovery studies presented in Section 11
           are from the extraction of 1.0 gram samples with 10 mL
           of solvent.  It should be noted that during sample ex-
           traction preparation, sodium sulfate is added to the
           sample prior to the sonication step rather than after
           sonication.  This change raised recovery of the 50 ug/g
           PCB spike into the multi-phase control sample from 50-60
           percent to 80-90 percent; recoveries of the B/N/A sur-
           rogate compounds were not detectably affected by the
           change.  The data in Tables 2 through 6 show variability
           of recovery due to matrix, pH, solvent, concentration,
           and analyst.  The B/N/A extracts for these studies were
           analyzed on an SE54 capillary column with an FID detector.
           The data in Tables 7 through 9 were obtained from capil-
           lary column GC/Ms analysis.  The GC/MS analysis differed
           from that used by contractor laboratories in that only
           phenanthrene-dlO was used as an internal standard for
           quantitation, and a 15M DBS column with a u urn film
           thickness was used rather than a 30M 0.25 urn film thick-
           ness column.  Section 11.3 presents data showing the
           performance of the method for VOA compounds; losses of
           very volatile compounds (gases) on the order of 20-40
           percent can be expected.

     11.2  The data in Tables 7 through 10 were obtained from
           analysis of quadruplicate spikes into three matrices.
           Matrices 1 and 3 were real samples whose only criterion
           for selection for spiking was that the level of chroma-
           tographable organics would allow the final extract to be
           concentrated to 1 mL.  Matrix 2 is the material referred
           to as  "MEIC dirt" which is described in Section 3.

     11.3  A possibility in the use of any extraction method for
           VOA compounds is the loss of volatile compounds during
           the extraction.  In order to investigate the possibility
           of losses during the sonication step of this procedure,
           replicate portions of standards in methanol were soni-
           cated  for various lenghts of time.  The results indicate
           that losses between  20 to 50 percent can be expected,
           using  this extraction procedure for compounds which are
                                  B-14

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June 1984                                             Page 10 of 10
Method:  RSL-902
           gases at room temperature (chloroethane, methyl bromide,
           irethyl chloride, vinyl chloride).  Losses of other com-
           pounds ranged from negligible up to the order of ten
           percent for a sonication of two minutes.  The developers
           of this method suggest that for the assumed application
           of this method, losses of ten percent can be considered
           negligible. Table 11 presents the results of the percent
           recovery as a function of sonication time study.  Table 11
           lists the average percent recovery and standard deviation
           for three determinations at each time.  The sonication
           study involved six replicate portions of a standard
           solution in methanol.  Three 10-mL portions were
           sonicated for one minute and 1 mL aliquots removed for
           analysis.  The other three portions were sonicated for
           two minutes before removing aliquots.  Each group of
           three aliquots for analysis after two and four minutes.
           This procedure gave aliquots for analysis after sonication
           times of one through six minutes.  However, the sonication
           time for periods greater than two minutes is not continuous,
           Solutions had an opportunity to cool before the next
           two-minute sonication period; sonicating continuously
           for the time periods shown could be expected to produce
           lower recoveries because of increased heating of the
           solutions.  The sonic probe was operated for sufficient
           time to bring the tip to a typical operating temperature
           before sonicating any of the VOA standards.  The
           analyses were performed by GC/MS.
           Approved by	 Date

           Reviewed by 	  Date
                                  B-15

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                         APPENDIX C


             ANALYTICAL PROCEDURES FOR PCDD/PCDF

         BREHM LABORATORY - WRIGHT STATE UNIVERSITY

                   MICHIGAN DIOXIN STUDIES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR EMISSIONS STUDY

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                                                                   Section 7.0
                                                                   Revision 0
                                                                   August 15, 1984
                                                                   Page 1 of 13
          7.0   GENERALIZED BREHM LABORATORY PROCEDURES FOR SAMPLE
               EXTRACT  CLEAN-UP AND ANALYSES OF ENVIRONMENTAL SAMPLES
               FOR  CDDs/CDFs
7.1  CLEAN-UP  AND  PRELIMINARY  FRACTIONATION OF SAMPLE EXTRACTS

       Extracts  of the  samples obtained as described in Section 5.0 are

cleaned-up and fractionated  using  the  following procedures.
    7.1 ..1   Clean-up  and  Liquid  Chromatographic  Separation

           a.   Add  50  mL of doubly  distilled water  to  the  vessel  containing the
               sample  extract,  reseal  the  vessel  and agitate for  10 minutes.
               Allow the vessel  to  stand for a  period  sufficient  for the aqueous
               and  organic  layers to  separate completely,  and remove and discard
               the  aqueous  layer.

           b.   Using the same procedure as applied  in  3a.,  wash the extract
               successively with 50 mL portions of  50% KOH, doubly distilled
               water,  concentrated  H2SOit,  and doubly distilled water,  in each
               case  discarding  the  washing agent.   The acid washing procedure
               with  concentrated sulfuric  acid  is repeated  until  the acid layer
               is visually  colorless.

           c.   Add  5 g of anhydrous sodium sulfate  to  the  washed  extract and
               allow to  stand in order to  remove residual  water.   Transfer the
               extract to a centrifuge tube and concentrate to near dryness by
               placing the  tube in  a  water bath at  55°C, and passing a gentle
               stream  of filtered,  prepurified  N2 over the  solution.

           d.   Prepare a glass  macro-column, 20 mm  OD  x 230 mm in length,
               tapered to 6 mm  OD on  one end.   Pack the column with a  plug of
               silanized glass  wool,  followed successively  by 1.0 g silica,
               2.0  g silica containing 33% (w/w)  1M NaOH,  1.0 g silica,
               4.0  g silica containing 44% (w/w)  concentrated H^SO^ and 2.0 g
               silica.  Quantitatively transfer the concentrated  extract from
               Step c. to the column  and elute  with 90 mL  hexane.  Collect the
               entire  eluent and concentrate to a volume of 1-2 mL in  a
               centrifuge tube, as  before.

           e.   Construct a  disposable liquid chromatography mini-column by
               cutting off  a Pyrex  10 mL disposable pipette at the 4.0 mL
               mark and  packing the lower  portion of the tube with a small  plug
               of  silanized glass wool, followed by three  grams of Woelm basic
               alumina,  whichhas been previously activated  for at least 16 hours
               at 600°C  in  a muffle furnace, and cooled in  a dessicator for
               30 minutes just  prior  to use.  Quantitatively transfer  the
               concentrate  from Step  d. onto the liquid chromatography column,
               rinse the centrifuge tube consecutively with two 1 mL portions
               of hexane, and also  transfer the rinses to  the chromatography
               column.

                                 C-l

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                                                         Section  7.0
                                                         Revision 0
                                                         August J.5, 1984
                                                         Page  2 of 13
f.  Elute the column with  15  ml  of  hexane  and  discard the
    eluent.

g.  Elute the column with  10  ml  of  8%  (v/v)  methylene chloride-in-hexane and
    discard  the eluent.

h.  Elute the column with  15  ml  50% (v/v)  nethylene chloride-in-hexane and
    retain the eluent.   Concentrate just to  dryness with a
    stream of nitrogen,  as described above.

i.  Take a 9-inch disposable  Pasteur pipette and cut  off a
    0.5 inch section from  the constricted  tip.  Insert a filter
    paper disk at the top  of  the tube,  2.5 cm from the constric-
    tion.  Add a  sufficient quantity of PX-21  Carbon/Celite 545
    (Prepared as  described in the Reagent  section of this
    protocol) to  the tube  to  form a 2  cm length of the Carbon-
    Celite.   Insert a glass wool plug.   Pre-elute the column
    in sequence with 2 ml  of  50% benzene-in-ethyl acetate,
    1  ml of 50% methylene  chloride-in-cyclohexane and 2 mi of
    hexane,  and discard these eluates.   Load the extract
    (reconstituted in 1  ml of hexane)  from Step h. onto the
    top of the column, along  with 1 ml  hexane rinse.  Elute the
    column with 2 ml of 50% methylene  chloride-in-hexane and
    2 ml of 50% benzene-in-ethyl acetate and discard these
    eluates.  Invert the column and reverse elute it with 4 ml
    of toluene, retaining  this eluate  for  CDD/COF analysis.

j.  Concentrate each of the retained fractions to a volume of
    approximately 1 ml by  heating the  tubes in a water bath while
    passing a stream of prepurified N* over the  solutions, as
    described above.  Quantitatively transfer the concentrated
    fractions into separate micro-reaction vessels for the
    appropriate analysis.   Evaporate the solutions in each of
    the micro-reaction vessels almost to dryness, using  the
    procedures just mentioned, rinse the walls of each vessel
    down with 0.5 ml CH2C12,  and reconcentrate just to dryness.
                          *
k.  Approximately 1 hour before gas chromatographic-mass
    spectrometric (GC-MS)  analysis, dilute the residue  in  each
    micro-reaction vessel  with an appropriate quantity of
    tridecane (depending upon the anticipated quantities of
    analytes  in each vessel)  and gently swirl the  solvent  in
    the  vessel to ensure dissolution of CDDs/CDFs.
    Inject  an appropriate aliquot of this solution  into  tne
    GC-MS instrument.
                          C-2

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                                                                       Section  7.0
                                                                       Revision 0
                                                                       August 15, 1984
                                                                       Page 3 of 13
    7.2  ANALYSIS OF SAMPLE EXTRACTS FOR PCDD/PCDF USING  COUPLED  GAS
         CHROMATOGRAPHY-MASS SPECTROMETRY (GC-MS)

        Sample extracts prepared by the procedures described in the  foregoing  are
    analyzed by GC-MS utilizing the following instrumental  parameters.   Typically,
    1  to 5 yl  portions of the extract are injected into the GC.  Sample  extracts
    are analyzed for the concentrations of total  tetra- through octa-CDDs  and  CDFs,
    and for 2,3,7,8-TCDD, and 2,3,7,8-TCDF.


7.2.1.  Gas Chromatograph

        a.  Injector:  Configured for capillary column, splitless/split
            injection (split flow on 60 seconds following injection),  injector
            temperature, 250°C.

        b.  Carrier gas:  Hydrogen, 30 Ib head pressure

        c.  Capillary Column:  For total tetra- through octa- CDDs/CDFs  and
            2,3,7,8-TCDD, 60 M x 0.25 mm I.D. fused silica DB-5;  temperature,
            programmed, see Table 1  for temperature program.
        d.  Interface Temperature:  250°C

7.2.2.  Mass Spectrometer

        a.  lom'zation Mode:  Electron impact (70 eV)

        b.  Static Resolution:  1:600 (10% valley) or 1:10,000 depending upon
            requirements.

        c.  Source Temperature:  250°C

        d.  Ions Monitored:  Computer-Controlled Selected-Ion-Monitoring, See
            Table 1for list of ion masses monitored and time intervals
            during which ions characteristic of each class of PCDD and PCDF
            are monitored.
 7.Z2   Calibration Procedures

        a.  Calibrating the MS Mass Scale:  Perfluoro Kerosene is introduced
            into the MS, in order to calibrate the mass scale through at
            least m/z 500.  The mass calibration is rechecked at least at
            8 hr. operating intervals.

        b.  Table 1A shows the GC temperature program typically used to resolve each
            chlorinated class of PCDD and PCDF from the other chlorinated classes,
            and indicates the corresponding time intervals during which ions
            indicative of each chlorinated class are monitored by the MS.  This
     -      temperature program and ion monitoring time cycle were established by
            injecting aliquots of Standard Mixtures A and B.   (See below for list

                                        03

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                                                                       sectxon /.u
                                                                       Revision 0
                                                                       August 15, 1984
                                                                       Page 4 cf 12


           of calibration standard mixtures).   Corresponding data was established
           for the PCBs by injecting Standard  Mixture D.

       c.  Checking GC Column Resolution for 2,3,7,8-TCDD.   Utilize the column-
           resolution TCDD isomer mixtures (Standard Mixture C)  to verify that
           2,3,7,8-TCDD is separated from the  other TCDD  isomers.  A 20% valley or
           less must be obtained between the mass chromatographic peak observed for
           2,3,7,8-TCDD and adjacent peaks arising from other TCDD isomers.

       d.  Calibration of the GC-MS-DS system  to accomplish quantitative analysis
           of 2,3,7,8-TCDD and 2,3,7,8-TCDF, and of the total tetra- through octa-
           CDDs and CDFs contained in the sample extract  is accomplished by
           analyzing a series of at least three working calibration standards.
           Each of these standards is prepared to contain the same concentration of
           each of the stable-isotopically labelled internal standards used here
           (Standard Mixture A) but a different concentration of native PCDD/PCDF
           (Standard Mixture B).  Typically, mixtures will  be prepared so that the
           ratio of native PCDD and PCDF to isotopically-labelled PCDD and PCDF
           will be on the order of 0.1, 0.5 and 1.0 in the three working calibration
           mixtures.  The actual concentrations of both native and isotopically-
           labelled PCDD and PCDF in the working calibration standards will be
           selected on the basis of the concentrations to be measured in the
           actual sample extracts.  Equations  for calculating relative response
           factors from the calibration data derived from the calibration
           standard analyses, and for calculating the recovery of the
           13C12-2,3,7,8-TCDD and the other isotopically-labelled PCDD and PCDF,
           and the concentration of native PCDD and PCDF  in the sample (from
           the extract analysis) are summarized below.  In these calculations, as can
           be seen, 2,3,7,8-TCDD is employed as the illustrative model.  However,
           the calculations for each of the other native  dioxins and furans in the
           sample analyzed are accomplished in an analogous manner.  It should be
           noted that in view of the fact that stable-isotopically labelled internal
           standards corresponding to each tetra- through octachlorinated class are
           not used here (owing to limited availability at this time) the
           following approach is adopted:  For quantisation of tetrachlorinated
           dibenzofurans 13d2-2,3,7,8-TCDF is used as the internal standard.
           For quantisation of tetrachlorodibenzo-p-dioxins, 13Ci2-2,3,7,8-TCDD
           is used as the internal standard.  For quantitation of PeCDD,
           HxCDD, PeCDF, and HxCDF, the labelled TCDD and TCDF standards,
           respectively, are used.  For quantitation of HpCDD, OCDD, and
           HpCDF, OCDF, the isotopically-labelled OCDD is used.   Inherent
           in this approach is the assumption  that the response factors for each
           of the isomers of each chlorinated  class are equal.
7.2.4.  Calibration Standard Mixtures

       a.  Standard Mixture A:      0.4ng/yl 37CU-2,3,7,8-TCDD
                                    0.4ng/ul 37CU-2,3,7,8-TCDF
                                    l.Ong/yl 13C12-2,3,7,8-TCDD
                                    l.Ong/yl 13C12-OCDD

       b.  Standard Mixture B:   i) 10 ng/yl of each of:  2,3,7,8-TCDD
                                                          1,2,3,7,8-PeCDD
                           _                             1,2,3,4,7,8-HxCDD
                                                          1,2,3,4,6,7,8-HpCDD
                                       \^ *" T"

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                                                                       Section 7.0
                                                                       Revision 0
                                                                       August 15, 1984
                                                                       Page 5 of 13
                                                           OCDD
                                                           2,3,7,8-TCDF
                                                           2,3,4,7,8-PeCDF
                                                           1,2,3,6,7,8-HxCDF
                                                           1,2,3,4,6,7,8-HpCOF
                                                           OCDF

                                            ii) 2ng/ul  of each of same isomers as in 4.b.

                                           iii) 0.4ng/yl  of each of same isomers as in 4.
         c.  Standard Mixture C:  EPA TCDD Column Performance Mixture
•7.2.5   Equations for Calculating Response  Factors.  Concentration  of 2,3,7,8-TCDD

        In An Unknown Sample, and Recoveries  of Internal  Standards
      Equation 1:  Response Factor (RRF) for native 2, 3, 7, 8-TCDO using
                   l3Ci2-2,3,7,8-TCDD as an internal standard.

           RRFd=  (ASC.S/A1SCS)

           where:  AS  » SIM response for 2,3,7,8-TCDD ion- at m/z 320 + 322

                   A.  = SIM response for lsCi2-2,3,7,8-TCDD internal standard
                     .
                     15
                          ion at m/z 332
                    C.   3  Concentration of the internal standard  (pg./yL.)

                    C    =  Concentration of the 2,3,7,8-TCDD  (pg./uL.)
                                             C-5

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                                                                 Section 7.0
                                                                 Revision 0
                                                                 August 15, 1984
                                                                 Page 6 of 13

Equation 2:   Response Factor  (RRF)  for37C\ -2,3,7,8-TCOD,  the  co-injected
             external standard


     RRFf *  (AisCes^A  C'  ^

     where:   A.  = SIM response  for 13Ci2-2,3,7,8-TCDD internal
                   standard ion  at  m/z   332

             A   = SIM response  for co-injected  37CU-2,3,7,S-TCDD  external
                   standard at m/z  328  - 0.009 (SIM response for native
                   2,3,7,8-TCDD  at  m/z  322)

             C^  - Concentration of the internal  standard  (pg./ul.)
                                                           I       e
             Cgs = Concentration of the external  standard  (pg./pL.)
  Equation 3:  Calculation of concentration of native 2,3,7,8-TCDD using
              -l3Ci2-2,3,7,8-TCDD as internal standard

  Concentration,   pg./g. = (Ag) (Is)/(Ais)(RRFd)(W)

      where:  A    =  SIM response for 2,3,7,8-TCDD ion at m/z 320 + 322

              A-   =  SIM response for the 13Ci2-2,3,7,8-TCDD internal
                     standard ion at m/z 332

              I    =  Amount of  internal standard added to each sample  (pg.)

              W    =  Weight of  soil or waste  in grams

             RRFd   =  Relative response factor from Equation 1



  Equation 4:  Calculation of % recovery of  13CL2-2,3,7,8-TCDD internal  standard

  % Recovery = 100(A1s)(Es)/(Aes)(Ii)(RRFf)

              A.   =  SIM response for  13Ci2-2,3,7,8-TCDD  internal  standard
                15   ion at m/z 332

              A   =  SIM response for  37CU-2,3,7,8-TCDD  external  standard
                     ion at m/z 328  -  0.009      (SIM Response for native
                     2,3,7,8-TCDD at m/z 322)

               E   =  Amount of  37CU-2,3,7,8-TCDD  external  standard
                     co-injected with  sample extract (ng.)

               I.   »  Theoretical amount  of  13Ci2-2,3,7,8-TCDD  internal
                     standard  in  injection

             RRFf  *  Relative  response factor from Equation 2


                                 C-6

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                                                                        Section 7.0
                                                                        Revision 0
                                                                        August 15, 1984
                                                                        Page 7 of 13
            As noted above,  procedures  similar to  these  are  applied to  calculate
        analytical  results for all  of the  other PCDD/PCDF determined
        in this method.

7.2.f   Criteria Which GC-MS Data Must  Satisfy for Identification  of PCB  and
        PCDD/PCDF in Samples Analyzed and  Additional  Details of Calculation"
        Procedures.

        In order to  identify specific PCDD/PCDF and PCB  in samples analyzed,
        the GC-MS data obtained must satisfy the following criteria:

        a.  Mass spectral  responses must be  observed at  both the molecular and
            fragment ion masses corresponding to the ions  indicative of each
            chlorinated class of PCDD/PCDF and PCB  identified  (see Tables 1A
            & IB) and intensities of these ions must maximize essentially
            simultaneously (within  +^ 1  second). In addition, the  chromatographic
            retention times  observed for each PCDD/PCDF  e-signal  must be
            correct  relative to the appropriate stable-isotopically labelled
            internal standard and must  be  consistent with  the retention time
            windows  established for the chlorinated group  to which the  particular
            PCDD/PCDF is assigned.

        b.  The ratio of the intensity  of  the molecular  ion  (M)+ signal to that of
            the (M+2)+ signal must  be within + 10% of the  theoretically expected
            ratio (for example, 0.77 in the  case of TCDD;  therefore the
            acceptable range for this ratio  is 0.62 to 0.92).

        c.  The intensities  of the  ion  signals are considered to be detected
            if each  exceeds  the baseline noise by  a factor of at least  3:1.
            The ion  intensities are considred to be quantitatively measurable
            if each  ion intensity exceeds  the baseline noise by a  factor of at
            least 5:13 .

        d.  For reliable detection  and  quantitation of PCDF  it is  also  desirable
            to monitor signals arising  from  chlorinated  diphenyl ethers which,
            if present could give rise  to  fragment ions  yielding ion masses
            identical to those monitored as  indicators of  the PCDF.  Accordingly,
            in Table 1A, appropriate chlorinated diphenyl  ether masses  are
            specified which  must be monitored simultaneously with  the PCDF
            ion-masses.   Only when  the  rasponse for the  diphenyl ether  ion mass
            is not detected at the  same time as the PCDF ion mass  can the signal
            obtained for an apparent PCDF  be considered  unique.
        a'  In practice, the analyst can estimate the baseline noise by measuring
    the extension of the baseline immediately prior to each of the two mass
    chromatographic peaks attributed to a given PCDO/PCDF.  Spurious
    signals may arise either from electronic noise or from other organic compounds
    in the extract.  Since it may be desirable to evaluate the judgement of the
    analyst in this respect, copies of original mass chromatograms must be
    included in the report of analytical results.
                                        C-7

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                                                                    oeu I_-LUU  / . w
                                                                    Revision 0
                                                                    August 15,  1984
                                                                    Page 8 of  13

         e.  Measurement of the concentration of the congeners in a
   chlorinated class using the methods described herein is based on the
   assumption that all of the congeners are identical to the calibration
   standards employed  in terms of their respective chemical and separation
   properties and in terms of their respective gas chromatographic and mass
   spectrometric responses.  Using these'assumptions, for example, the
   13Ci2-2,3,7,8-TCDD  internal standard is utilized as the internal
   calibration standard for all of the 22 TCDD isomers or congeners.
   Furthermore, the concentration of the total TCDD present in a sample
   extract  is determined by calculating, on the basis of the standard
   procedure outlined  above, the concentration of each TCDD isomer peak
   (or peaks for multiple TCDD isomers, where these coelute) and these
   individual concentrations are subsequently summed to obtain the concen-
   tration  of  "total"  TCDD.  Similar  procedures are  applied, of course for
   all tne  other PCDD/PCDF.


         f.  Frequently, during the analysis of actual  sample extracts,
   extraneous compounds which are present in the  extract (those organic
   compounds not completely removed during the clean-up phase of the analysis)
   can cause changes  in the liquid and gas chromatographic elution characteristics
   of the PCDD/PCDF (typically retention times for the PCDO/PCDF are prolonged).
   Such extraneous organic compounds, when introduced into the mass spectro-
   meter source may also result in a decrease in the sensitivity of the  MS
   because of suppression of ionization, and other affects such as charge
   transfer phenomena.  The shifts in chromatographic retention times are
   usually general shifts, that is, the relative retention times for the
   PCDO/PCDF are not  changed, although the entire elution time scale is
   prolonged.  The analyst's intervention in the GC-MS operating sequence
   can correct for the lengthened GC retention times which are sometimes
   observed due to the presence of extraneous organics in the sample
   extract.  For example, using the program outlined in Table 1, if the
   retention time observed for 2,3,7,8-TCDD (which normally is 19.5 minutes)
   is lengthened by 30 seconds or more, appropriate adjustments  in the
   programming sequence outlined in Table 1 can be made, that is, each
   selected ion-monitoring program  is delayed by a length of time propor-
   tionate to the lengthening of the retention time for the 2,3,7,8-TCDO
   isomer.  In the case of ionization suppression, this phenomenon  is
 •  inherently counteracted by the internal standard approach.  However,
   if loss of sensitivity due to ionization suppression is severe,
   additional clean-up of the sample extract may be required  in  order  to
   achieve the desired detection limits.


7.2.7   Quality Assurance/Quality Control

           Quality assurance and quality control are ensured by the following
        provisions:
                                   C-8

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                                                                       Section 7.0
                                                                       Revision 0
                                                                       Aug'ist 15, 1984
                                                                       Page 9 of 13
     .a.  Each sample analyzed is spiked with stable isotopically labelled
        internal standards, prior to extraction and analysis.  Recoveries
        obtained for each of these standards should typically be in the
        range from 60-90%.  Since these compounds are used as true internal
        standards however, lower recoveries do not necessarily invalidate
        the analytical results for native PCOD/PCDF or PCB but may result
        in higher detection limits that are desired.


     b.  Processing and analysis of at least one method blank sample is
        accomplished for each set of samples (a set being defined as 20
        samples or less).  Analyses of field and travel blanks may also be
        desirable.
7,3 REAGENTS AND CHEMICALS

        The following reagents and chemicals are appropriate for use in the
    procedures described above.  In all cases, equivalent materials from
    other suppliers may also be used.

7.3.1   Sources of Chemicals, Procedures Employed for Preparing Reagents
        a.  Potassium Hydroxide, Anhydrous, Granular Sodium Sulfate and
            Sulfuric Acid (all Reagent Grade):  J.T. Baker Chemical Co. or
            Fisher Scientific Co.  The granular sodium sulfate is purified
            prior to use by placing a beaker containing the sodium sulfate
            in a 400°C  oven for four hours, then removing the beaker and
            allowing it to cool in a desiccator.  Store the purified sodium
            sulfate in a bottle equipped with a Teflon-lined screw cap.


        b.  Hexane, Methylene Chloride, Benzene, Methanol, Toluene, Isooctane:
            "Distilled in Glass" Burdick and Jackson.


        c.  Tridecane (Reagent Grade):  Sigma Chemical Co.


        d.  Basic Alumina (Activity Grade 1, 100 - 200 mesh):  ICN Pharmaceuticals,
            Immediately prior to use, the alumina is activated by heating
            for at least 16 hours at 600°C in a muffle furnace and then
            allowed to cool in a dessicator for at least 30 minutes prior
            to use.  Store preconditioned alumina in a desiccator.
                                        C-9

-------
                                                               Section 7.0
                                                               Revision 0
                                                               August 15, 1984
                                                               Page  10 of 13
e.  Silica (Bio-Sil  A,  100/200 mesh):   Bio-Rad.  The following  procedure
    is recommended for  conditioning  the Bio-Sil A  prior to use.   Place
    an appropriate quantity of Bio-Sil  A in  a  30 mm x 300 mm  long glass
    tube (the silica gel  is held  in  place by glass wool plugs)  which
    is placed in a tube furnace.   The  glass  tube is connected to  a pre-
    purified nitrogen cylinder, through a series of four traps  (stainless
    steel  tubes, 1.0 cm O.D.  x 10 cm long)5:   1) Trap No. 1 - Mixture
    comprised of Chromosorb W/AW  (60/80 mesh coated with 5% Apiezon L),
    Graphite (UCP-1-100),  Activated  Carbon (50 to  200 mesh) in  a  7:1.5:1.5
    ratio (Chromosorb W/AW, Apiezon  L  obtained from Supelco,  Inc., Graphite
    obtained from Ultracarbon Corporation, 100 mesh, 1-M-USP; Activated
    Carbon obtained from Fisher Scientific Co.; 2) Trap No. 2'- Molecular
    Sieve 13 X (60/80 mesh),  Supelco,  Inc.;  3) Trap No. 3 - Carbosieve S
    (80/100 mesh), obtained from  Supelco, Inc.; 4) The Bio-Sil  A  is heated
    in the tube for 30  minutes at 180°C while  purging with nitrogen (flow
    rate 50-100 ml/minute), and the  tube is  then removed from the furnace
    and allowed to cool to room temperature.  Methanol (175 ml) is then
    passed through the  tube,  followed  by 175 ml methylene chloride. The
    tube containing the silica  is then returned to the furnace, the nitrogen
    purge is again established  (50-100 ml flow) and the tube  is heated at
    50°C for 10 minutes, then the temperature  is gradually increased to
    180°C over 25 minutes and then maintained  at 180°C for 90 minutes. Heating
    is then discontinued but the  nitrogen purge is continued  until the tube
    cools to  room temperature.   Finally, the silica  is  transferred to  a
    clean, dry, glass  bottle and capped with a Teflon-lined  screw cap
    for storage.

 f.  Silica Gel  Impregnated With Sulfuric Acid:  Concentrated  sulfuric
    acid  (44  g) is  combined with 100 g Bio-Sil A  (conditioned as
    described  above) in a  screw capped bottle and  agitated  to mix
    thoroughly.  Aggregates are dispersed with a  stirring  rod until a
    uniform mixture  is obtained.   The HLSO.-silica gel  is  stored  in a
    screw-capped  bottle (Teflon-lined cap).

 g.  Silica Gel  Impregnated with Sodium Hydroxide:   IN  Sodium hydroxide
    (39 g)  is  combined with 100 g Bio-Sil A (conditioned as  described
    above)  in  a screw  capped bottle and  agitated  to mix throughly.
    Aggregates  are  dispersed with a stirring  rod  until  a uniform  mixture
    is obtained.  The  NaOH-silica gel  is  stored in a screw-capped  bottle
    (Teflon-lined cap).

 h.  Carbon/Celite:   Comb:ne Amoco PX-21  carbon (10.7 g)  with Celite 545
    (Fisher  Scientific Co.)  (124 g) in a  250 mL glass bottle fitted with
    a Teflon-lined  cap.  Agitate the mixture  to combine thoroughly.
    Store in  the  screw-capped bottle.

 i.  Nitrogen  and  Hydrogen  (Ultra High  Purity):  Matheson Scientific

 j.  Fused Silica  Capillary Gas Chromatographic Column:   60 M fused
    silica  (0.25  mm I.D.)  capillary column  coated with DB-5  (0.25 y
    film  thickness), J &  S Scientific,  Inc.,  Crystal  Lake, IL.
                                 C-10

-------
                                                               Section 7.0
                                                               Revision 0
                                                               August IS, 1984
                                                               Pr.ge 11 of 13
k.   Chlorinated Dibenzo-p-dioxins and Dibenzofurans  Used As  Calibration
    Standards:   37CU-2,3,7,8-TCDD (SSY-6-123)  and 37CU-2,3,7,8-TCDF
    (DF-14) were obtained from KOR,  Inc.   13C12-2,3,7,8-TCDO (AWN
    1203-65) and 13Ci2-OCDD (SSY-8-78) were  obtained from  Cambridge
    Isotope Laboratores.   The 22 TCDD standards and  all other CDDs/
    CDFs employed in the  study were synthesized in the  Brehm Laboratory.
    A column performance  check standard was  obtained from  USEPA  (Check
    Standard Mixture #2)  which contained  1,4,7,8-TCOD;  2,3,7,8-TCDD;
    1,2,3,4-TCOD; 1,2,3,7/1,2,3,8-TCDD; 1,2,7,8-TCDO and 1,2,6,7-TCDO.
                                 C-ll

-------
                                                                                  TABLE  1
                                                                    Sequence  of  Operations  in GC-HS-DS_ Quant i tat ion  of
o
i—•
ro
             Elapsed
             Time
             (nun)      Event
                00
                00
                00
                00
                00
             14.00
             22.00

             22.60
23.00
26.00
            32.00

            32.50
           Injection, splitless
           Turn on split valve
           Gegin temp, program to 220°C
           Open column flow to mass spectrometer
           Column temperature hold
           Start Tetra Program; sweep *
           350 ppm; time/mass =  0.08 sec.
Stop Tetra Program

Start Penta Program; sweep -
 350 ppm; time/mass • 0.12 sec.

Begin temp, program to 235"
Column temperature hold
          Stop Penta  Program

          Start Hcxa  Program;  sweep  *
           350 ppm;  time/mass  •  0.20 sec.
LODs/CDfs

GC Column
Temperature*
(°C)
190
190
190
215
220









220



220
235


235








in Extracts of Environmental Samples
Ions Monitored
Temperature by Mass
Program Rate Spectrometer Identity of
(°C/min) (m/z) Fragment Ion


5
5

240.936
258.930
303.902
305.699
315.942
319.697
321.894
327.805
331.937
'H-COC11*
M-COC1J+
H]*
M»2]+
M]*
MJ*
H»2]*
M]»
M]'
373.840 [MJ*

274.899
290.894
337.863
5 339.860
353.858
355.855
407.801
310.857
326.852
373.021
375.02)
385.861
389.816
391.813
411.856
443.759
M-COCI1*
H-COC1J*
M]*
M'2]*
•H]*
Mf2]f
[M]*
,M-cocn*
M-COC1J*
M]*
M»Z]*
M]*
Ml*
Mt2]*
M]*
H]*



Compounds
Monitored





TCDF
TCOO
TCDF
TCOF
"CU-TCDF
TCOO
TCCH
"CK-TCDO
"CU-TCOO
HxDPEa-

PeCDF
I'eCOO
I'cCOF
PeCDF
PeCDO
PeCOD
HpDPE8-
llxCDF
HxCOD
HxCOF
llxCOF
1>C,,-IUCOF
HxCOO
llxCDD
"Cu-HxCOO
ODP£»-
                                                                                                                                          Ihcoret ical
                                                                                                                                          Pa 110
                                                                                                                                                          0.77
                                                                                                                                                          0.77
1.54

1.54
                                                                                                                                                          1.23


                                                                                                                                                          1.23
                                                                                                                                                          V > fO on
                                                                                                                                                          w  c  m IB
                                                                                                                                                          OQ  TO  < O
                                                                                                                                                          (D  C  H- rt
                                                                                                                                                             W  en H-
                                                                                                                                                          (— rt  p. o
                                                                                                                                                          K)    O O
                                                                                                                                                             t- 3
                                                                                                                                                          O  tn   -v4
                                                                                                                                                             00

-------
     I
                                                                        TABLE  1    (continued)
o
CO


tlapsed
Time
(win) Event
33.00
36.00
42.50
43.00






53.00
53.50

54.00
58. bO





6s. 00

65.00
71.00
75.00

*-|UHI
Begin temp, program to 250°C
Column temperature hold
Stop Ilex a Program
Start Hepta Program; sweep *
350 ppm; time/mass * 0.30 sec.





Stop Hepta Program
Start Octa Program; sweep -
350 ppm; time/mass = 0.30 sec.

Begin temp, program to 270°
Column temperature hold





Stop Octa Program
•
Ucijin temp. |iro $0 C/i
P> c it n>
OQ OP  r»
0) W H-
W O 3
H- O
t-h • O •
           di-l J< hlorod i|ili< iiyl  cllici i.
       •Ihc
•livi-n liciv JIG ,i|i|ilu.ilili; for « 60-nx'ter fused silica capillary  GC  column co.ited with DD-5.
                                                                                                                                                                   U)
                                                                                                                                                                      oo

-------
      APPENDIX D
  INCINERATOR EXHAUST
STUDY SAMPLING RESULTS

-------
                                    APPENDIX D
  I.   ORGANIZATION  OF  DATA

      The  analytical  results  of the  Dow  Chemical  Company Midland Plant Building
  703  incinerator emissions study encompass a wide variety of influent and effluent
  streams,  analyzed   for  the   following   generalized  categories  of  compounds:

          - Volatile   compounds,  or  those with  boiling  points  generally below
            100°C,
          - Semi-volatile compounds,  with boiling points greater than 100°C,  and
          - PCDD/PCDF.   These  were analyzed  separately  from other  semi-volatile
            compounds,  as described below.

  In addition,  incinerator  exhaust  gases  were  sampled  for  vinylidene  chloride
  using  a  direct capture  method  with immediate  instrumental   analysis,  as  the
  analytical methods  for other  volatile compounds were not  amenable  to vinylidene
  chloride. Further  detail concerning these analyses are contained in Appendix A,
  Section  III.C. of this report.

      In general,  the  data  are presented  below individually  for  each  type  of
  stream,  and   in  terms  of  volatile  compounds,  semi-volatile  compounds,   and
  PCDD/PCDF, in that  order.   Discussion  of quality assurance aspects relating to
  each category of  stream  and  compound  group  is  presented   to  highlight   the
  information  contained in the  data tables.
 II.   ANALYTICAL  LABORATORIES

      As  indicated  above,  PCDD/PCDF analyses  were  performed  by  an  analytical
  laboratory  other  than  that  involved with volatile and semi-volatile  compounds,
  owing to  the comparatively  limited number  of capable laboratories.  The  Brehm
  Laboratory  of Wright State University, Fairborn, Ohio, completed these analyses,
  while the EAL  Corporation of Richmond, California, was  selected  to analyze the
  samples for volatile and  semi-volatile compounds.


III.   ANALYTICAL  RESULTS

      A.   Acceptability

      In  the  sections to follow,  data are generally  presented in tables which are
  based on  concentration, with accompanying tables  showing  raw data  as presented
  by  the  analytical  laboratories.   Either of  these tables  may  include  quality
  assurance data  relating to  accuracy  (% recovery  of  known surrogate compounds
  introduced  to  the analyzed matrix  by  the  laboratory).
                                       D-l

-------
    1.   PCDD/PCDF

    For PCOD/PCDF, the ranges of acceptability defined in the Quality  Assurance
Project Plan7 for  the study  were  70  to 130%  recoveery for two  isotopically
labeled analogs  (13Cio 2378-TCDD  and 37C14  2378-TCDF)  and  50 to 150%  for  two
others  (37C1^ 2378-TCTjD and 1 C12 OCDD).  However, in comparing these acceptance
criteria to those  commonly  usecf in other  current  work  involving analyses  for
PCDO/PCDF, they  were  found to be overly stringent.  In judging the acceptability
of PCDD/PCDF data, therefore, a range of  recoveries of 50 to  150% was considered
acceptable.

    The internal standard  ^^12  2378-TCDD is a primary importance as the accuracy
determinant for  tetra- througn hexa-CDD;  those homologue groups  are of greatest
priority in assessing potential  risks to  health.  Recoveries  of the second 2378-
TCDD surrogate,  37C14 2378-TCDD, serves to confirm the recoveries of   Ci^ 2378-
TCDO.  In  summary,  if both  2378-TCDD  surrogates   are  recovered  witnin  the
acceptable range of  50 to 150%,,  the analytical  data are defined as acceptable
for the homologues of greatest concern.

    Recoveries of the  internal  standard   Ci£  OCDD  were frequently poorer than
for the  other standards.   However, this internal standard  measures analytical
accuracy for hepta- and octa-CDD and CDF homologues, which are of comparatively
low concern  in  terms  of  risk  assessment.    Recoveries  of 37C14  2378-TCDF  are
used to judge the accuracy of tetra- through hexa-CDF data, which, with respect
to risk, are of  lower priority than the corresponding PCDDs.

    In  the  PCDD/PCDF data  in  this  Appendix,  completeness  is  calculated  and
presented individually by  standard.   According to  the above  discussion,  the
value of  the PCDD/PCDF data should  be  judged  primarily  by  the  accuracy  of
recovery of the two labeled 2378-TCDD compounds.  Completeness in this area was
generally near  or  above 80%; this performance  confirms  the  overall  validity of
the analytical  data  in calculating general mass balances  and risk assessment.

    2.   Other Compounds

    The Quality Assurance  Project  Plan references ranges  of acceptable surrogate
recovery of 20  to  180% for semi-volatile compounds,  and 80 to 125% for volatile
compounds.  For semi-volatile compounds, six surrogates were used — three acid
and three  base-neutral, while for volatile  compounds three  or  four surrogates
were used,  depending  upon  the type of sample.   There is no currently accepted
guidance relating  specific   surrogates  to   particular analytes.   However,  the
evaluate the  acceptability  of  semi-volatile compound analyses,  if the recovery
of all  three  acid  surrogates  was  acceptable, then  the analysis  of any detected
acid compound was considered valid;  the same was done for base-neutral compounds.
On the  semi-volatile  compound  data tables  to follow  in  this  section  and in
Appendix D of this report, data which were treated in  this way are appropriately
labeled.   To  assess  overall  completeness,  however,  data were defined as valid
only if  all of  the semi-volatile surrogate compounds were analyzed within range.
                                      0-2

-------
    For volatile compounds, as there was no available  summary  of the ranges  of
compounds to  which  particular  surrogates  are  associated, data  points  were
considered acceptable only  if  the recoveries  of  all  three or  four  surrogates
were within the target range of  80 to 125%.  Detailed inspection of the volatile
compound data tables  which  include surrogate  recovery  information  reveal  many
cases in which the recoveries of  most  surrogates  were  very close to the target
range.  Therefore, the volatile compound data are probably more reliable than a
strict interpretation of the accuracy data would indicate.

    B.  Precombustion Air

    1.  Volatile Compounds

    These data appear in  Table 0-1 in terms  of concentration.  The raw analytical
data used to derive them are presented in Table 0-2.

    The method blank, which was comprised of 1.5 grams  of Tenax GC sorbent sent
directly from  GCA to the  analytical  laboratory,  EAL  Corporation,  showed  the
presence of measurable  amounts  of  chloroform,  perchloroethylene,  methylcyclo-
hexane, and 1,3-dichlorobenzene.   The  last two compounds  were  not  detected  in
any exposed sample.   However,  chloroform  and  perchloroethylene were  found  at
higher concentrations than in any  exposed sample,  indicating that both compounds
were present as laboratory contamination.

    Two of  the  eight  sample  sets were  acceptable in  terms  of  accuracy  (%
surrogate recovery, see Table 0-2).  Of the target  volatile compounds shown  in
Table D-l, three,

        - carbon tetrachloride (days 1 and 3)
        - monochlorobenzene (days 1 and 3), and
        - trichloroethylene (day 1 only),

were detected  in  the  concentrations   indicated.   However,  target  precision
criteria of £50%  RPD (between day  1  sample and field duplicate  results)  were
met only  for  monochlorobenzene.   Accuracy  (surrogate  recovery)  data  were
unacceptable for samples taken  on  the  second  sampling  day.  Other compounds  of
possible interest detected only on the first sampling day included ethylbenzene
and xylene (total xylenes); however, precision criteria were not met for either
compound.  Benzene and  toluene were noted on  the  third  sampling day,  but  as
there was  no  duplicate   sample  taken  on  this  day, this  result is  considered
tentative.

    Detection limit  objectives  of 1 ppb  in air  were  achieved for  all  of  the
above-listed detected compounds as shown in Table D-l.   Actual  detection limits
were in the range of 0.3 to 0.8 ppb for the compounds detected above.

    These samples  were  obtained with  a  14-day target  limit  for  holding  time
prior to  analysis.   Samples were  actually held for periods  of 19  to  27  days
before analysis.  Thus,  the results presented are considered to be conservative
it is possible  that  some compounds may have been  lost  or altered due to decay
or reaction in the time between sampling and analysis.
                                     D-3

-------
                                                      TABLE D-l
                                       VOLATILE COMPOUNDS - PRE-COMBUSTION AIR
                                    DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                  8/28, 8/30, 9/5/84
                                           COMPOUND CONCENTRATION (ug/m3)1
                             COMPOUNDS DETECTED
                              ACCURACY (% SURROGATE RECOVERY)
                              (SAMPLE TUBE/FIELD BLANK TUBE)
                                                                 APPROXIMATE
                                                               DETECTION LIMIT
                                                                IN AIR (ug/m3)



















SAMPLING DATE

8/28/84

8/28/84 (Field
Duplicate)
8/30/84

9/5/84


Precision (RPD)
8/28/84
Samples



































OJ
XJ
•1—
t_
o

x:
o
IO
l_
-»->
O>
4->

c
o
-Q
t_
(O
o

15.35

61.00

222.50

26.69


120






o>
c

c
0)
I—
>>
.c
+j
0)
0
c_
o
r—
-C
o
••—
t_
1—

0.64

3.12

16.98

—


132



CM
O)
c
0)
N
c
0)
J3
O
(_
0

JC
o
• r—
T>

«^-

i— 1

72.43

60.20

81.69

45.35


18











>
-C
4 >
LU

10.63

29.26

—

—


93











co
Q

1

01
c
m
3
r—
o


94/94

98/94

O*/ 106

86/100








O)
c
O)
N
C
01
j^
o
t_
o
3
p.
<*-
o
E
O
i_
CO

154/108

110/108

0*/86

92/116






i

Ol
c
fO
.C
4->
01
o
t_
o
r— «d"
JC Q
O
•r—
"O
1
C\J

r— 1

58/86

54/86

0*/60

87/78








0
i— •
Q

1

O)
c
O)
N
C
O)
.a

>»
_c

LU

186*/108

106/108

oviio

112/104















CO
LU
_l
OQ
<
1—
Q-
UJ
CJ
C__3
<

N/Y

N/Y

N/N

Y/N



























0.40 - 0.80

0.37 - 0.74

0.37 - 0.74

0.32 - 0.64






a
i
                   Notes:
1
2
3
Sample concentration less  field blank concentration.
Compound tentatively identified.
All  surrogate recoveries within target range (80-125%)
established in Quality  Assurance  Project Plan.
Recovery outside of acceptable range of 80-125%

-------
                                                                               TABLE  0-2
                                        QUANTITATED AND TENTATIVELY-IDENTIFIED VOLATILE  COMPOUNDS DETECTED IN PKECOMBOSTION
                                                             DOW  CHEMICAL  COMPANY  BOILD1NG 703 INCINERATOR
O
oi
          8/28/84  Sample
          Field Duplicate
              Field Blank
          8/30/84  Sample
              FTeld Blank
          9/5/84   Sample

              Field Blank

   Tenax GC« Method Blank
                                               QUANTITATED COMPOUNDS
                                                            TENTATIVELY-IDENTIFIED  COMPOUNDS
    ACCURACY (% SURROGATE
              RECOVERY)

C/1
h-
2
r
















»
•
9















E
O
Chloro

88
194



b4







645

tetrachloride
o

301
8/2
109


3373
347


84i

424



sroethylene
.c
0
L
t—

22
b3
14


290
b9




41



jroethylene
.c
o
t.
at
O-

m
182
'44



36


138

b2

403

orobenzene
Monoch

l&l
2b/







4b6





auazu;
.0
!>
-4->
LU

186
419
b3



22




29b



t/)
Ol
c
Oi
^
(O
4->
o
I—

786
1302
80


84bb
112




343



trichloro-
;thane
i


8/b







1^06






c

c
o
*o
4->
3
O
1
CVJ

















Benzen

90

57



1182


756





:hl orobenzene
•o
i
«*

1137
984
231


1192
81


1420

708



3PO-
sroraethane
i — 3
-C r—
0 <4-
L I_
1— *->

6481














:yclopentane
>>
£;
+-»
^

bb90














thylcyclo-
sxane

X -t-
,
JC
+-»
£














124

:hl orobenzene
T3
ro
f—«














4084

^1 pentane
3-methj










1390

7000



:hl orobenzene
T3
1
C\J


6b/







97





^1-1-pentane
jz
4-»
0)
e
i
C^J












700



>
.c
O>
03
H
C
01
CO


470













05
D
1
C
,
.c
4->
UJ

186
106
108


0
110


112

104

62

UJ
_l
CO
ACCEPT

No
No
Yes


No
No


Yes

No

No

Note:
                                             surrogate recoveries within target range (80-125%)
                                         established in Quality Assurance Project Plan.
COMPLETENESS - 25% (2/8)

-------
    2.  Semi-Volatile Compounds

    The results of these analyses are reported  in  Tables  D-3 and  0-4.

    The method blank, composed of  75 grams  of XAD-2 sorbent, was  analyzed  and
found free of  contamination  (see  Table 0-4).  However, this sample was  extracted
and diluted prior to analysis,  such that surrogate compounds added to the  matrix
were poorly detected.    Since  the  field  blank   samples   showed  the  presence
only of ubiquitous  phthalate compounds  commonly  considered laboratory-related,
and these  analyses  were  satisfactory  with  respect  to  surrogate  recoveries
(accuracy), it was determined that the sorbents employed in sampling  were  free
of background  quantities of  several  compounds  of interest detected in  sampled
air.

    As the data  presented  in Tables  D-3 and 0-4  indicate,  1,2-dichlorobenzene
and 1,2,4-trichlorobenzene  were  found on all three  sampling days;  field  dupli-
cate sampling  on  the second day indicated precision was within the objectives of
the study for  these  two  compounds.  Another dichlorobenzene, the 1,4 isomer, was
also detected  on  all  three  days, but precision could  not  be judged  as  it  was
not found  in  the field  duplicate.   Low concentrations of  1,3-dichlorobenzene
were detected  on the first  and  third  sampling days,  but none on the second  day,
when a field  duplicate was  obtained.

    Other target compounds  were detected, as follows:

        - 1-1  biphenyl  (day 1),
        - biphenyl (day 2,  but  not in field  duplicate), and
        - monochlorobenzene (days 1 and  2).

The latter is a  volatile compound  for which the  previously described volatile
air sampler was  considered  more  appropriate.  The precision of  the  analytical
method for volatile  compounds  appeared  better than that for semi-volatiles in
the case of monochlorobenzene.   In any event, the  concentrations  of monochloro-
benzene measured by both methods  were comparable  within an  order of magnitude.

    Naphthalene was  detected  on  all  three  sampling  days,  but  satisfactory
precision was  not  achieved,  as measured in  the  field  duplicate  sample  on  the
second day.   Several substituted  benzenes were seen on all three  days,  with  a
host of isomers in comparatively high concentrations observed on  the  first  day.

    The target detection  limit  criterion  of  5  ppb in  air  for  semi-volatile
compounds was  achieved;  actual  detection  limits, for 1,2,4-trichlorobenzene, for
example, were  on the order of 0.05 ppb.   Accuracy criteria (20 to  180% surrogate
recovery) were met  for  seven of  the  eight samples, including field  and  method
blanks and duplicates (see Tables D-3 and D-5).

    A summary assessment of  these  data  indicates  that  while a wide  variety of
semi-volatile  compounds were detected, the  presence of  only  two, 1,2-dichloro-
benzene, and  1,2,4-trichlorobenzene, could  be  established  and  supported  by
acceptable measures  of  accuracy.  The  presence   of  other  compounds  should be
considered a  tentative finding.
                                      D-6

-------
                                                                             TABLE  D-3
                                                           SEMI-VOLATILE  COMPOUNDS  -  PRE-COMBUSTION AIR
                                                           DOW  CHEMICAL COMPANY  BUILDING 703  INCINERATOR
                                                                       8/28.  8/30, 9/5/84
                                                                  COMPOUND  CONCENTRATION (ug/m3)1
SAMPLING DATE

8/28/84

8/30/84

8/30/84
Field Duplicat

9/5/84


Precision (RPD)
8/30/84
Samples

ACCURACY (% SURROGATE RECOVERY)
TARGETED COMPOUNDS OTHER COMPOUNDS DETECTED (SAMPLE TUBE/FIELD BLANK TUBE)
•obenzene
Monochlo

3.UB

O.b3

1.84
e

--


111



orobenzene
a
•o
i
CM
•— t

1.42

0.84

1.03


J./3


21



orobenzene
u
i
ro

O.lb

—

--


O.O/


—



orobenzene
JC
0
•o

1.41

0./4

--


3.24


—



chloro-
zene
i- t>
t-> -O
CM

l.bH

0.86

1.19


2.59


32



Naphthalene

0.44

U.UU

0.64


1.23


l&b



I,l'-biphenyl2

2.22

—

--


—






Biphenyl

—

0.90

--


—






c
01
ro
JC
JC
CL
ro
C
1
CM





0.25


1.65






Ethyl benzene?

2.19

0.50











1-ethyl -
2-methyl benzene2

2.41













Ol
<-> c
Ol Ol
E N
V Ol
-H J3

1.92













CM
Ol
C
Ol
c
Ol
Ol
•5
1
CM

2.78













Ol
c
Ol
1
01
1

1.26













CM
O>
C
0*
N
C
0)
.c
*

0.96













Diphenyl ether

4.74













Base-Neutrals
Nitrobenzene - D5

94/63

67/85

96/85


104/98






2-fluorobiphenyl

95/76

59/74

65/74


61/58


Terphenyl - D14

142/148

112/116

122/116


58/98


Acids
Ut
Q
1
O
C

-------
                                                                                                                  TABLE D-4
                                                                        QIMNTITATED ABD T£NTATIVEL»-IDENTIFIEO SEHI-VOLAI1LE COMPOUNDS DETECTED  IN PRECOMBUST10N AIR
                                                                                                DOM  CHEMICAL COMPANV BUILDING  703  INCINERATOR
l,2-d1chlorobenzene
~5BBJ
J-3fzd
I I"" '
I l,3-d1chlorobenzene
[m
\m\
Wi

jjjj-
H
limn I
1, 2, 4-tr1chl orobenzene
KS4T
#&
win
rrrr
Naphthalene
THTO
7741
4711
nrr
JDIecthylpnthalate 1
STJ


1 Anthracene I
TW

raar
Dt -n-butyl -
pnthalate
T75T
TW
WT
TWT
W7T
nrr
0*-n-octyl-
phthalate
7747
BWTT
mr
WiT
nmr
Twnr
Phenanthrene 1

m
TW
7S7
rr
Bis (2-etnylheiyl)-
1 phthal ate |

1T77
-im
TT7T
WSK
2««etnyl naphthal ene


STW
T-Tffll
TJ
5
o
il
iS
TI52T

LE|
Monochl orobenzene
T7777
TITO
itm

1
«->
uJ
904T
4£

l,3,S,7-cycloocta-
tet raene
T5555


l-(Mthylethyl)'
benzene
75W
7WJ1

l-ethyl-2-nethyl-
benzene
999S


3
£
T47W

TJ777
Octanethyl -
cyclotetrasilonane
H91B7


l.2-d1*thylD«iz*ne
TT52T


l,3-d4ethylbenzene
5207


1 ,2-d1ethenylbenzene
3978


1,1-blphenyl
9209


01 pnenyl ether
15647
~JOTT
now
Bis(2-aiethylpropyl)
pnthalate
23914

Ui
i
*

im
U- , . . 1
|

wre"

J,4-d1«ethyl-
2,3-hcptad1ene-
5-yne

TJTJT
TDBH
I 01 ethyl benzene

929

|

SOT

2-ethy!-l,4-d1nethyl-
benzene

~~B9T
TJBS7
!
Ik
.

n

1
1



i

7197

I*
|
*>.
I

2T

4t

[tt

ButylBethyl-
propylphthalate

TTO

*J
4-t

mm

|2-ethyl-l,l'-
1 blphenvl

^B7

2-butoiy-
dthanol


157T
2,6-d1iMthyl-
octane


2978"
Tndecane


T37SO"
Pentadecane


^500"
  8/28/64
         Sample
    Field (lank
  8/30/84
         Sample
  field Duplicate
    Field Blink
  9/5/84
         Sample
    Field (lank
   Netnod Blank
00
                     NOTE - Results stated In m/>».

-------
                                TABLE D-5

    QUALITY ASSURANCE DATA - PRECOMBUSTION AIR SEMI-VOLATILE COMPOUNDS

              DOW  CHEMICAL COMPANY BUILDING 703 INCINERATOR
                               ACCURACY (% SURROGATE RECOVERY)



















8/28/84
SAMPLE
FIELD BLANK


8/30/84
SAMPLE
FIELD DUPLICATE
FIELD BLANK

9/5/84
SAMPLE
FIELD BLANK

METHOD BLANK

Base-Neutrals



Lf)
0
1
O)
c


z

94
63



67
96
85


104
98

12




>>
c
O)
.c
Q.
•r~
.0
O
t_
o
3
^«
M-

CM

95
76



59
65
74


61
58

0






«s-
i— i
Q
|
f_>
>,

O)
.G
CL
t_
Ol


142
148



112
122
116


58
98

6

Acids







Lft
Q

1

f—
0
C
OJ
JZ
Q.

87
84



36
49
33


88
79

100





^—
o
c
OJ
-C
Q.
O
c_
o
3
r_
<^
1
CM

101
80



31
45
34


90
85

28

o
c
CJ
CL
O
1=
O
t_
ja
•r—
t_
4->
|
^O
A
*3-
•V
C\J

75
41



53
59
55


80
48

0












































f— i
'jj
_i
22

-------
    3.   PCDD/PCDF

    a.   All  Homologues

    In  Table 0-7 analytical data  are  presented  in terms of weight  per  sample;
these data are expressed in units  of  concentration  in  Table D-6.   The data  are
self-explanatory; note that  for the  two  homologues detected  in  both  samples
(actual  and  field duplicate) on August 28, the precision criterion  (50% RPD  or
less) was met for  both.   However,  accuracy criteria were  met  for  only one  of
the four  surrogates.   Field blank samples  were  free of detectable PCDD/PCDF,
with accuracies  as shown.

    In  summary,  while  OCDD and TCDF  were  detected  on  the first  sampling day,
the accuracy  of  quantification is  questionable  as   the  recovery  of  surrogate
compounds was unacceptable.  These and other homologues  were found on the  other
sampling days, but  accuracy  was unacceptable on  the second  sampling day,  and
precision was not  determined  on  the  third  sampling day.   Accuracy  criteria,
however, were met on the third sampling day.

    b.   TCDD Isomers

    These data are  shown in  raw form  in  Table 0-9,  and  expressed  as concentra-
tions in Table 0-8. On the  first sample day, TCDD was found  only as the 1368  and
1379 isomers, while on the  second day  a wider diversity  of isomers  was detected,
including the only  finding of the 2378  isomer in any  sample  obtained  in this
study.   The   third   sample  day  also  showed a  comparatively  diverse range  of
isomers.

    As  for  all  of  the  TCDO isomer analyses  conducted  during this  study,  no
accuracy data are  stated,  as  no  surrogate isomers  were added  to the  analyzed
matrices.  The precision and accuracy  limitations stated above  for the analyses
of all  homologues should also be applied to these data.

    C.   Liquid Waste Feeds

    1.   Concentrated Liquid Wastes

    a.   Volatile Compounds

    These data are  shown in Table D-10.   Substantial analytical  problems  were
encountered with  these  samples;  some of  these   are apparent  in   scanning  the
surrogate recovery  data  shown  in  these tables.   Other problems with individual
data are  described  in the  notes  included  in the tables.   Generally,  however,
internal  quality  assurance review  of  the volatile pollutant data  revealed that
they should be used with caution,  as  they  showed  a  high  level  of  contamination
of column degradation material.   As  a  result  of  delays  in   preparing  sample
extracts, volatile  organic analyses  were   not  performed  until   at  least  four
months  after  the  samples  were  first  obtained.    Surrogate recoveries  for four
data points  (see above-referenced table) were out of acceptable ranges owing to
dilutions necessary to respond  to peak saturation problems.  Calibration checks
                                      D-10

-------
                                                                                    TABLE D-6
                                                               INCINERATOR PRECOMBUSTION AIR - PCDD/PCOF ANALYSES
                                                                  DOW CHEMICAL COMPANY BUILDING 703  INCINERATOR
                                                                               8/28, 8/30, 9/5/84

SAMPLE IDENTIFICATION
8/28/84
MODIFIED METHOD 5 TRAIN
FIELD DUPLICATE
FIELD BLANK
8/30/84
MODIFIED METHOD 5 TRAIN
FIELD BLANK
9/5/84
MODIFIED METHOD 5 TRAIN
FIELD BLANK
2378-
TCDD
NO
(7.86)
NO
(11.32)

5.16

ND
(1.48)
ND
(0.55)
Total
TCDD
58.21
ND
(53.4)

17.99

38.90
ND
(0.35)
Total
PeCDD
ND
(11.01)
ND
(131)

ND
(2.30)

ND
(0.94)
ND
(0.40)
Total
HxCOD
ND
(6.62)
ND.
(125)
(Sample
10.39

ND
(1.46)
ND
(0.85)
Total
HpCDD
ND
(12.02)
ND
(5.43)
analyst:
235.10

98.14
ND
(2.15)
OCDD
216.60
335.14
not ret
802.08

306.51
NO
(4.83)
2378-
TCDF
ND
(7.89)
NO
(29.2)
urned fn
12.93

ND
(1.74)
ND
(0.39)
Total
TCDF
391.22
628.02
m labor.
12.93

206.60
ND
(0.29)

Total
PeCOF
ND
(6.07)
ND
(6.01)
tory.)
12.50

ND
(1.45)
ND
(0.37)
Total
HxCDF
ND
(16.2)
NO
(4.20)

14.23

ND
(1.42)
NO
(0.33)
HpCDF
ND
(27.50)
ND
(8.45)

108.48

37.43
ND
(3.08)
Accuracy

Total
OCOF
21.18
ND
(30.2)

113.67

30.95
ND
(4.21)
COMPLETENESS BY SURROGATE
1
00 O
r*. o
ro o
CM »—
f-4
o
no
84
2

99
100
89
77
71%
(^Surrogate Recovery
i
00 Q
r-~ o
m o
(M h-
*r
o
i^-
CO
85
125

92
90
92
97
86%
0
o
8
CM
O
CO
i—*
17
22

35
27
61
59
29%
i
CO U_
r~ o
M O
Cvj f-
«3-
CJ
r~-
n
100
100

100
48
100
76
71%
a
i
             Notes:     Data expressed In pg/m^.
                     1  All  surrogate recoveries  within target  ranges  of  50-150%.

-------
                                                                               TABLE D-7
                                                          INCINERATOR PRECOMBUSTION AIR - PCDD/PCDF ANALYSES
                                                            DOW CHEMICAL COMPANY BUILDING  703  INCINERATOR
                                                                         8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
HI-Vol Filter + XAD-2 sorbent
Field Blank
Field Duplicate
8/30/84
Hi-Vol Filter + XAD-2 sorbent
Field Blank
9/5/84
Hi-Vol Filter + XAD-2 sorbent
Field Blank
	 :
2378-
TCDD
ND(2.47)

ND(3.75)
1.59
ND(0.237)
ND(O.SOl)
ND(0.187)
	
TOTAL
TCDD
18.3

ND(17.7)
5.54
ND(0.129)
13.2
ND(0.120)
TOTAL
PeCDD
N0(3.46)

ND(43.4)
ND(0.709)
NO(0.66B)
ND(0.318)
ND(0.135)
TOTAL
HxCOD
ND(2.08)
(Sample .
ND(41.5)
3.20
ND(1.13)
N0(0.496)
ND(0.287)
TOTAL
HpCDO
ND(3.78)
nalysis m
N0(1.80)
72.4
ND(1.39)
33.3
N0(0.725)
OCDD
68.1
t returne
111
247
ND(3.65)
104
N0(1.63)
2378-
TCDF
N0(2.48)
d from labc
ND(9.67)
3.98
ND(0.342)
ND(0.590)
ND(0.132)
TOTAL
TCDF
123
iratory.)
208
3.98
ND(0.371)
70.1
ND(0.0973)
TOTAL
PeCOF
ND(1.60)

ND(1.99)
3.85
ND(0.603)
ND(0.492)
ND{0.124)
TOTAL
HxCDF
ND(4.27)

ND(1.39)
4.38
ND(l.Ol)
ND(0.483)
ND(O.llO)
TOTAL
HpCDF
ND(7.25)

ND(2.80)
33.4
ND(1.60)
12.7
ND(1.04)
OCDF
6.66

ND(IO.O)
35.0
ND(4.29)
10.5
ND(1.42)
a
i—'
ro
               NOTE:  Data expressed  in ng/g.

-------
                                                                              TABLE 0-8
                                                       INCINERATOR PRECOMBUSTION AIR - TCOD ISOMER ANALYSES
                                                          OOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                         8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
MODIFIED METHOD 5 TRAIN
FIELD DUPLICATE
8/30/84
MODIFIED METHOD 5 TRAIN
9/5/84
MODIFIED METHOD 5 TRAIN

1368
44.21


23.96

1379
13.99

4.32
7.57

1369





1247
1248
1378
1469


1.62
2.45

1246
1249





1268
1278





1478





1268
1279


0.97


1234
1236
1269


0.81
0.98

1237
1238


5.03
3.92

2378


5.16


1239





1278
1279





1267





1289





00
                                         Note - Data  expressed  in

-------
                                                                                            TABLE D-9
                                                                          INCINERATOR PRECOMBUSTION AIR - TCDD ISOMERS
                                                                          DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                       8/28, 8/30. 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Hi-Vol Filter + XAD-2 Sorbent
Field Blank
Field Duplicate
8/30/84
HI-Vol Filter + XAD-2 Sorbent
Field Blank
9/5/84
Hf-Vol Filter + XAD-2 Sorbent
Field Blank
1368
13.9

ND(247)
ND(0.204)
ND(0.129)
8.13
ND(0.120)
1379
4.40

ND(212)
1.33
ND(0.129)
2.57
ND(0.120)
1369
N0(2.31)

ND(141)
ND(0.204)
ND(0.129)
ND(0.611)
ND(0.120)
1247
1248
1378
1469
ND(2.70)
(San
ND(70.7)
0.500
ND(0.129)
0.830
ND(0.120)
1246
1249
ND(2.70)
pie analy
ND(17.7)
ND(0.204)
ND(0.129)
ND(0.611)
ND(0.120)
1268
1278
ND(2.70)
Is not re
ND(17.7)
ND(0.204)
ND(0.129)
ND(0.611)
N0(0.120)
1478
ND(2.70)
urned fron
ND(17.7)
ND( 0.204)
ND(0.129)
ND(0.611)
ND(0.120)
1268
1279
ND(1.16)
i laborator
ND(17.7)
0.300
ND(0.129)
ND(0.611)
ND(0.120)
1234
1236
1269
N0(2.70)
y.l
ND(17.7)
0.250
ND(0.129)
0.332
ND(0.120)
1237
1238
ND(2.70)

ND(17.7)
1.55
ND(0.129)
1.33
ND(0.120)
2378
ND(2.44)

ND(3.75)
1.59
ND(0.237)
ND(0.501)
ND(0.187)
1239
ND(1.54)

ND(17.7)
ND(0.163)
ND(0.129)
ND(0.611)
ND(0.120)
1278
1279
ND(1.54)

ND(17.7)
ND(0.196)
ND(0.129)
ND(0.611)
ND(0.120)
1267
N0(1.54)

ND(17.7)
ND(0.244)
ND(0.129)
ND(0.611)
ND(0.120)
1289
ND(1.54)

ND(17.7)
ND(0.204)
ND(0.129)
ND(0.611)
ND(0.145)
D           NOTE:   Data expressed In ng/g.

-------
                                                                             TABLE D-10
                                                        QUANTITATED VOLATILE COMPOUNDS - LIQUID WASTE INPUTS
                                                            DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                         8/28, 8/30, 9/5/84
OTHER
TARGET CHLORINATED BENZENE RING OTHER
COMPOUNDS COMPOUNDS COMPOUNDS COMPOUNDS

REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA Dilution
Nozzle BB ll
Nozzle BB *2
Nozzle BB *2 Dilution
Nozzle C
Nozzle C RERUN
Field Blank
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB 11
Nozzle BB 11 Field Duplicate
Nozzle BB *2
Nozzle BB *2 Field Duplicate
Nozzle BB 12 Field Duplicate RERUN
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Duplicate RERUN
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA Dilution
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C Dilution
Nozzle C Field Blank
Monochlorobenzene




15300













17700


(St


7490
4340





o





















1 BELO






446,270
283,000

Chloroform





















'I






2970
3260

Methylene chloride
11






50




















4136
3400


-------
of the GC column  revealed  sporadic  outliers, according to EPA  review  of these
laboratory data.  On  this  basis,  quality  assurance  review suggested  strongly
that the analytical   results  presented  here are biased  low by an amount  which
cannot be reliably quantitated.

    If these data are  used  for  qualitative purposes, some tentative trends  or
conclusions may be supportable:

        - Some  of the  liquid waste  incinerated appeared to contain  detectable
          quantities of benzene ring compounds  such as ethyl benzene,  styrene,
          toluene, and xylenes.
        - Chlorinated  compounds were  detected primarily on the  third  sampling
          day; however, these findings  were  largely affected  by the surrogate
          recovery problems highlighted above.
        - Of  the  chlorinated  ring  compounds,    only  monochlorobenzene  was
          detected.

    A listing of tentatively  identified  compounds  and  their  concentrations are
presented in Table  D-ll.   These data are included  for information only,  as  no
support can  be  offered  for  their  accuracy.   Hexamethylcyclotrisiloxane  was
found in  nearly all  of the samples  and thus  appeared  to  be a  laboratory
contaminant.

    b.  Semi-Volatile Compounds

    Table D-12  includes  data for  all  quantitated  semi-volatile   compounds;
several target and benzene  ring compounds  were detected,  and  accuracy  criteria
(80-125% surrogate recovery) were  met  for 15  of the 29 sample  runs  shown in the
table.  Note that problems  in surrogate recovery  occurred chiefly with  the acid
surrogates.  Therefore, the findings of the following compounds may be supported
as the surrogate compounds corresponding  to their pH range were recovered within
acceptable limits:

         Waste Nozzle        Sampling  Day      Compounds Detected

        BB (first feed)           1             2,4,5-trichlorophenol  (A)
                                               naphthalene (BN)
                                               2-methylnaphthalene (BN)

        BA    BA                  2             2-methylnaphthalene (BN)

        BB (first feed)           2             1,2-dichlorobenzene (BN)
                                               2-methylnaphthalene (BN)
                                               anthracene (BN)

         C                        2             1,2-dichlorobenzene (BN)
                                               2,4,5-trichlorophenol  (A)
                                               2,4,6-trichlorophenol  (A)
                                               naphthalene (BN)
                                               anthracene (BN)
                                               fluorene (BN).
                                      D-16

-------
                                               TABLE 0-11
                     LIQUID WASTE  INPUTS - TENTATIVELY IDENTIFIED VOLATILE COMPOUNDS
                              DOW  CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                         8/28, 8/30, and 9/5/84

REAfiENT BLANK I
RECENT BLANK 2

8/28/84
Nozzle 3A
Nozzle BA Dilution
Nozzle 88 11
Nozzle 88 »2
Nozzle BB 12 Dilution
Nozzle C
Nozzle C REftUN
Held Blank

8/30/84
Nozzle 3A
Nozzle BA Field Blank
Nozzle 88 11
Nozzle 3B fl Field Duplicate
Nozzle 36 *2
Nozzle 88 »2 Field Duplicate
Nozzle BB 12 Field Duplicate RERUN
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Duplicate RERUN
Nozzle C Field Blank

9/5/84
Nozzle BA
Nozzle 3A Dilution
Nozzle 58
Nozzle 38 Field Blank
Nozzle C
Nozzle C Dilution
Nozzle C Field Blank
Hexamethylcyclo-
trlsUoxane
0.2
0.2



0.2
0.2


0.2
0.2
0.2


0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2

0.2



' n.?

'0.?
0.?


1 rr.71
Dlethoxydimethyl-
silane
821
18816




96079
7655

4637




5375
4213
2333
4212
4375

27216
6250
2649
55492
13d9


WW
IHiM
1????
?3lO

?MM
2330
2 -methyl butane





14884





















34518
?ft44fi





Cyclohexane





20464














7561






"2875T
8630





Methoxytrlmethyl-
silane





17452






















66477





cu
c
n
*j
J
I
4j
1
•S
1

-------
                                                                       TABLE 0-12
                                                QUANTIFIED SEM1-VOLAMLE COMPOUNUS  -  LIQUID WASTE INPUTS
                                                      DOW CHEMICAL COMPANY BUILDING  703 INCINERATOR
                                                                   8/28, 8/30, 9/5/84
TARGET BENZENE KING
COMPOUNDS COMPOUNDS OTHER

URGENT BLANK 1
REAGENT BLANK 2

8/28/84
Nozzle BA
Nozzle BA, 5X Dilution
Nozzle DA, 20X Dilution
Nozzle BB 11
Noizle BB fl. 16X Dilution
Nozzle BB 11! 20X Dilution
Nozzle BB 12
Nozzle BB 12. 10X Dilution
Nozzle C
Field Blank (Nozzles BA i BB)

8/30/84 1
Nozzle BA 1
Nozzle BA Field Blank I
Nozzle BB il 1
Nozzle BB il Field Duplicate I
Nozzle BB 11 Field Duplicate. 5X Dilution |
Nozzle BB 12
Nozzle BB 2 Field Duplicate
Nozzle BB 12 Field Duplicate. IflX Dilution)
Nozzle C
Nozzle C F eld Duplicate
NbTTle C F eld Duplicate. IPX Dilution
Jjozz _§_C F eld BlSnk 	
9/57 4
Nozz e BA 	
Nozz e BA, 10X Dilution
Nozz e BB 	
Nozz e BB Field Blank 	
Nozz e C 	
Nb"iz e C. IPX Dilution 	
Nolz e C Field Blank
1,2-dichlorobenzene



















1406
Tim

1240

o
c
01
c
a.

























o
c
a>
c.
a.
o
i_
o
c
o
t_
*j
1
ift
**
c\*







4640
1900













44M1

2,4,6-trichlorophenol

















110

fl.VO
is;*)

4490

Naphthalene







144











6BU


'MS
~W

2-methyl naphthalene







77








3;J


n^
ItbU

~TT

Anthracene




















b6(J

~40

Fluorene



















190


T4T

0








10SOO
£3800






1390
1130



5930
— rro
~T70~

ACCURACY (% SURROGATE
RECOVERY)
Base-Neutrals
N1trobenzene-D5




44
25
45
110
40
20
' To"
20
Tfi
85


40
50
68
132
65
60
76
10
58
~4T
~ro
52
~nr

2-fluorobiphenyl




60
120
40
122
30
20
75
35
84
Bff


40
^5
BO
?8
3~5
64
~2TT
35
70
3D
~~5T

^*
o
1
">,
c
0)
c
0.
(_

*->
A3
Ol
o
t_
i_
3
t/1
ID
5




(T
N~
IP
T
N
N
V
N
Y
<


V
Y
Y
IT
IT
T
N
N
V
V
N
V
N
N
Y
Y
y
N
V
b2
Base-Neutrals











Y
»
Y


Y
V
y
N
I/
y
N
N
y
y
N
y
Y
N
y
Y
y
y
Y
83
Overall2




N
N
IT
1
N
N
¥
N
Y
Y


Y
1
i
N
N
I/
N
N
y
y
N
y
N
N
y
Y
y
N
y
52
a
 i
oo
              NOTES:   Data  expressed In ing/kg.
                      IA|| surrogate recoveries  within target range (20-180X) established
                       In Quality  Assurance Project  Plan.   N=No,  Y*Yes
                      ?Based on all  surrogate recoveries for both acids and base-neutrals within  target  range.
                                   of surrogates and overall.
                                  a  inittratP that  althnuuh accnr»e\t for all <;iirrn.i;«l-<^ ua<; nnt arronf^hfo   the

-------
In the above  summary,  "A" in parentheses denotes  an  acid compound  while "BN"
denotes a base-neutral  compound.   The  detection of  2,4,6-trichlorophenol,  an
acid, in the first nozzle  88  feed  on the second sampling day  is  not confirmed
as the recoveries  of  all  acid surrogates in  those samples was not  within the
acceptable range.  Note that  diethyl  phthalate,  a common analytical contaminant,
was detected on occasion,  and that analytical precision between sample dilutions
appeared generally poor.

    In Tables  0-13,  0-14, and  D-15  listings  of  tentatively  identified  semi-
volatile compounds  are  presented  sample  by  sample.Inadditionto"  these
tentatively identified  compounds,  a  number  of peaks  labeled "unknown"  were
listed.

    c.  Pesticides and Polychlorinated Biphenyls (PCBs)

    These data  are presented  in  Table D-16.  Most  pesticides  were detected on
the first and  second  sampling days,  with no PCB found in  any  sample.  However,
detection limits for the PCBs and for chlordane and toxaphene were in the range
of 1  to  10  mg/kg (ppm), much higher  than  the 5 ppb  detection  limit specified
for this study.  Also,  as  shown in Table D-16,  no  surrogate recovery data were
submitted by the  analytical  laboratory.  Therefore,  no  judgments can  be made
concerning the  accuracy of these results.

    d.  PCDD/PCDF

       (1)  All Homologues

        These  data, presented with accuracy  information  in Table  0-17 and with
    detection  limit data  in  Table  0-18, show  the  presence  of a  wide range of
    PCDO and PCDF homologues  in waste feeds from nozzles BB (first waste fed on
    the second  sampling day) and  C.   Precision data indicate generally good
    agreement  between  the two field  duplicate  samples  obtained   on  that day.
    Detection  limit  goals of 30 ppq  for TCDO  and TCDF,  and 90  ppq  for  other
    homologues, were  generally met   for the  latter; however,   more  frequent
    problems appeared on  the second sampling day, where higher detection limits
    were common.   The  completeness   criterion  of   90%,  based  upon  successful
     recoveries  of  all  four surrogate compounds, was  not  met  (see Table D-17).

       (2)  TCDD Isomers

        These  data  are  self-explanatory,  and  are shown  in  Table  0-20,  with
    detection  limit data  included.   Table  0-19  is  an abridged version  of this
    table, indicating  only those  isomers which were detected, and rounding the
    data as appropriate.

     2.  Low-STU Liquid  Waste (Dike Water)

     Dilute wastewaters  composed  of   collected  precipitation,  condensates from
tank  farm  carbon  adsorption system  regeneration, and  collected  runoff from
hydroblasting  operations  in  the Dow facility, were  incinerated on  the first and
third sampling days.
                                      D-19

-------
                          TABLE D-13
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
            DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                         REAGENT BLANK


! . . <*^/-oc-
-------
                          TABLE D-13 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
            DOU CHEMICAL COMPANY BUILDING 703 INCINERATOR
                        LIQUID HASTE NOZZLE  BA
                      8/28/84 LABORATORY RERUN
                                 D-21

-------
                                      TABLE  D-13 (contl)

           LIQUID  '-/ASTE  INPUTS - TENTATIVELY-IDENTIFIED SEM1 -VOLATILE COMPOUNDS
                       DOW CHEMICAL COMPANY BUILDING  703 INCINERATOR

                                   LIQUID HASTE  NOZZLE BA
                               8/28/84 SECOND LABORATORY RERUN
  CAS
                           Compound Nwrw
Fraction
Torcaijy
NumSST
   ErtJnvat»d
 Conc«ntntion
(ug/l
  fLflAr*1
 i jjy/-Pjj-7-
-triyrt
4.

e.
 9._
n.
                                                                     -7*70
is.
                                                                     77?
                   l 113.
ia..
   \MH-TH?
                                             D-22

-------
                          TABLE  D-13  (cont,-)
LIQUID WASTE  INPUTS  - TENTATIVELY-IDENTIFIED  SEMI-VOLATILE  COMPOUNDS

            DOW CHEMICAL COMPANY BUILDING  703 INCINERATOR
                     LIQUID WASTE NOZZLE BB (1145-1606 EOT)
                                 R/28/84
                           TABLE  D-13 (cont.)
LIQUID WASTE INPUTS  -  TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
            DOW CHEMICAL  COMPANY BUILDING 703 INCINERATOR
            LIQUID WASTE NOZZLE BB (1145-1606 EDT)  LABORATORY RERUN
                                                                      E>timai»d
                                                                    Cooc»ntratJon
                                                                   («•/»
                                  D-23

-------
                                 D-13 Icont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
            DOW CHEMICAL COMPANY BUILDING 703  INCINERATOR
 LIQUID HASTE NOZZLE BR (1145-1606  EOT)  - 8/28/84 SECOND LABORATORY RERUN
                           TABLE  D-13 (cont.)
  LIQUID  WASTE  INPUTS  - TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
             DOW CHEMICAL  COMPANY  BUILDING  703 INCINERATOR
                         LIQUID WASTE NOZZLE BR (1606-2020 EDT)
                                     8/28/84
1U 	





1 K
I 	 .

19 	

21 	 1

23 	

2S 	 	

I

	






















\f

A6M




















\


vK

3
7*3
121
•2*/O
ZZ3
977
?$7
/OO?
(Oft,
/O3O
/O'jG
/06ff
113-2-
tSb£

















                                  D-24

-------
                                     TABLE  D-13 (cont.)
           LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
                       DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                       LIQUID WASTE NOZZLE BB  (1606-2020 EOT)
                       8/28/84 LABORATORY RERUN
   CAS
   Wumb«f
                         Compound
Fraction
-ass
  Estimated
Concentration
                                t&^^
                                                        46N
2..

4..
6..
6..
                                                                   /etc,-?
                                                           \/_
                                     TABLE  D-13 (cont.)
            LIQUID WASTE  INPUTS  - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
                       DOW  CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                   LIQUID WASTE NOZZLE  C
                                         8/28/84
10.
                                            D-25

-------
              LIQUID WASTE  INPUTS  -       TmY-DENTFED SEMI-VOLATILE COMPOUNDS
                          DOW  CHEMICAL  COMPANY  BUILDING 703 INCINERATOR
                             LIQUID WASTE  NOZZLE FIELD BLANK - 8/28/84
 10..
'11..
112..
                                        TABLE  D-14
              LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
                          DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                            LIQUID WASTE NOZZLE BA - 8/30/84

-------
                                      lnDLC  3-14 (cont.)
           LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
                       DOW CHE-1ICAL COMPANY BUILDING 703  INCINERATOR

                   LIQUID WASTE  NOZZLE BB  (1000-1415 EOT) FIELD DUPLICATE SAMPLE
                                            8/30/84
30.
                                   ff
                                             D-27

-------
                                    TABLE  D-14  (cont.)
          LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
                      DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
      LIQUID WASTE NOZZLE BB  (1000-1415 EDT) FIELD DUPLICATE SAMPLE  LABORATORY RERUN
                                       8/30/84
   CAS
   Numb*
                         Compound MMTW
                                           Fraction
  Estimated
Cooe*ntr«tjfln
                  ^31-  /j«3j3-
2.

4.
5.

7. q?-<.Htb
                                                                   77 Z.
                                                                  10 /f
                               -k
                                        - /./'-jt+t4*uj
                                                                  /Y7.S"
                       - /. i ' ': ?' t "
  IB..
                                 it
                                     TABLE  D-14  (cont.)
           LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
                       DOW CH01ICAL COMPANY BUILDING 703  INCINERATOR
                        LIQUID WASTE  NOZZLE BA FIELD BLANK - 8/30/84
                                                        A6N
15.1
             (. 
-------
TABLE
 D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
            DOU CHEHCAL COMPANY  BUILDING 703 INCINERATOR
           LIQUID  HASTE  NOZZLE BB  (1000-1415 EPT) - 3/30/84
   CAS
   Mumbw
                Compound MMTM
M^nSSr
                                                                     Estinvitvd
                                                             SAJ
 1-
                                      TABLE  D-14 (cont.)
            LIQUID WASTE INPUTS -  TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
                        DOW CHEMICAL  COMPANY  BUILDING  703 INCINERATOR
                        LIQUID WASTE NOZZLE BB (1415-1700 EOT) - 8/30/84
                                            D-29

-------
                          TABLE  D-H (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
            DOW CHEMICAL COMPANY  BUILDING 703 INCINERATOR
               LIQUID HASTE NOZZLE C - 8/30/84
                             TABLE 0-14 (cont.)
    LIQUID WASTE INPUTS -  TENTATIVELY-IDENTIFIED SB'! I-VOLATILE COMPOUNDS
                DOW CHEMICAL COMPANY  BUILDING  703  INCINERATOR
               LIQUID WASTE NOZZLE C  -  3/30/84  FIELD BLANK
7
	
' 5
5
10
1 1
1?. 	 	
L(^rLSZ*a-*+3~>~1 —





A&l





5-73











                                     D-30

-------
                                    TABLE  D-14 (cont.)
          LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
                      DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                      LIQUID WASTE  NOZZLE C - 8/30/84 FIELD DUPLICATE  SAMPLE
0.
                                            D-31

-------
                             TABLE  D_14 (cont>)
   LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
               DOW CHEMICAL COMPANY BUILDING 703  INCINERATOR
LIQUID WASTE NOZZLE  C  -  8/30/84 FIELD DUPLICATE SAMPLE LABORATORY RERUH
                             TABLE  D-14 (cont.)
   LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
               DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
        LIQUID WASTE NOZZLE BB  (1415-1700 EDT) FIELH DUPLICATE SAMPLE
                             8/30/84

-------
                          TABLE  D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
            DOU CHEMICAL COMPANY BUILDING  703 INCINERATOR
LIQUID WASTE NOZZLE BB (1415-1700 EOT) FIELD  DUPLICATE SAMPLE LABORATORY RERUN
                            8/30/84
                                 D-33

-------
                          TABLE  D-15
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
            DOW CHEMICAL COMPANY BUILDING  703 INCINERATOR
                       LIQUID HASTE NOZZLE BA
                              9/5/84
                          TABLE   D-15  (cont.)
LIQUID WASTE INPUTS -  TENTATIVELY-IDENTIFIED SB-11-VOLATILE COMPOUNDS
            DOW CHEMICAL  COMPANY  BUILDING  703  INCINERATOR
            LIQUID WASTE NOZZLE BA LABORATORY RERUN - 9/5/84
                                                                             D-34

-------
                                     TABLE  D-15 (cont.)
           LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE  COMPOUNDS
                       DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                            LIQUID WASTE NOZZLE  BB  FIELH CLANK
                                        9/5/84
IV
12
• **
14
IS
1S . ... 	
/hs&tts <£&***<*/,
                  ,/
                                                                           t.tbl.Soo
                                                                  397-
                                                                             1.^12.7.00
16.
                                                                  7/0
                                                                  713
 20	
 ?i/fr/-gy-g
 22	
                       -   A / '-
                                      TABLE  D-15 (cont.)
            LIQUID  WASTE  INPUTS  -  TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
                       DOW  CHE1ICAL  COMPANY  BUILDING 703  INCINERATOR
                                    LIQUID WASTE NOZZLE C
                                            9/5/84
CAS
                        Compound
                                                        Fnctkm
1..
2._

4..
5..
6..
7..
3..
                                                                2.2.7
                                                         V
                                                                37/
                                                                -/V7
                                                                                       D-35

-------
          LIQUID WASTE  INPUTS  -  TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
     D'J5              DOW  CHEMICAL  COMPANY BUILDING 703 INCINERATOR
 (cont.)
                             HASTE NOZZLE C LABORATORY  RERUN  - 9/5/84
                                      TABLE  D-15 (cont.)
           LIQUID WASTE  INPUTS  -  TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
                       OOW CHE'IICAL  COMPANY BUILDING 703 INCINERATOR
                              LIQUID  WASTE  NOZZLE C FIELD BLANK
                                            9/5/84
1V-
12..
•»3.
14..
15..
IS..
                                             D-36

-------
                                                                            TABLE D-16
                                                     LIQUID HASTE INPUTS - QUANTITATED PESTICIDE/PCB COMPOUNDS
                                                           DOH CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                      8/28, 8/30, and 9/5/84
PESTICIDES PCB (AROCLORS)

REAGENT BLANK 1
REAGENT BLANK 2

8/28/84
Nozzle BA
Nozzle BB li
Nozzle BB »2
Nozzle C
Nozzles BA i BB Field Blank
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB *1
Nozzle BB ll Field Duplicate
Nozzle BB |2
Nozzle BB |2 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C Field Blank

Aldrin










1 4






1.1








O
X
CO
1
«o










7.1






11.7








O
DC
CD
1
Ol
CO




















0.2





0
a:
CO —
a
1 C
1C
ID T:
g c
csC




0.1
0.3









n.A




0.1





Chlordane


























o
o
a













fl.4



1.2








i—
o
o
1













O.fi









0.3


Oieldrin










2.5






3.1








Endosulfan II













n.4



1.4








Heptachlor






II. 1










1.2








Toxaphene


























vo
1—4
O


























1—t
CM
CM


























CM
CM


























CM
CM


























00
CM


























If)
CM


























O
CM


























ACCURACY (X SURROGATE RECOVERY)




















































































































(ACCURACY

BMIl







~TiAl




A N
1
'TED BY
I 1
ANALYTICAL

1
LABORATORY . )




































































1









































































































O

OJ
          NOTE:  Data expressed in mg/kg.
Where data are not  stated,  compound was not  detected.

-------
                                                    TABLE D-17
                                   LIQUID WASTE  INPUTS - QUANTITATED PCDD/PCDPI
                                  DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                              8/28,  8/30, and 9/5/84
                                                                                             ACCURACY
                                                                                           (% RECOVERY)

REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #2
Nozzle C
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #1 Field Duplicate
Nozzle BB #2
Nozzle BB #2 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BB
Nozzle BA Field Blank
Nozzle C
Nozzle C Field Blank

























Q
Q
O
1—
1
oo
r^
OO
CM
























Q
Q
O
t—

o
H-





1.2





0.9
0.4


2.6
4.2




Q
Q
0
Q.
:r

O





9.2
0.4




37.0
32.3


36.6
18.0



6.5
U-
Q
O
O)

O
f—





0.8





1.8
5.3


1.5
4.3



0.2
U-
Q
O
X
n:

0











O./



3.b
I.I




u_
o
C_J
Q-
(O
4->
O











0.6



8.1
8.2




u_
Q
0
0





1.2





0.6



/.4
/./




\NALYSIS NOT RETURNED FROM LABORATORY)









0.2









COMPLETENESS BY SURROGATE


























Q
Q
O
00
r-
co
CM
i
CM
i-H
0
OO
.— «



35
100
38
88
9b

88
100
100
100
//
57
75
97
100

100
100

99
75
84%
Q
Q
O
t—
1
OO
r~
oo
CM
1
*d-
o
r^
oo



119
90
118
112
105

96
91
90
113
88
94
98
9/
93

93
91

92
99
9b%
Q
Q
O
O
t
CM
i— 1
O
OO
t— 1



100
89
100
100
100

100
34
87
92
83
100
b3
23
49

75
53

40
64
/4%
Ll-
Ci
O
(—
1
OO
r~-
oo
CM
1
<3-
o
r^-
oo



44
61
39
75
81

84
82
75
85
75
60
100
100
57

50
90

100
56
84%
I
CO
CO
    NOTES:   1.   Data expressed in ng/g.
            o   mi  .	*• ~	 -

-------
                                                                                   TABLE  D-18
                                                                    LIQUID WASTE  INPUTS - PCOD/PCDF  ANALYSES
                                                                  DOW  CHEMICAL COMPANY BUILDING  703  INCINERATOR
                                                                              8/28,  8/30.  9/5/84
SAMPLE IDENTIFICATION
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB ll
Nozzle 66 12
Nozzle C
8/30/84
Nozzle BA
Nozzle ^A Field Blank
Nozzle BB 11
Nozzle BB 11 Field Duplicate
Nozzle BB |2
Nozzle BB 12 Field Duplicate
Nozzle C
Nozzle C Fleld^lant
Nozzle C Field Duplicate
9/5/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB
Nozzle C
Nozzle C Field Blank

2378-
TCDD

ND
ND
RTJ
Nb
ND
0.0066
0.0199
0.110)
0.0128
O156

ND
Nb
Nb
ND"
ND"
0.0035,
0.0117
0.0416
0.0603
0.0349'
ND:o.oi2Z
ND
ND"
TO"
0.152)
0.0396)
0.108)

ND( O.OOM)

NDf"
ND]
"ND
U.0<:44
0.0796
0.0096

TOTAL
TCDD

NU
NU
1
i

0.0419
0.0322!
>.79
).548
ND 0.0173)

NU
NU

0.0098
0.0044
~~33.0
30.7
ND(0.0208)

0.716
60.3
NDI0.0394)
21.8


ND 0.0013)




T.88
0.835
ND O.OOZ7)

TOTAL
PeCDO

ND
Nb
0.295
0.183
11.8
ND
Nb




0.371)
0.0398)

ND
NU

0.0289
0.0188
6.27
4.85
ND
Nb


0.0319
0.0661
3.45

ND(0.109I
6.13



ND(0.0084)

0.808
ND
ND
0.235
0.004





TOTAL
HxCDD

NU
Nu

ND
NU

NU
ND

0.399
'd.107
1.19
0.0782
0.0294

0.0757
0.0094'
~D.895
0.375
ND
NU
t
NU
i

0.135
0.309
?.61
0.0693)
1.24

ND; 0.0046)

NU
NU
NU

0.0892
0.217
0.003

TOTAL
HpCDO

NU
No

ND
NU

NU
ND


ND

TJV3ZT
0.557
2.79 "
0.265
0.126

0.122)'
0.0389
3.00'
2.64
0.266)
ND;0.0567)

3.80
ND;
-------
                                                                          TABLE D-19
                                                          LIQUID WASTE INPUTS - TCDO ISOMER ANALYSES
                                                         DOU CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                      8/28. 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB ll
Nozzle BB |2
Nozzle BB 12 Lab Duplicate
Nozzle C
8/30/84
Nozzle BA
Nozzle BA Lab Duplicate
Nozzle BA Field Duplicate
Nozzle BB 11
Nozzle BB 11 Field Duplicate
Nozzle BB 12
Nozzle BB 12 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB
Nozzle BB Lab Duplicate
Nozzle C
Nozzle C Field Blank

1368



1.2
0.3






21.8
19.3


39.9
8.8




4.1
4.2
0.6


1379



4.1
0.3






10.3
11.4


20.4
10.8




1.8
1.6
0.2


1369


























1247
1248
1378
1469











0.4




0.4





0.1



1246
1249


























1268
1278


























1478


























1268
1279


























1234
1236
1269


























1237
1238



0.5







0.4




1.4





0.1



2378


























1239
















0.3









1278
1279
















*









o
 I
O
       *   GC  retention time exceeded; therefore, this Isomer could not be quantltated.
          NOTE:   Data expressed  In ng/g.
                 Blank  spaces denote  isomer was not detected (see Table D-20).

-------
                                                                                       TABLE 0-20
                                                                            LIQUID WASTE INPUTS - TCDO ISOMERS
                                                                      DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                   8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB ll
Nozzle BB |2
Nozzle BB 12 Lab Duplicate
Nozzle !T
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB 11
Nozzle BB ll Field Duplicate
Nozzle BB 12
Nozzle BB 12 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB
Nozzle BB Lab Duplicate
Nozzle C
Nozzle C Field Blank

1368


TO IF. 0415"
TO

(
Nb
NU

NU
NU
i
TT.OJ2T
.19
i.276
0.0077,
0.0173

0.0098
0.0044
'1.8
9.3
ND(0.0450)
0.510
39.9

fiYBT
W 0.0394)


WO. 0015)



^4.05
4.16
0.636


1379

Nb
Nb
I

0.0419
0.0322'
.11
~0.272
NO"
Nb

Nb
NU

0.0033
0.0173

0.0098
0.0044
0.3
.1.4
ND(0.0277)
0.186
20.4
10.8
Nb(0.0394)


ND" 0.0013)



1.84
1.55
0.199


1369

m
Nb
ND
ND
ND
NU

0.0419)
0.0322)
0.206
0.031!

>
0.0033
0.0173

ND( 0.0098
ND"
ND
ND
ND
NU
NU
NU
NU
0.0044
0.537
0.346


0.0277
0.0258,
1.00)
0.270
0.0391




Nb(0.0013)

ND"
NU
NU
0.200
0.101


0.0660)


1247
1248
1378
1469

ND"
ND
ND
Nb
ND
NU

NU
NU
(
ND
Nb
0.0419
6.0322'
0.206)
6.0315
0.0033
5.0414

0.0098
0.0044
i.437
0.946)
0.0277)
0.0206
ND(2.01)
0.431
Nb(6.0334)

N0(0.0013)

ND(0.200)
0.084
ND(0.0660)


1246
1249

Nb(0.04l9
ND"
Nb
070322
0.206)
ND" 0.0315
ND"
NU

NU
NU
ND
Nb
ND
NU
NU
NU
ND
0.0033
0.0173

0.0098)
0.0044)
0.537
0.346
0.0277
0.0258
2.01)
0.270)
0.0394)

N0(0.0013)

ND
NU
Nb
0.200)
0.101)
0.0660)


1268
1278

ND"
Nb
ND
Nb
NU
NU
0.0419
0.0322
0.206)
0.0315
0.0033
0.0173

ND"
NU
ND
ND
ND
Nb
Nb
NU
Nb
0.0098
0.0044
0.537'
0.346
0.0277)
0.0129)
2.01)
0.270)
0.0394)

ND(0.0013)

NO
NU
Nb
l>.<>00)
0.101)
0.0660)


1478

NO
Nb
Nb
NU
NU
Nb
0.0419)
0.0322)
0.206)
0.0315)
0.0033
0.0207

ND
Nb
Nu
Nb
Nb
Nu
NU
NU
Nb
0.0098
0.0044
0.537
0.946
0.0277
0.0129,
2.01)
0.270)
0.0394)

Nb(0.0013)

ND
NU
0.200
0.101'
N0~(0.0660)


1268
1279

NO"
NU
ND
NO'
NU
Nb

0.0419)
0.0322)
0.206
0.03H

)
0.0033:
0.0173

ND"
Nb
Nb
ND
ND
Nb
NU
Nb
0.0098
0.0044
0.537
0.946


0.0277
0.0129
1.00)
0.270
ND~;0.039'





ND(0.0013)

ND
NU
0.200
0.101
N0(0.066(


J)


1234
1236
1269

ND
NU
ND
NU
Nb
Nb

Nb
NU
Nb
ND
ND
NU
NU
NU
NU

0.0419
0.0322
0.206
0.031

>
0.0033
0.0173

0.0098)
0.0044)
0.537
0.946
0.027


r
0.0129
1.00)
0.270
0.033



i

ND(0.0013)

ND
NU
NU
0.200
0.101
0.066




J)


1237
1238

Nb"
NU
0.0419
0.0322
0.493
NO"
NU
0.0315
0.0033
ND(0.0345

Nb"
Nb
I
Nb
Nb
Nb
NU

0.0098
0.0044
i.437
1.42)
0.0277)
0.0361)
2.01)
.40
NO 0.0394)

Nb(0.0013)

ND(0.200)
0.064
ND(0.0660)


2378

ND
NU
ND
Nb
Nb
Nu
0.0066
0.0199
0.110)
0.0129
0.0106
0.0156

ND(0.0035)
ND
Nb
ND
Nb
NU
NU
NU
0.0107)
0.0416)
0.0603'
0.0344'
0.0122)
0.152
0.180
1239

ND(0.0419
Nb 0.0322
Nb
Nb
NO
Nb
0.110)
0.0315
0.0033'
0.0173

ND
NU
ND
Nb
Nb
NU
ND

0.0098
0.0044
0.0416
1.42)
0.0208
0.0258
2.01)
1.323
TO; 0.0394) N0(0.0394)
!
ND(0.0034) Nb(0.0013)

ND
ND
Nb
0.0224
0.0214'
0.0796

NO
1 ND
1 NU
0.200)
0.202)
0.0660)


1278
1279

ND"
NO
Nb
ND
Nb
NU
0.0419
0.0322
0.206)
0.0315
0.0101
0.0173'

ND"
Nb
Nb
Nb
ND
Nb
Nb
0.0098
0.0044
1.07)
1.42)
0.0277)
0.0361)
2.01)
*
ND(0.0394)

ND(0.0013)

NO
NO
NU
0.200)
0.202}
0.0660)


1267

ND(0.0419
ND(0.0322
ND
ND
ND
0.206)
0.0315
0.0033
NDTff.0173

Nb"
Nb
ND
Nb
ND
Nb
0.0098)
0.0044)
0.537)
0.946)
0.0277
0.0258
ND(2.01)
*
Nb(0.0394)

N0(0.0013)

ND
Nb
NU
0.200)
0.101)
0.0660)


1289

ND"
ND
NO
NU
ND
Nb
0.0419
0.0322
0.206)
0.0315
0.0397
0.0173

ND
NU
Nb
0.0098)
0.0044)
0.537)
*
*
ND
Nb
0.0258)
2.01)
*
Nb(0.0394)

Nb(0.0013)
-
ND
Nb
O.ZOO)
0.101)
ND(0.0660)


NOTE:  Data expressed In ng/g.
     O

-------
    a.  Volatile Compounds

    Field blank samples were  found to contain relatively low levels of compounds
not generally found in samples of wastewater.  As with semi-volatile compounds,
no volatiles were detected in  first-day  samples  at levels higher than those in
the field blank.  On the third  sampling  day, however,  several  target  compounds
were detected, though not  all  were  found  in both  actual  and  field  duplicate
samples.  A summary of these  data appears below:

                                   Table D-21

                              Low-BTU Liquid Waste
                       Target Volatile Compounds  Detected
                                     9/5/84

                                            Concentration  (ug/L)

                                                         Field      Precision
Compound                                    Sample     Dupl icate      (RPD)

1,1-dichloroethylene (vinylidene chloride)     127         137           3.8
1,1-dichloroethane (ethylene  dichloride)        86          93           7.8
Chloroform                                     12          13           8.0
Tetrachloroethylene (perch!oroethylene)       378          ND*
Monochlorobenzene                             260          ND
Carbon tetrachloride                           ND        2916
Trichl oroethylene                              ND           8

    * ND = Not detected.

    As shown in detail  in Table D-23, other compounds  were  found in dike  water
samples from the third sampling day, summarized  as follows:

                                   Table D-22

                              Low-BTU Liquid Waste
                       Other  Volatile Compounds  Detected
                                     9/5/84

                                        Concentration (ug/L)

                                                     Field      Precision
       Compound                         Sampl e      Duplicate      (RPD)

       Methylene chloride                1127        1241           9.6
       Acetone                           1163        1302          11.3
       l-(methylethyl)-benzene           2791        6222          76.1

    The first  two  compounds  commonly  appear   as  contaminants  in  laboratory
analyses; therefore, their presence in dike water may be questionable.

    Accuracy criteria were met for all  five samples (see Table D-23).


                                      D-42

-------
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8/28/84
























1,1,1-trichloroethane
benzene
toluene
ethyl benzene
styrene
methylene chloride
acetone
vinyl idene chloride
ethylene dichloride
chloroform
perchloroethylene
chlorobenzene
total xylenes
carbon tetrachloride
trichloroethylene
hexamethylcyclo-
trisiloxane
l-(methylethyl )-benzene
propyl benzene
toluene - 08
bromofluorobenzene
1,2 - dichloroethane - D4

ACCEPTABLE1
TENTATIVELY
IDENTIFIED ACCURACY
COMPOUNDS (% SURROGATE RECOVERY)
                                                                                                                        o z:
                                                                                                                        z i
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-------
    b.  Semi-Volatile Compounds

    Field blank samples  taken  on  both days on which dike  water  was fed to the
incinerator were  generally  free of  detectable  contamination; a  phthalate was
noted in one  of  the blanks.  No detectable semi-volatile  compounds were found
in the composite  water  sample  taken on the first  day.   On the third day,  1,2-
dichlorobenzene, 2-methylnaphthalene, 1,4-dichlorobenzene, and 2,4,6-trichloro-
phenol were detected, but only in the field duplicate sample in the case of the
latter two.  Following is a summary of these results:

                                   Table D-24

                              Low-BTU Liquid Waste
                       Semi-Volatile Compounds Detected
                                     9/5/84

                                       Concentration (ug/L)

                                                    Field      Precision
        Compound                       Sample     Duplicate      (RPD)

        1,2-dichlorobenzene              121          95         24.1
        2-methylnaphthalene              174         809        129.2
        1,4-dichlorobenzene               ND*        313
        2,4,6-trichlorophenol              ND         167

            * ND = Not detected.

The presence of 1,2-dichlorobenzene  in this wastewater  stream on the third day
is affirmed within satisfactory  bounds of precision.  At the flow rate described
above, this concentration corresponds to a  mass  flow of 0.34 to  0.44 milligram
per day of  1,2-dichlorobenzene  to the incinerator  on  the third  sampling  day.
While 2-methylnaphthalene  was   present,  the  analytical  data failed  to  meet
established limits for precision.

    Other tentatively identified compounds  (Table  D-25),  some of them possibly
of interest as they are ring compounds,  were detected in the sample but not the
field duplicate,  and vice versa, on the  third  day.   In  the single case in which
a compound  was  found in  both   (a  substituted naphthalene),  quality  assurance
criteria for precision were not met.  Accuracy  goals,  as  measured  by recovery
of base-neutral  and  acid surrogate  compounds,  were met  for  four  of  the  five
samples in this category,  resulting  in  completeness  of 80%  (see  Table D-25).
Recovery of  an  acid  surrogate was   outside  of the  acceptable  range  in  the
sample not meeting the accuracy criterion.

    c.  PCDD/PCDF

       (1)  All  Homologues

        These data are presented in Tables  D-26  and D-27.  When compared to the
    liquid waste  feeds data in  Section B.l.d., the  concentrations  of PCDD/PCDF
                                     D-44

-------
                                                                              TABLE 0-25
                                                             LOW-BTU LIQUID WASTE - SEMI-VOLATILE COMPOUNDSl
                                                             DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                            8/28 AND 9/5/84




























8/28/84
Composite Sample
Field Blank

975/84
Composite Sample
Field Duplicate
Field Blank


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                                              established in Quality Assurance Project Plan.
                                             3By class of surrogates (acids and base-neutrals) and
                                              overall (combined).

-------
                                                                                  TABLE 0-26
                                                                  LOW-BTU LIQUID WASTE - PCDD/PCOF ANALYSES1
                                                                 DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                8/28 AND 9/5/84
                                                                                                                                     Accuracy  (X  Surrogate  Recovery)

SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
87 30/84
(NO SAMPLE TAKEN - Low-BTU lie
4/5/84
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
PRECISION(RPD) - SAMPLE AND
FIELD DUPLICATE
2378-
TCDD


luid was




Total
TCDD


e was nc
29.3
22.8

25
Total
PeCDD


t Inclru




Total
HxCDD
10.4

irated or




Total
HpCDD


i this dc
181
132

31
OCDD


y)
753
570

28
2378-
TCOF







Total
TCDF



33.9
46.4

31

Total
PeCDF







Total
HxCDF







Total
HpCDF







OCOF







COMPLETENESS BY SURROGATE
i
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60
62

45
84
100

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93
78
108

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                    NOTES:  1.  All data expressed in pg/g.
                            2.  All surrogate recoveries within target range of  50-15051.
                            3.  Blank spaces denotes homologue not detected.  Detection limits ranged from 0.3-3 ppq for
                                TCDD and TCDF. to 14-28 ppq for OCDD and OCDF.

-------
                                                            TABLE D-27
                                             LOW-BTU LIQUID WASTE - PCDD/PCDF ANALYSES
                                           DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                          8/28 AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
9/5/85
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
2378-
TCDD
ND
( .0008)
ND
(.0009)
ND
(.0102)
ND
(.0027)
ND
(.0002)
Total
TCDD
ND
(.0010)
ND
(.0010)
0.0293
0.0228
ND
(.0010)
Total
PeCDD
ND
(.0024)
ND
(.0026)
ND
(.0024)
ND
(.0035)
ND
(.0010)
Total
HxCDD
ND
(.0031)
ND
(.0027)
ND
(.0028)
ND
(.0055)
ND
(.0029)
Total
HpCDD
0.0104
ND
( .0068)
0.181
0.132
ND
(.0067)
OCDD
ND
(0.162)
ND
(.0089)
0.753
0.570
ND
(.0138)
2378-
TCDF
ND
(.0003)
ND
(.0005)
ND
(.0007)
ND
(.0009)
ND
(.0003)
Total
TCDF
ND
(.0010)
ND
(.0010)
0.0339
0.0464
ND
(.0010)
Total
PeCDF
ND
(.0011)
ND
(.0013)
ND
(.0016)
ND
(.0036)
ND
(.0046)
Total
HxCDF
ND
(.0016)
ND
(.0051)
ND
(.0015)
ND
(.0081)
ND
(.0025)
Total
HpCDF
ND
(.0061)
ND
(.0036)
ND
(.0040)
ND
(.0143)
ND
(.0013)
OCDF
ND
(.0098)
ND
(.0104)
ND
(.0047)
ND
(.0280)
ND
(.0166)
o
I
                             Notes:  Data expressed in ng/g.
Accuracy data appear in Table D-26.

-------
    are low, as may be  expected,  and limited to the tetra-, hepta-,  and  octa-
    CDD, and tetra-CDF homologues.   On  the third sampling day,  OCDD  comprised
    approximately 78%  by weight of the PCDD detected.

        Note, however, that none  of  the five sample analyses met  the accuracy
    criteria established  for  the  four   surrogate  compounds.   These  data  are
    therefore not suitable for quantitative purposes, despite the good  precision
    observed (see Table D-26).

       (2)  TCDD Isomers

        No 2378-TCDD or 2378-TCDF were detected.   The  isomers found (see Tables
    D-28 and D-29) were limited to 1368, 1378, and  1237/1238.

    D.  Incinerator Exhaust

    1.  Volatile Compounds

    Method blanks  of  the  Tenax  and  charcoal  adsorbents  appeared to  contain
measurable amounts  of several  contaminants;  however,  the analytical  accuracy
may be questionable as  none  of the four surrogates was  recovered.  Analytical
problems traceable to  poor fit of the  VOST tubes  in the  thermal  desorbing unit
were frequently cited  by  the  laboratory.  This  phenomenon usually first affected
the recovery of the surrogate l,2-dichloroethane-D4, but  not of the other three
surrogates.  The data  summaries (Tables 0-30, D-31, and D-32) indicate the data
points which were affected in this way.

    On the three sampling days, five or six sets  of VOSTs were exposed, usually
for 40 minutes,  with  single field blanks  for the   sorbents  and  condensates on
each day  covering the time period in  which  all five or six sets were operated.
Thus, where  compounds were detected  in the  field  blank,  the  amounts  trapped
were apportioned  to  each exposed  sample according to the  length  of sampling
time.  For  example, if  six VOSTs were employed  for 40 minutes  each,  resulting
in a total  sampling time  of  240 minutes, one-sixth  of  the  amount of a compound
in the field blank was subtracted from that in each exposed sample.

    In Tables D-30, D-31, D-32, no data are stated  for compounds trapped in the
collected condensates, which were pooled in  the field and analyzed  as composites
of all  of the  sample runs on  each  day.   With  few exceptions  (see  raw data,
Tables D-33, D-34, 0-35), no compounds other than methylene chloride and acetone
were detected,  and  it  is  suspected  that these  findings may be the  result of
typical laboratory contamination.

    The data tables present the compounds detected in terms  of those specifically
targeted, other  chlorinated  compounds, benzene  ring compounds,  and other  ring
compounds.   While the materials consumed in the 703 Building incinerator varied
from day to day, it  is apparent that carbon  tetrachloride and  1,4-dichlorobenzene
were present  in  exhaust  gas  almost  continuously.  Other  compounds,  such as
1,2-dichlorobenzenes, ethylbenzene,   1,1,1-trichloroethane,  and toluene,   were
found  in  measurable  concentrations  but   not  on  all  three  sampling  days.
                                      D-48

-------
                                                       TABLE D-28
                                           LOW-BTU LIQUID WASTE - TCDO ISOMERS
                                      DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                     8/28 AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
8/30/84
(NO SAMPLE TAKEN -
975/84
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
PRECISION(RPD) - SAMPLE AND
FIELD DUPLICATE
1368


Low-BTU
16.2
12.0

29.8
1379


liquid v
5.3
6.0

12.4
1369


tfaste was




1247
1248
1378
1469


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1246
1249


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1268
1278


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day.)




1268
1279







1234
1236
1269







1237
1238



3.4
2.0

51.9
2378







1239







1278
1279







1267







1289







Notes:  Data expressed  in  pg/g.
Blank spaces denote isomer was not detected.

-------
                                                                              TABLE 0-29
                                                                  LOW-BTU LIQUID WASTE - TCOD ISOMERS
                                                             DOW  CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                            8/28 AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
9/5/64
COMPOSITE
FIELD DUPLICATE
FIELD BLANK

1368
ND
(.0017)
ND
(.0010)
0.0162
0.0120
ND
(.0010)

1379
ND
(.0010)
NO
(.0010)
0.0053
0.0050
ND
(.0010)

1369
ND
(.0010)
ND
(.0010)
ND
(.0011)
ND
(.0010)
NO
(.0010)

1247
1248
1378
1469
ND
(.0010)
ND
(.0010)
ND
(.0011)
ND
(.0010)
ND
(.0010)

1246
1249
ND
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)

1268
1278
ND
(.0010)
ND
(.0010)
ND
(.0011)
ND
(.0010)
ND
(.0010)

1478
ND
(.0010)
ND
(.0010)
ND
(.0011)
ND
(.0010)
ND
(.0010)

1268
1279
ND
(.0010)
ND
(.0010)
NO
(.0010)
ND
(.0010)
ND
(.0010)

1234
1236
1269
ND
(.0010)
NO
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)

1237
1238
ND
(.0010)
NO
(.0010)
0.0034
0.0020
ND
(.0010)

2378
NO
(.0008)
ND
(.0009)
ND
(.0102)
ND
(.0027)
ND
(.0002)

1239
ND
(.0010)
NO
(.0010)
ND
(.0011)
NO
(.0010)
ND
(.0010)

1278
1279
ND
(.0010)
NO
(.0010)
ND
(.0011)
ND
(.0010)
ND
(.0010)

1267
ND
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)

1289
ND
(.0010)
ND
(.0010)
NO
(.0011)
NO
(.0010)
ND
(.0010)

c_n
O
                          NOTE:  Data expressed In ng/g.

-------
                                                                                     TABLE 0-30
                                                                 INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
                                                       USING VOLATILE ORGANIC SAMPLING TRAIN, IN TERMS OF CONCENTRATION IN AIR
                                                                    DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                       8/28/84

SAMPLE ID
FIRST FRONT TUBE 	
FIRST BACk TUBE 	
FIELD DUPLICATE FRONT TUBE
FIELD DUPLICATE BACk TUBE
SECOND FRONT TUBE 	
SECOND BACk TUBE 	
THIRD FRONT TUBE 	
THlWlACK TUBE
FOURTH FRONT TUBE 	
FOURTH BACK TUBE 	
FIFTH FRONT TUBE 	
FIFTH BACk TufiE 	
SIM PROMT TUBE 	
SIXTH BACK TUBE 	
FIELD BLANK
:RONT TUBE
BACK TUBE

UNITS
ug/m3
ug/m-5
ug/ra^
ug/mi
ug/rn3
ug/m3
ug/mj
ug/m-i
ug/rn3
ug/nv
ug/n\J
ug/m*
ug/mi
r ug/mj
ng
ng

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104
100
114
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-------
                                                       TABLE 0-31
                                    INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
                          USING VOLATILE ORGANIC SAMPLING TRAIN, IN TERMS OF CONCENTRATION  IN AIR
                                      OOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                         8/30/84

SAMPLE ID
FIRST FRONT TUBE
FIRST BACk TUBE
FIELD DUPLICATE FRONT TUBE
FIELD DUPLICATE BACk TUBE
SECOND FRONT TUBE
SECOND BACk TUBE
THIRD FRONT TUBE
THIRD BACK TUBE
FOURTH FRONT TUBE
rUUKIH BALK 1 Uot 1
FIFTH FRONT TUBE
FIFTH BACK TUBE
SIXTH FRONT TUBE
SIXTH BACk TUBE
FIELD BLANK
FRONT TUBE
BACK TUBE

UNITS
ug/m^
ug/m3
ug/mj
ug/m^
uQ/in
UQ/ITI
ug/m^
ug/rn^
ug/rn^
ug/m^
ug/m'
ug/m'
ug/m^

ng
ng

TARGET COMPOUNDS
CARBON TETRACHLORIDE
--
34
2b8
—
--

201
85
532
323
262
375
—




MONOCHLOROBENZENE
15
—

—
--

Ob
—
64
465
—
b
—




DICHLOROBENZENE*
—
10
b
—
--

--
—
--
—
--

—




1,2-DICHLOROBENZENE*
—
38

—
~

—
725
422
3517
~

—




1,3-DlCHLOROBENZENE*
—
56

—
—

--
—
--
—
--

—




1,4-DICHLOROBENZENE*
1234
59

ND
284

284
—
250
767T
303

7


2058

CHLOROFORM**
—
—

—
--

lol
b
9
	 5"
--

—

5


PERCHLOROETHYLENE
b
—

—
—

28
—
.... >
~5B"
--

—




TRICHLOROETHYLENE
- 	 	 1
—
1
11
—
—

5
6
14
— 6"
9
6
—




OTHER CHLORINATED
COMPOUNDS
1
—
















1,1,2-TRICHLOROETHANE
—
—
11
—
—
--











1,2-DICHLOROPROPANE
—
—
bb
—
—
--
2J
—
/I
~W
—
14
—




1,2, 3-TR I CHLOROPROPANE*

















DIBROMOCHLOROMETHANE
—

34

--
--

—









BENZENE RING
COMPOUNDS
BENZENE
—
—
--

—
--

—
92
~NTT

—
37
—


1238

ETHYLBENZENE
U
6
--

1
--

b/
bl
—
30
4
ND


210

STYRENE
—
--
—

^
--

—
--
~^~
—
--
—




TOLUENE
—
41
--

ND
ND

256
115
545
225
--
ND

548
1385

OTHER RING
COMPOUNDS
METHYLCYCLOPENTANE*
9
--
-•

--
--

--
2041
3757
—
--
--


2476

1,3-CYCLOPENTADIENE*

















1,3,5-CYCLOHEPTATRIENE*
--
—
--
—


--










METHYLCYCLOHEXANE*
—
113
--
--













ACCURACY
(% SURROGATE RECOVERY)
00
0
UJ
UJ
•=1
—t
o
1—
ion
82
104
6T
9T
122
116
97
TJ

~~G

0"

58
70

BROMOFLUOROBENZENE
112

82
nroo"
9
-------
                                                                           TABLE D-32
                                                       INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
                                             USING VOLATILE ORGANIC SAMPLING TRAIN, IN TERMS OF CONCENTRATION  IN AIR
                                                          DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                             9/5/84

SAMPLE ID
FIRST FRONT TUBE
FIRST BACk TUBE
FIELD DUPLICATE FRONT TUBE
FIELD DUPLICATE BACK TUBE
SECOND FRONT TUBE
SECOND BACk TUBE
THtRD FRONT TUBE
THIRD BACK TUBE
FOURTH FRONT TUBE
FOURTH BACK TUBE
FIFTH FRONT TUBE
FIFTH BACk TUBE
SIXTH FRONT TUBE
SIXTH BACK TUBE
FIELD BLANK
FRONT TUBE
BACk TUBE

UNITS
ug/m3
ug/ni3
u Q/fn
u Q/rn
ug/m3
ug/n)3
ug/m3
ug/m3
ug/m3
ug/m3
ug/n)3
ug/m3
ug/n)3
ug/m3

ng
ng

TARGET COMPOUNDS
CARBON TETRACHLORIDE
120
—


142
28
--
226

—
128
--
97


1160
SRI

MONOCHLOROBENZENE
94
—


—
—
—
—

—
—
--
56





HLOROBENZENE*
.r.

--
—


—
22
--
--

—
—
—
—





-DICHLOROBENZENE*
.

98
—


—
—
—
196

—
—
«
333



556

-DICHLOROBENZENE*
.

—
—


—
—
--
34

—
—
—
—



669

-DICHLOROBENZENE*
.

57
14


225
1089
202
282

78
--
192
21


2513


OROFORM**
3C

64
—


—
—
--
b

--
9
--
4





tCHLOROETHYLENE
UJ

36
—


38
—
--
--

—
15
--
14





CHLOROETHYLENE
ce

10
—


8
--
--
--

—
4
--
4


79


OTHER CHLORINATED
COMPOUNDS
,1-TRICHLOROETHYLENE
•

.-
—


—
—
—
—

—
—
—
—





,2-TRICHLOROETHANE
-



















>-DICHLOROPROPANE
-

21
--


4;
—
--
--
68
—
28
--
11
—




',3-TRICHLOROPROPANE*
•



















HBROMOCHLOROMETHANE



















BENZENE RING
COMPOUNDS
BENZENE
--
—


—
—
--
40
—
—
—
18
--
—

419
237

ETHYLBENZENE
26
--


4b
—
—
44
38
--
—
--
45
--

747
216

STYRENE
123
—


--
--
--
—
--
—
--
--
—
--




TOLUENE
--
—


—
--
--
--
—
—
—
--

NO

1840
306

OTHER RING
COMPOUNDS
METHYLCYCLOPENTANE*


















1,3-CYCLOPENTADIENE*
6
--
















1,3,5-CYCLOHEPTATRIENE*


















METHYLCYCLOHEXANE*


















ACCURACY
(% SURROGATE RECOVERY)
CO
a
i
Ul
z
UJ
o
(—
73
94


74
78
90
86
106
100
110
94
94
82

86
76

BROMOFLUOROBENZENE
bb
94


66
82
100
92
76
94
108
90
84


92
104

1,2-DICHLOROETHANE - D4
1U1
72


/4
127
136
28
16
86
J2
96
36
32

0
82

ETHYLBENZENE - DIO
4U
78


lib
124
124
82
146
146
88
10
106
92

64
84

ACCEPTABLE1
NO
NO


NO
NO
NO
NO
NO
NO
NO
NO
NO


NO
NO

on
CO
Notes - 1 All  surrogate recoveries  within  taryet  range  (80-125%)
          established in Quality  Assurance Project  Plan.
        * Tentatively-identified  compound.
       ** Breakthrough volume exceeded during  sampling.
       ND Compounds present on blank  tubes In  higher concentrations
          than on exposed sample.
                                                                                                                                                 COMPLETENESS = 0/16 = Ot

-------
                                                                                          TABLE 0-33
                                                                       INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
                                                                             USING VOLATILE ORGANIC SAMPLING TRAIN
                                                                         DOW CHEMICAL COMPANY BUILDING  703  INCINERATOR
                                                                                           8/28/84
UNITS
METHOD BLANKS
VOST TENAX/TENAX-Charcoal
VOST CONDENSER
VOST TUBES
FIRST FRONT TUBE
FIRST BACk TUBE
SECOND FRONT TuBE
SECOND BACK TUBE
THIRD FRONT TUBE
THIRD BACK TUBE
FOURTH FRONT TUBE
FOURTH BACK TuBE
FIFTH FRONT TUBE
FIFTH BACK TUBE
FIELD BLANK (Composite
of 5 Runs)
VOST CONDENSER
COMPOSITE SAMPLE (5 Runs)
FIELD BLANK


ng
ug/L

ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng

ug/L
ug/L

QUANTITATED COMPOUNDS
METHYLENE CHLORIDE

18000
3518



11


55

157

14Z7


1??
49

TOLUENE

428


2152
857
2524
1791
2766

3478

28

1089




ETHYLBENZENE

344


1191
105
1256
1337
909

2334
276


802
?nn




STYRENE

264






3144



44






UJ
z:
UJ
-J
X
t~
O

295


1016
482
714
11925
731

1360
1511


9482
811




CHLOROFORM*




282

514
blO
280

97

66

820
?0




UJ
CD
(\J




1115









440




UJ
Z

-------
99-Q

1

~













£















O -ri t/i -rJ
0 — — — -J
3C m x x -S
•0 n 1- -H -H -H -H
OOO I X I =C -H
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t-n z 7T Z 7* Z 0 O 3t
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CD A ^ re CO ^ A i
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^ a - -
— n so ;o
3D O J ro wi o
g 5 CHLOROFORK*
«* 0=
2 2-BUTANONE
o
J S S CARBON TETRACHLORIDE*
S SI, 2-OICHLOROPROPANE
S 1,1,2-TRICHLOROETHANE
BENZENE
S « TETRACHLOROETHYLENE*
i £ CHLOROBENZENE*
3 rv>2 TRICHLOROETHYLENE*
n uj LJ
ACETONE
£ DIBROHOCHLOROMETHANE
00
S BROMOFORM
rg
-d "« 1,4-DICHLOROBENZENE*
w ~3 o
Ch «-M O
1,2-DICHLOROBENZENE*
a
I HEXANE
g i HEXAMETHYLCYCLOTRISILOXANE
o
S DIBROMOMETHANE
^
- METHVLCrCLOPENTANE
CO
U)
5 TRICHLOROFLUOROMETHANE
UJ
S 3-METHYLPENTANE
w BENZOFURAN
C S OICHLOROBENZENE*
U) -«J
^ g 1,3,5-CYCLOHEPTATRIENE
CO A
1,3-OICHLOROBENZENE*
S METHYLCYCLOHEXANE
o(




,0
?
^
o
0
13
o
c
z
o~.












— 1
m
z
-4
<
m
i—
c
m
z
Tn
pn
f)
i
"O
c
z
o
LO






                                                                        S-H3.
                                                                        »— * CO
                                                                        %3

-------
                                                                                        TABLE D-35
                                                                    INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
                                                                           USING VOLATILE ORGANIC SAMPLING TRAIN
                                                                       DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                          9/5/84
UNITS
VOST Tubes
First Front Tube
First Back Tube
Second Front Tube
Second Back Tube
Third Front Tube
Third Back Tube
Fourth Front Tube
Fourth Back Tube
Fifth Front Tube
Fifth Back Tube
Sixth Front Tube
Sixth Back Tube
Field Blank
(Composite of 6 Runs)
VOST Condenser
Composite Sample (6 Runs)
Field Blank


ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng

ug/L
ug/L

QUANTITATED COMPOUNDS
ne chloride
1?
4-*
2




61










2t)
140


c
01
3
"o
t—











192

1840
306




nzene
.0
1?
+j
UJ

638

1000


1036
866



1016
92
747
216





c
at
i_
>>
+j


24b3
















in
S
a>
">.
10
4-1
o
t—

463

b/4


4855

bU


1083
!>26
1033
300




*
o
o
c_
o
!c
o

12/2




100


1/4

77






o

2btt6

29lb
b4b

4532

J14
2/62

2104

1160
351




1,2 - dichloropropane

412

H96



905

bM

220






91
C
OJ
c
01
on


36



967

44

561

91
419
237







III

762





Mb

280






>robenzene*
JC
CJ

lt)63









1136






hloroethylene*
i_
t—

i!0b

16b





48

98

79




o>
c
o
o>
£











1354



39U
950

TENTATIVELY IDENTIFIED COMPOUNDS
1,4 - dichlorobenzene*

1557
278
4728

20560
3735
4165

1944

4195
410
2513




1,2 - dichlorobenzene*

1944




4173




6550

556




Hex ane













810




Hexamethyl cyclotri si 1 oxane


200

200



200

200

200
200
200




Oxi sane















16


2 - (methoxyethyl ) -
trimethylsilane















14


Trlchlorofluoromethane












96b«





3 - methyl pentane


100



9711



50

8/J
1150
1100




Hexamethy Idi si 1 oxane


500















Dichlorobenzene*




429













Fluorotrimethyl s i 1 ane




1500













2,4 - dimethyl -1-pentene




500



/Ob









1,3 - dichlorobenzene*






J13/






669




2 - methyl pentene













1850




1,3 - cyclopentadiene

117
















o
en
                         * Target Volatile Compound

-------
    The distribution of  these  compounds appeared generally  random  between  the
front and back detection  tubes  when  measurable quantities were  found  in  each.
Also, several  cases appear in which the  same  compound  was detected  only in  the
front tube during one run, and only in  the back  tube in another.  Field duplicate
samples taken during the first of six runs on  the  second  sampling day were  not
comparable for any  compound, and  no evaluation  of precision  could  be  made.
Field blank samples showed no clear,  consistent pattern of blank contamination;
in some  cases,  denoted  by  the  label "NO",  compounds  were  present  in  higher
concentrations on blanks than on exposed samples.

    For screening  purposes,  these data, despite  their variability,  appear to
suggest strongly that several compounds  were  regularly present in exhausts from
the 703  Building  incinerator stack.  However, any  contributions of  organics
resulting from the venting of gases from  the activated carbon bed filter serving
the liquid  waste  tank  storage  area   cannot   be  assessed   from  these  data.
Therefore, emissions of the  above  compounds  cannot  be differentiated according
to their source.

    A detection  limit  goal  of  1 ppb  was  set with  respect to  collection of
volatile compounds  using  the VOST.  Actual  method  sensitivities were 0.25 to
0.50 microgram/cubic meter,  and  indicated  the  objective was met.  However,  the
completeness goal of 90%  was not  met, as only  5% of the samples submitted were
analyzed such that  surrogate recoveries  were  within the acceptable  range  of 80
to 125%  (see Tables D-30, D-31, and D-32).

    2.  Semi-Volatile Compounds

    Method blanks of the  glass  fiber  filter,  XAD-2  sorbent,  and impinger  catch
(distilled, deionized  water)  were  found free  of  contaminants other  than  two
phthalates commonly considered ubiquitous in  laboratory analyses.

    The physical  limitations  of the sampling  site  at  the  incinerator outlet,
and the  need  to  sample  simultaneously  at  the same  location  for  PCDD/PCDF,
precluded taking  field duplicate  samples  to  judge  precision.   In  any  event,
sampling of incinerator exhaust gases for semi-volatiles revealed few compounds
in detectable concentrations, with the  exception  of three base-neutral chloro-
benzenes and  naphthalene found  only  on the   second day  of  sampling.  As  the
recovery of  the   base-neutral  surrogates in  the  XAD-2 sample was  within  the
acceptable range  (see  Table  D-36), these findings  are  supportable;  however, it
is suspected  that  breakthrough  volumes  for  dichlorobenzenes  on   XAD-2  were
exceeded in  this  sample.   Therefore  these data  may  be  biased low.   None of
these compounds was found in any component of  the Modified Method 5 train other
than the  primary XAD-2  sorbent  cartridge.   However,  the presence  of several
substituted benzene,  naphthalene,  and   phenyl  compounds  in  the field  blank
sample on this day  may point to contamination  during sampling.

    The  chlorobenzene  concentrations found on  the second day of sampling, shown
below, correspond to daily  emissions  of  the  following  quantities of the listed
compounds:
                                     D-57

-------
                                                      OUANTITATED AND TENTATIVELY  IDENTIFIED SEMI-VOLATILE COMPOUNDS DETECTED IN INCINERATOR EXHAUST
                                                                 DOM CHEMICAL  COMPANY BUILDING 703 INCINERATOR - 8/28, R/30, and 9/5/04

8/28/B4
Filter • Probe Mash
Field Blank
XAD-2 Cartridges
Field Blank
Inplngers 1 Rinses
Field Blank
Backup XAD-2
Field Blink
8/30/84
Filter « Probe Mash
Field Blank
XAD-2 Cartridges

Implngers I Rinses
Field Blank
Backup XAD-2
Field Blank
9/S/B4
Filter « Probe Mash
Field Blank
UD-2 Cartridges
Field Blank
[•plngers 1 Rinses
Field Blank
Backup XAD-2
Field Blank
METHOD BLANKS
Filter
Probe Wash
XAO-2 Cartridges
laiplnger
1.2-OICHLOROBENZENE










27540
219

















1,4-DICHLOROBENZENE










24140


















NAPHTHALENE










7820


















BENZOIC ACID














1600














ISOPHORONE









3120



















BIS(2-ETHYLHEXYL)
PHTHALATE
24


859
6.5
11
67



9010

30

428
~T7B



44
40

330




117
69
OI-N-OCTYL
PHTHALATE







4375






476














OI-N-BUTYL
PHTHALATE



14J


422
1537


330
1047



470





2/44
1466






-t 4
X <
t- X



























5(0































TETRACHLORO-
BENZENE










5500


















BIPHENYL
















1875












1,4-DIMETHOXY-
BENZENE








4592




















3.5-DIMETHOXY-2-
CYCLOHEXENE-1-ONE








4353




















o
X
O














633














2-ETHYL-
1-HEXANOL

















2300




27
625





BUTYL-2-METHYL
PROPYLPHTHALATE






















IB






1,3,5-TRITHIANE






















3






1.4-OIHYDRO-1.4-
ETHANONAPHTHALENE











11027

















2-ETHYL-l,!'-
BIPHENYL











5125

















METHYL-
DIPHENYLSILAHE











14(80

















1,1'-(1,2-ETHENOIYL)-
BIS(Z)BENZENE











7511

















r-f
r-j ix











4403

















TERPHENYL











5026

















1-NONANOL













1795











'



3-METHYL-6- ( 1-METHYLENE I -1
DENE)-2-CYCLOHEXENE-l-ONE













5058















'All surrogate recoveries within target range (20-1801)
established In Quality Assurance Project Plan.
By class of surrogates (acids and base-neutrals) and overall (combined).
7.7'-OICHLORO-BICYCLO-
(4,1.0) HEPTANE

















"T4T3











BIS-2-METHYL-
PROPYLPHTHALATE























2020





i
ug/L
uij/L
ug/kg
ug/kg
ug/L
ug/L
ug/kg
ug/kg
ug/L
ug/L
ug/kg
ug/kg
ug/L
ug/L
ug/kg
ug/kg
us/L
ug/L
ug/kg
ug/kg
ug/L
ug/L
ug/kg
ug/kg



ug/kg
uq/L

































I COMPLE1ENESS?
ACCURACY (I SURROGATE RECOVERY)
Base-Neutrals
UJ
ae
UJ
i
58
47
0
110
101
70
61
32
2240
36
57
78
56
110
55
(1

31
0
50
43
42
64
91

67
10
71
91
§UJ
X
CNJ
89
80
0
273
81
51
85
37
120
55
68
74
85
86
64
80
34
71
0
30
58
58
97
111

(2
5
77
68
TERPHENYL-D14
54
15
0.2
133
43
25
38
23
204
21
85
fifl
" 47
75
52
77
56
71
1
84
75
65
42
44

84
0
122
106
Base-Neutrals
791
Acids
0
i
Ui
46
nl
0.1
51
50
101
52
40
2
27
8
7!
48
46
35
40
0
0
0
0
0
0
56
51

52
0
71
64
2-FLUORO-
PHENOL
24
44
(1
2(1
6J
25
^
29
0
22
0
96
41
41
75
85
0
0
0
0
0
0
85
43

51
0
57
71
Acids
5/1
2,4,6-TRIBROMO-
PHENOL
104
6(1
(1
(1
22
2(1
0
72
0
53
0
41
56
65
46
48
0
0
0
0
0
0
25
20

48
0
86
100

ACCEPTABLE1
YES
VFS
HO
m
VE5
VFS
NO
VES
NO
VES
NO
YES
YFT
VES
YTS"
YFS
NO
"10
NO
NO
NO
NO
VES
VFS

VES
(0
'ES
rffS
Overall
571 (16/28)
en
CO

-------
                                   Table D-37

                              Incinerator Exhaust
                            Semi-Volatile Compounds
                                    8/30/84

                                     Concentration      Daily Emissions
        Compound                        (ug/m3)              (grams)

        1,2-dichlorobenzene               115               141-150
        1,4-dichlorobenzene               102               125-133
        Tetrachlorobenzene                 25                 31-33

In addition, 40 to 43 grams per day of naphthalene (33 ug/m3) were emitted from
the incinerator at the operational  level of the  second sampling day.

    Raw analytical data are presented in Table D-36; these show the  presence of
compounds not  appearing  on the target  list  (Table V-l).  In  the table,  it is
shown in completeness data that generally better accuracy  (% surrogate recovery)
was achieved  for  base-neutral  compounds than  for acid  compounds.   Phthalate
compounds, considered to be common  laboratory contaminants, were also frequently
found.  Also,  substantial  contamination  by  several compounds appeared in field
blank samples,  particularly  on the  second  sampling  day; however,  though  the
surrogate recovery  performance for  those  samples  were generally  acceptable
for both  acids and  base-neutrals,  those contaminants  rarely appeared  in  the
corresponding exposed samples.  The  detection  limit objective of 5  ppb  in  air
was achieved,  with   actual  sensitivities on  the  order  of  1 to  2  ug/m3,  or
generally less than  1 ppb.

    As indicated previously, recoveries  of  acid  surrogates  during analysis  was
frequently poor,  especially  from  handling  solid  sorbent media or  mixtures  of
solids and  liquids.   The  recognized  strong affinities  to  water exhibited  by
the phenolic  (acid)  surrogates may  have been  a   factor  in  the  poor  observed
recoveries, as  the  exhaust gases  that passed through the sorbents  were  nearly
saturated with  moisture.   In any event,  overall completeness for this category
of samples was  57% (16 of  28), including method blank samples  (see Table D-36).

    3.  PCDD/PCDF

    a.  All Homologues

    In Table  D-40,  these data show a full  range  of homologues were present in
incinerator exhaust  gases, particularly  on the  second  sampling day.  Tetra-
homologues appeared  to be  present  universally,  while octa-homologues were also
found frequently.  Also  of interest  is  the  apparent tendency of most collected
constituents  to  reside  in  the  XAD-2   cartridge;  however,  the  backup  XAD-2
cartridges on  the second and third sampling  days were not  analyzed successfully,
and an  evaluation  of  breakthrough  was  thus   not  possible  on   these  days.
Particularly  high concentrations of  TCDD and TCDF were  found  on the third day;
however,  accuracy measurements indicated these data to  be questionable.
                                      D-59

-------
    Overall  completeness  (see  Table  D-38),  taking  into  account  satisfactory
accuracy and availability of data,  did not meet  the 90%  goal established  for
this study.   Detection limit criteria of 5 ppt  for tetra-homologues  and  15  ppt
for other homologues, were  met.   The  data  in Table  D-38 are  restated  in  terms
of concentration in  air  in Table D-39; also included  is information with respect
to the conditions placed  on the  summed data  for the entire  Modified  Method  5
train, when   precision,  duplicate  analysis,  and  spike analysis  problems  are
considered.   The analytical data  presented in  Table D-39 represent the  total
emissions of PCDD/PCDF  homologues;  these  data were  calculated  by summing  the
homologues caught in each portion  of  the  Modified Method 5 trains.  Note from
Table D-38 that  some  of these  individual  analyses were acceptable in  terms  of
accuracy, while other analyses were marked by unacceptable surrogate recoveries.

    b.  TCDD Isomers

    These data, presented in Table D-43 and in abridged form  in  Table D-41,  are
largely self-explanatory.   When  TCDD  was  present,  the  1368 isomer was most
common, followed by the  1379 and  1237/1238 isomers.   No 2378-TCDD was  detected
in any of these samples.  These data  are  restated  in  Table  D-42 in  terms  of
concentration in air.

    4.  Vinylidene Chloride

    The results  of  instrumental   (GC-ECD)  analysis  of  Tedlar bag samples  for
vinylidene chloride  are  presented  in  Table D-44.  Of the 20  samples obtained,
all but  one was  analyzed  in  triplicate.   Three  individual  data points were
rejected as   being  much  more  than   one   standard   deviation  from  the  mean.

    These data  suggest  that vinylidene  chloride  was present  in exhaust  gas
continuously throughout the three  sampling periods.  However, analyses of  the
same samples by Dow Chemical  using  GC-MS  indicated  those peaks  identified as
vinylidene chloride  were attributable to other compounds.

    As with  the VOST samples, the  vent of  the  incinerator  liquid  waste tank
farm activated carbon bed filter  system was located  upstream of the bag sampling
location.  Therefore,  the  compounds   identified  above may   not  be  traceable
entirely to emissions from the  incinerator.

    Table D-45  presents  the  results  of  a  series  of  replicate analyses  for
vinylidene chloride  carried out  on  the  contents  of the  same Tedlar  bags,
approximately 24 hours  apart.  These data were intended to demonstrate possible
changes in  bag  contents  from the time  of  sampling  until later  analysis.  The
results appear  to  show  random  differences   which   are  sufficiently  small   to
indicate that delays  between  sampling and  analysis did not  cause  significant
errors.
                                      D-60

-------
                                                                          TABLE D-38
                                                           INCINEKATOR EXHAUST - PCDO/PCDF ANALYSESi
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
8/30/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
9/5/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
2378-
TCDD
























Total
TCDD
10.2

283

16.6

1.4

19.0

206

24.4

Samp
Total
PeCDD


42.5





3.0

8.1



Total
HxCDD


5.8





1.2



0.9

Total
HpCDD


1.4





3.5



1.3

OCDD
2.8

1.3

2.3
2.2


11.4

1.5

1.5

2378-
TCDF
0.6

9.3





0.5

8.3

0.7
.
Total
TCDF
29.2


21'
1.2

287


32. d

264

33.8


,14:

e analysis not returned from laboratory.
Sample analysis not returned from laboratory.
10.2
0.4
15,9

2.1

Samp


















4.3
1.7






0.3






191
6.0
313

36.1

e analysis not returned from laboratory.
Sample analysis not returned from laboratory.





Total
PeCDF
4.0

84.8





6.2

11.8

6.3



1.0







Total
HxCDF
1.1

16.2





2.8

3.2

5.1











Total
HpCDF


1.7





1.8



1.4











Accuracy (% Surrogate Recovery

OCDF


0.4





1.0















COMPLETENESS BY SURROGATE
oo o
ro o
OJ h-
CJ
,— *
o
ro
100
100
2T
55"
100
IUO"
65
80
67
78
63
100
58
100


100
57
100
100
100
72


79%
i
00 O
r- o
ro o
CJt—
i
o
ro
96
92
54"
54
53
53
55
91
96
94
93
88
96
57


95
94
§2
93
90
108


83%
o
o
%,
0
ro
95
44
100
100
49
61
100
100
100
loo
53
82
150
54


89
100
57
64
33
100


75%
1
GO U_
r-- o
ro o
e\j t—
O
ro
84
65

55
94
90
55
78
37
51
1(50
57
51
P


90
35
98
62
87
44


67%
o
01
                Notes:
                1.   Data expressed in nanograms per total  sample.   Detection limit data appear
                    in Table 0-40.
                2.   All  surrogate recoveries within target range of 50-150%.

-------
                                                           TABLE D-39

                                            INCINERATOR EXHAUST - PCDD/PCDF ANALYSES
                                       EXPRESSED IN TERMS OF CONCENTRATION IN AIR (ng/m3)
                                         DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                       8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
Modified Method 5 Train
Catches
8/28/84
8/30/84
9/5/84


2378-
TCDD






Total
TCDD

[45.95]
43.75
4.92
NOTES
0 -
[ ] -

Total
PeCDD

6.49
1.94

Total
HxCDD

(p.88J
0.37

Total
HpCDD

0.21
0.84

OCDD

0.93
2.52
0.47
2378-
TCDF

1.51
1.67

Total
TCDF

[81.22]
76.98
94.53
Total
PeCDF

[12.95]
4.28
0.17
Total
HxCDF

[2.47]
1.95

Total
HpCDF

0.26
0.55

OCDF

0.06
0.17

Data out of control with respect to precision criteria (+50% RPD)
Bracketed data denote homologues detected in filter and probe wash portion
of Modified Method 5 train were deleted owing to unacceptable duplicate
analysis results. Only a small fraction of total concentration detected
was affected (see data in Table 0-38).
Matrix s
Fil
XAD
Other me
pike ana
ter and
-2 cartr
dia in t
lyses in
probe wa
idge - H
he sampl
dicated recoverie
sh - PeCDD and Hx
pCDD and HpCDF
ing train showed
II
s out of
CDF
acceptab
control
le matri
for the
x spike
followi
recoveri
ng
es.
cr>

-------
                                                                     TABLE D-40

                                                       INCINERATOR EXHAUST - PCDD/PCDF ANALYSES
                                                            FROM MODIFIED METHOD 5 TRAINS
                                                    DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                 8/28, 8/30, 9/5/84
O
 i
CTl
CO
SAMPLE IDENTIFICATION
8/28/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
8/30/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
9/5/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
2378-
TCDD
ND
(0.638)
ND
(0.107)
ND
(3.63)
ND
(.0630)
ND
(0.436)
ND
(0.236)
ND
(0.135)
ND
(.0862)
ND
(0.597)
ND
(.0736)
ND
(16.6)
ND
(0.132)
ND
(0.374)
ND
(0.137)


ND
(0.324)
ND
(0.109)
ND
(0.198)
ND
(0.801)
ND
(0.442)
ND
(0.153)


Total
TCDD
10.2
No
(0.111)
283
ND
.0209)
16.6
ND
(0.162)
1.35
ND
.0542)
19.0
ND
.0150)
206
ND
(0.154)
24.4
ND
(0.280)


10.2
0.369
15.9
ND
(1.04)
2.11
ND
(0.111)


Total
PeCDD
ND
(0.160)
ND
(0.276)
42.5
ND
(0.143)
ND
(0.430)
ND
(0.613)
ND
(0.146)
ND
(0.340)
2.96
ND
(.0558)
8.10
ND
(0.421)
ND
(0.274)
ND
1.30)


ND
(0.160)
ND
(.0769)
ND
(.0787)
NO
(1.86)
ND
(4.60)
ND
(0.558)


Total
HxCDD
ND
(0.301)
ND
(0.191)
5.75
ND
(0.119)
ND
(0.470)
ND
(0.485J
ND
(.0768)
ND
(0.180)
1.22
ND
(.0425)
ND
(0.339)
ND
(0.411)
0.878
ND
(0.790)


ND
(0.109)
ND
(.0483)
ND
(.0616)
ND
(1-74)
Nb
(3.90)
ND
(0.447)


Total
HpCDD
ND
(0.431)
ND
(1.27)
1.36
ND
(0.127)
ND
(0.709)
ND
(0.898)
ND
(.0605)
ND
(0.216)
3.52
ND
0.119)
ND
(0.358)
ND
(0.345)
1.26
ND
(5.02)


ND
(0.443)
ND
(0.129)
ND
(0.371)
ND
(2.73)
ND
(278)
ND
(0.753)


OCDD
2.80
ND
(5.49)
1.33
0.341
2.29
2.19
ND
(0.441)
ND
(0.338)
11.4
ND
(0.271)
1.46
ND
(0.369)
1.52
ND
(3.81)


4.30
1.65
ND
(0.281)
NO
(2.69)
ND
(16.2)
ND
(1.89)


2378-
TCDF
0.584
ND
(0.138)
9.32
ND
(0.297)
ND
(0.463)
ND
(0.180)
ND
(0.481)
ND
(.0704)
0.532
ND
.0433)
8.26
ND
(0.170)
0.712
ND
(0.259)


ND
(0.379)
ND
.0264)
ND
(0.322)
ND
(0.847)
ND
(0.488)
ND
(0.138)


Total
TCDF
29.2
ND
(0.186)
213
1.23
287
ND
(0.169)
32.0
ND
(.0649)
264
ND
(.0171)
33.8
ND
(0.175)
141
ND
(0.302)


191
5.98
313
ND
(0.905)
36.1
ND
(0.173)


Total
PeCDF
3.95
ND
(0.154)
84.8
ND
(0.357)
ND
(0.680)
NO
(0.471)
ND
(.0778)
ND
(0.148)
6.23
ND
(.0623)
11.8
ND
(0.230)
6.34
ND
(0.661)


0.967
ND
(.0555)
ND
(.0734)
ND
(1.28)
ND
(0.823)
ND
(0.413)


Total
HxCDF
1.09
ND
(0.223)
16.2
ND
(0.470)
ND
(0.469)
ND
(0.364)
ND
(.0742)
ND
(0.130)
2.79
ND
(.0663)
3.23
ND
(0.333)
5.11
ND
(1.12)


ND
(0.124)
ND
(.0939)
ND
(.0566)
ND
(1.93)
ND
(2.54)
ND
(0.456)


Total
HpCDF
ND
(0.428)
ND
(0.662)
1.70
ND
(.0707)
ND
(0.968)
ND
(0.495)
ND
(0.112)
ND
(0.301)
1.76
ND
(.0833)
ND
(0.360)
ND
(0.345)
1.39
ND
(1.57)


ND
(0.771)
ND
(0.132)
ND
(0.340)
ND
(3.24)
ND
(3.82)
ND
(0.819)


OCDF
ND
(0.592)
ND
(3.56)
0.400
ND
(0.122)
ND
(0.830)
ND
(0.694)
ND
(0.105)
NO
(0.326)
0.967
ND
(0.218)
ND
(0.646)
ND
(0.368)
ND
(0.207)
ND
(2.39)


ND
(0.220)
NO
(0.125)
ND
(0.556)
ND
(2.00)
ND
(25.0)
ND
(0.621)


                    NOTES:  Data expressed in nanograms per total  sample.  Accuracy (surrogate recovery) data appear in Table D-38.

-------
                                                                              TABLE D-41



                                                                    INCINERATOR EXHAUST  -  TCDD  ISOMERS

                                                              DOM CHEMICAL COMPANY BUILDING  703  INCINERATOR

                                                                          8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank*
Backup XAD-2
Field Blank
8/30/B4
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2*
Field Blank*
9/5 /b4
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2*
Field Blank*
1368
0.69

122 ~

B.94

0.88

8.70

74.8

12.3



4.51
0.81
8.67

2.11



1379
3.74

75.9

4.51

0.37

4.96

60.6

6.65



2.82
0.07
4.68





1369
























1247
1248
1378
1469


11.0





0.52



0.62



0.32

0.52





1246
1249
























1268
1278
























1478
























1268
1279
























1234
1236
1269
























1237
1238
5.29

73.5

3.16

0.10

4.79

64.3

4.81



2.50
0.12
1.99





2378
























1239
























1278
1279
























1267
























1289
























a
 i
                    NOTE:  Data expressed In nanograms per total  sample.



                           * Sample analysis not returned from laboratory

-------
                                                                                   TABLE D-42


                                                                       INCINERATOR EXHAUST- TCDO ISOMERS
                                                                   EXPRESSED IN TERMS OF CONCENTRATION IN AIR


                                                                 DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                               8/28, 8/30. 9/5/84
SAMPLE IDENTIFICATION
Notified Method 5 Train
Catches
8/28/84
8/30/84
9/5/84

1368


20
17
2.9

1379


13
13
1.3
NOTE -
1369





lata exp
1247
1248
1378
1469


1.8
0.2
0.2
•essed 1
1246
1249





i ng/m3
1268
1278






1478






1268
1279






1234
1236
1269






123?
1238


12.5
13
0.8

2378






1239






1278
1279






1267






1289






a
 i
CTl
Ol

-------
                                                                           TABLE 0-43
                                                               INCINERATOR EXHAUST - TCDO ISOHERS
                                                           AS MEASURED USING MODIFIED METHOD 5 TRAINS
                                                         DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                     8/28. 8/30. AND 9/5/84


                                                       (All data expressed in nanograms per total sample.)
SAMPLE IDENTIFICATION
8/28/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2
Field Blank
8/30/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2
Field Blank
9/5/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2
Field Blank
1368
0.694
ND
(0.111)
122
ND
( .0209)
8.94
NO
(0.162)
0.879
ND
(.0867)
8.70
ND
(.0150)
74.8
ND
(0.165)
12.3
ND
(0.280)
(S
{£
4.51
0.176
8.67
ND
(1-39)
2.11
ND
(0.111)
(S<
1379
3.74
ND
(0.111)
75.9
ND
( .0209)
4.51
ND
(0.162)
0.372
ND
(.0542)
4.96
ND
(.0150)
60.6
ND
(0.154)
6.65
ND
(0.280)
ample an
ample ar
2.82
0.0732
4.68
ND
(1.04)
ND
(0.581)
ND
(0.111)
mple an;
1369
NO
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0209)
ND
(0.434)
ND
(0.162)
ND
(.0431)
ND
(.136)
ND
(0.217)
ND
(.0150)
ND
(3.78)
NO
(.154)
ND
(0.307)
ND
(0.280)
ilysls r
ilysls r
ND
(0.231)
ND
(.0272)
ND
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
lysis n<
1247
1248
1378
1469
0.980
ND
(0.111)
11.0
NO
( .0209)
ND
(0.651)
ND
(0.162)
NO
(.0647)
ND
(.0542)
0.522
ND
(.0150)
ND
(3.78)
ND
(0.154)
0.616
ND
(0.280)
)t retur
at retur
0.319
NO
(.0272)
0.520
NO
(1.04)
ND
(0.581)
NO
(0.111)
it returr
1246
1249
NO
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0209)
ND
(0.434)
ND
(0.162)
NO
(.0647)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
NO
(0.614)
ND
(0.280)
led fron
led frorr
ND
(0.231)
ND
( .0272)
ND
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
ed from
1268
1278
ND
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0209)
ND
(0.434)
NO
(0.162)
ND
(0.108)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.280)
laborat
laborat
NO
(0.231)
ND
(.0272)
ND
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
laboratc
1478
ND
(0.258)
ND
0.111)
ND
(3.09)
ND
(.0209)
ND
(0.434)
ND
(0.162)
ND
(.0518)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.280)
>ry.)
>ry.)
ND
(0.231)
ND
(0.127)
NO
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
ry.)
1 1
(Sample analysts not returned from laboratory.)
1268
1279
ND
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0290)
ND
(0.434)
ND
(0.162)
ND
(.0431)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
NO
(0.307)
ND
(0.280)


ND
(0.231)
ND
(0.272)
ND
(0.428)
NO
(1.04)
ND
(0.581)
ND
(0.111)


1234
1236
1269
NO
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0290)
ND
(0.651)
ND
(0.162)
ND
(0.431)
No
( .0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
NO
(0.307)
ND
(0.280)


NO
(0.231)
ND
(.0363)
ND
(0.428)
ND
(1.04)
ND
(0.581)
NO
(0.111)


1237
1238
5.29
ND
(0.111)
73.5
NO
(.0290)
3.16
ND
(0.288)
0.0997
ND
(.0542)
4.79
ND
(.0150)
64.3
ND
(0.154)
4.81
ND
(0.5601


2.50
0.121
1.99
'ND
(1.04)
ND
(0.697)
ND
(0.111)


2378
NO
(0.638)
ND
(0.107^
ND
(3.63)
ND
(.0630)
ND
(0.436)
NO
(0.236)
ND
(0.135)
ND
(.0862)
ND
(0.597)
ND
(.0736)
ND
(16.6)
ND
(0.132)
ND
(0.374)
ND
(0.137)


ND
(0.324)
NO
(0.109)
NO
(0.198)
ND
(0.801)
ND
(0.442)
NO
(0.153)


1239
NO
(0.258)
ND
(0.111)
ND
(3.09)
NO
(.0290)
ND
(0.434)
ND
(0.162)
NO
(.0431)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.350)


ND
(0.231)
ND
(0-272)
ND
(0428)
ND
(1.04)
ND
(0581)
ND
(0.111)


1278
1279
ND
(0.258)
NO
(0.111)
NO
(6.17)
ON
( .0290)
ND
(0.434)
ND
(0.162)
ND
(.0431)
ND
(.0542)
NO
(0.217)
ND
(.0150)
NO
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.350)


NO
(0.231)
ND
(0.272)
ND
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)


1267
NO
( .0258)
ND
(0.111)
ND
(3.09)
ND
( .0290)
ND
(0.434)
ND
(0.162)
NO
(.0431)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.350)


ND
(0.231)
ND
(0272)
ND
(0.428)
ND
(1.04)
ND
(0581)
ND
(0.111)


1289
ND
(0.258)
NO
(0.111)
ND
(6.17)
ND
(.0290)
ND
(0.434)
ND
(0.162)
NO
(.0431)
NO
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.350)


NO
(0.231)
ND
(0.272)
ND
(0.428)
ND
(1.04)
NO
(1-16)
ND
(0.111)


a
 i
CTi
CTl

-------
                                      TABLE  D-44

                     RESULTS OF SAMPLING  FOR VINYLIDENE  CHLORIDE
                    DOW CHEMICAL COMPANY  BUILDING 703 INCINERATOR
DATE
8/28/84






8/30/84





9/5/84






SAMPLE RUN
1
2
3
4
5
6
7
1
2
3
4
5
6
1
2
2 DUPLICATE
3
4
5
6
SAMPLE
COLLECTION TIME (EOT)
1230-1330
1405-1510
1525-1625
1640-1735
1750-1845
1850-1930
1935-2015
1000-1050
1100-1200
1210-1250
1300-1350
1400-1450
1500-1550
1000-1045
1100-1150
1100-1150
1200-1245
1400-1445
1500-1545
1600-1630
VINYLIDENE CHLORIDE
CONCENTRATION (ppbv)
88.6 (83.1, 88.0, 94.7)
68.3 (72.1, 72.3, 60.2)
64.3 (113.0*, 67.5, 61.1)
74.5 (73.9, 74.7, 74.8)
88.9 (94.2, 88.4, 84.1)
112.4 (113.6, 111.2, 138.6*)
104.4 (102.1, 107.8, 103.3)
149.7 (150.0, 154.9, 144.3)
187.6 (180.9, 189.3, 192.7)
241.6 (263.7, 219.5, 402.7*)
279.8 (275.3, 285.9, 278.3)
218.0 (219.6, 216.3)
28.1 (28.9, 27.9, 27.6)
88.7 (94.3, 93.3, 78.5)
70.3 (69.4, 68.9, 72.6)
79.3 (76.7, 81.9, 79.3)
157.8 (156.4, 152.5, 164.4)
154.3 (162.2, 143.5, 157.2)
156.0 (154.7, 161.6, 151.8)
143.5 (146.6, 143.3, 140.6)
STANDARD
DEVIATION
5.8
6.9
4.5
0.5
5.1
1.7
3.0
5.3
6.1
31.3
5.5
2.3
0.7
8.8
2.0
2.6
6.1
9.7
5.0
3.0
* Rejected as greater than one standard deviation from mean of three analyses,
                                         D-67

-------
                                      TABLE D-45

                      RESULTS OF SAMPLE AND BAG STABILITY TESTS
                           FOR VINYLIDENE CHLORIDE SAMPLES
                    DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                   8/28 AND 9/5/84
DATE
8/28/84


9/5/84


SAMPLE RUN
5
6
7
1
5
6
COMPARATIVE CONCENTRATION
ANALYSIS DAY
88.9
112.4
104.4
88.7
156.0
143.5
FOLLOWING DAY
63.5 (47.6*, 65.6, 61.4)
104.7 (108.4, 102.8, 103.0)
105.4 (112.2, 100.9, 103.2)
84.8 (single value only)
178.4 (182.5, 183.9, 168.8)
179.1 (171.1, 183.2, 183.1)
DIFFERENCE (%)
-28.6
-6.9
+1.0
-4.4
+14.4
+24.8
* Rejected as greater than one standard deviation from mean of three analyses.
                                         D-68

-------
    E.  Incinerator Ash

    1.  Semi-Volatiles

    Analyses of  incinerator ash  (see  Table  0-46)  revealed  the  presence  of
1,2- and  1,4-dichlorobenzene;   1,2,4-trichlorobenzene;  phenol;  and  biphenyl,
among the targeted  compounds.   However, the  first  three  compounds  wera  found
only in the  field  duplicate sample on the second  sampling  day,  in the low ppm
range.  Phenol and  biphenyl were  detected  at the  0.5 ppm level  on the  third
sampling day.  Tentatively identified  in the ash collected  on the second sampling
day, in the  sample and  field  duplicate,  were the  following ring  compounds:

                                   Table D-47

                            Semi-Volatile Compounds
                                Incinerator Ash
                                    8/30/84

                                               Concentration
                                                  (mg/kg)
Compound

Methyldi phenylsi 1ane
l,l'-(l,2-ethendiyl)bis(z)benzene
1,1':2',l-terphenyl
1,1':3',l-terphenyl
1,1':4',1-terphenyl
Sample
52.838
11.628
4.932
10.792
11.243
Field
Duplicate
44.757
5.661
9.919
6.245
9.965
Precision
  (RPD)

  16.6
  69.0
  67.2
  53.4
  12.1
    Quality assurance  criteria  with  respect  to accuracy  (surrogate  recovery)
were met for all  of  the samples analyzed.  However, two  of  the  seven samples,
field blanks for the  second and  third  sampling days, were lost prior to analysis
by the laboratory.

    2.  PCDD/PCDF

    a.  All Homologues

    These data,  presented  in Table D-48,  appear  to  indicate  that  among  the
PCDDs, the homologues  were  detected in concentrations  increasing  according to
their chlorine substitution;  OCDD was  most common.  With PCDF, this relationship
did not hold;  total  TCDF  were  generally  most  prevalent,  followed  by  OCDF  and
hepta-CDF.

    Accuracy criteria for the four  surrogate  compounds  were  not  met for two of
the six completed analyses;  the  seventh analysis was not accomplished, resulting
in 57% completeness for the incinerator ash PCDD/PCDF analyses.   Note, however,
that the  surrogate  recovery criteria  for  1-3C]_22378-TCDD  and  •37C142378-TCDF
(70-130%) were missed by only 5 to 6%.  The precision goal of +50% was achieved
for most  homologues  detected in  the  field duplicate  samples obtained  on  the
                                    D-69

-------
                                                                                        TABLE D-46
o










8/28/84
8/28/84
field blank
8/30/84
8/30/84
field dup.
8/30/84
field blank
9/5/84
9/5/84
field blank
01
4->
(D
OJ .C
c *J a;
aj a> .c c
0) a» N •*-* o. at
c c c ia M
01 a; Of •— a/ c
N N £* to -*-> 'T Ol
CCO -C (O O1 JO
ai a) i. <-> •— 5; i
^3 ^) O -C 10 ^ *t
00.- CL J=. ;f -r-
i- 1- -C 4-* ^ XI
0 0 U r- .C JT> 1
r— r— -r- >, O- fj >,
-c -c «- <-> % x
U U •»-* 3 •— y O

"O T3 ** O 1 -C .^ . ^H
1 1 C C +J "

i-i t-l t-H O-TJT3^1^H
433 201


1933
520 460 867 1733 (0663
(SAMPLE ANALYSIS NOT RETURNED
363 1110 423530
(SAMPLE ANALYSIS NOT RETURNED
INCINERATOR ASH SEMI-VOLATILES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
(Results in fig/kg )
~ ACCURACY (% SURROGATE RECOVERY)
IO >i
QJ XI C Ol QJ --^
r->, C C C O '*- f— Ct
•f- -t- a> - o
r— irt T3 XTXIXI-r- | t/ll_
>,r-C O-D-Cin- ^-d
c:>>o» c (. i. -i- f-* >i r—
QJ C -C O) QJ QJ U - C >, QJ
d x: OJ ^>^O.QJr—
^ XI -r- CM 0) - - *X:X'«-Era
>t^-X) *N- - - 4->O-C IX:
1_ C >-1r-£-tCC\JO->«3- QJ C »— eg -p
3O*x: v,;Taj 	 E> — -c

3-i-lQJ » »*»OlQJ-r-
t/>XICMGr-t i-Ht-Hf-HOfMEXl
2722


TltS 5UJ9 11624 4932 W792 11243
44757 M«l MM CMS JX5 tO« 3«l
FROM LABORATORY)
170 435 321 1069
FROM LABORATORY)
1
QJ
M
C
QJ
Xt
O

•r-
C
10?

65
96
30

63
Com
c.

-------
                                                                                     TABLE  D-48


                                                                        INCINERATOR  ASH  - PCOD/PCDF  ANALYSES1
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30. AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84 '
COMPOSITE SAMPLE
FIELD BLANK
8/30/84
COMPOSITE SAMPLE
FIELD DUPLICATE
PRECISION (RPD)
FIELD BLANK
9/5/84
COMPOSITE SAMPLE
FIELD BLANK
2378-
TCDD
ND
(27.7)
ND
(8.2)
ND
(23.1)
NO
(11.8)


ND
(6.9)

Total
TCDD
1170
NO
(9-6)
131
107
20

71
(Ani
Total
PeCDD
ND
(19.1)
ND
(35.8)
ND
(13.6)
ND
(15.6)


ND
(16.2)
lytical
Total
HxCDD
793
ND
(17.5)
129
111
15

ND
(10.9)
data noi
Total
HpCDD
6060
NO
(12.7)
806
498
47

76
returns
OCOD
32,700
ND
(25.8)
3180
2370
29

266
d from 1
2378-
TCDF
66
ND
(12.6)
17
ND
(11.3)


NO
(6.5)
aboratory
1 J
Total
TCDF
9160
ND
(12.8)
594
263
77

540
.)

Total
PeCDF
68
ND
(21.2)
NO
(5.4)
ND
(7.3)


ND
(7.8)

Total
HxCDF
455
NO
(19.6)
44
37
17

ND
(19.5)

Total
HpCOF
1520
NO
(15.9)
449
248
58

NO
(20.2)

OCDF
2570
ND
(23.4)
573
399
36

78

COMPLETENESS BY SURROGATE
Accuracy (%Surrogate Recovery
i
CO o
r-~ Q
CO O
CM h-
C\J
O
ro
88
74
65
64

100
84

86*
i
OO O
r- O
ro o
CM (—
«»
<->
i —
ro
97
91
92
95

97
98

86%
o
o
8
CM
LJ
CO
100
100
100
100

78
100

86%
00 U.
r- o
ro o
CM I—
*3-
<3
r-~
ro
80
70
73
65

93
78

86%
O
 I
                             NOTES:  Iflata expressed In pg/g.

                                     2A11 surrogate recoveries within target range of 50-1502.

-------
second day.  Detection limit goals  of  5 ppt for TCDD and TCDF, and  15  ppt  for
other homologues, were generally met;  detection  limits  of 0.5 to  1.9 ppt  were
achieved for TCDD  and TCDF,  and  about 0.3 to  2.0 ppt  for higher  homologue
groups.

    b.  TCDD Isomers

    The 1368,  1379,  and  1237/1238  isomers appeared  in  all   samples;  no  2378
isomer was found.  Duplicate samples  from the second day yielded  satisfactory
results for precision (see Table D-49).

    F.  Aqueous Influents and Effluents

    This category  of samples  refers  to those  water streams  circulated on  a
once-through basis  in air  pollution  control   equipment  associated  with  the
Building 703 incinerator, and the returned  treated wastewaters ("service water")
used to make up  the  bulk of water  supplied to these devices  (except the  ESP,
see Section  V.A.2.d, and  the   ash  pit,  see   Section  V.A.3  of  this  report).

    1.  Volatile Compounds

    Owing to the  small   volume of  water  samples  taken  (40  ml  for  volatiles
compared to  one  gallon  for  semi-volatiles)   and   the  correspondingly  small
fraction of  solid matter  in  these samples,  data  with  respect  to  volatile
compounds in influent and effluent  waters  were reported  in  terms  of micrograms
per liter.   Quality  assurance  criteria  for  accuracy  (percent  recovery  of
surrogates) were met for  all but two of the 22  samples analyzed in this category;
however, the analytical  procedures  did not achieve  the target detection limit
of 1 ppb, as  the detection limit for most of the compounds  of  interest was 5 ppb.

    The behavior of volatile  compounds  in air pollution control equipment waters
appeared similar to  that of  the semi-volatiles discussed  previously.  That  is,
many compounds  present  in   influent   (service)  water  appeared   to  have  been
volatilized in  contact with  scrubbed  exhaust  gases from the incinerator.  This
phenomenon (see  Tables   0-50,  D-51, and  D-52) was  observed  in  the cases  of
chloroform, carbon tetrachloride, and  some other compounds.

    The data revealed the  regular  presence of  no distinct compounds.  However,
on the second sampling day, a number of compounds were found in ash pit effluent,
among them  the target compounds 'perch!oroethylene  and monochlorobenzene,  and
other constituents   of   interest,   such  as  chloroethane,  chloromethane,  and
ethylbenzene.   This  corresponds to a  previously described   finding  of  several
semi-volatile  compounds  in  ash  pit solid  matter  on the  second  sampling  day.

    Field  duplicate  samples  were obtained  only of the ESP  water  stream on the
second  sampling  day.  Analytical  results  could  be compared  only  for methylene
chloride  and dimethoxymethane;  precision appeared  good  for  the former but poor
for the  latter.
                                     D-72

-------
                                                                             TABLE  D-49


                                                                   INCINERATOR  ASH  - TCOI) ISOMERS

                                                          OOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                      8/28,  8/30,  AND 9/5/84
 i
^~j
CO
SAMPLE IDENTIFICATION
8/26/84
COMPOSITE SAMPLE
FIELD BLANK
/JO/84
COMPOSITE SAMPLE
FIELD DUPLICATE
PRECISION (RPD)
FIELD BLANK
9/5/84
COMPOSITE SAMPLE
FIELD BLANK

1368
620

65
57
13

35


1379
248

35
31
12

23
(An,

1369







lytical

1247
1248
1378
1469
37

8




data noi

1246
1249







returm

1268
1278







d from :

1478







aborator

1268
1279







y.)

1234
1236
1269









1237
1238
267

23
19
19

14


2378









1239









1278
1279









1267









1289









                                 NOTE:  Data expressed in pg/g.

-------
                                                                                                               IA6LE D-50


                                                                                           AQUEOUS  INFLUENIS AND EFFLUENTS - VOLATILE COMPOUNOSl
                                                                                              DOW  CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                                                 8/2H/84






SAMPLE IDENTIFICATION
INFLUENT
SERVICE WATER
EFFLUENTS
QUENCH WATER
VENTURI/DEM1STER
UATEK
ESP UMER
ESP UATER
FIELD DUPLICATE
ASH PIT UATER
FIELD BUHV5
EFFLUENT MATER
EFFLUENT UATER
DUPLICATE



TARGET COMPOUNDS



t
o
o
£
U

4'






t'











16






lo simp






c
1
fe
L.








e taker






|
|
e
I








•j





OTHER VOLATILE COMPOUNDS


S
O
I
\

41







6

232

169



V
w
I















£
o
"c
u
t-
-i















c
2
O
O
5
~.

6















•1
*
1
















I
|
L.
0
U
















|
•^t
O
JC
u

















g
4->
E
















C
c
1
«u
















i
&
o

















f
tl
a
"o
*j














TENTATlV£iy IDENTlflfO
COMPOUNDS

£
1

t
ts

289



73
173







S
O
L.
a
o
o
u
t
tsi

















ft*
x















I
1
I
".

















_




















4,
IB
M















ACCURACY
(t SURROGATE RECOVERY


S
i
3
"o


111

111

104
104


103

102

102

I
1

|


91

99

103
111


103

n;

111
s
1
g
0
c
(M


84

103

91
97


102

103

103
Note - ID«U expressed In uj/l. Completeness «
established tn Quality Assurance Project Plan.
• Estimated value.






ACCEPTABLE?

YES

YES

YES
YES

—
YES

YES

YES



O
 I
--J
-O

-------
                                                                                                                TABLE  D-51

                                                                                           AQUEOUS INHUENIS ANU EFFLUENTS  - VOLATILE  COMPOUNDS!
                                                                                               DOH CHEMICAL  COMPANY BUILUING 703 INCINERATOR
                                                                                                                  8/30/84






SAMPLE IDENTIFICATION
INFLUENT
SERVICE WATER
EFFLUENTS
QUENCH WATER
VENTODI/DEMIsTEK
MATER
ESP WATER
ESP WATER
FIELD DUPLICATE
ASH PIT MATER
FIELD BLANKS
EFFLUENT HATER
EFFLUENT WATER
DUPLICATE



TARGET COMPOUNDS



r
chlorofo

7










*

etrachlor
*>
o

71












oethylene
perchlor







218






|
1











Note - lOata expressed
?AI1 surrogate
OlHtH VOtAMIE COMPOUNDS


«
o
5
ftt
1
*

68
5
8
,.


S

20
19




acetone



19



30

33
15

S
c
Ichloroet
-;

9











£
1
O
O
•5
(V)















benzene









11
7



I
chloronte







94






I
chloroet







37







2-butano







41






«
eth/lDen







96






j
o
4-1







117







toluene







184



TENIATIVELV IDENTIFIED
COMPOUNDS



I
S




3







S
o
Ichlorop
~:

17












S
1













*
thylbuta
I











Ol
c
X
o


ylcyclot
M















41










32
ACCURACY
(1 SURROGATE RECOVERY)



§
toluene

96
90
93
89

94
97


91


S
S
1
o
bromofli

80
104
88
94

99
95


84

t
£
|
o
u

84
104
108
96

10S
106


112
In uq/L Completeness -
recoveries xlthln target range (80-1251) "8 ' 88t
established In Quality Assurance Project Plan.
* Estimated value.






ACCEPTABLE2

YES
YES
YES
YES

YES
YES


YES



o

c_n

-------
                                                                                                               1ABLE D-52

                                                                                          AQUEOUS INFLUENTS AND EFFlUENtS - VOLATILE COMPOUNDS'
                                                                                              DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                                                 9/5/84







SAMPLE IDENTIFICATION
INFLUENT
SERVICE MATER
EFFLUENTS
QUENCH UATER
VENTURl/OEHISTER
MATER
ESP MATER
ESP UATER
FIELD DUPLICATE
ASH PIT MATER
FIELD BLANKS
EFFLUENT MATER 	 ,
EFFLUENT MATER
DUPLICATE



TARGET COMPOUNDS





chlorofona
21




(









110




o samp







g
perchloroetnyl
4




e take







!
o





. )


1
OTHER VOLATILE COMPOUNDS





•ethylene chlo
55
24
2600
16



70
26





acetone


1198




„
44





~
6






5



c

o
u
r*j
16













}
4
5
,
7


4

4





chl oroKthane














chloroethene














I








J





ethylbenzene














o


5











|
3
*O







1.6*

TENTATIVELY IDENTIFIED
COMPOUNDS




c
dlmcthoxyiKth



225






C
3.
O

O
O
£
l_
*J
ro
CM














S
41
O











g

4-)
E
4->
I!
7
f*l









1






200
200












hexane









ACCURACY
(I SURROGATE RECOVERY





toluene-08
97
99
99
99


98
93
101


¥


brow)fluorobe
99
100
107
98


118
108
91

S
c
m

1,2-dlchloroe
80
91
92
81


96
115
96
Not. - lOata expressed In ug/L. C°»J""?OW "
established In Quality Assurance Project Plan.
* Estimated value.







ACCEP1A8LE*
YES
YES
YES
YES


YES
YES
YES



a\

-------
    2.  Semi-Volatile Compounds

    Quality assurance criteria with  respect  to  accuracy (surrogate  recoveries)
were generally met  for the  analyses  of aqueous  samples and  solid  filtrates.
However, detection limit goals of  5  ppb  in  liquids  and solids were not achieved,
actual detection  limits  being on the  order of  10 ppb.  The  analytical  data,
Tables D-53, D-54, and D-55, show  that few  semi-volatile compounds were detected
in any of the wastewater  liquid and solid streams at levels higher than those in
influent service waters.  This appears  to  indicate that  such compounds present
in influent  waters  may  have  volatilized  out   of  the  liquids  as they  passed
through the incinerator air pollution control devices.

    Effluent waters were found to  contain only  the following targeted compounds
on the sampling days indicated:

                                           Concentration
  Compound               Sampling  Day          (ug/L)          Effluent Stream

  Tetrachlorophenol            2                  13           Venturi/Demister
  Monochlorobenzene           2                 157           Ash Pit
  l,l'-biphenyl               2                 285           Ash Pit

However, surrogate recoveries from the sample from which the last two compounds
were analyzed  did  not meet  the  quality assurance goals  established for  the
study, and these data should therefore be considered tentative.

    Little was detected in  the filtered  solids portions of the effluent streams.
As the data  in Tables 0-53, D-54,  and  D-55  indicate,  several  phthalates  were
found regularly,  and  many  effluent  streams  contained  solid  elemental  sulfur.
Of possible interest  is the  finding  of  biphenyls in electrostatic precipitator
and ash pit effluent solids on  the third sampling day, and a variety of benzene,
biphenyl, and  terphenyl  compounds  in  ash  pit  effluent  solids  on  the  second
sampling day.  Note  that  several of these compounds also  appeared in  incinerator
ash on that day.

    3.  PCDD/PCDF

    a.  All Homologues

    It will be recalled  from  previous  descriptions of  the Dow  facility  that
service water  circulated in  most  incinerator air  pollution  control  devices is
composed of  a  stream of  wastewater  from  the  plant's  wastewater  treatment
system.  Low concentrations of tetra- and octa-CDD and  CDF were detected  on  the
first and  second  sampling  days, along  with  traces of other  homologues  on  the
latter day; no PCDD or PCDF were found on the third day  (see Tables  D-56, D-57,
and D-58).

    Effluent water stream concentrations of all  homologues appear several  orders
of magnitude higher than  in service water.  However,  note  that  PCDD  and  PCDF
reside almost exclusively in the suspended  (filterable)  solids present in these
                                    D-77

-------
                                                                                                                 TABU 0-53

                                                                                          AQUEOUS  INFLUENIS AND EFFLUENTS - SEHI-VuLAIlLE CONFOUNDS
                                                                                                00* CHEHICAL COMPANY BUILDING 703 INCINEKAKW
                                                                                                                   «/28/84

SAMPLE IDEHIIFICA1IOH
Service Hater
Quench Hater
(Deter Portion)
Quench Hater
(Solids Portion)
Venturl/Denlster Hater
(Deter Portion)
Venturl/DCMlster Deter
(Solids Portion)
ESP Heter
(Hater Portion)
ESP Hater
Deter Field Oupllcete
ESP Heter
(Solids Portion)
ESP Deter
Solids Field Duplicate
Ash Pit Hater
(Deter Portion)
Ash Pit Hater
(Solids Portion)
Effluent Heter Field Blank
Effluent Heter Backup
Field Blenk
uHiis
"%
u%
"%,
•%,
u,/t
"%
u,/L
"%,
"'/k,
""/I
"'/kg
»%
U,/L
IARGEI COHPOUNOS
*o
1













tetrechlorophenol






(No

(No




2,3,4,6-tetrachloroohenol






a»pl

r
amp)




pefttachlorophenol*






tak

tak




1
a






n.)

n.)




1
J













I













\
5
,


18

21


100


34.750


dtethyl pnthalete







132





D1s(2-«thylhexyl)pht halite*










82.725


di-n-octyl pnthelate*













bi s ( 2-chl oroethyl ) ether*













benzole acid*













S
S
28









107.155


3


35

32





242.536


bts(2-ecthylpropyl ) pnthilate







336


36,212


butyl -2-avnhyl propyl
phthalite













f













2-ethyl-l,l'-elpMnyl













•ethyldlphenylstlane













l,2-ethendtyl)b1S'(2)-
zene
:•*













l.l':2',l-t«rpHe»iyl













j














1.1-dlpMnrllMfJtene













5
*>,













bu ty 1 octadeca noa te













2,2l-oxyt>1setn*nol













1.3-41.Mthylbenzene













l-butoxy-2-propanol













£3 Ull surrogate recoveries within terget range (20-1801) established In
o
c
eV
O
i













1,1.3-trltjethylcyclopentane













l-(2-butOKyethoxy) ethenol













COUPLE IENESS2
Accuracy
(1 SurroQete Recoverv)
Base-Neutrals
nitrobenzene-OS
57
72
57
72
24
83

72

54
32
61
46
J
i
1
60
59
67
63
30
70

04

48
38
66
50
1
77
9,
98
81
44
95

46

58
22
96
66
1001
Acids
phenol -05
69
37
37
82
22
26

43

2H
31
21
17
"o
S
3
51
35
73
84
26
101

J7

61
38
39
49
2,4,6-trlbromooheno!
54
67
71
68
32
90

67

51
52
0]
85
91»
ACCEPTABLE'
YES
IES
YES
YES
IES
YES

YES

US
,ES
IES
NO
Hi
10/11)
-^J
CO
                       2B,  ,
                                                                      s)  and overall (combined).

-------
                                                                                                                              AQUEOUS INFIUCNIS Mil EFflUENIS - SEHI-YOIMIIE COMPOUNDS

                                                                                                                                   DON CHEM1I AL COMPANY BUILDING JUJ INC I NERAIOR

                                                                                                                                                       8/30/8*
O
 I

SAMPLE t«*r tf ic*ftG*r
Service Water
Quench Miter
(Mater Portion)
Quench Miter
(Soltdi Portion)
(Miter Portion)
(Soltd> Portion)
ESP Meter
(H*tir Portion)
Mater Field Ow»)tc*te
ESP Miter
(SoHdi Portion)
ESP Miter
iollai Field Duplicate
Aih Pit Miter
(Mater Portion)
AlF> Pit M»ter
(Solldl Portion)
Effluent Meter Field •link
Field I lint
MOltS - All co»pounOUNOS
I
I


19









I
S



11









a
1













tMtltlv.lv l'

ecqterf)
Acldt
e




It,
86
»
44
86
»
10
ins
I.
44
52

j
a




68
36
52
»
99
6]
H2
187
101
96
in

921 J
i
3



ffS
«s
YES
»;
,E,
If S
IES
MO
US
IfS
TES
U 11
(ll/IJJ

-------
08-Q
Ifffs
f=l?5
isz.£i
itjij
I-
ill
Hi
ll!
I!
1=.
il
If
sz
• 3
I
i
a
i
a
1
i
s
s
"S 31
i
I
1
re tentittvtli Identified imleti Indicated by «« *il«rlit
j
|
1
i
I
f













~

















E
1
C













*
















S
J




*






"i
i
•»




s
i
~



i




[f
J

s
*
i
i
i
S.
S
(^ Hitrr
Solid! Field Duplicate
^

f
i
r
s~



g
5



















i
I
i
i ~






fSP H«ttr
ISolttfl Portion)
c




I





is
a
p
>
1
^r

t
1
£
-






«

S



o



























•j
£





i !







(IV Uttr
IIMtcr Portion)
jf

s

>
I
c
*•
1
o
9





ll
n
j













8































i
1




~










s
\
"c





i
Ifcnturt/Dmtiter Vitcr
c


*










s


















jf
i *
c











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s




s
1









1
s


s




;f
i!
c













I


















1
;
J
~

=




i-

-



«


2















SMPIE IDCNIIFICAIKW
!
!,'.<•

-trlchloropftenol*
mr.UI.-MMi.)
2.3,4
, 6-tet r «cM oropn«no 1
D»«t«hloropn«»ot*
klpM
i.r-
nyl
blpnwyl
•~C""K~"""«
l.!H)(ck).r«».n,«.-
1 .2 , 4-t rl ch) aroMnzttw*
1.2,4
, 5~ tit r*ch 1 oroocn z*n«
1-"""-Z-""""""""
41-fl-
Butyl iffrthilKc*
dtetnyl phth*lit*
t>U(2-«thy)h«jiyl IpntniUte'
— «" ^^
61s(2-en)oroethyn ether"
bcnzoi c *ciO*
n«iadecino-trlBethylcyclopent*nc

oo*nieie-Di ?
Uoro0,p«n,l »
htmi -an |
Ol-Oi
uoropnenol -
6-tr10r.«pnen0l !

\f
f s . s ' s : s ' : s's|~ s s ! ACCEPTABLE' '
                                                           1-
                                                           l!
                                                          U» m

-------
                                                                                TABLE D-56

                                                          AQUEOUS  INFLUENTS AND EFFLUENTS -  PCDD/PCDF ANALYSESl
                                                              DOW  CHEMICAL COMPANY BUILDING  703  INCINERATOR
                                                                                  8/28/84
                                                                                                                                      Accurac

SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturl/Demlster Water
(Water)
Venturi/Demister Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
2378-
TCDD
ND
(.0021)
NO
(.0013)
NO
(15.6)
ND
(.0011)
ND
(2.98)


NO
(.0003)
ND
(19.8)
ND
(.0003)
NO
(.0002)
Total
TCDD
0.0384
ND
(.0010)
432
ND
(.0010)
238
(Samp It
(Sampli
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
Total
PeCDD
NO
(.0043)
NO
(.0010)
54.9
NO
(.0027)
82.0
analys
: analys
ND
(.0010)
ND
(171)
ND
(.0016)
ND
(.0054)
Total
HxCDD
ND
.0086)
NO
(.0042)
43.7
ND
(.0026)
55.1
s data r
s data r
ND
(.0027)
ND
(94.3)
ND
(.0026)
ND
(.0115)
Total
HpCDD
ND
.0073)
ND
.0079)
274
ND
(.0059)
265
ot retur
tot retut
ND
(.0058)
ND
(126)
ND
(.0083)
ND
(.0275)
OCOD
0.198
ND
(.0206)
1437
ND
(.0147)
1113
•ned from
1
1
•ned from
ND
(.0289)
323
NO
(.0130)
ND
(.0447)
2378-
TCDF
ND
.0011)
NO
.0005)
11.0
ND
(.0002)
8.52
laboratc
1
1
laborati
ND
(.0003)
ND
(27.4)
ND
(.0002)
NO
(.0003)
Total
TCDF
1.26
0.0025
170
0.0393
137
>ry.)
iry.)
ND
(.0010)
189
ND
(.0010)
ND
(.0010)

Total
PeCDF
ND
(.0026)
NO
(.0015)
66.4
ND
(.0022)
100


ND
(.0031)
ND
(45.1)
ND
(.0039)
ND
(.0037)
Total
HxCOF
ND
(.0057)
ND
(.0029)
117
ND
(.0018)
130


NO
(.0012)
ND
(42.5)
ND
(.0014)
ND
(.0075)
Total
HpCDF
0.0558
ND
(.00551
427
ND
(.0030)
337


ND
(.0066)
NO
(91.5)
ND
(.0055)
ND
(.0167)
Total
OCDF
ND
(.0130)
NO
(.0118)
379
ND
(.0139)
284


ND
(.0121)
ND
(118)
ND
(.0098)
ND
(.0284)
COMPLETENESS BY SURROGATE
i
OO Q
P~ Q
CO CJ
(VJ t-~
Csj
r- 1
0
ro
100
100
93
62
47


100
46
100
30
55%
1
00 O
r- Q
ro O
CVJ t—
«3-
(_>
r-.
m
91
81
94
89
95


90
95
84
80
82%
o
o
o
O
OJ
r-t
O
m
r-*
63
87
84
100
100


98
100
43
10
64%
1
OO U_
r- O
CO O
00 K-
*r
G
r*.
m
81
62
100
57
49


59
55
62
20
64%
(% Surrogate Recovery)
o
 i
oo
            Notes - lOata expressed In ng/g.
                    ^Al 1 surrogate recoveries within range of 50-150%.

-------
                                                                                   TABLE D-57
                                                             AQUEOUS INFLUENTS AND EFFLUENTS - PCDD/PCDF ANALYSESl
                                                                 DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                    8/30/84

SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
ESP Water (Water)
Field
ESP Water (Water) Duplicate
ESP Water (Solids)
Field
ESP Water (Solids) Duplicate
Venturl/Demlster Water
(Water)
Venturl/Demlster Water
(Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
2378-
TCDD
NO
(.0027)
ND
(.0007)
ND
(11.1)
ND
(.0009)
ND
(.0028)
ND
(35.3)
ND
(65.5)
ND
(.0006)
ND
(2.08)
ND
(.0010)
ND
(1.08)
ND
(.0005)
ND
(.0005)
Total
TCDO
0.0464
ND
(.0010)
707
.0062
.0189
4212
1864
ND
(.0010)
307
ND
(.0025)
ND
15.9
ND
(.0010)
ND
(.0010)
Total
PeCDD
ND
(.0019)
ND
(.0024)
99.3
ND
(.0011)
ND
(.0019)
885
393
ND
(.0012)
49.2
NO
(.0240)
ND
(3.09)
ND
(.0011)
ND
(.0080)
Total
HxCDD
ND
(.0021)
ND
(.0042)
75.3
ND
(.0028)
ND
(.0029)
147
205
ND
(.0021)
27.6
NO
(.0227)
ND
(3.14)
ND
(.0021)
ND
(.0063)
Total
HpCOD
0.0179
NO
(.0115)
460
ND
(.0057)
NO
(.0044)
417
515
ND
(.0089)
162
NO
(.0292)
21.5
ND
(.0031)
ND
(.0083)
OCDD
0.187
ND
(.0301)
2358
NO
(.0192)
ND
(.0077)
2199
2530
ND
(.0075)
707
NO
(.0453)
94.9
ND
(.0053)
ND
(.0104)

2378-
TCOF
ND
(.0012)
ND
(.0001)
15.4
ND
(.0004)
ND
(.0004)
45.3
47.7
ND
(.0005)
3.22
NO
(.0022)
ND
(1.71)
NO
(.0006)
NO
(.0014)
Total
TCDF
1.42
0.0223
182
0.287
0.607
539
6574
0.0682
168
NO
(.0038)
114
ND
(.0010)
ND
(.0025)

Total
PeCDF
0.0088
NO
(.0037)
NO
87.5
ND
(.0051)
ND
(.0039)
405
345
ND
(.0021)
64.6
ND
(.0120)
ND
(3.15)
NO
(.0024)
ND
(.0077)
Total
HxCDF
ND
(.0067)
ND
(.0028)
124
ND
(.0037)
ND
(.0017)
75.7
58.6
ND
(.0033)
82.9
ND
(.0110)
ND
(2.93)
ND
(.0017)
ND
(.0128)
Total
HpCDF
0.0167
ND
(.0131)
785
ND
(.0055)
ND
(.0070)
150
161
ND
(.0056)
199
ND
(.0232)
10.0
ND
(.0052)
ND
(.0046)
OCDF
0.0477
ND
(.0168J
641
ND
(.0182)
ND
(.0099)
200
226
ND
(.0164)
283
ND
(.0269)
12.5
NO
(.0037)
NO
(.0127)
COMPLETENESS BY SURROGATE
Accuracy (% Surrogate Recovery
CO 0
r- O
CO O
 o
tM I-
*f
0
l-~
ro
66
57
100
44
73
95
27
46
57
29
65
36
17
54%
O
 I
00
ro
          NOTES  -  !Data  expressed In ng/g.
                       surrnaatc rt»r
-------
                                                                                TABLE D-58


                                                          AQUEOUS INFLUENTS AND EFFLUENTS - PCOO/PCDF ANALYSES1

                                                              DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR

                                                                                  9/5/84

SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturl/Demlster Water
(Water)
Venturl/Demlster Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
2378-
TCDD
ND
(0.341)
ND
(.0004)
ND
(1.10)
ND
(.0008)
ND
(1.29)
ND
(.0014)
ND
(28.2)
ND
(.0003)

ND
(.0013)
ND
(.0003)
Total
TCOO
ND
(0.229)
ND
(.0010)
73.9
ND
(.0010)
56.3
0.0052
247
ND
(.0010)
(Sam|
ND
(.00101
NO
(.0010)
Total
PeCDD
ND
(0.556)
ND
.0024)
ND
(7.43)
NP
(.0021)
17.5
ND
(.0104)
61.5
ND
(.0012)
ile anal.
ND
(.0016)
NO
(.0048)
Total
HxCDD
ND
(0.720)
ND
(.0027)
ND
(3.19)
ND
(.0031)
7.35
ND
(.0039)
20.3
ND
(.0017)
•sis dati
ND
(.0071)
NO
(.0027)
Total
HpCDD
ND
(0.318)
ND
.0018)
69.0
ND
(.0036)
44.3
ND
(.0087)
96.0
ND
(.0029)
not re
ND
(.0067)
ND
(.0039)
OCDD
NO
(0.520)
ND
(.0020)
236
ND
(.0064)
261
ND
(.0051)
423
NO
(.0025)
.urned fr
NO
(.0088)
NO
(.0058)

2378-
TCDF
ND
(0.192)
ND
(.0001)
ND
(1.93)
ND
(.0001)
2.05
ND
(.0015)
9.70
ND
(.0001)
om labor.
ND
(.0023)
NO
(.0002)
Total
TCDF
ND
(0.517)
0.0058
830
0.0157
723
0.0995
90.0
ND
(.0010)
tory.)
ND
(.0022)
NO
(.0010)

Total
PeCDF
ND
(0.299)
ND
(.0015)
7.09
ND
(.0010)
22.3
ND
(.0041)
47.0
ND
(.0010)

ND
(.0080)
NO
(.0025)
Total
HxCDF
ND
(0.351)
ND
(.0015)
16.1
ND
(.0024)
19.7
ND
(.0030)
14.7
ND
(.0010)

ND
(.0025)
NO
(.0027)
Total
HpCDF
ND
(0.627)
NO
(.0012)
125
ND
(.0017)
69.1
ND
(.0026)
68.2
ND
(.0021)

ND
(.0049)
NO
(.0026)
OCDF
ND
(0.396)
ND
(.0011)
103
ND
(.0035)
84.8
ND
(.0061)
82.1
ND
(.0037)

ND
(.0057)
ND
(.0039)
COMPLETENESS BY SURR OGATE
Accuracy (% Surrogate Recovery)
i
co a
r— a
fO {_>
CM h-
C\J
f-4
CJ
ro
r~t
100
53
81
84
100
53
70
100

70
48
82%
1
CO O
r- a
ro o
CM 1—
«*
o
r-.
ro
93
107
96
89
92
97
91
110

93
94
91%
0
a
8
CM
f— i
O
CO
r-4
58
100
48
53
94
35
39
48

100
100
55%
i
00 U-
r- O
<"•> O
C\J (—
-»•
o
r-
n
82
30
100
53
100
54
100
89

17
26
64%
a
 i
oo
OJ
        NOTES  -  iflata  expressed  In  ng/g.

                2A11  surrogate recoveries within  range of 50-150%.

-------
once-through effluents.   A  full   range  of homologues  was  found  on all  three
sampling days, though  from these  data  it did  not appear  that  PCDD and  PCDF
appear consistently in any particular wastewater stream.

    No 2378-TCDD was  detected on any  day, but 2378-TCDF was found on  three days.
In general, the  range and  concentrations  of  all homologues was greater  by  one
to two orders of magnitude  on  the second sampling day than  on  the  other days.
Particularly high concentrations  of tetra- and  octa-CDD and CDF  were present in
the solids fractions  of  the wastewaters.

    Complete data  sets  covering  all  wastewater streams were not  returned  from
the analytical  laboratory  for any  but  the  second  sampling  day.   Overall
completeness, taking  accuracy criteria into account, was 17%  (6 of 35).   Twenty-
six of the  29 data  sets  were  incomplete  because  of  unsatisfactory accuracy.
Field duplicate  samples  were  taken  only  on  the second day,  of the ESP  water
stream.  Calculations shown in Table D-59  reveal mixed precision  between these
sample data;  generally  good  precision  was  achieved  with  higher  homologues.

    Detection limit criteria:

                      2378- and Total Tetras       Penta- through Octa-

          Waters              30 ppq                     90 ppq
          Solids               5 ppt                     15 ppt,

were not met  for water  fraction  analyses, with actual  detection  limits  in the
range of about 20  to  1600 ppq, nor  for  solids  analyses,  where detection limits
were in the 0.6 to 6.0 ppb range (see Tables  D-56,  D-57, and 0-58).

    b.  TCDO  Isomers

    As indicated previously, no 2378-TCDD  was  detected at any time  in  influent
or effluent water  streams.  The  data presented in Tables  D-60,  D-61,  and D-62
indicate most TCDD appeared as the  1368,  1237/1238, and  1379  isomers.   Occa-
sionally, the 1369 isomer was  observed,  and on the second day, when the highest
concentrations of  PCDD/PCDF appeared,  the 1247/1248/1378/1469  combination  was
noted.

    Precision data obtained for the second day's samples are presented in Table
D-63 and indicate  generally poor performance in this area.  The detection limit
goals of  30 and  90 ppq,  respectively, for  water and  solids fractions,  were not
achieved for the latter, with actual sensitivities one to  two orders  of magnitude
lower.
                                    D-84

-------
                                                            TABLE D-59

                                     AQUEOUS INFLUENT  AND  EFFLUENT WASTEWATER SAMPLE PRECISION
                                                       PCDD/PCDF MONOLOGUES
                                           DOW CHEMICAL COMPANY  BUILDING 703 INCINERATOR
                                                              8/30/84
SAMPLE IDENTIFICATION
WATER FRACTION
ESP Water
ESP Water
Field Duplicate
Precision (RPD)
FILTERABLE SOLIDS FRACTION
ESP Water
ESP Water
Field Duplicate
Precision (RPD)

2378-
TCDD







Total
TCDD
0.0062
0.0189
101
4212
1864
65

Total
PeCDD



885
393
77

Total
HxCDD



147
205
33

Total
HpCDD



417
515
21

OCDD



2199
2530
14









2378-
TCDF



45.3
47.7
5

Total
TCDF
0.287
0.607
56
539
6574
170

Total
PeCDF



405
345
16

Total
HxCDF



75.7
58.6
25

Total
HpCDF



150
161
7

OCDF



200
226
12

CO
in
                     NOTE - Concentration data in ng/g.

-------
                                                                                TABLE  D-60



                                                              AQUEOUS INFLUENTS AND EFFLUENTS -  TCOO ISOMERS

                                                               DOM  CHEMICAL  COMPANY BUILDING  703  INCINERATOR

                                                                                 8/28/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturi/Demlster Water
(Water)
Venturi/Demlster Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
1368
0.0172
NO
( .0010)
183
NO
(.0013)
113


ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1379
0.0095
ND
( .0010)
113
ND
(.0011)
ND
(3.91)


ND
( .0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1369
ND
(.0022)
ND
( .0010)
ND
(4.57)
ND
( .0010)
7.83
( Sampl i
( Sampl
ND
(.0010)
ND
(23.3)
ND
( .0010)
ND
( .0010)
1247
1248
1378
1469
ND
(.0012)
ND
( .0010)
7.32
ND
( .0010)
ND
(3.91)
: analys
? analys
ND
( .0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1246
1249
ND
(.0010)
ND
(.0010)
ND
(4.57)
ND
(.0010)
ND
(3.91)
s data
s data
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1268
1278
ND
(.0010)
ND
( .0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)
lot retu
lot retu
ND
( .0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1478
NO
.0010)
ND
(.0010)
ND
(9.14)
ND
(.0010)
ND
(3.91)
*ned fra
•ned froi
ND
(.0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1268
1279
NO
(.0010)
ND
(.0010)
ND
(4.57)
ND
(.0010)
ND
(3.91)
i labora
i labora
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1234
1236
1269
ND
.0010)
ND
(.0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)
:ory)
:ory)
ND
(.0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1237
1238
0.0100
ND
(.0010)
128
ND
( .0010)
117


ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
2378
ND
(.0021)
ND
(.0013)
ND
(15.6)
ND
(.0011)
ND
(2.98)


ND
(.0003)
ND
(19.8)
ND
(.0003)
ND
( .0002)
1239
ND
(.0010)
ND
(.0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)


ND
( .0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1278
1279
ND
(.0010)
ND
(.0010)
ND
(4.57)
ND
(.0010)
ND
(3.91)


NO
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1267
ND
(.0010)
ND
(.0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)


ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1289
ND
(.0010)
ND
( .0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)


ND
(.0010)
ND
(23.3)
NO
(.0010)
ND
(.0010)
o
I
oo
                                             1
                                              Data expressed In ng/g.

-------
                                                                               TABLE p-61

                                                              AQUEOUS INFLUENTS AND EFFLUENTS - TCDD ISOMERS1
                                                              DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                8/30/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
ESP Water (Water)
Field
ESP Water (Water) Duplicate
ESP Water (Solids)
Field
ESP Water (Solids) Duplicate
Venturl/Demister Water
(Water)
Venturl/Demister Water
(Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backuo Field Blank
1368
0.0198
ND
( .0010)
290
0 .0038
0 .0074
1968
486
ND
(.0010)
130
ND
(.0025)
74.7
ND
(.0010)
ND
(.0010)
1379
0.0154
ND
( .0010)
183
0.0025
0.0057
945
ND
(32.8)
ND
( .0010)
85.5
ND
(.0025)
3.97
ND
(.0010)
ND
(.0010)
1369
ND
(.0010)
ND
(.0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
65.6
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
(0.998)
ND
(.0010)
ND
(.0010)
1247
1248
1378
1469
ND
(.0016)
ND
( .0010)
14.5
ND
(.0010)
ND
(.0010)
59.0
ND
(32.8)
ND
(.0010)
7.77
ND
(.0025)
0.934
ND
(.0010)
ND
(.0010)
1246
1249
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
(.998)
ND
(.0010)
ND
(.0010)
1268
1278
ND
(.0010)
ND
(.0010)
ND
(7.23)
ND
(.0010)
ND
( .0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
NO
(.998)
ND
(.0010)
ND
(.0010)
1478
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
NO
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
(.998)
ND
( .0010)
ND
(.0010)
1268
1279
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
ND
( .0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
NO
( .0025)
ND
(.998)
ND
(.0010)
ND
(.0010)
1234
1236
1269
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
( .998)
ND
(.0010)
ND
(.0010)
1237
1238
0.0093
ND
(.0010)
220
ND
(.0031)
0.0058
1240
1313
ND
(.0010)
84.2
ND
(.0025)
3.50
ND
(.0010)
ND
(.0010)
2378
ND
(.0027)
ND
(.0007)
ND
(11.1)
ND
(.0009)
ND
(.0028)
ND
(35.3)
ND
(65.5)
ND
(.0006)
ND
(2.08)
ND
(.0010)
ND
(1.08)
ND
(.0005)
ND
(.0005)
1239
NO
(.0010)
ND
(.0010)
ND
(7.23)
ND
( .0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
NO
(0.998)
ND
(.0010)
ND
(.0010)
1278
1279
ND
(.0010)
ND
(.0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
NO
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
(0.998)
ND
( .0010)
NO
(.0010)
1267
ND
(.0010)
ND
(.0010)
ND
(7.23)
ND
( .0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
NO
(.0025)
NO
(0.998)
ND
(.0010)
ND
(.0011)
1289
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
*
ND
(1.20)
*
*
o

CO
                                              Data expressed  In  ng/g.
                                       * Denotes  data  not  reported by  laboratory.

-------
                                                                               TABLE  p-62
                                                             AQUEOUS  INFLUENTS AND EFFLUENTS - TCDD ISOMERSJ
                                                              DOW CHEMICAL COMPANY BUILDING 703  INCINERATOR
                                                                                  9/5/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturl/Demister Water
(Water)
Venturl/Demister Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
1368
NO
( .0229)
NO
( .0010)
26.9
NO
( .0010)
28.2
ND
(.0033)
15.8
NO
( .0010)

NO
(.0010)
ND
(.0010)
1379
ND
(0.229)
ND
( .0010)
24.7
ND
( .0010)
ND
(0.985)
ND
( .0048)
ND
(5.66)
ND
( .0010)

ND
( .0010)
ND
(.0010)
1369
ND
(0.229)
NO
(.0010)
ND
(1.31)
ND
(.0010)
2.01
ND
( .0032)
6.79
NO
( .0010)
(Sampli
ND
( .0010)
ND
( .0010)
1247
1248
1378
1469
ND
(0.229)
ND
(.0010)
ND
(2.62)
ND
(.0010)
NO
(0.985)
ND
(.0018)
NO
(5.66)
ND
(.0010)
analys
ND
( .0010)
ND
.0010)
1246
1249
ND
(0.229)
ND
(.0010)
NO
(1.97)
ND
( .0010)
ND
(0.985)
ND
( .0032)
ND
(5.66)
ND
( .0010)
s data i
ND
(.0010)
ND
(.0010)
1268
1278
ND
(0.229)
ND
( .0010)
ND
(1.97)
ND
(.0010)
ND
(0.985)
ND
(.0032)
ND
(5.66)
NO
(.0010)
ot retui
ND
(.0010)
ND
.0010)
1478
NO
(0.229)
ND
( .0010)
ND
(1.97)
ND
( .0010)
ND
(0.985)
ND
( .0032)
ND
(5.66)
ND
( .0010)
ned froc
ND
( .0010)
ND
.0010)
1268
1279
NO
(0.229)
ND
( .0010)
ND
(1.97)
ND
(.0010)
ND
(0.985)
ND
(.0032)
ND
(5.66)
ND
(.0010)
i laboral
ND
(.0010)
ND
.0010)
1234
1236
1269
ND
(0.229)
ND
(.0010)
NO
(1.97)
ND
(.0010)
ND
(0.985)
ND
(.0013)
NO
(5.66)
ND
(.0010)
ory)
ND
( .0010)
ND
.0010)
1237
1238
ND
(0.229)
ND
( .0010)
22.2
ND
( .0010)
26.1
0.0052
224
ND
( .0010)

NO
(.0010)
ND
( .0010)
2378
ND
(0.341)
ND
( .0004)
ND
(1.10)
ND
( .0008)
ND
(1.29)
NO
(.0014)
ND
(28.2)
ND
( .0003)

ND
(.0013)
ND
( .0003)
1239
ND
(0.229)
ND
( .0010)
ND
(1.97)
ND
( .0010)
NO
(0.985)
NO
( .0025)
ND
(5.66)
ND
(.0010)

ND
(.0010)
ND
(.0010)
1278
1279
ND
(0.229)
ND
(.0010)
ND
(1.97)
ND
( .0010)
ND
(0.985)
NO
(.0013)
ND
(5.66)
NO
(.0010)

NO
( .0010)
ND
( .0010)
1267
ND
(0.229)
ND
(.0010)
ND
(1.97)
ND
(.0010)
ND
(0.985)
ND
(.0019)
ND
(5.66)
ND
( .0010)

ND
(.0010)
NO
( .0010)
1289
ND
(0.229)
ND
( .0010)
NO
(1.97)
*
ND
(0.985)
ND
(.0032)
ND
(5.66)
ND
(.0010)

*
*
o

00
00
                                            1 Data expressed in ng/g.


                                      * Denotes data not reported by laboratory.

-------
                                      TABLE  D-63

              AQUEOUS  INFLUENT  AND  EFFLUENT  WASTEWATER  SAMPLE PRECISION
                                     TCDD ISOMERS
                    DOW  CHEMICAL  COMPANY  BUILDING  703  INCINERATOR
                                       8/30/84

                               (Data expressed in ng/g.)

WATER FRACTION

tbr water
ESP Water
Field Duplicate

Precision ^Kruj^
FILTERABLE SOLIDS FRACTION

tbr water
ESP Water
Me i u uu pn cate

Precision \Kru;


1368
Onn^s
.UU JO
Or\r\~! A
• UU/4
CA
O't

1 Q£Q
lyoo
AQK
too




1237/1238


Onnt\8
.UU So



1 940
1^'tU
1 -31 -3
1 01 J
f.
D

ISOMERS
1379
n nn?^

n nn^7
U .UUD /
70
/ o

Q^C
y+o






1247/12W
1378/1469







CQ n
oy «u






1369









fit; fi




*Re1ative percent difference,
                                        D-89

-------
IV.   SUMMARY  OF  RESULTS  FOR  PCDDs  AND  PCDFs

     The analytical  data for PCDDs and PCDFs, and for TCDD isomers,  are  presented
 in  Tables  D-64 through  D-69, to  show the concentrations of these compounds  in
 influent and effluent streams around the Building  703 incinerator on  the three
 sampling days.   Those data were combined with the flow rate information  appearing
 in  Tables  D-64  through  D-66,  to derive  the  loadings,  in  grams  per  year, of each
 PCDD and PCDF  homologue and  TCDD  isomer,  which are  presented  in Tables D-70
 through D-75.   The  data for  PCDDs  and PCDFs were  averaged  by homologue over the
 three sampling  days  and summarized  in  Figures  D-l through D-10, illustrating
 the probable destruction,  transfer,   or formation  of  each   homologue  in  the
 incineration process.   As described previously,  data  for loose solid wastes fed
 to  the incinerator  could not be  gathered as  no representative sampling method
 was available.   Figures  D-l  through D-10  should  be  interpreted accordingly.
                                      D-90

-------
                                                                                            TABLE  0-64
                                                                            INFIUEN1 AND EFFLUENT PCDO/PCF1F CONCENTRATIONS
                                                                           UOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                            8/28/84
Sample Identification
INFLUENTS
~ TTK 	

Service Hater (Sec. Frtd.)
TlUabiwtsstt River Uattr
Liquid UasU Mottle B» 	
Liquid UasU HoiiU BB1
Liquid Uastt Nozzle C
Low-BTU Liquid Waste 	
SOLID
Loose and Containerized
Solid Hastes
EfHU£»7S
THR 	
Incinerator Exhaust
LIQUID 	 — 	



jencn lower Mater
jench Tower Sol Ids
enturl/Oenlster Mater
venturl/uenlstcr solids
E

5r Mater '
sti Pit U.t.T 	
Ash Pit Solids 	



237B-
TCDO


	 (Mi



(N01











Total
TCDO

58.3/HO*
lO
5M6/S4B


SAMPLED)

4Z.fi

432

2M





Total
PeCDD



11800/NO




P. MS

54.9

82.0





Total
HxCOO



1190/ND




0.88

43.7

55.1


1 	


Total
HpCDD



2790/NO
TF? 	



0.21

274

265





OCDO

217/335*
198
22000/ND




0 93

1437

1113


~?n 	 ~


2378-
TCDF








1.51

11.0

8.5



	

Total
TCDF

391/628*
1260
imm




" 86.1
25.0
170
39.3
"13) -•


' 189


lotal
PeCOF



845/ND




13.6

66.4

160





Total
HxCDF








?,64

117

Uo





Total
HpCDF


55,9 	





0.26

427

33?





OCOF

21.2/ND*

1240/WD




0.06

3)9

284





UNITS

pq/m3
T^T~
nq/L
nail
nq/L
nu/L



"1/mj
nq/L

nq/L
nq/q
nq/L
nq/4
nq/L
ng/g

"9/9
FLOW KATE

30.4?8 dscfm 	
5.33 * 10" L/dav 	 	
9 80 x 10? L/dav 	
1.92 x lO'/l.oe x 10* L/dav
2.57 x IP' L/dav 	
4,35 x 10' L/dav



30.478 dscfm
3.86 x 10b L/dav

1.47 x 10° L/dav

0.95 x 106 L/day




•Field duplicate sample result
                                                                                                    aSt" *re Stit'd
                                      |0lnonhUn7n'l                                                   S"M>le  analysis  not  returned from laboratory
                                      Loadings  (Table  0-70) were calculated based on the length of time each waste was
                                      burned  during  the emissions test   NO denotes homologue was not detected.

-------
                                                                                                               TABLE  0-65
                                                                                              ItirillfNI  AND EFFLUFNT  PCDD/PCDF  CONCENTRAIIONS
                                                                                              OOU CHEMICAL COHPANT BUILDING 703  INCINERATOR
                                                                                                                  8/30/84
Sample Identification
INFLUENTS
AIR

LIQUID ••"•*" '"' 	
Service Uater (Sec. Md.)
Tlttabaoassee Pl.er Water
Liquid Uaste Nouli U 	
Liquid Uaste Nonle B>l
Liquid Uaste Motile C 	
— loJ-BTU Liquid" Uatte ' 	
501 ID 	 !CJ 	
Loose and Containerised
Solid Mattel
EfFLUE
~nun
Ven
ESP
ESP
— KK
Ash
NTS
IB 	 ~
nch To«
nch Towe
turl/0e«l
turl/Oe.i.1
Nater

Solids 	
Ister Uater 	
stcr Solid!

Solids
Pit Uater 	
Pit Solids 	
SOLID


TGK 	

23/8-
TCDO













Total
TCDD



/NOT SAMI
60300/21800*
(NOT SAMF
43.8
"707
lOl
6.2/18.9*
J2|2/1B64*
TO 	 	


Total
PeCDO



TOT 	
3450/6130*
EO)
~ T94
99.3
"TO

885/393*



Total
HiCDO




2610/4240^

—07 	
^-751 	

147/205*


0.13/0.11*
Total
HpCOO




38QQ/569Q*

1 O4
162

417/515*
— fT5 	

0. 81/0. 50
OCDO



	 187 	
19800/19800*

2.52
7358 	
"To? 	

2199/2530*
$4.9

3.2/2.4*
2378-
ICOF




NO/2100*

j 1.67 |
JM_

45.3/47.7*


Q.02/ND*
Total
TCDF


12.9

36600/18000*

77.0
22.3
287/607*
539/6574*
114
	

Total
PeCDF


12,5
8'8
17BO/ND
1510/4320*

4.28
87.5
64 6

405/345*



Total
HxCOF


14.2

749/HD 	
3510/7130*

1.95
124
82 9

75. 7/58. S'



Total
HpCOF


	 108-5 	
16.7
593/NO
8070/8160*

0.55
785
199

150/161*
10.0


OCOF




6Z5/HD
7430/7680*

0.17
641
283

200/22S*
12.5


UNITS

	
P
-------
                                                                                                           IA11E  0-66
                                                                                         InfllllNI AND EFFIUEN1 PCOO/PCOF CONCENIRAIIONS
                                                                                         DOM  CHEMICAL  COMPAIK 10IIOIMC 10) INCINEMlOft
                                                                                                             9/S/B4

mriucms
'Ml
Stoic* Water (J*c. Trtd.)
P TlttakwMiM llw Vttw
lljl.1 Uaitl hill. II
loi-ItU liquid U4»U
5H.1D
loon and CofltalMHlerf
IFFl
11
11
I
1
nclncrator Eihaust
miiB 	
jtnch Towvr Hat«r
itnch Towtr Solldt
Kiturl/Dmlitir Hater
tSf Uattr
t5l> Solid.
»ik Pit Uater
Ath Ml Sol Ml 1
MHO 	
Inclntrator Ask
237a-
ICOO





local
ICOO

\\
UM
	 (HQf j
i«
73.9
'
0.07
Iota)
PtCDO

*>»I-H>1
toe

J 	
lotal
HuCDO




2Q-3
lolil
HpCDO

98.1
p^
69,0
. 86. Q 	
. 0,08
ocoo

_^^_
1210
047
236
J2J 	
4,27
ICOf


J37

2.05
9.70
lotal
ICOF

206.6
•il^JJ
^
	 OB 	
436
90.0
lOtil
•eCOF


	 Ui 	
7.09
it 3

lotal
M«COf



. 3.M
"19 )

lotal
HpCOF

37.1 	

	 125
69 T~~

OCOF

3o.a 	

103
34. B
or
UNI IS

j^L
'3/1-
nq/l,
rw/q
nq/q
nq/C
nq/q
nq/q
FLOU KAIE

I3.5S1 dSf'-
^.m . 100 L/dax
I.Z7 A 1C L/Sy
51 K 18' L/da,
5.17 « 10" L/da»
33.599 dscfm
3.91 » 100 i/da»
1 19 x To^lj-daj
0 95 » Id* I/da,
0 5J « lO6 l/dsy
 I
VO
CO
                 •field duplicate simple reiult
                                                              analysts not  returned  frOM  laboratory.

-------
                                                                                    TABLE  D-67

                                                                  INFLUENT AND EFFLUENT TCDO ISOMER CONCENTRATIONS

                                                                  UOW CHEMICAL COMPANY  BUILDING  703  INCINERATOR

                                                                                      8/28/84
Sample Identification
INFLUENTS
AIR
Precanbgs.ttgn. A.1r
LI
quiu
Service Mater (Sec. Trtd.)
Tlttabawassee River Water
Liquid Waste Nozzle BA
•Liquid Waste Nozzle BB~
Uquia Haste Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Wastes
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID
(
(
\
jench Tower Hater
mnch Tower Sot Ids
inturl/Dealster Uater
Venturl/DeMlster SoHds
ESP Water
ESP Solids
Ash Pit Uater
Ash Pit Solids
SOLID
Incinerator Ash

1368


44.2

lfl.0


1189/276






20.4


183

113





0.62

1379


14.0

9.9
TNOT SAI

4108/272



{NOT SA*


13.0


113

7.8J





0.25

1369





PLED)





PLED)















1247
1248
1378
1469














1.69


7.32







0.04

1246
1249



























1268
1278



























1478



























1268
1279



























1234
1236
1269



























1237
1238




10.5


493/ND






12.6


J28

117





0.27

2378



























1239



























1278
1279



























1267



























1289



























UNITS


pg/m3

ng/L
ng/L
ng/L
ng/L
ng/L
ng/L




nq/ni-1

nq/X
pq/q
ng/L
nq/q
nq/L
nq/q
na/L
nq/q

nq/q

o
 i
10
          *Two distinct wastes Incinerated.   Analytical results for both wastes are

            stated  In  a manner  similar to that In  Table  0-64.

-------
                                                                                    TABLE  0-68
                                                                  INFLUENT AND EFFLUENT TCDD  ISOMER CONCENTRATIONS
                                                                   DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                      8/30/84
Sample Identification
INFLUENTS
AIR 	

1
'recombustlon Air
'QUID
Service water (Sec. Trtd.l
Tutabawassee River Water
Liquid Haste Nozzle BA
Liquid Haste Nozzle BB *
I
1368



20.6


WLK'WL'MI
1379

	 04—

16.1
(NOT SAMPL

IBHSHMl
1369




:o)


Lt nt'm.t m •, 'j««u »^^^» pmili7/:l:l[iL' K
cn
          'Field duplicate sample.
Two distinct wastes Incinerated.   Analytical
results for both  wastes  are  stated,  in
similar manner as in Table 0-65.
No waste incinerated.

-------
                                                                                   TABLE D-69
                                                                INFLUENT AND EFFLUENT TCOO 1SOHER CONCENTRATIONS
                                                                  DOU CHEMICAL  COMPANY BUILDING 703 INCINERATOR
                                                                                    9/5/84
Sample Identification
INFLUENTS
AIR

"T
'recombustion Air

Service Uater (Sec. Trtd.)
Tlttabawassee River Hater
Liquid Uaste Nozzle BA
Liquid Uaste Nozzle BB
— i

.{quid Uaste Nozzle C
.ow-BTU Liquid Uaste
5H.IO
Loose and Containerized
Solid Hastes
EFFLUENTS
AIR

— T
•i
1
'
nclnerator Exhaust
QUID
uench Tower Hater
jtnch Tower Solids
enturl/Denlster Uater
VenturlVDenlster Solids


:SP Uater
ISP Solids
Ash Pit Uater
Ash Pit Sol Ids 1
SOLID
Incinerator Ash


1368


24.6




4050

19. 1m. 4'




129


26.9

26.2

15.8



0.04

1379


7.58


(NOT

1940
199
6.23/6.00*

(NOT


70.7


24.7







0.02

1369





SAMPLED)





AMPLED)







2.01

6.79





1247
1248
1378
1469


2.45











O.Qfi












1246
1249



























1268
1278



























1478



























1268
1279



























1234
1236
1269


Q.9B
























1237
1238


3.92






4.PO/2.40*




0.46


22.2

26.1
&. 2
224



0.01

2378



























1239



























1278
1279



























1267



























1289



























UNITS


pq/m-1

nq/L
ng/L
ng/L
ng/L
ng/L
ng/L




ng/mJ

ng/L
na/a
nq/L
ng/g
ng/L
ng/q
ng/L
ng/g

ng/g

 I
ID
         •Field duplicate sample results.
Sample analysis  not  returned  from  laboratory.

-------
                                                                                                   TABLE   D-70

                                                                                     INFLUENT AND EFFLUENT PCDD/PCDF LOADINGS
                                                                                  DOW  CHEMICAL COMPANY  BUILDING 703  INCINERATOR
                                                                                                     8/28/84
                                                                                               (in grams  per year)
Sample Identification
INFLUENTS
AIR
Precombustion Air
LIQUID
Service Water (Sec. Trtd.)
Tlttabawassee River Utter
1
1
I
(quid Uaste Nozzle BA
(quid Uaste Nozzle BB '
iquid Uaste Nozzle C
Low-BTU Liquid U«ste
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year)
EFFL
UENTS
AIR
Incinerator Exhaust
LIQUID
t
<
v
jench Tower Water
jench Tower Sol ids
enturi/Demister Utter
Venturi/uemisier >onas
1 ESP Utter ?
1 ESP Solids^
Ash Pit Utter
Ash Pit Solids
SOLID 	
Incinerator Ash 	
TOTAL EFFLUENTS (grains year
2378-
TCDO























Tottl
TCDD


0,026

74.8
(NOT S

42.7



(NOT S
117.5


21.6


4.32

9.83

3.84-5.12
40.2
Total
PeCDD





MPLEO)

82.7



WLED)
82.7


2.94


5.50

3.33 	

11.8
Total
HxCOD







8.32




8.32


0.40


4.37

2.26

2.60-3.47
10.1
Total
HpCDD







195

0.16


195


0.09


27.4

1Q-9

19.9-26.5
61.6
OCDD


0.099

385


154




539


0.44


144

	 46.0 	
O2
107-143
316
2378-
TCDF















0.69


1.10

^13 	

0.22-0.29
2.41
Total
TCDF


0.18

2451


65.6




2517


38.9

35.2
17.0
21.1
	 	 3.0° 	
0.07
30.0-40.1
153
Total
PeCDF







5.92




5.92


6.14


6.65

	 q.in 	

0.22-0.30
17.2
Total
HxCDF















1,20


11.7
c 17


1.49-1.99
20.0
Total
HpCDF




106







108


0.12


42.7
11 Q


4.99-6.65
62.5
OCOF


0.003




8.69




8.69


0.03


37,9
11 7


8.43-11.2
59.4
UNITS























'Total of two wastes incinerated. 2Sample analysis not returned from laboratory.
o

-------
                 TABLE D-71
   INFLUENT AND EFFLUENT PCDD/PCOF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                   8/30/84
             (in grams per year)













o
IO
00












Sample Identification
INFLUENTS
AIR
Precombustlon Air
LIQUID
Service Water (Sec. Trtd.)
Tittabawassee Rtver Water
Liquid Waste Nozzle BA
Liquid Waste Nozzle BB *
Liquid Waste Nozzle C
Low-BTU Liquid Waste z
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year)
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID
Quench Tower Water
Quench Tower Solids
VentuH/Deaister Uaier
Venturl/Denister Solids
ESP Uater
ESP Solids
Ash Pit Uater
Ash Pit Solids
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year)
2378-
TCOO


0.002

























Total
TCDD


0.008

89.8
(NOT

89.4
280


(NOT
459


20.8


111

20.9
2.15
23.4

0.20

0.43-0.57
179
Total
PeCDD





SAMPLED)

17.0
16.0


iAMPLED)
33


0.92


15.6

3.35

4.89




24.6
Total
HxCOO







2.42
12.1



14.5


0.17


11.8

1.87

0.82



0.42-0.56
15.2
Total
HpCDO




34.7


8.14
17.6



60.4


0.40


72.5

10.98

2.31

0.31

2.65-3.53
89.6
OCDD




362


31.1
91.8



485


1.20


371

48.0

12.2

1.46

10.4-13.9
446
2378-
TCOF


0.006




0.77




0.78


0.79


2,41

0.22

0.25



0.05-0.07
3.73
Total
TCOF


0.006

2748


100
171



3019


36.6

31.7
28,7
35.1
11.4
99.5
2.99

1.78

1.95-2.60
250
Total
PeCDF


0.006

17.2


4.82
7.01



29.0

2.03


13.8

4.42

2.25




22.5
Total
HxCDF


0.007




2.03
16.3



18.3

0.93


19.6

5.63

0.42



0.15-0.19
26.8
Total
HpCDF


0.005

32.5


1.61
37.4



71.5


0.26


124

13.5

0.83

0.14

1.47-1.97
140
OCDF


0.065

92.3


1.69
34.5



128


0.08


101

19.2

1.11

0.20

1.88-2.51
124
UNITS




























•Field duplicate sample result. *Total of two wastes Incinerated. No waste incinerated.

-------
                                                                                       TABLE D-72
                                                                         INFLUENT AND EFFLUENT PCOD/PCDF LOADINGS
                                                                      DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                         9/5/84
                                                                                    (in grams per year)
Sample Identification
INFLUENTS
Alft
Precombustlon Air
LIQUID
Service Water (Sec. TrtdY
Tittabawassee River Water
Liquid Waste Nozzle BA
Liquid Waste Nozzle BB
Liquid Waste Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year)
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID
tench Tower Water
ench Tower Solids
nturi/Demister Water
Venturi/Demister Solids
ESP Water" "
ESP Solids
Ash Pit Water 1
Ash Pit Solids 1
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year)
2378-
TCDD




























Total
TCDD


0,019


(NOT

70.2
5.82
0.55

(NOT S
76.6


2.46


13.4

4.10
1.80
20.7



0.23-0.31
42.7
Total
PeCDD





SAMPLED)

9.64.



WPLED)
9.64







1.29

5.22




6.51
Total
HxCOD




















0.54

1.69




2.23
Total
HpCDD


0.047






3.40


3.40





11.1

3.26

7.98



0.25-0.33
22.6
OCOD


0.153




14.5

14.1


28.8


0.23


42.8

19.1

31.7



0.87-1.16
94.6
2378-
TCDF







2.83




2.83







0.14

0.78




0.92
Total
TCDF


0.102




77.3
1.26
0.62


79.3


47.2

8.28
151
6.82
53.0
34.5
7.48



1.77-2.36
310
Total
PiCOF







2.12




2.12


0.09


1.27

1.61

3.95




6.92
Total
HxCDF


















2.94

1.46

1.27




5.7
Total
HpCDF


0.019









0.019





22.6

5.05

5.65




33.3
OCOF


0.015









0.015





18.7

6.24

6.78



0.26-0.34
32.0
UNITS




























Sample analysis not returned from laboratory.

-------
                                                                                     TABLE  D-73

                                                            INFLUENT AND EFFLUENT TCDD ISOMER LOADINGS (In grams per year)

                                                                    DOW CHEMICAL  COMPANY  BUILDING 703 INCINERATOR

                                                                                      3/28/84
Sample Identification
INFLUENTS
AIR
Precombustlon Air
LIQUID
Service Water (Sec. Trtd.)
Tlttabawassee River Water
Liquid Waste Nozzle BA
1 Liquid Waste Nozzle BB
Liquid Waste Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID '
tench Tower Water
ench Tower Solids
nturl/Demlster Water
Venturl/Demlster Solids
ESP Water
ESP Solids
Ash Pit Water
Ash Pit Solids
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year
1368


0.02

35.1


9.39




44.5


9.18


18.2

4.68





2.03-2.71
34.5
1379


0.01

19.3
(N01

29.9



(NOT
49.2


5.85


11.3







0.81-1.09
18.1
1369





SAMPLED)





SAMPLED)








0.32






0.32
1247
1248
1378
1469















6.80


0.74







0.12-0.16
1.68
1246
1249




























1268
1278




























1478




























1268
1279




























1234
1236
1269




























1237
1238




20.5


3.45




24.0


5.68


ii;.au

4.84





0.37-1.17
24.3
2378




























1239




























1278
1279




























1267




























1289




























o
o
            Total  of two wastes  Incinerated.

-------
                                                                                     TABLE  0-74
                                                           INFLUENT AND EFFLUENT TCOD ISOMER LOADINGS (in grams per year)
                                                                    DOW  CHEMICAL  COMPANY  BUILDING 703 INCINERATOR
                                                                                       8/30/84
Sample Identification
INFLUENTS

Precombustion Air
LIQUID
Service Water (Sec. Trtd.)
ittabawassee River Water
. Liquid Waste Nozzle BA
1 Liquid Waste Nozzle BB
Liquid Waste Nozzle C
Low-BTU Liquid Waste '
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year)
EFFLUENTS
• yfc 	 — 	 	
AIR
incinerator Exhaust
LI


^
IJUIU
uench Tower Water
j encn Tower Solids
entu rl/Demlster Water
Veniuri/uemister ion as
ESP water
SP Solids
Asn IMt Water
Ash Pit Solids
— tn\ ii\ 	 ' 	
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year;
1368




45.0


59.1

185


289


7.98


45.7

8.83
I73T
10.9

0.11

). 21-0. 28
75.1
1379


0.002

35.6
(NO'

27.3

94.6

(NOT
158


6.02


28.9

5.81
0.87
572?

Q.Q«

0.11-0.15
47.1
1369





SAMPLED)





SAMPLED)
















— IH7 	
1248
1378
1469


0.0008




1.18




1.18


0.10


2.28

0.53

0.33

0.01

0.03-0.03
3.30
1246
1249




























1268
1278


0.0005









0.0005















1478




























1268
1279




























1234
1236
1269


0.0004









0.0004















1237
1238


0.002

9.78


1.18




11.0


6.16


34.6

5.72

" 6.87

0.06

0.03-0.10
53.5
2378


0.002









0.002















1239




























1278
1279




























1267




























1289




























o
I—1
o
              Total of two wastes incinerated.
                                                       No waste incinerated.

-------
                                                                                    TABLE 0-75
                                                           INFLUENT AND EFFLUENT TCDD ISOMER LOADINGS (in grams per year)
                                                                   DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
                                                                                      9/5/34
Sample Identification
INFLUENTS
AIR
i tP«hiCJ?mbMSt1on ^1r
LIQUID
Service Tfeter (Sec. Trtd.)
Tlttabawtssee River Hater
Liquid Waste Nozzle BX
Liquid Waste Nozzle BB
Liquid Waste Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year!
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID
Quench Tower Water
Quench Tower Sol Ids
Venturl/Demlster Water
Venturl/Demlster Solids
ESP Water
ESP Solids
Ash Pit Water l
Ash Pit Sol Ids l
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year)
1368


0.012




48.3
4.43
0.36


53.1


64.3


4.90

2.07

1.34



0.11-0.15
72.7
1379


0.004


(NOT 5

22.0
1.39
0.12

(NOT S
23.5


35.3


4.46







0.08-0.10
39.9
1369


0.001


\MPLEb)





WPLED)
0.001







0.14

0.56




0.70
1247
1248
1378
1469















0.03











0.03
1246
1249




























1268
1278




























1478




























1268
1279




























1234
1236
1269


0.0005









0.0005















1237
1238


0.002






0.07


0.073


0.21


4.03

1.92
1.80
18.6



0.05-0.06
26.6
2378




























1239




























1278
1279




























1267




























1289




























o
ro
            Sample analysis  not  returned  from  laboratory.

-------
                   FIGURE D-i
                   TCDD LOADINGS
   DOW CHEMICAL COMPANY BUILDING  703  INCINERATOR
NOTE -  Loadings stated in grams per year,
       and calculated as averages of
Sdmpic
                          o«c of
                                                         11
                                                       ii
                                                    TOTAL LOADINGS OF TCDD
                                                       In
                                                                      Out
218

-------
                  FIGURE  D-?
                PeCDD LOADINGS
   DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE - Loadings stated in grams  per year
      and calculated as averages of    '
                                                    Aw*. 4*704.
                                                        r
                                                    *M
                                                      6 5
                                                      al
TOTAL LOADINGS OF PeCDD

 In              Out

-------
                  6URE  D-3
DOW CHEMICAL
                              703 INCINERATOR
NOTE - Loadings  stated In grams per year,
       and calculated as averages of
       three sampling days (8/28, 8/30,
       and 9/5/84).
TflTAL LQADIMSS OF HxCDD

 In

 7.6

-------
                FIGURE D.-4

              HpCDD LOADINGS            .„
 DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE - Loadings stated 1n grams per year,
       and calculated as averages of
       three sampling days (8/28. 8/30,
       and 9/5/84).
TOTAL LOADINGS OF HpCDP

 In               Out
 86
                                                                        58

-------
                FIGURE n-5
                OCOD LOADINGS
DOW CHEMICAL COMPANY BUILDING  703  INCINERATOR
NOTE -
  Loadings stated in grams  per year
  and calculated as averages  of

                             8/3°'
                                                     TOTAL LOADINGS OF PC DP

                                                      *"               Out
                                                 351

-------
                            1
                            S
                                              -L3/M
                                                                                             u.
                                                                                             o
                                                                                             o
oo

CM
CSJ



-------
                  FIGURE D-7

                PeCDF LOADINGS
  DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
               7Xco*o trrtu+rr Mwrat
                                                 if
                                                   £
                                                II
                                                              (2.8
NOTE -
Loadings stated  1n grams per year.
and calculated as averages of
thr«« sampling days (8/28. 8/30.
and 9/5/84).
 Staple *»*lys«* r»
                   ««««f
                                                     TOTAL LOADINGS OF PeCDF

                                                      In               Out
12.3    (%)   15,5

-------
                FIGURE  iw*.

              HxCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING  703 INCINERATOR
NOTE -
     Loadings stated 1n grains per year.
     and calculated as averages of
     three sampling days (8/28, 8/30.
     and 9/5/84).
TOTAL LOADINGS OF HxCDF

 In  _            Out

 6.1    (%)
                                                                      17.5

-------
                FIGURE D-9

               HpCDF LOADINGS
 DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE -  Loadings stated In grams per year,
       and calculated as averages of
       three sampling days (8/28. 8/30.
       and 9/5/84).
TOTAL LOADINGS OF HpCDF

 In               Out.
 ~—'

 60
                                                                      79

-------
                FIGURE D-1CJ
                OCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE -
  S»«|»l«
   Loadings stated in grams per year
   and calculated as averages of
   th*;ee sampling days (8/28, 8/30,
   and 9/5/84).

                      <"« of -tAw.
                                                      TOTAL  LOADINGS OF  QCDF

                                                        In                Out
                                                      45.6
                                                                     72

-------
                        APPENDIX E
DETAILED DESCRIPTIONS OF AMBIENT AIR MONITORING EQUIPMENT
                   AND SAMPLING METHODS
                 MICHIGAN DIOXIN STUDIES
      MIDLAND, MICHIGAN, AMBIENT AIR SAMPLING STUDY

-------
                                    APPENDIX  E
     In  the following  narrative,  each  individual  type  of  sampling  device  used  in
 the  ambient  air  study is  described  in  terms  of  its  components.


 I.   HIGH-VOLUME  SAMPLER  FOR  PCDD/PCDF

     Previous studiesll»12,13 snowec| the  applicability of a  modified  high-volume
 sampler in the collection of pesticides and other semi -volatile compounds  in
 air. More recently,  the use of this  sampler was  extended  to  apply  to  PCOD and
 PCDF.   The modified sampler, shown  in  an exploded  view in  Figure  E-l, consisted
 of  a high-volume  sampler with  a   shelter,  motor,  timer,  and  flow  controller
 arranged in  a manner similar to that  described  in the April 30,  1971,  Federal
 Register (Vol. 36, Number 84).  However, an extended throat section was  inserted
 between the  glass fiber filter and  the motor, to hold  a cylindrical polyurethane
 foam (PUF) plug.

     Standard glass  fiber filters (Whatman 934-AH)  of  the type  specified in the
 above Federal  Register  were  used;  that  is, they were  at least  99% efficient  in
 trapping particles  of  0.3-micron  average  diameter.   Filters  were  used   as
 supplied,  and  were not subjected to any precleaning  steps.  The  PUF plugs were
 manually cut  from  3-inch  stock  of   open-cell  polyether-type  material, into
 cylindrical  shapes  10 to  11 centimeters in diameter.   Initial  cleanup  of the
 PUF  plugs  was  accomplished by the  field  contractor, GCA/Technology Division,  by
 Soxhlet extraction  for  14  to 24  hours  at  four  cycles per hour, three times,
 using 95:5 V/V hexane/ethyl  ether.   Extracted  PUF   was placed  in  a vacuum oven
 evacuated  by a water aspirator, and  dried  at  room temperature for two  to four
 hours until  a  solvent odor was absent.  Each plug  was  then  placed in  a  cleaned,
 labeled hexane-rinsed sample container,  using hexane-rinsed forceps,  for trans-
 port to the sampling  sites.  A  representative  sample  of every  lot of  cleaned
 PUF  was analyzed  at  GCA for background levels of  contaminants.   The results  of
 these tests  are  presented in Table  E-l.


II.   HIGH-VOLUME  SAMPLER  FOR CHLOROBENZENES AND  OTHER  SEMI-VOLATILE COMPOUNDS
     Lewis  and  MacLeod  cite    data  indicating  the collection  efficiency of  a
 sampler with  PUF alone  as  the  sorbent  decreases  dramatically  for  chlorobenzenes
 below Cls.   On  this  basis  it  was  decided  that, to  sample  for  semi-volatile
 compounds,  a  backup  sorbent  would  be  employed  in a  separate  set of  samplers
 constructed similarly to the PCDD/PCDF samplers described above.   The  extended
 throat beneath  the  glass-fiber  filter  was  packed  with a  sorbent  "sandwich"
 consisting  of  two  PUF  plugs  of  the  same  size  as  in  the  PCDD/PCDF  sampler,
 surrounding a  layer  of  75 grams  of 16/50 mesh  Amberlite  XAD-2  (Rohm &  Haas,
 Philadelphia,  Pennsylvania)   resin.    To  facilitate  handling  of  this  finely
 divided sorbent, it was  contained  in a Teflon  cup, as  shown in  Figure E-2.   The
                                      E-l

-------
                                         Filter holder support
                                         Teflon gasket
                                         Teflon gasket
                                         Aluminum throat extension
                                         and foam plug
                                         Aluminum flange & motor
                                         support
                                         Hi-Vol motor
                                         Sheet metal adaptor for
                                         exhaust duct
                                         Flow controller & sensor
                                         Power cords
                                         Exhaust duct
                  FIGURE E-l
EXPLODED VIEW  OF AMBIENT AIR SAMPLER FOR PCDD/PCDF
                      E-2

-------
                                                         TABLE E-l

RESULTS
OF QUALITY CONTROL
CHECKS ON UNEXPOSED POLYURETHANE
FOAM PLUGS

Concentration (ug)*
Sample
QC 365
QC 366
QC 367
QC 368
QC 369
Die thy 1
Phthalate
0
120.05
231.78
53.44
220.23
Bis 2-Ethyl
Hexyl Phthalate
ND
24
ND
ND
ND
Adipate
Alkyl Ester
ND
Found
ND
ND
ND
Phenolics
ND
ND
ND
ND
ND
PCDDS and
Biphenyls
ND
ND
ND
ND
ND
c6-c8
Hydrocarbons
100 - 500
ND
ND
ND
ND

Higher
Boiling Point
Hydrocarbons
ND
ND
ND
ND
100
71  *Detection Limits

       Phenolics:  ND  =  <50 ug
       TCDD:       ND  =  <100 ug
       Biphenyls:  ND  -  <100 ug
       Priority pollutants  - <10 - 50 yg
1  Identity of quality control samples:
      QC 365 - Laboratory blank.   Solvent KD concentrated to 10 mL.
      QC 366 - Two PUF plugs from Lot //I ("Old PUF")
      QC 367 - Two PUF plugs from Lot #1 ("Old PUF")
      QC 368 - Two PUF plugs fr.om Lot #7 ("New PUF")
      QC 369 - Two PUF plugs from Lot //7 ("New PUF")

-------
1
I
1
I
I
I
i
I
 1
 I
 I
TEFLON CUP  <
               ALUMINUM
                THROAT
                                        StCOND PUF PLUG
                                        75 9- XAD-2
                                        FINE MESH SS SCREEN
                                        SNUG FIT BETWEEN TEFLON CUP
                                        AND ALUMINUM THROAT
                                                                FIRST PUF  PLUG
                                                                            NE  MESH  SS  SCREEN
                                            FIGURE E-2


                                  HIGH-VOLUME SAMPLER ATTACHMENT

                   TO SAMPLE FOR CHLOROBENZENES AND OTHER  SEMI-VOLATILE COMPOUNDS
                                                     E-4

-------
  cup  included  a 40-mesh  stainless  steel  screen  bottom, and  was  filled  in  the
  field  with  preweighed  aliquots  of  XAD-2 delivered  from containers  sealed  at  the
  GCA  laboratory.   The sampling assembly  was  constructed by  placing  a  PUF plug in
  the  aluminum  throat, a Teflon  cup containing XAD-2  atop the  plug, and a  second
  PUF  plug  into the top  of the cup.   The  prefilter head  was  secured  to the  top of
  the  extended  throat, forming a  tightly-packed  sorbent  assembly.

      A  representative sample of every lot of  XAD-2 used  in this study was  analyzed
  by the supplier,  Supelco, Inc.   These data  are  shown in Table E-2,  and  show  the
  sorbent to  have met  requirements established by EPA for the maximum  content  of
  contaminants  in unexposed sorbent. 14


III.  LOW-VOLUME SAMPLER FOR VOLATILE COMPOUNDS

      As the  compounds selected to be sampled in  this  study  included  several with
  boiling points lower than 100°C, a sampling method  appropriate to the collection
  of these  more volatile  pollutants was   found  in the  work  of Riggin.6   Carbon
  molecular sieve  (CMS)  adsorbents  were  determined  to be appropriate  to collect
  selected  volatile organic  compounds,  specifically,  certain  nonpolar  organics
  with boiling  points  between -15°  and 120°C.  The performance of  CMS adsorbents
  was  described by  Riggin as superior to and more sensitive than other sorbents,
  such as Tenax GC, for a wider  range of compounds.   With  the  guidance  of  the
  document  cited above,  a  low-volume sampler  incorporating  Spherocarb® adsorbent
  was  constructed,  as  shown in Figure E-3.

      The sampling   system  consisted   of  a   pair  of  sorbent   cartridges, each
  approximately three  inches long,  constructed  of 1/4-inch O.D. stainless  steel
  tubing.  Each tube  was  loosely  packed  with 0.4 gram  of 60/80 mesh  Spherocarb
  held in place with  precleaned  glass  wool  plugs;  the  direction  of  sampled  air
  flow was  engraved  on   the body  of   the  tubes to  assure  that  the  tubes were
  assembled correctly  in  sampling and analysis.   The  tubes were equipped with
  Swagelok  fittings at  both ends,  and  were  prelabeled  such that  one tube  was
  designated  an inlet  or primary tube.   The primary tube  was mated with a secondary
  or backup tube to evaluate penetration of  compounds through  the primary  tube.
  The  tube  pair was  connected  by  a length  of  Teflon  tubing  to  a duPont  model
  P-125  or  Alpha 2 constant  flow  pump  capable of maintaining  accurately the  low
  flow rates  required  (approximately 30 to 70 mL/min).

      In field  use, the cartridge pair was hung  vertically  from a support  built
  onto one  of the high-volume samplers  described  above.   It  was  found  that  during
  heavy  rains,  water  was  drawn  into the  unprotected  inlet  of the primary  tube.
  A funnel  formed of aluminum foil attached to the lower  end of the cartridges  was
  successful  in eliminating this  problem.

      To guard  against the  battery-powered sample pumps becoming discharged  during
  use, they were operated while connected to  battery chargers at all  times.  This
  procedure was effective  in assuring  reasonably  constant air flows  through  the
  samplers  over entire sampling periods.
                                         E-5

-------
                         TABLE £-2
                QUALITY ASSURANCE ANALYSES
       XAD-2 RESIN LOTS USED IN AMBIENT AIR SAMPLING
XAD-2 Lot Number
     Residual
Organics (ug/g)
Total Chromatographable
	Organics (ug/mL)
      221
      222
      223
      224
      225
      226
      227
      228
      229
      230
     29.14
     39.40
     84.50
     97.20
     69.30
     77.50
     64.70
     87.30
     69.30
     62.30
         0.00
         0.00
         0.00
         0.83
         3.66
         8.27
         0.00
         0.00
         0.32
         7.87
NOTE  Guidelines established by EPA allow for the presence of a
      maximum of 1000 ug/g of residual organics, and 20 ug/mL of
      total Chromatographable organics in unexposed sorbent media.
      (IERL-RTP Procedures Manual:  Level 1 Environmental Assessment,
      2nd Edition, EPA 600/7-78-201.  U.S. Environmental Protection
      Agency, Research Triangle Park, NC, October 1978).
                             E-6

-------
 TO  DUPONT
     PUMP
(LOW FLOW)
                                   TEFLON TUBING
                                FOIL TUBE SHELTER
                                     CMS TUBES

                                   BACKUP TUBES

                                   SWAGED UNIONS

                                   PRIMARY TUBES



                                   FOIL FUNNELS
                                 SHELTER SUPPORTS
TO DUPONT
PUMP
(HIGH FLOW)
                                   FIGURE E-3
                  AMBIENT  AIR  SAMPLER FOR VOLATILE COMPOUNDS

-------
IV.   LOW-VOLUME  LIQUID IMPINGER  SAMPLER  FOR  FORMALDEHYDE

     In  selecting  the methods to be used  in sampling for the compounds of interest
 in  ambient  air, it  was  discovered  that  the  solid  sorbent  method  described  above
 for volatile compounds  was  not  appropriate  to  sample  for  formaldehyde,  owing  to
 apparent  problems with  retention on the sorbent  and  artifact  formation.   A wet
 chemical  method involving bubbling ambient air through a mixture of 2N  HC1/0.05%
 2,4-dinitrophenylhydrazine  (DNPH)  and isooctane was chosen.  Reference  6 to this
 report  describes  this  method  as  applicable  to  detect aldehydes  and   ketones.
 Samples were analyzed by  high-performance  liquid  chromatography.

     The samplers  (see Figure E-4)  consisted of a  short length  of  Teflon tubing
 connected to a pair  of midget  impingers,  each  containing the DNPH-isooctane
 absorbing reagent.   The system was  powered  by a  duPont  constant  flow  sampling
 pump similar to that  employed  in  the low-flow  CMS sampler.   The  pump was joined
 to  the  impinger  system by  Tygon  tubing.  Like the  CMS   samplers, the  inlet  of
 the sampler was protected from rain by wrapping  in  a short  funnel  of aluminum
 foil.
                                        E-8

-------
                                                        TYGON  TUBING
                      FOIL
                   FUNNEL
i
UD
                                       TEFLON
                                       TUBING
                            DNPH
                            ABSORBING
                            SOLUTION
       DUPONT  P-125
            PUMP
MINI IMPINGERS
SILICA  GEL
                                            STYROFOAM
                                               BASE
                                                  FIGURE E-4
                                      AMBIENT AIR  SAMPLER FOR FORMALDEHYDE

-------
                    APPENDIX F
     DETAILED DESCRIPTION OF CONDUCT OF STUDY
AND CARBON MOLECULAR SIEVE METHOD VALIDATION STUDY
             MICHIGAN DIOXIN STUDIES
  MIDLAND, MICHIGAN, AMBIENT AIR SAMPLING STUDY

-------
                                   APPENDIX F
I.  HIGH-VOLUME SAMPLER FOR PCDD/PCDF

    As indicated previously in the description of this sampler, the polyurethane
foam (PUF) plugs were preextracted in the  GCA  laboratory, dried,  and  placed  in
a cleaned, labeled sample jar for transport to the study area.  At the beginning
of each sampling day, the filter supports,  Teflon gaskets,  and extended throats
were cleaned,  rinsed  with  hexane,  and  dried  in a  resistance-heated  oven  at
approximately 150°C.  These parts were assembled and wrapped  at  both  ends  with
hexane-rinsed aluminum foil for transport  to the monitoring  sites.   The serial
numbers of  the  glass  fiber  filters  were  associated  with  the  appropriate
monitoring sites and  recorded in  a  field log book maintained  by  the  GCA field
team coordinator.  As the  PUF plug  was  removed  from its container  and placed
into the sampling assembly with  hexane-rinsed forceps, the identity of the site,
run number,  and date  of  sampling  was  written  on  the  exterior  of  the  plug
container.

    Completed sampling  assemblies  were  transported  to  the  monitoring  sites,
where the  protective  foil  covers were  removed,  and  screwed  tightly  onto  the
appropriate high-volume  samplers.  The  sampler timers were then  activated  and
the flow  controllers  set to provide a target  flow  rate of  20 cubic  feet  per
minute (0.57 m3/min).   In practice, however, the resistance to air flow presented
by the PUF  plug occasionally  overcame  the  capacity of the  sampler  motor  to
provide this flow  rate.   In this  case, the  flow controller  was set  for  the
highest flow rate  attainable.   Prior to leaving  each  site,  time,  and ambient
temperature, pressure,  and  relative  humidity were  recorded  by the  field  team
coordinator.

    At the  conclusion  of each   sampling  run,  about 24 hours  later,  final  flow
rate data  were  taken,  the samplers  were disassembled  and  the  filter portions
of the assembly  were  covered with  hexane-rinsed aluminum  foil.  The  samplers
were then  reassembled and  restarted  for  the  next sampling  period.  As the  four
monitoring sites were serviced  in  sequence,  the  sampling periods at  each  site
were necessarily slightly different.

    After each  sampler was  serviced,  the exposed samples were  returned  to  the
mobile laboratory,  where  the  glass-fiber   filter  was  removed,   folded  inward
lengthwise, and placed in a wrapper  of hexane-rinsed aluminum  foil.   This  foil
was folded twice to form an envelope, labeled by filter, site, and  run number,
and stored flat in the mobile laboratory.

    The PUF plugs were  removed  from  the  sampler  assembly and  returned to their
original  labeled  container using hexane-rinsed  forceps.   Filter supports  and
the interior of the extended throats were  rinsed with  hexane into the PUF  plug
containers, and  the   containers  were  sealed  for  shipping  to the  analytical
laboratory.
                                  F-l

-------
   .  Sites  1,  2, and  3 were equipped  with single  samplers  for PCDD/PCDF.   On
 every  sampling  day, field  blank  and field duplicate  samples  were obtained  at
 site 4,  this  being the  site  expected  to  be downwind  of Dow  Chemical  most
 frequently.   Method blanks,  one each for  the  filter and  the  PUF, were  submitted
 separately to the  analytical  laboratory;  neither  of these  blanks was exposed  to
 ambient  air in Midland at any time with the exception of the brief  period  between
 removal  of a random  filter from the  stock  of unexposed  filter  media  and  its
 immediate  wrapping in  aluminum  foil  for shipment.

     It was initially intended  in this study  to obtain PCDD/PCDF  samples  daily
 and  to  submit  most  for analysis.   However,  analytical  cost  and laboratory
 scheduling limitations were such that samples  from three of the 18  total sampling
 days were  analyzed.  The selection  was based  upon  examination of  ambient wind
 data for direction  and  probable  persistence  on  each sampling day.   By  these
 measures,  samples  from runs  4,  6,  and  16  were  forwarded  for  analysis.


II.   HIGH-VOLUME  SAMPLER  FOR  CHLOROBENZENES AND OTHER SEMI-VOLATILES

     These  samplers were assembled in a manner  similar to  that  of  the  PCDD/PCDF
 units, with exceptions owing to the insertion of XAD-2 sorbent  and  an additional
 PUF  plug  in  the high-volume  sampler's extended  throat  (see Figure IV-7).   To
 accomplish this,  the first  PUF  plug  was placed in the throat;  its  container  was
 labeled  as with the PCDD/PCDF  samplers.   A prewashed Teflon  cup  was  inserted
 atop the first  plug in the throat and filled with  75  grams  of XAD-2 resin from
 a preweighed  container;  that container was also labeled  appropriately  according
 to  site, run number, and date.   The second PUF  plug  was  then fitted into  the
 top  of  the Teflon cup  with hexane-washed  forceps, and  the  assembly  pressed
 together.   As with  the  PCDD/PCDF samplers,  both ends  of the filter  assembly
 were wrapped  in hexane-rinsed  aluminum   foil  for  transport to the monitoring
 sites.

     At the sites,  sampler  assembly  was  completed  similarly  to   the  PCOO/PCDF
 samplers.   A target sampling flow  rate of 20 cfm  was again selected; however,
 this rate  was achieved or exceeded  during only two  of the  86 successful  sampler
 runs,  because of  the  severe  resistance   to  air  penetration  presented  by  the
 tightly-packed  sorbent  materials.   Moreover,  on  some  days, perhaps  due  to
 humidity,  much   less  than the  target sample  volume  of 800  cubic meters  was
 collected.  While  runs of this  kind  would not  have  been  of concern with  respect
 to sorbent breakthrough, the  sensitivity of  the  analytical method could have
 been reduced.

     Following each  run   at  each  site,  the  sampler  assembly,   covered   with
 hexane-rinsed aluminum foil at its  inlet  end,  was  dismantled, with the exposed
 sorbents returned  to their original  containers.  The granular XAD-2 sorbent  was
 poured quiescently from the Teflon cup into  its container.  The filter supports
 and throat assemblies  were rinsed  into  the  container holding both PUF plugs.
 Each container  was then sealed  for shipping.
                                         F-2

-------
      As  for  PCDD/PCOF,  sites  1,  2, and  3 were equipped  with single  samplers.
  Field blank  and field  duplicate  samples  were taken  daily at  site 4.  Method
  blanks,  one  each for the  filter  and  PDF, and of two  of  the ten lots of  XAD-2
  used in  the  study,  were submitted for analysis for the components  of  interest.

      Samples  from each  site, along with  field  blanks- and field duplicates  from
  site 4,  were shipped for  analysis  for  all  18 sampling days regardless of  wind
  or other meteorological  conditions.


III.  LOW-VOLUME  SAMPLER  FOR SEMI-VOLATILES AND  VOLATILES

      A.   CMS  Field Methods

      The  CMS  sorbent  cartridges   described  previously were preconditioned  and
  packed  at the  GCA laboratory  according  to the  following  procedure:

          Swagelok plugs,  ferrules, unions, and  empty  stainless  steel   tubes  were
          washed, rinsed  with methylene chloride, and  heated at 250° +_ 20°C  for
          one  hour.   The  hardware  was then assembled  (see  Figure IV-8).

          Each tube   was   packed   with  approximately   0.4   gram  of   60/80  mesh
          Spherocarb  and  glass  wool  end plugs.

          Tubes  were  conditioned in bulk  at 400°C  for  16 hours under   a   purified
          nitrogen purge  flow of  100 cc/min.  The exit end of each cartridge  was
          capped  and  the  entire cartridge was removed  from  the  flow  line  and  the
          other  end   cap   immediately  installed.   Sealed  cartridges  were  then
          placed  in a metal  friction-top  can containing two  inches of  granulated
          activated charcoal  beneath  a  retaining  screen.    Paper  tissues  were
          placed  in  the can  to avoid damage to the  cartridges during  shipment.

  Tubes were  conditioned  in  this  manner  no more than 30 days  prior  to their  use
  in sampling.

      Prior to each sampling day,  two  pairs  of CMS tubes  per sampling site  were
  joined  together by  Swagelok  unions.  As  indicated previously, the  direction  of
  air flow through the tubes was  clearly  labeled; thus, primary and  backup  tubes
  were designated in  each  pair.   Sampling  site  identifications and  run  numbers
  were written on metal  tags fastened  on  each individual  tube.  Assembled  tube
  pairs were  carried  to the  sampling sites in metal  cans.

      Each site   included  two  low-volume   samplers  operating  at  flow  rates  of
  30 mL/min (low-flow)  and  70 mL/min (high-flow).   These flow rates were  selected
  out of  concern  that sorbent breakthrough volumes may have  been exceeded  at  high
  sampling rates  on days in  which  high  ambient temperature  and/or humidity  were
  experienced.  Prior to each sampling run, pumps were calibrated to yield  sampling
  flow rates  corresponding  to the  above.
                                        F-3

-------
    At each  monitoring  site,  a  low-  and  high-flow  pump  and  tube pair  were
assembled as shown in Figure  IV-8.  Pumps were started, times and meteorological
data were taken, and the samplers allowed to run for about 24 hours.

    At the  conclusion  of  each run,  a  final flow rate  check of each pump  was
performed; those varying by more than  +_5%  from  initial  flow rates  were  flagged
and the  sampling  runs  were  considered  invalid.  Exposed  CMS tube  pairs  were
removed, their ends closed  with Swagelok caps, and placed in a can for transport
back to the mobile laboratory.  At the laboratory, the primary and  backup tubes
were separated and open  ends  were closed tightly with Swagelok caps.  Individual
tubes were then placed  in  a can containing a two-inch  bed of activated charcoal
and stored in a cooler  packed with ice.

    Sites 1, 2, and  3  were  equipped with  a low- and high-flow  CMS  sampler  on
selected sampling days.  Site  4  included  these  in addition  to  field duplicate
samplers operating  in  both flow  rate  ranges.  A  single field  blank,  made  up
from an individual unexposed  CMS tube, was supplied from site 4.  Thus,  on each
sampling day 21 tubes (primary, backup, and blank) were exposed.

    Analytical laboratory   resources to analyze these  samples  were  limited such
that only  180  tubes  could  be  analyzed.   Thirty of these  analyses  were  to  be
associated with the  method  validation  study to  be  described  in  the  Section
III.B of this appendix.  A reasonable analytical  scheme incorporating 150 total
analyses was  devised,   based  upon  ambient temperature,  humidity,  and  wind
direction on the sampling  days.

    Sampling days were  first  selected on the basis  of weather forecasts available
locally.  If persistent winds  were expected in  directions  likely  to establish
good upwind-downwind relationships between two or more sampling sites, then the
CMS samplers  were activated.   At the  conclusion of  the  run,  if  winds  were
favorable, 15  of  the 21 tubes utilized  that day  were  selected  for  analysis
based on temperature and humidity  conditions.   If the high  temperature  in the
sampling period exceeded 80°F, with associated high humidity, the following CMS
tubes were submitted for analysis:

    - All primary low-flow samples
    - All backup low-flow samples
    - Field blank
    - Primary and backup low-flow field duplicates (site 4)
    - Primary and backup high-flow samples from  the two
      sites most closely downwind of Dow Chemical

    On cooler days with lower humidity, the following  tubes  were  to be analyzed:

    - All primary high-flow samples
    - All backup high-flow samples
    - Field blank
    - Primary and backup high-flow field duplicates (site 4)
    - Primary and backup low-flow samples from the two
      sites most closely downwind of Dow Chemical

Samples were  shipped from  runs 3, 4, 6,  10,  11,  12,  15, 16, and 17, resulting
in a total of 135 samples  submitted for analysis.
                                       F-4

-------
    B.  CMS Method Validation Study

    Because the  range  of compounds projected  to  be determined  using  the low-
volume sampler  was wide,  and  sufficient  information  concerning spiking  and
recovery efficiencies and breakthrough volumes  on  Spherocarb was not available
from any previous source, a  short-term laboratory validation  study was conducted
to test the procedure.   Eight volatile compounds,  as  shown  in  Table F-l, were
selected to span  a  range of boiling  points  from 37°  to  173°C.   The  validation
study consisted  of  two  segments:   determination  of  spiking  and  recovery
efficiency, and  validation  of  sampling  procedures  and  breakthrough  volumes.
Spiking and ambient  conditioning  of  prepared  CMS  tubes  was performed  by GCA,
while sample analysis was conducted by a contract laboratory.

    To conduct the determination  of spiking efficiency, each of the compounds
of interest was  combined in the  liquid  phase  in  a spiking  carrier  matrix.   A
known volume was  drawn  with  a micro liter syringe and  injected into the inlet
of a sorbent tube  by way of a heated gas chromatography  injector assembly.   A
total of 20 carbon molecular  sieve  sorbent  tubes were spiked at an approximate
level of 100 ng per compound of interest (concentration range -  54-82 mg/L) and
analyzed by the laboratory.   Five CMS tubes were spiked at an approximate level
of 20 ng of each  compound  of interest (concentration  range - 5.4-8.2 mg/L) per
tube.

    For validation of  sampling procedures and  breakthrough  volumes,  a  system
was configured to provide scrubbed (organic free), humidified air at 86°F (30°C)
and 85 percent relative humidity to spiked CMS  tubes attached to duPont constant
flow pumps.  A schematic of this system is shown in Figure F-l.   These validation
conditions were  selected  to represent the  worst-case ambient  temperature  and
humidity conditions expected to be encountered in the field during the sampling
program.

    A total of 30  CMS  tubes  were used in the  validation  study, allowing for a
range of spiking  quantities,  sampling rates, and total  sample  volumes.   These
data are presented  in   Table  F-2, and show  that the  tubes  were  divided  into
seven distinct sets, five of  which  contained five  tubes  each, and two  of which
included three and two  tubes, respectively.   Set 1  was spiked but not subjected
to the  simulated ambient  sampling conditions  described  above;  this  set  was
intended to provide a measure of spiking and recovery efficiency alone, without
considering breakthrough volumes.   Sets  2 through  5  were spiked prior to being
conditioned, at the air  flow  rates  shown,  for various sample volumes.   Set  6,
including three tubes,   was  conditioned  but  not spiked, while the  two  tubes  in
Set 7  were neither  spiked  nor  conditioned, and  were thus  considered to  be
method blank samples.

    As described in  Section  VI.E.3 of the  report  of which this  appendix  is  a
part, only four of the  30 CMS  tubes  in the validation study were  analyzed by the
contract laboratory within desired holding times.   Analytical  results for those
four tubes showed that  seven of the eight compounds shown in  Table F-l  were not
detected.  The  last  compound,  perchloroethylene   (tetrachloroethylene),  was
detected, but  not  in  consistent  agreement  with the  known levels spiked  (see
Table VI-10 of report).
                                     F-5

-------
                                   TABLE F-l
                       COMPOUNDS USED  FOR VALIDATION  STUDY
               Compound
Boiling Point (°C)
1,1-Dichioroethylene (Vinylidene Chloride)




Chloroform




Carbon Tetrachloride




Aerylonitrile




Benzene




Tetrachloroethylene




Chlorobenzene




o-Dichlorobenzene
        37




        61.7




        76.5




        77.5




        80.1




       121




       132




       173
                                   F-6

-------
                       HG.
                  THERMOMETER
ERLENMEYER FLASK
2-HOLEO STOPPER
(EXCESS MOISTURE
KNOCK-OUT FLASK)
               FLOW
              METER
                                                           5.5 LITER  MANIFOLD
                                                           (AT  ELEVATED
                                                            TEMPERATURE)
                                  FLOW
                                  METER
               ERLENMEYER  FLASK
               3-HOLED STOPPER
               HOT PLATE (AIR HEATER,
               HUMIDIFIER)
                                                                     DIGITAL
                                                                     PYROMETER
  COMPRESSED,
PURIFIED AIR
(CARRIER)
     LOW VOLUME,OUPONT CONSTANT
     FLOW PUMPS
                                     FIGURE F-l

                         SIMULATED AMBIENT AIR GENERATION  SYSTEM

                               CMS TUBE  VALIDATION STUDY

-------
                                   Table F-2

                           CMS Tube Validation Study
 Tube       Run          Flow Rate
  Set     Duration        Average        Sample Volume
Number     (min.)     (L/min., std.)    (Liters, std.)   Comments

   1          NA           NA                NA          No carrier air
              NA           NA                NA          Spiking level - 100 ng
              NA           NA                NA
              NA           NA                NA
              NA           NA                NA

   2       1,440          0.0283           40.701        Spiking level - 100 ng
           1,440          0.0271           38.980
           1,440          0.0272           39.163
           1,440          0.0274           39.391
           1,440          0.0280           40.365

   3       1,440          0.0626           90.070        Spiking level - 100 ng
           1,440          0.0649           93.451
           1,440          0.0657           94.644
           1,440          0.0667           96.066
           1,440          0.0642           92.462

   4         420          0.0658           27.654        7 hour run
             420          0.0623           26.162        Spiking level - 100 ng
             420          0.0629           26.410
             420          0.0635           26.647
             420          0.0643           26.999
                                 f -*
   5       1,440          0.0280           40.314        Spiking level - 20 ng
           1,440          0.0276           39.723
           1,440          0.0276           39.767
           1,440          0.0270           38.820
           1,440          0.0281           40.491

   6       1,440          0.0655           94.369        Blank with carrier air
           1,440          0.0646           92.980
           1,440          0.0650           93.609

   7          NA           NA                NA          Blanks without carrier  air
              NA           NA                NA
                                        F-8

-------
IV.    LOW-VOLUME LIQUID IMPINGER FOR FORMALDEHYDE

      Sampling trains composed of the parts described in Section IV of Appendix £
  were assembled as  shown in  Figure E-4.   Samples were  collected  and  handled
  according to the protocols  outlined  in  pages 40 to 43 of  Reference 19 to this
  report.   Owing to  limitations  on  the  number of samples that  could  be  analyzed
  by the contract laboratory, and the requirement that  DNPH  absorbing  reagent  be
  used for sampling within 48 hours  of its initial  preparation, it was determined
  that samples  for   formaldehyde  would  be  obtained on  six  of the  18  sampling
  days which  encompassed  the ambient  air  study  period.   The  DNPH  reagent  was
  prepared in the GCA laboratory and air-shipped to  the Midland sampling  sites by
  commercial carrier,  when  requested by  field contractor representatives  based
  upon predictions of favorable  wind directions.
                                          F-9

-------
                      APPENDIX  G

                 RAW ANALYTICAL DATA
            AMBIENT AIR  PCDD/PCDF  SAMPLING
IN VICINITY OF  DOW CHEMICAL  COMPANY,  MIDLAND,  MICHIGAN

  ANALYTICAL LABORATORY  -  MIDWEST  RESEARCH  INSTITUTE
                          KANSAS CITY,  MISSOURI

-------
               TABLE G-l

     Raw PCDD/PCDF Analytical Data
    Ambient Air Study in Vicinity of
Dow Chemical  Company, Midland, Michigan

UK I Sample Ho.
1149E-1-NFA-1
I149E-2-NPA-2
M49E-3-FA-3
1149E-4-PA-4
1149E-5-FA-5
1149E-6-PA-6
1149E-7-FA-7
11A9E-8-PA-B
1149E-9-FA-9
1149E-10-PA-10
1149E-11-FA-11
1149E-12-PA-12
11A9E-13-FA-13
11A9E-14-PA-14
I149E-MB1-15
1149E-39-HNF-16
1149E-15-FB-17
1149E-16-FB-18
1149E-18-FB-19
11A9E-19-FB-20
1149E-20-FB-21
11A9E-AO-NMP-22
11A9E-15-PB-23
1IA9E-16-PB-24
1149E-17-PB-25
1149E-18-PB-26
HA9E-19-PB-27
11A9E-20-PB-28
11A9E-17-FB-29
11A9E-MB2-30
I149E-A1-NMF-31
liA'JE-21-FC-32
11A9E-22-FC-33
11A9E-23-FC-3A
I1A9E-2A-FC-35
SAS
Sample
No.
11A9E-1
11A9E-2
11A9E-3
1IA9E-A
11A9E-5
11A9E-6
1149E-7
11A9E-8
11A9E-9
11A9E-10
11A9E-11
11A9E-12
1149E-13
11A9E-1A
11A9E-39
11A9E-15
11A9E-19
11A9E-21
11A9E-23
11A9E-25
11A9E-AO
11A9E-16
11A9E-18
1149E-20
11A9E-22
11A9E-2A
11A9E-26
11A9E-17

1IA9E-A1
11A9E-27
1IA9E-29
11A9E-31
1IA9E-33

Total TCDF
1.0
1.0
ND (0.11)
0.65
36
180
7.5
3.9
1.2
d
ND (0.03)
ND (0.03)
0.92
A.O
ND (0.09)
1.0
5.6
5. A
2.2
ND (0.05)
1.5
0.82
5.8
6.9
29
8.7
ND (O.A1)
5.1
2.2
ND (0.04)
0.9A
3.0
58
4.6
72

2.3.7.8-TCUF
'•°b
i.ob
ND (0.11)
ND (0.06)
ND (0.69)
ND (0.40)
ND (0.20)
ND (0.28)
NO (0.09)
d
NO (0.03)
ND (0.03)
ND (0.06)
ND (0.13)
ND (0.09)
1.0b
ND (0.10)
ND (0.11)
ND (0.11)
ND (0.03)
ND (0,05)
O.B26
ND (0.1A)
ND (0.15)
ND (0.18)
ND (0.16)
ND (0.10)
ND (0.10)
ND (0.04)
ND (0.04)
0.94b
Nl) (0.06)
Nl) (0.81)
ND (0.10)
ND (1.1)
Total
TCDD
1.3
1.5
0.88
0.80
3.7
33
1.6
1.7
0.76
0.84
0.65
0.28
0.70
0.61
0.84
1.5
1.1
0.94
1.3
1.0
0.66
1.3
0.77
1.8
6.0
D.7A
3.5
0.57
0.43
0.26
1.3
0.29
4.5
0.71
9.3

2.3.7,8-TCDD
0.75b
0.93b
ND (0.10)
ND (0.10)
ND (0.10)
ND (0.70)
ND (0.18)
ND (0.12)
ND (0.07)
ND (0.02)
ND (0.05)
ND (0.08)
ND (0.08)
ND (0.12)
ND (0.02)
0.85b
ND (0.06)
ND (0.06)
ND (0.13)
ND (0.08)
ND (0,08)
0.836
ND (0.15)
ND (0.15)
ND (0.82)
ND (0.12)
ND (0.61)
ND (0.10)
' ND (0.03)
ND (0.03)
0.87b
ND (0.03)
ND (0.03)
ND (0.07)
ND (0.20)
Total
PSCDF
ND (0.20)c
ND (0.46)
ND (0.09)
NO (2.0)
4.0
28
0.25
3.2
0.91
ND (0.12)
ND (0.07)
ND (0.10)
ND (0.67)
1.1
ND (0.12)
ND (0.09)
ND (0.06)
ND (0.36)
0.58
ND (0.06)
1.0
ND (0.03)
ND (2.3)
ND (0.67)
1.7
0.25
ND (0.79)
0.78
ND (0.03)
ND (0.18)
ND (0.04)
ND (0.09)
2.2
ND (0.09)
6.3
Total
P6CDI)
0.42b
0.56b
ND (0.16)
ND (0.29)
ND (0.48)
6.0
ND (0.38)
ND (0.25)
ND (0.07)
ND (0.03)
ND (0.11)
ND (0.13)
ND (0.24)
ND (0.20)
ND (0.03)
0.36b
ND (0.11)
ND (0.61)
ND (0.24)
ND (0.05)
ND (0.38)
l.O6
ND (0.30)
ND (0.27)
ND (0.39)
ND (0.12)
ND (0.10)
ND (0.25)
ND (0.09)
ND (0.21)
0.55b
ND (0.22)
ND (0.25)
ND, (0.29)
ND (0.45)
Total '
HxCDF
ND (0.19)
ND (0.18)
ND (0.13)
ND (0.30)
2.3
ND (1.1)
ND (0.30)
ND (0.25)
ND (0.51)
ND (0.18)
ND (0.48)
ND (0.16)
0.57
ND (0.11)
ND (0.04)
ND (0.11)
ND (0.49)
ND (0.19)
ND (0.14)
ND (0.01)
ND (0.23)
ND (0.09)
ND (0.20)
ND (0.64)
ND (1.0)
ND (1.0)
ND (0.31)
ND (0.47)
ND (0.60)
ND (0.35)
ND (0.14)
ND (0.24)
3.7
NO (0.13)
2.4
Total
llxCUD
a.s:
7.3
0.72
ND (0.64)
ND (0.69)
ND (0.51)
ND (0.26)
ND (0.20)
0.67
ND (0.15)
ND (0.35)
ND (0.11)
ND (0.24)
ND (0.87)
ND (0.06)
6.2e
ND (0.80)
NU (0.13)
ND (0.12)
NO (0.01)
ND (0.82)
3.4e
ND (0.45)
ND (0.48)
ND (0.91)
2.3
ND (0.89)
ND (0.08)
ND (1.6)
ND (0.28)
5.1e
ND (0.17)
0.45
ND (0.33)
0.22
Total
HpCDF
ND (0.74)
ND (0.73)
ND (0.52)
ND (0.66)
4.1
ND (0.74)
ND (0.65)
ND (0.45)
ND (0.28)
ND (0.41)
NO (0.85)
ND (0.70)
ND (0.43)
ND (0.90)
ND (0.21)
Nl) (0.38)
ND (0.09)
ND (0.16)
ND (0.13)
ND (0.07)
ND (0.08)
ND (0.12)
ND (1.7)
ND (1.2)
ND (0.95)
ND (0.71)
ND (0.77)
ND (3.2)
ND (0.96)
ND (0.51)
ND (0.35)
ND (0.53)
2. A
ND (0.46)
2.4
Total
HpCDD
5-°:
4.7
0.61
ND (0.41)
1.7
ND (0.36)
1.7
ND (0.35)
0.78
ND (0.46)
ND (0.88)
ND (0.32)
1.2
ND (0.16)
ND (0.26)
4.9e
2.3
0.50
0.18
ND (0.05)
0.28
3.1e
ND (0.22)
ND (2.2)
ND (0.91)
1.7
0.71
ND (0.96)
ND (1.2)
ND (0.56)
4.6e
ND (0.64)
2.2
0.46
0.91
Total
OCDF
*6|
5.2
0.75
ND (0.51)
2.8
ND (0.49)
0.47
0.65
1.3
ND (0.43)
ND (0.98)
ND (0.21)
Nl) (0.66)
ND (0.98)
ND (0.17)
7.8f
0.78
0.62
ND (0.42)
ND (0.10)
ND (0..25)
A. 1
ND (0.72)
ND (1.4)
ND (1.2)
3.6
1.5
ND (2.0)
ND (2.1)
ND (0.59)
7.3f
ND (1.0)
1.1
ND (0.53)
3.7
Total
OCDD
5.8}
6.) *•
. 2
0.87
0.53
5. 1
1.2
6.0
1.2
2. 1
ND (1.5)
ND (1.6)
0.70
3.2
ND (0.26)
ND (0.40)
7.0f
1.3
3.9
2. 1
ND (0.20)
3.3
7* !•
. 1
ND (2. A)
ND (4.2)
ND (4.0)
5.4
2.2
ND (2.3)
ND (2.1)
ND (0.67)
8.2f
ND (2.3)
6.2
2.3
3.2

-------
TABLE G-l (continued)
SAS
Sample Total
Mill Sample No. No. Total TCDF 2,3,7,8-TCDF TCDD
1149E-25-FC-36 1149E-35 4.5 ND (0.10) 1.1
1149E-26-FC-37 1149E-37 100 ND (1.1) ?0
1149E-21-PC-39 1149E-28 3.8 ND (0.10) 0.78
1149E-22-PC-40 1149E-30 82 ND (0.10) 19
1149E-23-PC-41 1149E-32 9.7 ND (0.04) 1.6
1149E-42-NMP-38 1I49E-42 3.6 0.92b 1.7
1149E-24-PC-42 1149E-34 240 ND (1.3) 52
1149E-25-PC-43 1149E-36 8.0 ND (0.15) 1.1
1149E-26-PC-44 1149E-38 5.1 ND (0.25) g
1149E-MB3-45 - ND (0.02) ND (0.02) 0.44
, a All data reported as nanograms (ng)/sample.
b Sample originally spiked with 1 ng of this compound.
c Value in parenthesis reflects estimated detection limit.
„ d Sample analyzed after additional cleanup by carbon column.
I e Sample originally spiked with 5 ng of a single isomer.
ro f Sample originally spiked with 10 ng of a single isomer.
g The 2,3,7,B-TCDD-13C,2 internal standard was not recovered

2,3.7,8-TCDD
ND (0.12)
ND (0.46)
ND (0.06)
ND (0.04)
ND (0.06)
1.2b
ND (1. 3)
NO (0.07)
g
ND (0.04)


TCDD and TCDF


Calculations
Total
PECDF
ND (0.10)
U
ND (0.12)
3.9
ND (0.19)
ND (0.06)
23
ND (0.07)
ND (0.30)
ND (0.03)


internal'


for TCDF,
Total
PSCDD
ND (0.36)
ND (0.91)
ND (0.12)
ND (0.26)
ND (0.40)
0.4?
1.09
ND (0.12)
ND (0.30)
ND (0.05)


Total
HxCDF
ND (0.10)
3.4
ND (0.16)
ND (0.40)
ND (0.06)
ND (0.06)
ND (1.8)
ND (0.46)
ND (0.19)
ND (1.0)
*


Total
HxCDD
ND
0
ND
ND
ND
4
ND
ND
ND
ND


(0.
.75
(0.
(0.
(0.
.le
(3.
(0.
(0.
(2.


25)

12)
09)
12)

4)
70)
3D
0)


Total
HpCDF
ND (0.69)
2.1
ND (0.32)
ND (0.56)
ND (0.67)
ND (0.29)
ND (0.74)
ND (2.4)
ND (1.0)
ND (0.61)


Total
llpCDO
ND (0.33)
1.1
ND (0.37)
ND (0.32)
ND (0.09)
5.4e
ND (1.3)
ND (1.5)
ND (1.0)
ND (1.4)


Total
OCDF
ND (0.58)
5.1
0.12
0.21
0.59
7.5f
ND (0.96)
ND (0.60)
ND (0.98)
ND (1.3)


Total
OCDD
ND (0.72)
3.4
0.28
5.5
ND (0.77)
8.0f
ND (1.2)
ND (1.7)
ND (2.5)
ND (3.0)


standards not recovered.
*

P6CDF and


PgCDD based


on


2,3










,7,8-TCDF-13C,2.

-------
                            TABLE G-2

                   Key to Sample Identification
                  Ambient Air PCDD/PCDF Sampling
      In Vicinity of Dow Chemical Company, Midland, Michigan
     SAS
Sample Number
   (1149E-

      1
      2
      3
      4
      5
      6
      7
      8
      9
     10
     11
     12
     13
     14
     15
     16
     17
     18
     19
     20
     21
     22
     23
     24
     25
     26
     27
     28
     29
     30
     31
     32
     33
     34
     35
     36
     37
     38
     39
     40
     41
     42
Sample Identity
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/12-13/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/22-23/84
9/12-13/84
9/12-13/84
9/22-23/84
9/22-23/84
   1
   1
   2
   2
   3
   3
   4
   4
   4
   4
   4
   4
 Field
 Field
Glass Fiber Filter (GFF) Method Blank
Polyurethane Foam (PDF) Method Blank
     "GFF
       PUF
       GFF
       PUF
       GFF
       PUF
       GFF
       PUF
             Blank GFF
             Blank PUF
       Field Duplicate GFF
       Field Duplicate PUF
         GFF
         PUF
         GFF
         PUF
         GFF
         PUF
         GFF
         PUF
               Blank GFF
               Blank PUF
       4 Field Duplicate GFF
       4 Field Duplicate PUF
         GFF
         PUF
         GFF
         PUF
         GFF
         PUF
         GFF
         PUF
               Blank GFF
               Blank PUF
Site
Site
Site
Site
Site
Site
Site
Site
Site
Site
Site
Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  Site
  GFF Method
  PUF Method
     1
     1
     2
     2
     3
     3
     4
     4
     4
     4
   Field
   Field
       Field
       Field
       Field Duplicate GFF
     4 Field Duplicate PUF
           Blank
           Blank
GFF
PUF
Method
Method
             Blank
             Blank
                              6-3

-------
             APPENDIX H

 RESULTS OF REANALYSIS OF SELECTED
PCDD/PCDF SAMPLES BY USEPA-EMSL-RTP
    AND EXPLANATORY INFORMATION

-------
              UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
              RESEARCH  TRIANGLE  PARK,  NORTH CAROLINA  27711
DATE:     MAY 2, 1985

SUBJECT:  ANALYSIS FOR  CDDs  AND  CDFs IN EXTRACTS OF AMBIENT AIR
HxOr..     ROBERT L.  HARLESS,  RESEARCH CHEMIST
          METHODS DEVELOPMENT BRANCH/EMSL-RTP (MD-77)

TO:       Dr. NORBERT  JAWORSKI,  DIRECTOR.
          ENVIRONMENTAL  RESEARCH CENTER-DULUTH and
          HO LIASION FOR NATIONAL DIOXIN STUDY
    Background   information   regarding these analyses is  brie-fly
summarized.  Ambient   air  samples  were collected  in  Region  V
utilizing high volume  air  samplers.  The samples were subjected to
Midwest   Research   Institute   "*:'1/1985.  HRGC-HRMS analyses were per-formed on the  standards
and  extracts  utilizing  a  60m SP-2330  fused  silica  capillary
column  -for resolution o-f  components.  The concentrations o-f  MRI
analytical   standards  were  compared  with  EMSL-RTP  and   ECL
«.-. r-.l •/1 i cal  standards.   Four extracts specified by Region V  were
subjected   to    analysis  for   TCDDs*, TCDFs  and  penta-CDFs   as
requested.  Preliminary analytical  results were  discussed  with
Frank  Thomas,   Region V,  in mid March at which time I indicated
that  this report would not  be  written until a TCDF  isomer  that
was needed for identification purposes was received.  The work is
now  complete.   Analytical  results  are shown in  Table  1,  and
summarized below.

     #  The  stated  concentration of labeled and native  237S-TCDD
and  TCDF  in  MRI  standards are  in  reasonable  agreement  with
concentrations of ECL  and  EMSL-RTP standards.

     *  MRI  standards   were   used  for  quantification  purposes.
Comparisons of MRI  and EMSL-RTP results indicate that in general
most  values agree  from the  standpoint of low or high amounts  in
each extract. ./'

   '  *  The high  amounts of TCDF in the extracts  is due to one  or
more of the following  isomers,    1238-,1467-,2468-,1236-TCDF that
elute  simultaneously  from a 60m SP-233O fused   silica  capillary
column.   A  2468-TCDF   isomer  was  obtained  for   identification
purposes.  The retention time is within  acceptable  agreement, one


                                H-l

-------
second,  with the  isomer  or- isomers  in  the extracts.  The TCDFs in
the  extracts by themselves are unusual.   Dr.   Rappe's work in ES
and T, Vol. 18, no. 3,  1984   was  used -for  reference purposes since I
do not have these  •four  individual  isomers. Many isomers including
these are -found in effluents -from  incineration  processes.  Also,
some are present in  chemical products.   For example,  2468-TCDF is
an impurity in 246-trichlorophenol.

    * Several extracts  o-f  soil -from  the study performed last year
were  analyzed  again to  determine if  this speci-fic TCDF or  TCDF
isomers  were present.  The analyses o-f 13394 indicates that  the
same  i somer  or group  o-f  isomers  is also present  in  the   soil
extract.

    * The distribution  o-f  TCDD isomers in the extracts o-f ambient
air is also similar  to  those -found in  e-f-fluents -from incineration
processes  and  the   extracts  o-f soil  that were analyzed  in  the
study last year. However,  there are  some di-f-f erences in the ratio
o-f various isomers in the extracts o-f  ambient air.

    * Chlorinated  diphenyl ethers are responsible -for some  (20  to
50%) o-f the concentration reported as penta-CDFs in the extracts.
Region V did  not request  or instruct MRI to perform this  analysis
required  to  di-f f erenti ate CDFs -from chlorinated  di phenylethers.
It should be  done  in future studies.

    In summary,  the TCDFs,TCDDs,and F'CDFs present in extracts of
ambient  air  were  also  present in the extracts of soil  from  the
general  area that   were analyzed in the study  last  year.  The
distribution  of   TCDD   isomers  is  similar  to  those  found  in
effluents from incineration processes. The TCDF isomer or  isomers
by  themselves  are  not similar to those  found  in  incineration
processes. However they were present in the extracts of soil  that
were   analyzed last  year.  The amounts of 2378-TCDD and 237S-TCDF
in  the ambient air  extracts are very low and or not detected  in
most   cases.   Evaluation  of  the   data  indicates   that   the
TCDFs,TCDDs,  and  PCDFs  in the ambient air extracts may be due to:
 (1)   airborne particulate matter from incineration processes  on  a
daily  basis  or  (2) contaminated soil in the  area  that became
airborne   during  the time that the air sampler was in  operation.
The   air  sampler  collection and retention efficiency for  CDDs and
CDFs   has  not   been  validated.  Therefore,  results  should  be
considered   as   minimum  values and   actual   maximum   values   are
unknown.

    The   MRI   extracts and  analytical standards   are   stored   for
reference.  Please call  me  if  you have any questions.
 CC:C.ROSS
   'M.DELLARCO
    N.WILSON
    J.CLEMENTS
    R.LEWIS
                                H-2

-------
TABLE 1. ANALYTICAL RESULTS FOR TCDFs AND TCDDs IN  EXTRACTS  OF
         AMBIENT AIR               •                 ...-..,,.-           -.

COMPOUNDS          SAMPLE ID AND ESTIMATED AMOUNTS  (ng)  IN THE EXTRACTS

 '1V-''»1';-'-  -        1149E-5  1149E-6  1149E-7* 1149E-8  -"" . IT . . L   ,*  ,
             a     	  	  	.  	
2378-TCDF"RT"          O.2     -        -         0.4
                                                     b
TOTAL TCDFs           28.0     131.0      2.2     26.0

2378-TCDD              0.4

TOTAL TCDDs            9.0     29.0      0.8      1.4


         a  The concentrations shown above for 2378-TCDF are  for  the
            specific time window exhibited by 2378-TCDF  analytical
            standard. However, NOTE, conclusive assignment of 2378-TCDF
            in these extracts  can not be made because the other two
            TCDF isomers required for conclusive identification purposes
            are not available.

         b  Average of two analyses performed on separate days.

         Refer to text for comments regarding these analyses.
                                    H-3

-------
              APPENDIX J
DETAILED DISCUSSION OF AIR DISPERSION
    MODELING TO DETERMINE POINT OF
     MAXIMUM GROUND-LEVEL IMPACT

-------
     Possible Association of Stack Emissions and Ambient. Monitored
     Concentrations of CDDs/CDPs
     A fundalmental question arises as to the possible orlqln of the ambient
monitored concentrations of COOs/CDFs 1n Midland, *1ch1qan.   flow Chemical
Company has concluded that, "dispersion of ashes and vent stack oartlculates
from historical Incineration operations are the probable source of the
trace TCOO levels now found 1n the local (Midland) environment (Dow, 19*41."
This qualitative conclusion was reached by comoarlno current emissions of
2379-TCOD with levels measured In the ambient air and 1n Midland soil.  An
Independent panel of experts reviewed the Oow report and concluded:  "The
major Identified source of 2373-TCDD Into the air and soil of the Midland
area 1s the waste Incinerator stack with an estimated release of 0.33 
-------
the concentration of COOs/COFs  measured with ambient monitors.   The EPA's
Human Exposure Model predicted  the maximum annual averaqt concentration  of
2378-TCOO equivalence emitted from the waste Incinerator stack  to occur
approximately one kilometer northeast and east-northeast downwind of the
facility.  This agrees qualitatively with the placement of samollng Stations
2 and 4 for ambient air sampling 1n Midland, Michigan.  Station 2 1s
aoproxlmatelv 1.3 km northeast  of the Incinerator, and Station  4 1s
approximately 1.8 km east-northeast of the Incinerator.  Station 2 measured
approximately 3.5 og 2378-TCOO  equlvalence/m^ of air, and Station 4 measured
about 2 pq 2378-TCOO equlvalence/m^ of air.  The dlsoerslon model predicted
about 0.10 oq 2378-TCOO equlvalence/m2 of air, however, this concentration
reflected five years of average meteorology.  In addition, the  mass emission
rate of 2378-TCOO equivalence was an average emission rate over three days
of stack sampHnq.  The ambient monitoring was not conducted 1n concert
with the stack testing, therefore, 1t 1s likely there would be  no perfect
correlation between the relative maanltude of the predicted concentration
and the ambient monitored concentration.  The aonarent aqreement. with the
predicted fallout area using dispersion wode!1n
-------
         TABLE *.  Average Percent Distribution of COOs and CHFs 1n
                  Both Stack Emissions o* the Dow Incinerator anH
                  Ambient Monitored Concentrations 1n Midland, MI.
      Pollutant
      2378-TCOO
      TotalTCOO
      PentaCOO
      HexaCOO
      HeotaCDO
      OctaCDO
      2378-TCOF
      Total  TCOF
      PentaCDF
      HexaCDF
      HeotaCOF
      OctaCOF
Incinerator^
 Emissions
 (Percent)
   86.06
    7.72
    1.15
    1.03
    3.10
    1.70
   86.37
    9.04
    2.41
    0.45
    0.13
 Station
  Ambient
 Ion* toH nq
  (Percent)
    0.38
   37.00
Mot Reoorted
   13.88
   10.01
   34.41
    0.78
   71.57
   14.13
    0.24
    0.24
   13.07
HOTE:  Percent distribution 1s  determined by CDO, and COF
                                         TotaTTDO   TbTTl COF.
    Incinerator distribution was  determined as an average o* EPA stack
    tests on 8/28 and 8/30.
    Averaqe distribution of 3 sampling days at Station 4.
                                    J-3

-------
emissions, does  suggest that the Incinerator emissions  may  be contributing
to the COOs and  COFs measured by the monitor.  For examole,  237R-TCr»n 1s
less than 1% of  total COO emissions 1n both Incinerator emissions and 1n
ambient measured concentrations.  Total TCOO Isomers  oredom^nate 1n both
sampling regimes (Incinerator emissions and ambient monitoring.  OctaCOO
1s about 34* of  COO concentration measured 1n the  ambient,  whereas OctaCOO
1s only about 5% of Incinerator emissions of COOs. This mav suggest
atmosoheHc transformation 1n the Isomer ratios of the  Incinerator emissions
as the COOs are  dispersed from the stack to the ground.  However, this 1s
only speculation since such phenomena are currently poorly  understood, and
have only recently been hypothesized (Czucwa, 1986).   In any case, given the
fact that ambient sampling and stack testing occurred over  different time
periods, there 1s relatively good agreement 1n the homologue distribution
patterns of the two  sampling regimes.  A similarity 1n distribution of COFs
can also he seen.  For example, 2378-T.OF 1s a minor  constituent (£  1%) of
the total COFs measured  1n Incinerator stack emissions and  1n ambient
monitoring.  The predominant COF 1n both measurements 1s total TCOF 1 sowers.
PentaCDF  Isomers constitute the second most frequent  Isomers 1n emissions
of COFs 1n both Incinerator emissions  and 1n the a"*l«nt concentrations.
      Althouqh there  1s not a perfect comparison 1n the distribution pattern
of COFs/COOs, there  appears to  be  relatively good agreement between the two
sampling  regimes to  sugaest a continued cpntrlbutlon  of the waste Incinerator
to  ambient concentrations  of COOs/COFs 1n the Midland, Michigan, envlronnwnt.
The  measured  ambient concentrations confirm the significance of even low
 levels of emissions  from stationary combustors, 1f these levels  are a daily
 occurrence,  and continue over  a long  period  of time.
                                    J-4

-------
    This "fingerprint" analysis 1n which  the  area  of  maximum fallout  from


Incinerator emissions, and the oercent distribution of  COOs/CDFs  1n

Incinerator emissions 1s compared with the  ambient measured  concentrations,

can only suggest an association between the Incinerator and  ambient levels

of COOs/COFs 1n Midland.  Perhaos a riaorous  analysis o* emissions using

mlcrometeorology recorded for the nearby  nuclear nower  plant project  woul*

helo resolve a quantitative association.   In  addition,  mornholoqlcal
                 *
comoarlsons of particulate matter emitted from  the waste Incinerator  to

narticulate matter captured 1n ambient samplers could also help resolve a

quantltate association between emissions  and  ambient  levels  1n lidland.

Electron microscopy could aid such an analysis.


     This report cannot rule out the possibility that sources other than,

or In addition to,  COO/CDF emissions from the waste incinerator may be

contributing to COOs/COFs measured at ambient wonitorimi stations in  lidlanH,

These possibilities include:  fugitive process  emissions durina chemical

manufacturing at Oow; fugitive emissions  at both the  electrical powerhouse

and waste incinerator at Dow, and re-entra1nwent of contaminated  soil and

dust particles.
                                   J-5

-------