EPA-600/2-77-213
October 1977
Environmental Protection Technology Series
                         SAMPLING AND ANALYSIS
                OF COKE-OVEN  DOOR  EMISSIONS
                               Industrial Environmental Research Laboratory
                                     Office of Research and Development
                                    U.S. Environmental Protection Agency
                               Research Triangle Park, North Carolina 27711

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                    RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental Protec-
tion Agency, have been grouped into nine series. These nine broad categories were
established to facilitate further  development and application of environmental tech-
nology. Elimination of traditional grouping was consciously planned to foster technology
transfer and a maximum interface in related fields. The nine series are:

          1. Environmental Health Effects Research
          2. Environmental Protection Technology
          3. Ecological Research
          4. Environmental Monitoring
          5. Socioeconomic Environmental Studies
          6. Scientific and Technical Assessment Reports (STAR)
          7. Interagency Energy-Environment Research and Development
          8. "Special" Reports
          9. Miscellaneous Reports

This report has been assigned to the ENVIRONMENTAL PROTECTION TECHNOLOGY
series. This series describes research performed to develop and demonstrate instrumen-
tation, equipment, and methodology to repair or prevent environmental degradation from
point and non-point sources of pollution. This work provides the new or improved tech-
nology required for the control and treatment of pollution sources to meet environmental
quality standards.
                             REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved for
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This document is available to the public through the National Technical Information
Service, Springfield, Virginia 22161.

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                                                                      /AN ! 9 1978
                 JNiTED 3':'AT£::; t:WVi R O \< >..•'! h NT-•.!.. PROTECTION AGENCY
DATE:     January  17, 1978

SUBJECT:  Final Report  "Sampling and Analysis of Coke-Oven Door
          Emissions" EPA-600/2-77-213
From:     Robert C. McCrillis   /) clty~t.> f
          Metallurgical Processes Branch

TO:       Distribution

Enclosed  for your use is one copy of  the  subject report.   This work was
completed for EPA by Battelle-Columbus Laboratories under  EPA contract
68-02-1409, Task Numbers 16 and  34.

The work  described consisted of  the development of a  test  method for
collecting emissions from  coke-oven doors and  then collecting and
analyzing emission samples from  a production coke-oven.  Analysis
included  organic analysis  by IR  spectroscopy,  gas chromatigraphy-mass
spec  (GC-MS) , thin film liquid chroma tography  (TLC) and high resolution
mass  spec (HRMS) and bioassay analysis of bacterial mutagenesis (Ames
test) and mammalian cell cytotoxicity (RAM test) .

The test  method did not preclude the  deposition of sample  on the interior
surfaces  of the equipment  ahead  of the filters and adsorber.  This
deposited material was not included in any of  the subsequent analyses.
Therefore, the analyzed samples  represent an unknown  and perhaps atypical
fraction  of the total emission.

..If you have any questions  or comments please call me  at 629-2733.

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                      Errata       EPA-600/2-77-213
pg. 7    fourth paragraph, second line should read, ".... positive
         mutagenic response to 0.5 ul of the sample."
pg. 36   (a)  second full paragraph, second sentence, Table 1
              should be Table 2.

         (b)  third full paragraph, first sentence should read,
              ".... is the fact that the average particulate
              emission rate for Test 2 was 3 times greater than
              the emission  ...."

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                                             EPA-600/2-77-213
                                                  October 1977
     SAMPLING AND ANALYSIS
OF COKE-OVEN  DOOR  EMISSIONS
                         by

                   R.E. Barrett. W.L. Margard,
                   J.B. Purdy, and P.E. Strup

                  Battelle-Columbus Laboratories
                     505 King Avenue
                    Columbus, Ohio 43201
                   Contract No. 68-02-1409
                       Task No. 34
                  Program Element No. 1AB604C
                EPA Project Officer: Robert C. McCrillis

              Industrial Environmental Research Laboratory
                Office of Energy, Minerals, and Industry
                 Research Triangle Park, N.C. 27711
                       Prepared for

              U.S. ENVIRONMENTAL PROTECTION AGENCY
                Office of Research and Development
                    Washington, D.C. 20460

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                  FINAL REPORT
                       on
SAMPLING AND ANALYSIS OF COKE OVEN-DOOR EMISSIONS
                       to
      U.S.  ENVIRONMENTAL PROTECTION AGENCY
         (Contract 68-02-1409,  Task 34)
                       by
            P.  E.  Strap,  J.  B.  Purdy,
         W. L.  Margard, and R.  E. Barrett
               November 4, 1977
                   BATTELLE
             Columbus Laboratories
                505 King Avenue
             Columbus, Ohio  43201

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                              CONTENTS (Continued)
References	   79
Appendices

     A.  Thermal Analysis of Coke Oven Doors	   80
     B.  Heat Transfer Analysis for Hood	110
     C.  Field Data and Calibration Sheets	122
     D.  Reconstructed Gas Chromatograms,  Electron Impact
            lonization Mass Spectra, and Methane lonization
              Mass Spectra of Emissions from Coke Oven Doors. .  .  .  123

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                               FIGURES

                                                                 Page
1.  Sketch of Test Equipment Arrangement on Top of Oven
    No. 41, "A" Battery	   10

2.  Sampling Arrangement for Particulate and Gas Samples.  ...   13

3.  Particulate Emission Concentration vs Time Into
    Coking Cycle	   37

4.  Particulate Emission vs Time Into Coking Cycle	   38

5.  Absorbance Infrared Spectra 	   45

6.  Absorbance Infrared Spectra 	   46
                                TABLES


1.  Identification of Test No.  2 Samples	    18

2.  Test No. 2 Flow for Air Input, Hi-Vol Sampler,  and
    Duct Orifice	    31

3.  Summary Data,  No. 1 Test,  Coke Oven Door Leakage	    32

4.  No.  2 Test, Coke Oven Door  Leakage	    34

5.  Level 1 Analyses, Gravimetric Results 	    40

6.  Level 1 IR Analysis of LC  Filter Fractions	    41

7.  Level 1 IR Analysis of LC Adsorber Fractions	    42

8.  GC-MS Analyses of Selected  Coke Oven Door Sample
    Fractions	    47

9.  Semiquantitation of Selected Coke Oven Door Sample
    Fractions	    49
                                 VI

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                                  ABSTRACT
          Emissions generated by leakage from a coke oven door were collected
and sampled during a 16-hour coking cycle.  Extensive analyses, including
organic and bioassay analyses, were conducted on selected fractions of the
emission samples.
          A sealed-hood was fabricated to fit over the door of a coke oven so
that gases leaking past the door during the coking cycle would be contained and
representative samples could be obtained.  Additional criteria for the hood
included not severely altering the normal door leakage and not interfering
with coke oven operation.  Initial tests of one hood design suggested modi-
fications which were incorporated into the final design.  The final hood was
used for conducting two sampling runs at an operating coke oven.
          Analysis of the coke oven samples included:
               1.  Particulate emissions determination
               2.  Trace metal analyses
               3.  Gas analyses
               4.  Organic analyses by IR spectroscopy,  GC-MS, TLC, and
                   HRMS on entire samples or LC fractions of the samples
               5.  Bioassay analyses of bacterial mutagensis and
                   mammalian cell cytotoxicity.
          Results of the particulate mass emission determination show that a
considerable variation can exist in emissions of coke ovens from cycle to
cycle.   Also,  results of the bioassay analyses confirmed that the samples were
mutagenic,  as  the chemical analyses would lead one to expect.
          This report was submitted in fulfillment of Contract No.  68-02-1409
by Battelle-Columbus under the sponsorship of the U.S.  Environmental Protection
Agency.  This  report covers the entire effort and was completed on September 30,
1977.
                                     111

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                               CONTENTS
Abstract	   iii
Figures	    vi
Tables	    vi

     1.  Introduction 	     1
     2.  General Conclusions	     4
            Conduct of Test	     4
            Interpretation of Results 	     6

     3.  Sampling Procedures	     9
            Sampling Equipment	     9
            Conduct of Sampling Runs	    14
            Condition of Sampling Equipment After Two Tests ....    16
            Comments on Sampling Procedure. 	    17

     4.  Analytical Procedures	    18
            Mass Determination	    19
            Preparation of Adsorbent Column and
              Filter Samples	    19
            Level 1 Type Analysis	    20
            Gas Chromatography-Mass Spectroscopy
              Analysis of Selected Samples	    21
            Analysis by Thin Layer Chromatography 	    23
            Analysis by High Resolution Mass Spectrometry  	    24
            Trace Metals Analysis	    24
            Analysis of Flask Samples of Gases	    25
            Bacterial Mutagenesis Bioassay	    26
            Mammalian Cell Cytotoxicity 	    28

     5.  Results	    30
            Door Leakage and Flow Data	    30
            Particulate Mass Emissions	    31
            Results of Level 1 Analyses	    39
            Gas Chromatgraphy-Mass Spectroscopy Results  	    44
            Thin Layer Chromatography Results 	    52
             High  Resolution Mass Spectrometry Results  	    52
             Trace  Metal  Results	    52
             Gaseous  Emissions  	    52
             Results  of Bacterial Mutagenesis Analysis  	    63
             Results  of Mammalian Cell Cytotoxicity  Studies	    68
             Discussion of  Results 	    77
             Recommendations  	    73
                                   IV

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                          TABLES (Continued)
10.  TLC Quantitation Results for BaP	    53

11.  Low Voltage Mass Spectrometric Results Obtained
     on Fiber Samples	    54

12.  Low Voltage Mass Spectrometric Results Obtained
     Adsorber Samples 	    55

13.  High Resolution Mass Spectrometric Results 	    56

14.  SSMS Analysis of Filter Samples	    57

15.  Mass Spectrographic Analyses of Coal & Coke'^)	    59

16.  Oven No. 41 "A" Gas Phase,  Test No. 1	 .  .   .    60

17.  Oven No. 41 "A" Gas Phase,  Test No. 2	    61

18.  Gaseous Emission Estimates  	    64

19.  EPA Coke-Oven Samples(5)	    65

20.  EPA Coke-Oven Samples	    69
                                 Vl'l

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                                SECTION 1
                              INTRODUCTION

          In connection with a program to develop and evaluate concepts
 for minimizing emissions  from coke-oven doors  (EPA Contract No. 68-02-
 1439), Battelle's Columbus Laboratories (BCL)  initiated development of a
 system for measuring these emissions.  The basic equipment consists of a
 metal hood that extends over the buckstays adjacent to an oven door, thus
 capturing emissions from around the door and permitting these emissions
 to be channeled to an exit duct where they can be conducted to measuring
 devices.
          The initial hood design was tested on a Koppers coke oven at
 Empire-Detroit Steel in Portsmouth, Ohio (see Appendix A, Figure 1).
 Although the system was judged to operate satisfactorily, it was believed
 that use of the sampling hood caused the oven door temperature to rise
 above normal, due to the hood eliminating natural convection currents
 that normally flow over the door and provide cooling.
          To determine the amount of temperature rise above normal caused
 by the hood,  an oven door at Portsmouth was instrumented with eight
 thermocouples and door temperatures were then measured throughout a com-
 plete coking cycle of approximately 15 hours (see Appendix A,  Figures
 2-8).   A subsequent test with the sampling hood in place indicated a
 temperature rise above normal of about 28 C (50 F) during a 2-hour test.
A heat transfer analysis made of the system showed that the temperature
 rise could be minimized by painting both sides of the hood black and
 installing vertical fins on the outside of the hood to enhance heat
 transfer from the hood to the ambient air.
          Following this development work on the sampling hood, EPA
authorized emission measurement tests to quantify particulate and gaseous
emissions due to coke-oven-door leakage and to establish operating pro-

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cedures and system reliability under real-life conditions.  When these
measurements were authorized, coke production at Portsmouth had been cur-
tailed to the extent that samples could not be obtained from a represen-
tative coking cycle.
          After delays while waiting for resumption of normal coke
production at Portsmouth, it was decided to seek another test site.
Republic Steel Corporation gave permission for emission measurement runs
to be conducted at their Poland Avenue coke plant in Youngstown, Ohio.
Two sampling runs were conducted at coke oven No. 41, Battery A, at this
Republic plant during the week of March 29 through April 2, 1976.
          During the test period, the following samples were collected:
          1.   Particulate samples;  the samples were collected
              on a filter by using a Hi-Vol sampler.
          2.   Adsorbent column samples of volatile species; these
              were collected on a Tenax adsorbent column.
          3.   Flask samples for gas analysis
          Extensive analyses were conducted on the samples collected from
this test,  as follows:
              Sample
     Filter Samples
     Extract of filter and adsorbent
       column samples
     Gas Samples
         Analyses
Mass, by drying and weighing
Trace metals by  spark-source
  mass spectroscopy
Level 1, by infrared spectro-
  scopy
Compounds by gas chromatography-
  mass spectroscopy
BaP by thin-layer chromatography
  (EPA)
Compounds by high resolution-
  mass spectroscopy (ERDA)
Bacterial mutagenesis (Stanford
  Research Institute)
Mamalian cell cytotoxicity
  (Northrup Services)
Compounds by mass spec and C!C

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Analytical efforts were conducted by Battelle-Columbus, unless otherwise
indicated.
          This report describes the preparation leading up to the field
test, conduct of the field test, and presents results of the analyses.
Where possible, conclusions regarding the procedures used for sampling
and analysis, and regarding the results of this test, are presented.

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                              SECTION 2
                         GENERAL CONCLUSIONS

CONDUCT OF TEST
Sampling
     Generally, the use of a finned hood over the door of a coke oven to
contain door leakage gases and provide for sampling of these gases worked
successfully in that samples were collected without damage to the coke
oven or severe distruption to plant activities.
     Improvements that should be considered for  future efforts on sampling
emissions from coke oven doors include:
     1.  Use of a larger blower so that more air could be fed into the
         hood.   This would more accurately represent the normal air
         flow with a breeze, etc., and would provide better
         cooling of the oven door.
     2.  Redesign of the hood to permit insulating the outside
         surfaces to reduce condensation of volatile organics
         on the inside of the hood while providing adequate
         door cooling by increased air flow.
     3.   Insulation  of  ducts  carrying gases withdrawn from the hood
          to reduce condensation .
     4.  Obtaining a continuous printout or, at least, frequent read-
         ings of air and gas flow rates so  that leakage, etc., can be
         calculated.  Because flow rates may change as filters become
         loaded, it is desired to obtain readings at intervals no
         greater than about 10 to 15 minutes early in the test.  For
          the later stages of the  test, hourly readings should surfice.
     5.  For a portion of a run, or for another trial of this hood
         system, it might be useful to add  a tracer gas to the supply
         air so that leakage might be estimated more accurately.

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     6.  To determine emission rates (mass of total particulate or certain
         compounds or elements per unit time) , all material coming from
         the coke oven should be known.  That would require collecting
         condensed material off of the inside of the hood and the gas
         ducts and attributing this material to the gas flow in some way.
         Three problems this introduces are  (a) how to clean the hood
         and ducts safely when the residue being washed off may contain
         carcinogenic species, (b) how to clean the very large hood
         surfaces, and (c) how to equate the condensed mass to gas flow
         - obviously, more of the condensed mass would be collected early
         in the test.
     The rather large differences in emission rates for the two runs on the
same coke oven cell suggest that single tests will not be useful in pre-
cisely defining emissions from these sources.
Analysis
     Due to the presence of large quantities of organics in the coke oven
samples, and the increasing concern over health hazards related to organic
materials, the possibilities for modifying or extending the analysis pro-
cedure are limited only by the imagination and the budget.  Obviously, it
would be desirable to conduct semiquantitation of all LC fractions of each
sample.  However, for this single test such an approach could have in-
creased the number of GC-MS analyses to 88, rather than the 12 that were
conducted.  Also, for the semiquantitation analyses conducted there are
significant unidentified fractions (e.g., 81 percent for Sample Al, Frac-
tion 5) - of what does the missing material consist?  Further, it might be
desirable to conduct the HRMS, the trace metal analyses, and the bioassay
analyses on LC fraction of samples, rather than on the entire samples.
Again, material removed (in some future test) from the inside of the hood
and gas ducts should be analyzed.
     To facilitate interpretation of future test results, the quantity of
sample used for all analyses should be precisely defined and blanks should
be provided and run for all analyses.

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INTERPRETATION OF RESULTS
     Mass emissions from coke oven door leakage vary greatly over the
cycle, ranging from over 1000 mg/min during the first hour to less than Img/
min during the latter portion of the cycle.  The fraction of the  sample
collected in the filter was about 90 percent for the first hour of Test 2,
but dropped to about 45 percent for the period from about 8 hours to 13
hours into the test.
     A major observation is the variation in mass emissions from one run
to another.  For example, the average mass emission rate for the first
hour of the test was 410 mg/min, whereas,  the mass emission rate during
the same period for Test 2 was 1003 mg/min.  These data suggest that the
care taken in sealing the door can have a major effect on emissions, and
that estimates of emission rates (or factors) based on a small number of
runs could be inaccurate.
Chemical Analysis Results
     The coke oven samples, as expected, were very complex mixtures of
organic compounds.   Even after separating the samples into 8 fractions
by liquid chromatography (LC), the fractions were still complex mixtures.
Because of the complex nature of the samples and the fact that several of
the specifies identifications were of a qualitative nature, it is impossible
to make exact comparisons of results achieved by the various chemical
analyses.   However,  the LC fractions,  the  GC-MS analyses, and the HRMS
analyses produced results that generally were consistent.
     Significant emissions were found  of several organic compounds that
have been identified as carcinogenic,  as follows:
          benzo pyrenes
          dibenzo anthracene
          benzo phenanthrene
          benzo anthracenes
          benzo fluoranthenes
          indeno pyrene.
The presence of these compounds is adequate to account for the positive bio-
assay results.

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 Bioassay Results
     Complex mixtures such as the coke-oven samples submitted for bio-
 logical analysis contain large numbers of materials which may be mutagenic,
 cytotoxic, or both.  The chemical analysis of the samples indicated that
 mutagenicity was to be expected.  The samples contained  numerous poly-
 cyclic hydrocarbons which have been confirmed to be both mutagens and
 carcinogens.  Benzo fluoranthene and benzo-a-pyrene are  but examples.
     Mixtures are always difficult to assay.  Sometimes  a sample may give
 a positive mutagenic response at one concentration but the mutation rate
 may  fall off dramatically at  the next higher concentration  due  to  the  toxic
 effect of the same  material,  or a  second material  effecting the mutagenesis
 of the first or the viability of the mutants.  A large number of synergistic
 or antagonistic interactions may take place which can exaggerate or diminish
 net  bioassy responses.
     The fact that Ames assay found mutagens in all of the samples serves
 to confirm the chemical analyses.  The samples were found to be moderately
 mutagenic at the very dilute concentrations analyzed.  Thus the data
 really suggests that the particulates entrapped on the filters  were heavily
 laden with mutagens when the  total sample is taken into  account.
     In general, both the filter and the adsorbent column sample extracts
 showed a moderate but positive mutagenic response 0.5 pi of the sample.
The 0.5 yl sample represents only 0.0007 percent of the extract of the
 filter which was submitted for bioassay analyses.   The extract sample was
obtained from one-eighth of the total filter area.   When more of the sample
extract was analyzed the mutagenic response was increased until the concentra-
 tion was sufficient to elicit a toxic response.   It thus becomes quickly
apparent that the total sample contained thousands of times larger amounts
of mutagenic substances.
     It has been shown by Commoner-'- that the mutagenicity of a complex
mixture of environmental pollutants can be the sum of the mutagenicity of
the individual  fractions.   Such a possibility may  account for the quantity
of mutagenic substances in the filter samples.   In this investigation it

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was ascertained that the quantity of benzo-a-pyrene (BaP) in the filter
extract representing the first hour of the coking cycle was approximately
700 ug.  The mutagenic detection level for BaP is approximately 1 pg per
plate with the Salmonella tester strains.  Therefore the BaP is present in
the filter extract samples in 100 fold less concentration than the mutagens
detected.  Thus it is suggested that those mutagens which were detected
were either present in much greater quantities than BaP, were mutagenic
in significantly smaller quantities, or an additive effect of the total
mutagenic compounds was operative, as Commoner suggests.
     The  results "of  the rabbit alveolar  macrophage assay must be considered
on a preliminary basis only.  The particulate was unevenly distributed on
the filter medium, due to uneven deposition aggravated  by the loss of large
quantities during  transit.  Thus, reliable representative quantitative
samples  could  not  be obtained.  Clean  unused  filter media was not available
as a control.
     The  relatively  clean border of  the  filters was used and found to be
nontoxic  to  the macrophages.  The samples cut from the  center of the filter
media  caused a significant reduction in  cellular viability.

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                                SECTION 3
                           SAMPLING PROCEDURES

SAMPLING EQUIPMENT
          A new sampling hood with vertical corrugations acting as cool-
ing fins, and black paint applied to both sides, was constructed for the
tests at Youngstown, Ohio.  The new features incorporated were a result
of analytical and field work reported in Appendices A and B.  After being
checked out at BCL for satisfactory operation, the hood was taken to
Youngstown and used for the program to measure emissions from a coke-oven
door.
                  *
          Figure 1  shows the sampling hood in place clamped to the
buckstays on either side of the oven from which emissions were to be
sampled.  As shown in Figure 1 the hood consisted of 5 full sections and
a single half section, all held together by piano-type hinges.  On the
back of each section, placed vertically along the edge, were magnetic
tape strips which aid in maneuvering the hood into place and holding it
to the buckstays.  However, the magnetic strips were not capable of hold-
ing the hood firmly in place and preventing gas leakage.  Special clamps
attached to lengths of angle iron were used to firmly clamp each side of
each hood section to the buckstay.  All edges of the hood and the hinges
were sealed with furnace tape and then further sealed with furnace cement
to prevent leakage of gases out, or of air into, the cavity behind the
hood.   Also shown in Figure 1 is the layout of the sampling equipment on
top of the coke-oven battery during the test.
* Regulations at Republic in Youngstown prohibited the taking of any
  photographs at the test site.   Therefore, Figure 1 is an artist's
  sketch showing the general layout of the sampling hood over a coke-
  oven door.

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             Vorioc lor Hi-Vol blower
                speed control
     Flow to Hi-Vol

   Hi-Vol somplers
Orifice pressure drop
Monomclcr lo mcosure pressure
    beneoth hood

• Adsorber flow melcr

        Blower
    Pressure lap
Furnace cement
   seal
                                                      Compressed
                                                      air supply
   Hinges covered
     wit'i furnace tape
    Hood sections,
       corrugated and   '
       pointed black to
       dissipate heat
    Edges of hood
       sealed with
       furnace tape
       and cement
                                                                              Orifice
                                                                            Hood exhaust duct
           Metered o.r supply to
              bottom of overt door
                                           Neighboring coke oven doors
      FIGURE   1.  ARTIST'S  SKETCH OF TEST EQUIPMENT  ARRANGEMENT ON  TOP OF
                    OVEN NO. 41, "A" BATTERY -  liEPUtlUC STEEL CORPORATION,
                    YOUNGSTOWN, OHIO
                                      10

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          A supply of compressed air was delivered through a 1-inch pipe
 to a horizontal air distributor below the bottom of the oven door.  The
 distributor consisted of a 1-inch diameter length of pipe with drilled
 holes  that allowed air to blow upward over the door, mix with the door
 leakage gases, and pass on to the suction blower.  The compressed air
 fed to the door originated from an air compressor.  Ordinarily, a plant
 supply line could be used as the air supply, but at Youngstown it was
 necessary to rent a compressor for air supply because the plant compressed
 air supply system had excessive water in the lines.  The compressed air
 supply to the hood was carefully metered by a rotometer.
          The principle used to measure the leakage of emissions from
 around the coke-oven door was based on measurement of air fed under the
 hood and measurement of total gas flow away from the hood.  This required
 that the blower draw gases away from the door area enclosed by the hood
 at the same rate as gases were generated by the air supply plus the door
 leakage, thus maintaining a zero gage pressure behind the hood.  Positive
 pressure could cause leakage of gases from behind the hood and negative
 pressure could induce air leakage into the hood enclosure.  As shown in
 Figure 1, a pressure tap was installed in the top plate seal, near the
 top of the buckstays.  This pressure tap was connected to an inclined
manometer sensitive to 0.001-inch of water, and efforts were made to keep
 the pressure reading on the manometer at zero to assure no leakage into
or out of the door area.   During the sampling period, the highest pres-
sure differential recorded on the inclined manometer was 0.56 mm (0.022-
inch)  H^O,  and most of the time it was kept at zero.   There was every
indication that significant leakage did not occur during testing; all
sealing materials were intact at the end of the test.
          As a result of having the hood sealed in place and maintaining
a zero pressure differential across the hood wall, all emissions leaking
past the coke-oven door were induced to exit the hood through the duct
identified in Figure 1 as "Hood exhaust duct".  As the gases passed
through this duct, part of the flow was pulled off by the Hi-Vol sampler;
this part was measured and recorded at the Hi Vol.   The remaining gases
flowed on toward the blower and the flowrate was measured at an orifice
mounted in the line.   Thus, the gas flow measured at the Hi Vol plus the
                                  11

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flow measured at the orifice gave the total flow being drawn from within
the hood enclosure.
          Between the orifice and the hlower there was an adjustable
valve which could be used to restrict the flow of gas going to the
blower.  Also between the adjustable valve and the blower, a tee was
installed in the duct; one leg of the tee was an open leg which contained
an adjustable butterfly valve.   By opening the butterfly valve, unmetered
air was drawn to the blower, thus reducing the quantity of gases pulled
from the hood to the blower.
           The capacity of the blower limited the amount of metered air
that could be fed to the air distributor beneath the hood (even with the
butterfly'valve in the closed position).  When the volume of metered air
plus oven gas leakage from the door equaled the capacity of the blower
plus the gas drawn to the Hi-Vol sampler, no more air could be supplied
because the additional air would increase the pressure beneath the hood
and cause leakage from beneath the hood.
          It would be desirable that the blower have greater capacity so
that much more air could be fed beneath the hood.  Whereas the blower used
                                             3
for this effort had a capacity of about 300 m /hr (180 scfm),  a capacity
                 3
of at least 500 m /hr (300 scfm) would be desirable to provide additional
cooling for the door.  Also, the additional air would further dilute
gases going to the Hi-Vol sampler which should cause less plugging of the
filter on the Hi-Vol.
          It was anticipated that filters on the Hi-Vol sampler might
have to be changed frequently at the beginning of the coking cycle;
therefore,  two Hi-Vol samplers were provided.   Quick connect and discon-
nect flexible duct connections were provided so that gas sampling could
be quickly switched from one Hi-Vol to the other.  In addition, to pro-
vide better chart records, each Hi-Vol was modified by installing a
special motor giving one complete chart revolution per hour instead of
the normal one revolution per 24 hours.
          Figure 2 is a schematic diagram that shows the arrangement of
the Hi-Vol sampler and related sampling equipment.   Flow from the hood
passed through the 0.20 x 0.25 m (8 x 10-inch) Hi-Vol filter.   Down-
stream of the filter there was a tap which connected to an adsorber
                                   12

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           Tar film on inside
           surfaces after tests
After tests Tygon tubing
dark and discolored
but no heavy deposits
                                                         8" x 10" filter
      Adsorber
                        Gas sample
                        pump
                                                     Blower and motor section
                                                     Positive pressure area
                                   Purge line from
                                   positive pressure
                                   side of blower
Flow from
hood sample
                                                       Transducer tap for
                                                       measuring flow
FIGURE 2. SAMPLING ARRANGEMENT  FOR PARTICULATE AND GAS SAMPLES
                                 13

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 column, a dry gas meter or  flow meter, and a gas  sampling  pump  in  that
 order.  The  adsorber  column contained  35/60 mesh  Tenax-GC, which has  the
 capability of removing the  heavy molecular weight  hydrocarbons  from a
 gas  sample passing  over it.  After passing through the adsorber column,
 the  gas passed  through a  dry gas meter which was  used to measure the
 quantity of  gas sampled by  the adsorber column and a pump  which main-
 tained the sample flow.
          A  tee was installed in the sample line  immediately downstream
 of the adsorber.  The exit  leg of the  tee had a stopcock and a  tapered
 fitting which enabled an  evacuated flask sample bottle to  be attached
 for  taking a sample of the  gas that has just passed through the adsorber.
 As shown in  Figure  2, a purge line (consisting of  rubber tubing terminat-
 ing  with a stopcock) was  attached to the positive  side of  the blower-
 motor section of the Hi-Vol  sampler.  Before and during attachment of
 the  flask sampler,  gas from  the hood was blown over the connections to
 help ensure  that air was  not collected in the sampling flask.
          The hood-exhaust  duct, from the top of  the hood  to the blower,
 was  not insulated as it was  thought that the relatively high flow  through
 this duct would not result  in excessive sample loss via condensation  on
 duct walls.  The line from  the tie in the hood-exhaust duct to  the Hi-
 Vol  sampler was insulated.   In retrospect, it would probably have been
 better to heat and  insulate  the entire duct between the hood and the
 Hi-Vol sampler.
 CONDUCT OF SAMPLING RUNS
          Two sampling runs were conducted at the  Republic Steel Corpor-
 ation Coke Oven No.  41, Battery A, during the week of March 29  through
 April 2, 1976.  The first test was conducted on March 31, beginning at
 3:10 a.m. and concluding  at  6:45 p.m.  The second  test was begun on
 April 1 at 1:03 p.m. and  completed on April 2 at 2:15 a.m.  The second
test  was  about 3 hours shorter  than  the first  due  to process  demands;  the
coke  was pushed  after a shorter coking time.

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          No effort was made to select either a well-sealed or poorly-
sealed door on which to conduct the test.  Rather, the intent was to
sample a "typical" door.  A coke oven near the end of the battery was
selected for the test to minimize the disruption of the test due to
plant equipment moving past the sampling area.
          The operation of an individual coke oven at this plant is
approximately as follows:
          •  push previous charge
          •  oven remains open for 5 to 15 minute interval
          •  put door in place
          •  charge oven with fresh coal (up to 5 minutes)
          •  seal charging doors
          •  coking period of 12 to 16 hours
          •  doors removed for 15 to 30 minute interval prior to push
          •  push coke (about 2 to 3 minutes)
The hood was put in place and sampling begun as soon as possible after
the door was closed.  Thus, sampling was begun during the charging opera-
tion, but did not include the entire charging period.  Sampling was
continued until about 15 to 30 minutes before the end of the coking
cycle.  Sampling was stopped to allow sufficient time to remove the hood
and sampling equipment before coke pushing was to begin.
          Prior to sampling runs,  it was empirically decided that the
coking cycle of approximately 16 hours should be divided into time seg-
ments for purposes of taking samples for analysis.  The length of these
six sampling segments were assigned as follows:
               Segment No.        Length of Segment,  hours
                    1                      1
                    2                      1
                    3                      2
                    4                      4
                    5                      4
                    6                      4
                                  15

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Length of the segments was based on the knowledge that emissions  from
coke oven doors decreased as time into the cycle increases.  Therefore,
to obtain suitable sample quantities for analytical purposes, longer
sampling times are required as the coking cycle progresses.  A flask
sample was planned midway through each of the six segments designated;
thus, flask samples were taken at about 0.5, 1.5, 3, 6, and 10 hours
elapsed time and at some convenient point during the last sampling segment,
          Concerning the sampling and deposits on the duct, some deposits
were observed on all of the duct with the heaviest deposits being found
on the duct between the tee and the blower.   It was  noted that the temp-
erature drop from the hood exit to the Hi-Vol sampler did not exceed
93 C (200 F).   The Hi-Vol filter temparature was 82  to 107 C (180 to
225 F) during the sampling period.
CONDITION OF SAMPLING EQUIPMENT AFTER TWO TESTS
          At the conclusion of the two Youngstown tests,  the five full
sections of hood subject to direct radiant heat from the  oven door were
covered with a thin coat of black tarry material giving the appearance of
a coat of black spray paint.   The top hood section,  about half the height
of other sections and subject  to less radiant heat,  had a thicker coat of
tar appearing more like a brush coat  of black paint.
          The metal lid that  covered  the top of the  buckstays had a thick
paint-like coat of tar with a  run buildup around the gas  exit hole.
          The 4-inch flexible  duct leading from the  buckstay lid to the
metal ductwork contained a progressively heavier coating  from beginning
to end,  with the exit end having a coating like shiny,  heavy black lacquer.
          The 2-inch flexible  duct leading to the Hi-Vol  sampler con-
tained progressively heavier  tar deposits with run deposits up to 1/16-
inch thick at the exit end.
          The sampler metal cap upstream of  the filter had an inside
coating appearing as a heavy black spray paint.
          Tygon tubing that carried gas samples from downstream of the
filter to the adsorber column  had some discoloration but  not the deposit
evidenced in other parts of the system.
                                 16

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          The metal surface of the sampler downstream from the filter
 had some deposit similar to very light spray paint.
          The 4-inch metal duct leading to the exhaust fan had heavy
 deposits like brushed paint.  When the fan was laid on its side after
 tests, with an approximately 6-foot-long metal duct projecting verti-
 cally upward, tar deposits 1/16-inch thick were formed on the fan parts
 from warm tar dripping from the duct walls.
 COMMENTS ON SAMPLING PROCEDURE
          In general, the sampling hood and associated sampling equipment
 performed satisfactorily during the two Youngstown tests.  The one equip-
 ment weakness at Youngstown was in the exhaust blower that pulled the
 gases from behind the sampling hood.  A greater blower capacity would
 permit a larger flow of air to be passed over the oven door for cooling
 purposes, and more dilution of leakage gases would reduce rapid filter
 loading.  Also, heating and insulating the duct between the hood and the
 tee would reduce loss of condensibles.
          The intent of the sampling system that was used was to provide
 a constant flow at the Hi-Vol sampler and at the POM sampling point.
 Fluctuations in gas leakage would be compensated for by adjusting the
 butterfly valve controlling bleed air to blower system.   An alternative
would have been to sample particulate (and POM) from the duct to the
blower and to have omitted the Hi-Vol sampler.   However,  to do this, the
 sampling rate would have to be adjusted to provide isokinetic sampling
with changes in air flow rate.  The latter system would be slightly more
 cumbersome to operate, but, theoretically,  would provide a more logical
 sampling procedure in that sample collection rate would match leakage rate.
                                  17

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                                SECTION 4
                          ANALYTICAL PROCEDURES

          This section of the report describes the procedures used to
analyze the samples obtained during the sampling effort conducted on
the Republic Steel Corporation coke oven.  Initial analysis conducted
on the coke-oven samples was a gravimetric determination of the mass
collected on the filters.  Subsequently, the extract from the filters
and the adsorbent samples was subjected to a number of detailed
analyses related to determining the environmental hazard of coke-oven
emissions.
          Because  Test 2 contained 4.1 times the particulate concen-
tration as Test 1 and a more accurate recording of test parameters was
made, Test 2 was chosen as the test run to be analyzed.  Table 1
identifies the filter and adsorber column samples for Test No. 2.  The
sample numbers shown in Table 1 are used in reporting most of the
analytical results.


             TABLE 1.   IDENTIFICATION OF TEST NO. 2 SAMPLES
Sampling Time
1303-1411
1414-1506
1506-1708
1708-2105
2105-0215
Compressor
air supply
(Blank)
Filter Nos.
119-131
132-136
137-147
148-155
156-161
BCL Code
A IF
A2F
A3F
A4F
A5F
Adsorber Nos.
2.1, 2.2
2.3, 2.4
2.5, 2.6
2.7, 2.8
2.9, 2.10,
2.11
TP.4
BCL Code
Al
A2
A3
A4
A5
A6
                                 18

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          Section 5 presents the results obtained in conducting the analyses
described in this section.

MASS DETERMINATION
          The mass of deposit collected on the filters was determined by
desiccating the filters for 24 hours and then weighing them.  Tare weights
of the desiccated filters were subtracted from the final values to determine
the mass of material collected.
          To the extent possible, the samples were stored in a cooled dark
location prior to analysis.  Desiccation and weighing were conducted at
room temperature, and the weighing was done in the presence of light.
However, the precautions taken should have protected most compounds from
photo reaction.

PREPARATION OF ADSORBENT COLUMN
AND FILTER SAMPLES
          From the group of filters representing a portion of a specific run,
each filter was divided into quarters using a long-bladed lab spatula.  Filters
to be used for certain analyses were not to be extracted; these filter
portions were set aside.  The remaining filter sections were Soxhlet extracted
sequentially with methylene chloride and methanol until the solvent around the
Soxhlet thimble remained clear (approximately 3 days).   Extracts were combined
and reduced in volume.  The extracted samples were then divided and, together
with the filter sections that had not been extracted, were distributed to
Battelle (BCL), U.S.  Bureau of Mines (USBM), and EPA as follows:
          •  BCL (Organic) 1/4 of each filter group, extracted
             as above.
          «  BCL (Inorganic) 1/4 of each filter group,  no extraction.
          •  USBM (Organic) 1/4 of each filter group, extracted
             as above.
                                  19

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                                                                    *
          •  EPA (Bioassay)  1/8 of each filter group,  no extraction;
             1/8 of each filter group, extracted as above
          The Tenax-GC adsorbent columns were Soxhlet  extracted with pentane
for a period of 24 hours.   The appropriate extracts were combined, reduced
in volume and one-fourth of each extract was distributed as follows:

          BCL for  organic analysis by Level 1 and GC-MS
          EPA bioassay analysis by Ames  (mutagenicity) and Ram
             (cytotoxicity) tests
          USBM  for Organic Analysis by HRMS
          BCL saved for possible  future  analysis

 LEVEL 1 TYPE ORGANIC  ANALYSIS
           Level 1 organic analysis was  conducted  on each set  of filters
 and  adsorbent column  samples  using  the  analysis procedure described in the
 EPA  publication listed as Reference  2.   The objective of this Level 1
 analysis is to  semiquantitate the predominant classes of organic compounds
 present.  This  is achieved  by subjecting the extracted sample to liquid
 chromatography  (LC) using  solvent gradient elution.  Each sample is separated
 into eight fractions  containing different organic classes which may present.
 Because of the  large  amounts  of material collected on the 0.20 x 0.25 m
 (8 x 10 inch) filter, only  1/600 (0.25  ml) of the sample was  used for liquid
 chromatography.  All  the material extracted from  the  adsorbent columns was
 subjected to this analysis.

 Gravimetric Analysis
           Following liquid chromatography, the solvent was evaporated from
 each fraction  in air until a constant weight was achieved.  After recording
 the weights, the fractions were redissolved in methylene chloride prior to
 analysis by infrared spectroscopy.  Results are reported  in Table 5.
   *Following removal by EPA of small segments for the cytotoxicity tests the
    filter group was extracted with cyclohexane for BaP analysis.
                                    20

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Infrared Spectroscopy
          Infrared spectra were obtained on the eight liquid chromatographic
fractions of each of the 11 samples.  The samples were prepared for the in-
frared analysis by depositing a film (from Me^Cl™ solutions) of each frac-
tion on an infrared transmitting (KBr) crystal.  The spectra were obtained
using a Fourier Transform infrared (FT-IR)  system.   FT-IR systems use an
interferometer (instead of a monochromator) to generate the spectral data
in terms of an interferogram.  A dedicated computer then makes the Fourier
Transform of the interferogram (light intensity versus time) to the more
usable infrared spectrum (light intensity versus wavelength).   The sensi-
tivity of the interferometer coupled with the data handling capability
of the dedicated computer are two of the advantages of FT-IR systems
over conventional dispersive infrared spectrophotometers.  The use of
FT-IR systems is not a normal part of Level 1 type analysis, but the
ability to subtract spectra (see subsequent discussion) provides quali-
tative identifications that are not possible without this capability.
          The liquid chromatographic separation roughly separates the
samples into classes or types of compounds, but each class is still a
complex mixture of many compounds.  Since resolution is not sufficient
to isolate individual compounds,  it is extremely difficult to identify
individual compounds by IR, or even distinct compound  types.  However, by
 using FT-IR (with  the  capability  to subtract  the spectra of consecutive
 fractions),  such specific identifications are  possible.

GAS CHROMATOGRAPHY-MASS SPECTROSCOPY ANALYSIS OF SELECTED SAMPLES
          Following infrared analysis of the 88 sample fractions, repre-
sentative filter and adsorber samples from each LC class fraction were
chosen to undergo further analysis using gas chromatography-mass spectro-
scopy (GC-MS) to obtain a semiquantitation of the amount of various species
present.   The GC-MS semiquantitation procedure used was similar to procedures
described in Reference 2.   The samples were chosen on the basis of their
representation of the classes of compounds found to be common in each class
fraction as determined by IR.   Whenever IR indicated any difference in
                              21

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 these  class  fractions,  these  differing  samples were  also  subjected  to  GO-MS.
 Fractions  selected  for  GC-MS  are  indicated with  an asterisk  in  Tables  6  and  7.
          Gas chromatography separation was carried out using a 1.8 m
 (6-ft), 3 percent OV-101 column programmed from 70 to 300 C at 4 C min
 Both,  chemical ionization  (CI) and electron impact (El) mass spectra were ob-
 tained using a Finnigan 3200 quadrupole mass spectrometer.
          CI mass spectra were obtained using methane as the reagent and
GC carrier gas.  The mass spectra thus obtained are usually characterized
by a prominent protonated molecular ion (M+l)  together with adduct ions
at (M+29) and (M+41) due to the addition of C H  and C H  in the mass spec-
trometer.  The advantage of CI mass spectrometry is that it is usually pos-
sible to obtain reliable molecular weight data on unknown compounds.  Since
CI is a relatively low-energy process  compared to El, it generally pro-
duces less fragmentation which is characterized by the loss of neutral mole-
cules and relatively stable ions.
           El,  while less sensitive than CI, is  the most  common  method  for
 obtaining mass spectra.  Since El is  a  higher  energy process, it  produces
 more fragmentation  giving  rise to a more  unique  mass  spectrum for any
 compound and,  thus, is  more useful for  spectra matching.   Reference mass
 spectra are usually available using  the El  mode.

           Mass spectral interpretation  was  further aided  by  a spectral
 matching routine  whereby El mass  spectra  are  compared directly  with more
 than 30,000 known spectra  in  the  Battelle mass  spectral  data bank.   The
 10  best spectral  matches are  printed  out  based  on a  dissimilarity index
 of  the fraction of  unmatched  intensities.   Compound  matches  with  a
 dissimilarity  of  0.3 or less  and  with concurrence of the  reference
 spectrum from  an  8-Peak Spectral  Index  were considered  to be  identified
 with a high degree  of certainty.
           Following El  and CI GC-MS analysis,  the individual components  in
 each fraction  were  assigned structures  on the basis  of  CI  molecular weight
 determinations and  fragmentation  patterns,  and on  the basis  of  El reference
                                 22

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spectra and spectral matching.  Where several structural isomers were
possible, no attempt was made to identify each isomer since this was be-
lieved to be beyond the scope of this work.  A tabulation of the compounds
identified in each sample examined is given in Table 8 in Section 5.
          Semiquantitation for the identified GC-MS components were achieved
by ratios of the sum of all measurable peak heights in a given sample to
the height of the known GC component.  The ratio was then multiplied by the
total amount of material in the fraction.  Whenever an identified component
did not exhibit an easily measurable GC peak, the reconstructed gas
chromatogram was expanded.  The expanded GC component area was then measured,
divided by the amount of expansion and proportioned by the sum of the total
peak heights as obtained before expansion.  This ratio was then multiplied
by the total amount of material in the fraction as above.
          This semiquantitation procedure assumes that all the components
in a given sample pass through the GC column and that they are recorded as
a measureable peak in the gas chromatogram.  Although this requirement is
not always met, the procedure will give an indication as to the relative
amounts of each species present in a given sample.
          The results of the semiquantitation analysis are presented in
Table 9 of Section 5.
ANALYSIS BY THIN LAYER CHROMATOGRAPHY
          Quantitation for benzo-a-pyrene only was performed by Dr. Joseph
Bumgarner (EPA) on the filter extracts using thin layer chromatography (TLC).
These filter extracts were prepared by Dr. Bumgarner by extracting filter
portions designated for cytotoxicity testing.   Very small segments were
first removed for the cytotoxicity work; the remainder was then extracted
with cyclohexane.  The TLC plates were scanned using a Perkin-Elmer MPF-3
fluorescence spectrophotometer for benzo-a-pyrene using an excitation wave-
length of 388nm and read at an emission wavelength of 430nm.
  *See Mannalian Cell Cytotoxicity write up (p.28) for description of
   condition of samples.
                                   23

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           Recovery studies based on spiked blanks showed an average
 recovery of 98.9 ± 5 percent.  The limit of detection is O.lng haseoon  the
 standard of a peak being twice the background.

ANALYSIS  BY HIGH RESOLUTION MASS  SPECTROMETRY
          High resolution mass spectrometric (HRMS) analyses were  conducted
on 1/4 of the methylene chloride  filter extracts and 1/4 of the adsorbent
sampler extracts.  This work was  performed by Dr. A. G, Sharkey of the
U. S. Energy Research and Development Administration.
          Low voltage mass spectrometry was initially performed on all
samples to identify the molecular ions prior to analyses by HRMS.

TRACE METALS ANALYSIS
          The elemental composition of emissions from coke oven doors was
determined by spark-source mass spectroscopy (SSMS) of samples .from Test
No. 2.  To make this analysis, the 1/4 portions of unextracted 8" x 10"
filters and of a blank filter were subjected to SSMS.
          Each of the fiber glass filter samples (A1F through A5F) and
blank (A6F) were extracted in hot HCl'HNOo.  The extract which contained
the collected sample as well as some dissolved fiber glass was taken to
dryness and mixed with graphite in the weight ratio of 3 sample to 1 gra-
phite.  The graphite is added to provide electrical conduction and to aid
in forming a sound sample briquette for analysis by SSMS.
          Standardization of SSMS was carried out by comparing the SSMS
data with data for high concentration elements from analysis by optical
emission spectroscopy.
          Additionally, SSMS was conducted on 100 mg of coal and coke as
obtained from the Youngstown facility.   These analysis were conducted simi-
larly to that of the glass filter samples above.
                                 24

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ANALYSIS OF FLASK SAMPLES OF GASES
          All samples were analyzed on an "as received" basis by the mass
spectrometer to provide information on mass to charge ratio of 1 through
100.  Each sample was then analyzed by gas chromatography using both a ther-
mal conductivity detector and a flame ionization detector.  Sample No. 1,
Test No. 2 was concentrated by using a liquid nitrogen trap to remove the
noncondensables while pumping to approximately 2 torr pressure.  This con-
centration step removes oxygen, nitrogen, argon, methane, and carbon mon-
oxide and leaves the condensable compounds in the trap.  The trap is then
warmed to evaporate the condensables and condensables are analyzed by mass
spectrometry.  This concentration step increases sensitivity and accuracy of
analysis for C,. to C7 hydrocarbon compounds.  As the hydrocarbon detected
using the concentration step were not significantly greater than without this
step, it was not included in the analysis procedure for remaining samples.
      The specific  gases  identified by  each  technique  is  as  follows:
      Mass spectroscopy
           -nitrogen
           -oxygen
           -argon
           -carbon  dioxide
           -hydrogen
           -benzene
           -toluene
      Gas chromatography-thermal  conductivity detector
           -carbon monoxide
           -methane
      Gas chromatography  in  flame ionization detector
           -acetylene and ethene
           -ethane
           -propene
           -propane
           -1-butene
           -iso-butane
           -n-butane
                               25

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These techniques are sensitive to about 50 ppm, 10 ppm, and 0.1 ppm,
respectively.
BACTERIAL MUTAGENESIS BIOASSAY
          Stanford Research Institute examined seven coke-oven samples
(A1F, A3F, ASF, Al, A3, A5, and A6) for their potential bacterial
mutagenesis.  The assay was conducted according to the recommendations
of Ames using four of his testor strains with and without the rat
liver microsome induced system.  Each sample was examined twice on
separate days by a single plate incorporation dose response assay.  The
following was transcribed directly from their report to EPA (Ref.5) with
only minor format changes to conform with the rest of this report.
          The Salmonella typhimurium strains used were all histidine
auxotrophs by virtue of mutations in the histidine operon.  When  these
histidine-dependent cells are grown on a minimal media petri plate
deficient in histidine, only those cells that revert to histidine
independence (his+) are able to grow (mutants).  The spontaneous
mutation frequency of each strain is relatively constant, but when a
mutagen is added to the agar the mutation frequency is increased  3 to
100 times.  In addition to having mutations in the histidine operon,
all the indicator strains have mutations in the lipoplysaccharide coat
(rfa~) and deletions that cover a gene involved in the repair of uv
damage (uvrB~).  The rfa~ mutation makes the strains more permeable to
large molecules, thereby increasing their sensitivity to these molecules.
The uvrB~ mutation decreases repair of some types of chemically damaged
DNA and thereby enhances sensitivity to some mutagenic chemicals.
Strain TA1535 is reverted to histidine prototrophy (his"1") by many
mutagens that cause base-pair substitutions.   TA100 is derived from
                                                          o
TA1535 by the introduction of the R factor plasmid pKMlOl.   The intro-
duction of this plasmid, which confers ampicillin resistance to the
strain,  greatly enhances the sensitivity of the strain to some base-pair
substitution mutagens.   Mutagens such as benzyl chloride and 2-(2-furyl)-
                                   26

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3-(5-nitro-2-furyl) acrylamide (known as AF2) can be detected in plate
assays by TA100 but not by TA1535.  The presence of this plasmid also
makes strain TA100 sensitive to some frameshift mutagens—e.g. ICR-191,
benzo-a-pyrene, alfatoxin B^, and 7,12-dimethylbenz-a-antracene.  Strains
TA1537 and TA1538 are reverted by many frameshift mutagens.  TA1537 is
more sensitive than TA1538 to mutation by some acridines and benzanthracenes,
but the difference is quantitative rather than qualitative.  TA98 is
derived from TA1538 by the addition of the plasmid pKMlOl, which makes
this strain more sensitive to some mutagens.
          For each experiment, an inoculum was taken from a frozen
repository (-80°C), grown overnight at 37°C in a nutrient broth consisting
of 1 percent tryptone and 0.5 percent yeast extract.  After stationary
overnight growth,  the cultures are shaken for 3 to 4 hours to ensure
optimal growth.  Each culture was checked for sensitivity to crystal
violet.  The presence of the rfa~ mutation makes the indicator  strains
sensitive to this dye, whereas the parent strain, rfa+, is not  sensitive
to the dye.  However, the mutation is reversible, leading to the accumula-
tion of rfa+ cells in the culture.  Therefore, the cells must be tested
routinely to ensure their sensitivity to crystal violet.  Each  culture
also was tested by specific mutagens known to revert each test  strain
(positive controls).
          Some carcinogenic mutagens (e.g., dimethylnitrosamine) are inactive
unless  the bacteria  strains  are  converted  to  their  active  form  by  being metabolized
Ames has described the metabolic activation system used. '^  Adult male rats
(250 to 300 g) are given a single 500 mg/kg intraperitoneal injection of a
polychlorinated biphenyl (Aroclor 1254).   Four days after the  injection,
the animals'  food was removed.  On the fifth day, the rats were killed and
the liver homogenate prepared.
          The assay itself was conducted in the following manner.  To sterile
13 X 100mm tubes containing 2 ml of 0.6 percent agar containing  .05 mM histidine
and .05 mM biotin were added in order
          0.05 ml of indicator organisms
          0.5 ml of metabolic activation mixture (when used)
                                  27

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          Up to 50 yl of a solution of the test chemical.
This mixture was stirred gently and then poured onto glucose minimal agar
having the following composition:
          15 g of agar, 20 g of glucose, 0.2 g of MgS04'7 H20, 2 g of
          citric acid monohydrate, 10 g of fc^HPO^, and 3.5 g of NaHNffy
          PO^ 'H20 per liter.
After the top agar had solidified, the plates were incubated at 37C for 2 days.
          The number of his  revertants is counted and recorded.  Some of the
revertants are routinely tested to confirm that they are his , require biotin,
and are sensitive to crystal violet (rfa~).
          All of the samples were analyzed as they were received.
Dilutions of the samples were made in dimethylsulfoxide (DKSO).  The
amount of sample added per plate is expressed as the pi of sample in
50 yl of DMSO.  The results of these investigations are reported in
Tables 19 and 20 (Presented in next Section).

MAMMALIAN CELL CYTOTOXICITY
          Preliminary cytotoxicity testing of filter samples A1F, A2F,  A3F,
A4F, and ASF was preformed by Northrup Services utilizing cultured rabbit
alveolar macrophages .  The filter segments  as received had suffered some
degradation as a result of handling and shipping.   Some of the particulate
material had flaked off the filters and was  lying loose in the containers.
As is often the case in filters collected in the field, the particulate was
not evenly distributed all over the surface  of the filter.  This situation
was aggravated by the loss of some of the particulate.   An attempt was  made
to remove the particulate from the filter however, it was impossible to do
this without also removing some of the filter fibers that were imbedded in
the particulate, thus it was decided that the test would be conducted by
removing squares of material from the filters and utilizing these squares in
the test.  Therefore, small, medium, and large squares were removed from each
                                  28

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filter in an effort to develop a dose response.  However, due to the
heterogeneous distribution of particulate on the filters, the dose response
data generated are highly questionable and are not reported.
          No control filters were provided which lead to the decision that
the relatively clean edge of each filter would be removed and used as a
control.
                                 29

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                                  SECTION 5
                                   RESULTS

     Test No. 1 was in some ways a preliminary test, in that problems in re-
cording data, changing filters and adsorbers, and in recording flows could
not be anticipated as they could for Test No. 2.  Test No. 2 was better
organized and the various flows were more accurately recorded; therefore, of
the two tests completed at Youngstown, Test No. 2 (on April 1-2) was chosen
for the more complete analysis, including particulate mass and gas analysis
and, in most instances, the data obtained in Test No. 2 are used in presenting
results.
     Although the two sampling runs were made on the same oven, the concentra-
tion of emissions was greatly different for the separate runs made only about
a day apart.  Test No. 2 showed an overall particulate emission rate about
three times that measured in Test No. 1, and total light hydrocarbon concen-
trations about two times as great as measured for Test 1.   The fact that such
wide variations in emissions occur on a single oven served to illustrate the
wide range that can exist between emissions data obtained  on different coke
ovens.
DOOR LEAKAGE AND FLOW DATA
     Table 2 gives a summary of flow data taken at irregular periods through-
out Test No.  2.   Test No.  2 started  at 1303 April 1, and Table 2 shows that
                                                                o
leakage was relatively high around the door with a value of 99 m /hr (58 cfm),
at 1320, or 17 minutes later.   Theoretical calculations indicate that if an
0.8 mm (1/32-inch) crack is present  around half of the perimeter of a door
4.1 m (13.5 ft)  high and 0.7 m (2.25 ft) wide,  leakage would be 217 m3/hr
                                 30

-------
               TABLE 2.  TEST NO. 2 FLOW FOR AIR INPUT, HI-VOL
                          SAMPLER, AND DUCT ORIFICE

Date
and
Clock
Time
4/1-1320
4/1-1600
4/1-1737
4/1-1910
4/1-2237
4/2-0203
Hood Air
Input
(Rotometer
Flow}scfm'a
14.5
37.3
41.0
41.0
41.0
41.0
Hi-Vol Sampler Flow
Orifice
Gas Flow,
' scfm
47.6
49.0
50.5
45.8
46.8
45.8

Uncorrected,
scfm
29.2
15.6
16.0
26.3
30.7
30.0
/ v \
Corrected,^0'
scfm
24.5
13.1
13.4
22.2
25.8
25.2
Coke Oven
Door Leakage'0'

scfm(c)
58
25
23
27
32
30
3
m /hr
99
42
39
46
54
51

(a)  At 29.92" Hg and 70 F
(b)  Net flow is gross Hi-Vol corrected for calibration factor.
(c)  Door leakage = Hi-Vol flow + Orifice flow - Hood air input.

       3    *
(128 ft /min ), assuming a gas pressure of 8 mm H.O in the oven, and a gas

temperature at the crack of 316 C (600 F).  Table 2 shows that leakage  had
                3          3
declined to 42 m /hr (25 ft /min) about three hours after the start of the
                                                 3                3
test, leakage remained in the range of 39 to 54 m /hr (23 to 32 ft min)

for the remainder of the test.

PARTICULATE MASS EMISSIONS

     Although adsorber flows and overall data from Test No. 1 were not as

accurate as Test No. 2, filter weights and flows from the Hi-Vol samplers

were available.  Accordingly, Table 3 summarizes the filters and their

weights, and the flow of gases through the filter from Test No. 1.

     Table 4 summarizes filter weight and flow data from the Hi-Vol samplers
for Test No. 2.  Door leakage in Test No. 2 was much greater than the door

leakage in Test No.  1.   Table 3 shows that Test No.  1 required 18 filters

*  Gas pressure = 8 mm = 0.011 psi; temperature at leakage point = 600 F
   Area of opening around door = (27 + 4.5) x 1/32 x 1/12 x 1/2 = 0.04 ft
   Gas density p = 0.075 x (460 + 70)/(460 + 600) = 0.0375
   Then velocity V = 96.3 x (0.011/0.0375) = 52.2 ft/sec
   and volume Q + AV = 0.041 x 52.2 x 60 = 128 ft3/min.
                                  31

-------
                                             TABLE 3.  SUMMARY DATA, NO. 1 TEST. COKE OVEN DOOR LEAKAGE
                                                      REPUBLIC STEEL, YOUNCSTOWN, OHIO A/1-2/76




Approximate
Hours
Clock Time Into Filter
On
3:10
3:21
3:30
4:12
4:25
5:05
6:05
6:35
7:10
8:10
9:45
10:45
11:10
12:25
1:10
2:10
3:10
5:10
Off
3:21
3:30
4:12
4:25
5:05
6:05
6:35
7:10
8:10
9:45
10:45
11:10
12:25
1:10
2:10
3:10
5:10
6:45
Test


1

2
3

4
5


8

10
11
12
14
16
Number
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
Average
Uncorrected
Filter
Flow As
Recorded
on Hl-Vol .
Chart. cfmU;
32
34
38
36
38
39
38
39
38
39
39
39
37
40
40
41
43
41

Filter
Flow

Corrected With Hl-Vol
Filter Flow, Calibration Dilution
... ' Correction, Correction
scfm(b) 8cfmXcJ Factor^)
24
26
29
27
29
29
29
29
29
29
29
29
28
30
30
31
32
31
24
22
29
23
29
24
29
24
29
24
29
24
28
26
29
28
30
28
.58
.57
.61
.58
.67
.79
.80
.59
.62
.59
.62
.59
.61
.51
.53
.52
.53
.52
Net
Leakage
Flow
Through
Hi-Vol,
scfra
14
13
18
13
19
19
23
14
18
14
18
14
17
13
15
15
16
15
Time of
Flow
Through
Filter,
minutes
11
9
42
13
40
60
30
35
60
95
60
25
75
45
60
60
120
95

Total
Time,
minutes
11
20
62
75
115
175
205
240
300
395
455
480
555
600
660
720
840
935


Leakage Flow
Through Filter,
ft3 o,3
154
117
756
169
760
1140
690
490
1080
1330
1080
350
1275
585
900
900
1920
1425
4.361
3.313
21.410
4.786
21.523
32.285
19.541
13.877
30.586
37.666
30.586
9.912
36.108
16.567
25.488
25.488
54.374
40.356
TOTALS
15.6
18
                                                                                                                         935

-------
TABLE 3.  SUMMARY DATA, NO. 1 TEST, COKE OVEN DOOR LEAKAGE
          REPUBLIC STEEL, YOUNCSTOWN, OHIO 4/1-2/76 (Continued)
Particulate Partlculate
Approximate Weight Concentration
Hours on In Leakage Gas,
Clock Time Into Filter Filter.
On Off Test Number grams mg/ra
3:10 3:21 100 5.9494 1364
3:21 3:30 101 9.3877 2834
3:30 4:12 1 102 10.0692 470
4:12 4:25 103 3.8342 801
4:25 5:05 2 104 5.7531 267
5:05 6:05 3 105 5.0010 155'
6:05 6:35 106 1.9813 101
6:35 7:10 4 107 5.6064 404
3:10 8:10 5 108 3.1818 104
8:10 9:45 109 2.7937 74
9:45 10:45 110 1.3152 43
10:45 11:10 8 111 0.8054 81
11:10 12:25 112 1.2681 35
12:25 1:10 10 113 0.6783 41
1:10 2:10 11 114 0.0528 2
2:10 3:10 12 115 0.0482 2
3:10 5:10 14 116 0.0488 1
5:10 6:45 16 117 0.0616 2
TOTALS 15.6
(a) Average flow from Hl-Vol flow chart as recorded during period
(b) Average gas temperature reading (208 F) and average barometer
correction factor of 0.77; corrected to 29.92" Hg and 70F.
(c) Odd numbered filters used with No. 1 Hi-Vol and even numbered
calibration correction in the range operated of -16 percent;
which it operated.
(d) Dilution factor • Hi-Vol, cfm + Orifice, cfm - cfm air input
Hi-Vol, cfm + Orifice, cfm
(e) Period refers to discrete test periods of 1 hr, 1 hr, 2 hr, 4
Particulate
Weight
for(e)
Period. '
grams


25.4063

9.5873


12.5887



8.0961



2.0474

0.1104
57.8362
Leakage
Flow
Through
Filter for
Period (e)
n,3


29.084

26.309


65.703



108.75



103.651

94.730
428.227
Particulate
Concentration
in Leakage Gas
for Period/6'
mg/m


874

364


192



74



20

1
135
Particulate
Emission
Rate,
mg/min


409.8

180.9


100.7



33.7



8.5

0.5
61.9
of flow through filter.
reading (29.01" Hg) at filter during test used to establish
filters used with No. 2 Hi-Vol; No. 1 Hl-Vol required a
No. 2 did not require calibration correction in the range at
under hood
hr, 4 hr, and 4
hr.



-------
                                                   TABLE 4.   MO.  }  TEST.  COKE OVEN  DOOR LEAKAGE
                                                              REPUBLIC  STEEL. YOUNCSTOWN, OHIO
                                                                         4/1-2/76
Cloc
ON

1303










1400





1416





1555




1654


1741
1755
IB25
1912
1922
2000
2105
2150
2225
2325
2351
0100
< Time
OFF

1304










1405





1506





1607




1708


1755
IE2S
1912
1922
2000
2105
2150
2225
2325
2351
0100
0215

Approximate
Hour a
Into
Teat











1





2





3




4


5

6

7
8
9

10
11
12
13

Filter
Number
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
Uncorr^ctcd
Filter
Flow Aa
Recorded
on Hl-Vol
Chart, clsO*'
38
28
38
28
37
20
35
30
32
30
36
23
30
32
32
40
30
32
30
35
30
28
32
38
30
34
36
32
25
30
30
34
33
36
33
37
35
30
35
38
30
38
40

Corrected
Filter
.cfift>
29
22
29
22
28
15
27
23
25
23
28
22
23
25
25
31
23
25
23
27
23
22
25
29
23
26
28
25
19
23
23
26
25
28
29
28
27
23
27
29
23
29
31
Flew
Through
With Hl-Vol
Calibration
Correction,
aofm(e)
29
IB
29
18
28
13
27
19
25
19
28
18
23
21
25
26
23
21
23
23
23
18
25
24
23
22
28
21
19
19
23
22
25
24
29
24
27
19
27
24
23
24
31

Dilution
Correction
Factor(d)
.81
.78
.81
.78
.81
.76
.81
.78
.80
.78
.81
.78
.79
.79
.80
.80
.79
.79
.79
.79
.79
.78
.DO
.49
.48
.47
.52
.48
.45
.45
.48
.43
.46
.45
.45
.41
.44
.37
.44
.41
.41
.41
.47
N«t Leak-
age Flow
Through
Hl-Vol,
ncfai
23
14
23
14
23
10
22
IS
20
15
23
14
18
17
20
21
18
17
18
18
18
14
20
12
11
10
15
«• 10
9
9
11
9
12
11
13
10
12
7
12
10
9
10
13
Time of
Flov
Through
Filter ,
plnutaa




1








7
8
16
10
10
11
7
14
6
11
12
12
11
12
12
14
17
16
14
30
47
10
38
65
45
35
60
26
69
7J

Total
Tl n«
I IDA .
mlnutca
1
2
6
9
25
34
37
40
43
48
52
57
63
70
78
94
104
114
125
132
146
152
163
175
187
198
210
222
236
253
269
283
313
360
370
408
473
518
553
61.3
639
708
783

Leakagi
Through
ft3
23
1.4
92
42
368
90
66
45
60
75
92
70
108
119
160
336
160
170
198
126
252
84
220
144
132
110
180
120
126
153
176
125
360
517
130
3.10
780
3 -.5
420
600
2 34
690
112}

Flov
Filter,
m
0.65
0.40
2.61
1.19
10.42
2.55
1.87
1.27
1.70
2.12
2.61
1.98
3.06
3.37
4.53
9.52
5.10
4.81
5.61
3.57
7.14
2.38
6.23
4.08
3.74
3.12
5.10
3.40
3.57
'..33
4.93
3.57
10.20
14.04
3.63
10.76
22.09
8.92
11.89
16.99
6.62
H.54 •
31.86
•rorALs
                 13.2
                           43
                                                                                                                  783

-------
                                             TABLE  4.   HO.  2  TEST,  COKE OVEN DOOR LEAKAGE
                                                        REPUBLIC  STEEL,  YO'JNCSTOWH,  OHIO
                                                              4/1-2/76    (Continued)
1
Clock Tlmo
Approxlait*.
ON OFF Hour*
Into
Te«c
1303

1400





1456





1555




1654


1741
1755
13?5
1912
1022
200J
2105
2150
2225
2325
2351
0100
TOfALS
13

1405





1506





1607




1708


1755
IB25
1912
1922
2000
2105
2150
277'i
2325
2351
0100
0215



1





2





3




4


s

6

7
8
9

10
11
12
13
13.2
Filter
Number
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140 '
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
15/
158
159
160
161
43
Partlculet*.
WetGht •
on
Filter,
grama
0.0162
2.3429
1.5054
7.6181
9.9949
10.0939
4.4263
5.1016
4.8536
5.3571
4.2589
4.9861
2.4750
5.0502
7.46/.0
7.9094
5.4523
5.5386
5.2461
3.5385
3.5813
3.1257
3.3512
3.3360
2.9323
2.6086
2.1009
2.2416
2.2274
2.6734
1.9769
2.1100
3.1065
2.2147
1.07H1
2.8207.
3.0858
2.0096
1.5319
1.3301
0.5264
0.2584
0.0761

Pertlculat*
Concentration,
in Leakage
Caa,
mg/n3
948
5057
577
6402
959
3?58
2307
4017
28S5
2527
1632
2518
009
1499
1648
831
10IS9
1151
935
911
502
1313
538
818
784
836
412
659
624
617
397
591
305
151
233
262
140
225
129
73
80
13
2

Parclculac*
Weight

for Period .<•> P«lod (•) .g/.tB


29.37





30.39





29.01




18.93


12.88

24.84

14.44
22.09
8.92

28.88
6.62
19.54
31.86
277.77


2082





1115





763




640


523

214

270
140
225

99
80
13
2
3S5


1002.5





555.6





363.6




198.3


143.8

69.1

81.2
47.5
'.4.7

30.1
20.2
3.7
1.0
195.1

Footnote* •«»• u TABLE 3, p«g« 33.

-------
  over a period of 935 minutes,  collected 57.8 grams of particulate from a
  calculated  gas flow through  the  filters due  to  door leakage  of  428 cubic
  meters,  and indicates an overall particulate concentration in  the door
  leakage gas of 135  mg/m3.  By  comparison,  Table 4  shows  that Test No.  2
  required 43 filters over 783 minutes,  collected 154 grams of particulate
  from total  door leakage  gas  flow through the filters of  278  m3,  and
  indicates an overall particulate concentration  in  the door leakage gas
             o
  of 555 mg/m .
       Figure 3 is a  graphic presentation of particulate concentrations  for
  the door leakage gas plotted against  time  in hours into  the  test.   Figure  4
  shows the emission  rate  in mg/min,  for Test  Nos. 1 and 2.  For  these figures,
  each curve  point is established  by  data for  one sampling segment and is
  plotted against the time mid-point  of  that time segment.
     It is important  to recognize  that  gas flow values for the Hi-Vol sampler
presented in  both Tables 3 and 4 are values obtained from  the  recorder  charts
on the samplers.  Conversely,  Hi-Vol flow values  shown in  Table  1 are in-
stantaneous values recorded during the  test.
     One important result from Tables 3 and 4  is  the fact  that the overall
particulate concentration for  Test 2 was 4.1 times as great  as the emission
rate measured in Test No.  1.   There are a number  of  possible reasons for this
wide difference in particulate emission rate,  none of which  can  be supported
by very specific data.  The most probable explanation is that  the oven  door
did not fit on as tightly for  Test No.  2 as had been the case  for Test  No. 1.
It appeared to members of the  research  team that  the oven  door and the  door
frame did not receive as thorough  a cleaning prior to the  coking cycle  of
Test 2 as in  the case of Test  No.  1.   However, there was no  comparative  mea-
sure available for cleaning of deposits from the  oven door.
     Other factors that might  affect door leakage are oven temperature  and
pressure.  No detailed data on these parameters were available for both  tests,
however, operating personnel reported that S-mm-^O  back pressure was main-
tained on all batteries.  In response to a request for temperature and  pres-
sure information, the following coke-side flue temperatures were measured at
approximately 1500 hours April 1.
                                   36

-------
2400
    0
  6          8          10
Time From Beginning of Test, hours
12
14
                                                                                      16
          FIGURE  3.  PARTICIPATE EMISSION  CONCENTRATION FOR  DOOR-LEAKAGE  GAS
                     VS TIME  INTO  COKING  CYCLE

-------
          1000 -
OJ
OO
                                   4         6          8          10         12
                                           Time From Beginning of Test, hours

                           FIGURE 4. PARTICULATE EMISSION VS TIME INTO COKING CYCLE
14
16

-------
                                      Temperature,
            Flue No.                  _C	F
                1                     1338    2440
                2                     1371    2500
                3                     1382    2520
                4                     1382    2520
                5                     1382    2520
                6                     1371    2500
                7                     1382    2520
                8                     1393    2540
                9                     1382    2520
               10                     1360    2480
               11                     1360    2480
               12                     1349    2460
               13                     1327.    2420
In general, operating personnel reported pusher side flue temperatures to be
1316 C  (2400 F) and coke side to be 1371 C  (2500 F).   They also mentioned
that, in the past, normal back pressures had been as high as 14-mm H20.
RESULTS OF LEVEL 1 ANALYSES
Gravimetric-Analysis
     Table 5 presents results for the gravimetric analysis conducted on the
filter and adsorber samples as part of the Level 1 analysis.  Results are pre-
sented in mass units per hour.  Each filter weight was corrected for the
total amount of material that would have been obtained if the entire sample
extract had been analyzed.
Infrared Spectroscopy
     The interpretation of the infrared spectra (and  subtracted spectra) of
the 88 samples (8 fractions of 11 samples) are summarized in Tables 6 and 7.
For several of the fractions, the spectra indicated only the presence of in-
organic Si-0 components.  From past samples we have demonstrated that these
inorganic components arise from background components and not from the col-
lected sample.   Thus,  the samples where only inorganic material has been ob-
served have been marked insufficient sample.  From the method of preparing
the sample for infrared analysis and from the method  of running the spectra,
this means that less than 100 nanograms of organic material was present.
     An example of the FT-IR technique and the subtractive procedure is the
identification of  carbozole in Fraction 3 of several  of the samples; this is
                                    39

-------
             TABLE  5.   LEVEL  1 ANALYSES, GRAVIMETRIC RESULTS
Fraction
Filter
A1F
A2F
A3F
A4F
ASF
Adsorber
Al
A2
A3
A4
A5
A6(*)
1

8.28
2.79
1.52
.88
.31

1966.40
3275.03
1000.43
1202.53
581.42
20.98
2

22.
20.
11.
4.
•

2704.
1429.
1097.
879.
1067.
3.
3

71
36
70
99
15

20
73
24
45
07
26

7.
4.
3.
1.
•

159.
213.
81.
10.
44.
1.

93
95
44
33
33

29
51
54
43
56
01
4
1
6.62
3.75
2.60
1.20
.26
Hi
335.43
613.83
189.34
137.74
106.57
.96
5
;/hr
2.88
3.74
1.40
.88
.23
;/hr
497.72
571.13
127.58
271.89
231.11
1.10
6

.87
.96
1.68
.58
.08

103.42
143.35
106.22
27.09
17.17
.91
7

10.
9.
3.
1.
•

321.
293.
96.
75.
64.
6.

09
25
94
39
30

35
83
69
91
89
37
8

.50
.61
.74
.10
.01

5.08
7.37
2.60
3.66
2.89
.18
(a)
    Compressor  Air  Blank.
                                40

-------
                       TABLE 6.   LEVEL 1 IR ANALYSIS OF LC FILTER FRACTIONS
Fraction
Sample
A1F
A2F
A3F
A4F
A5F
I
. Aliphatic Hv
Fused

Aliphatic Hv
Fused

Aliphatic HV
Fusee
*
Aliphatic ti\
Fusee;

Aliphatic Hv
Fus

2
drocarbons
Ring Aromati
(a)
drocarbons
Ring Aromati

drocarbons
Ring Aromati

drocarbons
jling Aromati

drocarbons *
ed Ring Aroma

3
:s
Possible
Carbazole


cs
Carbazole

C=N(d)
cs

Carbazole
*
CSN
(a)
tics v '
Ketone

4
*
Phenol (c>
c=N(d)

s=Nw;


Phenol

Phenol

Phenol


5
Phenol
(b)
*

Pheno

(b)
A

(b).
A


_E

6
or Amine
(b)


romatic Carbo:

comatic Carbo

Aromatic Ca
Acid
*
cf-pT PhfV^glaf

7
Aromatic
Carboxylic
Acid(b^
Aromatic
Carboxylic
Acid

*
cylic Acid

cvlic /\rid

rboxylic
^

8
Insuff icier
Sample
Insuff icier
Sample
Insuff icier
Sample
Insuff iciei
Sample
Insuff iciei
Sample
t
t
t
.t
it
(a)   Possibly contains pyrene and/or benzpyrenes.
(b)   Possibly S compounds.
(c)   Possibly carbazole types.
(d)   Possibly C^N or (less  likely)  C=C.
*  Sample subjected to GC-MS analysis.

-------
TABLE 7.  LEVEL 1 IR ANALYSIS OF LC ADSORBER FRACTIONS
Fraction
Sample
Al
A2
I
A3
A4
A5
A6
1
Aliphatic
Hydrocarbo
Aliphatic
Hydrocarbo
Napht-ha
A
Aliphatic
Hydrocarbo
Nflnhrha"

Aliphatic
Hydrocarbo
Mo^t-,l-V,^1
11J.pllLU.ii-l.
Aliphatic
Hydrocarbc
Naphtha

Aliphatic
Hydrocarbi
2

is
Fused Riru
Aromatics
(a)

is
e.ne
Fn«(=rl Rinp
Aromatics (a

is
'HP
"Ril eprj 1^ -f no
AromaticsX3

ns
CJQp
Fused Ring
Aromatics <-a
*
ns
ene
Fused Ring
Aromatics (a

ns A
Silicons

3
Nitrile ' Nnr(
nj . Ket^n0 A
nols

Ketone tr

Phthalat
ester
-coni . Ket<

cient
le
7
le B

le B

np R
A
np R

e *
ne B

Non-conj .
Ketone
A
Phthalat<
8

Insuf fi
cient
Sample
T
cient
Sample
Insuffi-
cient
Sample
Insuffi-
cient
Sample
Insuffi-
cient
Sample
Insuffi-
cient
Sample

-------
Footnotes for Table 7.

(a)  Pyrenes and benzpyrenes are likely in this fraction.
(b)  Probably primarily carbazole.
(c)  Nitrile is most likley but the possibility of C-C cannot be excluded
       in dramatic p subs nitrile is most likely.
(d)  Can be conjugated ketone, quinone or mixture of both.

 *   Sample subjected to GC-MS analysis.
                                  43

-------
illustrated in Figure 5.  The top spectrum is an absorbance spectrum of Frac-
tion 4 of Sample A1F; the bottom spectrum is an absorbance spectrum of Frac-
tion 3 of Sample A1F.  The two spectra in the middle of Figure 4 are the
resultant of subtracting the spectrum of Fraction 3 from two different ratios
of Fraction 4.  These two subtracted spectra show:
     (1)  Carbazole is the main component of Fraction 3
     (2)  Similar components in both Fraction 3 and Fraction 4
     (3)  Correct intensities of Fraction 4 by removing the
          contribution (carbazole) of Fraction 3, thus aiding
          in the identification of Fraction 4.
     Another example of the subtraction technique is given in Figure 6.  At
the top of this figure is an absorbance spectrum of Fraction 6 of Sample A2.
At the bottom is a spectrum of Fraction 3 of this same sample.  Note that
these spectra show many similarities making it difficult (because the separa-
tion might not be clean) to identify the unique components of each fraction.
In the middle of Figure 6 is the resultant of subtracting the spectrum of
Fraction 5 from that of Fraction 6.  The absorption pointing up and down near
1700 cm   clearly determines that:
     (1)  Fractions 5 and 6 have different (but very similar)
          carbonly absorptions
     (2)  The positions (frequencies) of each carbonyl vibration
          coupled with the other observed bands in each fraction
          identifies both as non-conjugated ketones, and each
          fraction as having a different ketone structure.   These
          ketones were designated as Ketone A and Ketone B,
GAS CHROMATGRAPHY-MASS SPECTROSCOPY RESULTS
     The major species determined by the GC-MS analysis of  selected samples
are listed in Table 8.  Examples of El and CI reconstructed  gas chromatograms,
with the more abundant species labeled,  are shown in Appendix C.   Individual
mass spectra for the CI GC-MS analysis are also given in Appendix C.
     Results obtained by the semiquantitation procedure for  identified  GC-MS
components are listed in Table 9.
                                    44

-------
                                                         A.  Fraction 4 of AlF
                                                         B.  15 percent Frac-
                                                             tion 4 - 100
                                                             percent Fraction 3
                                                         C.  75 percent Frac-
                                                             tion 4 - 100
                                                             percent Fraction 3
                                                         D.  Fraction 3 of AlF
1800
   1600              1000                600  cm

FIGURE 5.   ARSORBANCE INFRA RKD  SPECTRA
                                                             _ 1
                                                             m A.
                          45

-------

1
!

i '
.
i

;
. . .. .
i -
. • — ---
|


V'\.N
1
1
I





!
;




j
1





\
\ i
i
,
1
, i
i
it i
*'





1




\
i ...
(j ;
I '
If*











_

,V







•


i
J
I
'''"
..-.











|
\ '• / *
	




'





_ .
i
l;x ,
'

'


1

]
i
1

	 ;.._.
i

	










.1...-
•
i
i,











._

-
                                                    A.   Fraction 6 of A2
                                                    B.   100 percent Fraction
                                                        6 - 100 percent
                                                        Fraction 5
                                                   C.   Fraction 5 of A2
1800           1400            1000

   FIGURE 6.   ABSORIiANCK INFRARED SPECTRA
(>6o cm"1

-------
 TABLE 8.   GC-MS ANALYSES OF SELECTED  COKE  OVEN  DOOR  SAMPLE FRACTIONS




Fraction	Sample	Compounds  Identified^	

                           Adsorbent Samplers

   1           A2       Naphthalene, methylnaphthalenes, dihydro-
                          naphthalene,  C2~naphthalene

   2           A5       Naphthalene, methylnaphthalenes, anthracene,
                          acenaphthalene, methyl acenaphthalene/
                          fluorene,  biphenyl acenaphthene/
                          methyl biphenyl,  tetrahydronaphthalene,
                          indene

   3           Al       Indole,  naphthylisocyanide, carbazole
                          methyl carbazole

   3           A5       Carbazole, methyl, carbazole

   4           Al       C2~phenol

   5           Al       C2~phenol, C3~phenol

   6           A2       No positive  identification

   7           A3       Quinoline, phthalate,  acridine

   7           A3       No positive  identification

   8           All      No GC components

                                Filters

   1           A3F      Anthracene,  methylanthracene, fluorene,
                          methylfluorene, fluoranthene, methyl-
                          fluoranthene, pyrene,  methylpyrene,
                          phthalate

   2           ASF      Anthracene,  methylanthracene, fluoranthene,
                          methylfluoranthene,  pyrene, methylpyrene,
                          benzphenanthrene, chrysene, benzopyrene,
                          benzofluoranthene, methyl chrysene/
                          methyl benznathracene, methyl benzopyrene/
                          methyl benzfluoranthene, coronene

   3           A3F      Carbazole, methylcarbazole, benzanthrone,
                          cyanofluorene,  dimethyl carbazole

-------
  TABLE 8.  GC-MS ANALYSES OF SELECTED COKE OVEN DOOR SAMPLE FRACTIONS


                              (Continued)




                                                        (a\
Fraction	Sample	Compounds Identifiedv '	
               A1F      (2)C3-phenol, C2-benzaldehyde, naphthol,

                          methylnaphthol, hydroxyfluorene, methoxy-

                          fluorene, benzanthrone
5
6
7
8
2
3
7
A1F
A5F
A4F
A1F
A6
A6
A6
No identification
Filters
Quinoline, phthalate
No GC components
Compressor Air Supply (Blank)
No positive identification
Naphthalene, anthracene
Phthalate
 Cat
 v  ' See  text.

-------
TABLE 9.  SEMIQUANTITATION OF SELECTED COKE OVEN DOOR
          SAMPLE FRACTIONS
Percent of
Fraction Sample Compound Total Emission
1







2

















3





4








A3F Fluorene
Methyl fluorenes
Anthracene
Methyl anthracenes
Pyrene
Methyl pyrenes
Fluoranthene
Phthalate
ASF Anthracene
Fluoranthene
Pyrene
Methyl pyrenes/methyl
fluoranthenes
Dimethyl pyrenes /dimethyl
fluoranthenes
Benzo phenanthrenes
Chrysene
Methyl chrysenes/benzoanthracenes
Dibenzo anthracenes
Benzo fluoranthenes
Benzo pyrenes
Methylbenzopyrenes/methylbenzo-
f luoranthenes
Indeno pyrene
Benzo perylene
Coronene
A3F Carbazole
Methyl carbazoles
Dimethyl carbazoles
Cyanofluoranthene
Benzanthrone
Phthalate
A1F C2 benzaldehydes
03 phenol
Methyl allyl phenol
Methyl indenone
Naphthol
Methyl naphthols
Hydroxy fluorene
Methoxy fluorene
Benzanthrone
2
2
21
12
10
10
12
5
5
15
10

4

1
4
21
4
2
15
11

1
4
4
1
29
13
6
5
3
3
6
7
3
5
7
14
7
1
6
Emission
Rate,
mg/hr
30
30
320
180
150
150
180
75
7.5
22
15

6.0

1.5
6.0
31
6.0
3.0
22
16

1.5
6.0
6.0
1.5
95
43
20
16
10
10
400
460
200
330
460
920
460
65
400

-------
TABLE 9.  SEMIQUANTITATION OF SELECTED COKE OVEN DOOR
          SAMPLE FRACTIONS (Continued)
Fraction
7

1



2

















3




3


4
5

Sample Compound
A4F Quinoline
Phthalate
A2 Naphthalene
Methyl naphthalenes
Dimethyl naphthalenes
Dihydroxy naphthalene
A5 Indene
Naphthalene
Methyl naphthalene
Tetrahydro naphthalene
Acenaphthalene
Biphenyl/acenaphthrene
Methyl biphenyl/methyl
acenaphthrene/f luorene
Anthracene
Methyl anthracene
Dimethyl anthracenes
Trimethyl anthracenes
Fluoranthene
Pyrene
Methyl pyrenes/methyl fluor-
anthenes
Benzophenanthrene
Chrysene
Al Indole
Methyl indole
Carbazole
Methyl carbazole
Naphthyl isocyanide
A5 Carbazole
Methyl carbazole
Phthalate
Al C2 phenol
Alkyl phenol
Al C2 phenol
Co phenol
Percent of
Total Emission
19
16
35
26
8
5
10
33
19
3
11
6

6
3
1
0.05
0.05
1
1

0.1
0.05
0.07
19
6
25
3
25
57
16
16
53
20
11
8
Emission
Rate,
mg/hr
265
220
1100
850
260
160
100
350
200
30
120
60

60
30
10
0.5
0.5
10
10

1.0
0.5
0.7
30
9.0
40
5.0
40
25
7.0
7.0
180
68
55
40
                        50

-------
TABLE 9.  SEMIQUANTITATION OF SELECTED COKE OVEN DOOR
          SAMPLE FRACTIONS (Continued)
Fraction Sample Compound
7 A5 Quinoline
Methyl quinolines
Dimethyl quinolines
Acridine
Methyl acridines
Benz acridines
3 Phenyl propanilide
Methyl 3 phenyl propanilide
Phthalate
Percent of
Total Emission
15
3
5
7
4
1
10
6
53
Emission
Rate,
mg/hr
10
2.0
3.0
4.5
2.5
0.6
6.5
4.0
34
                       51

-------
THIN LAYER CHROMATOGRAPHY RESULTS
     Results of the quantitation of BaP as determined by TLC are listed in
Table 10.  This quantitation was performed only on the filters extracted by
EPA with cyclohexane.
HIGH RESOLUTION MASS SPECTROMETRY RESULTS
     The results of the HRMS analyses conducted by Dr. Sharkey are listed in
Tables 11, 12, and 13.  The nine formulas, listed in Table 13, include highly
carcinogenic PNA's.  Few of these possible structures were found in the ex-
tracts of the absorber column, while there were strong indications for all
except 3-methyl-cholanthrene (mass 268) in the filter extracts.
TRACE METAL RESULTS
     Results of trace metals emissions, as determined by the SSMS analysis
described earlier, are presented in Table 14.  Each element is reported in
yg above the blank for the entire sample collected.
     Differences among samples in detection limits of a given element arise
from differences in items such as degree of plate fogging and/or plate sen-
sitivity and sometimes differences in sample composition.  In these analyses,
differences are related to plate characteristics.   Also,  detection limits for
many of the elements are mandated by the elemental blank levels of the glass
fiber.   This is especially true for the alkali and alkaline earth elements as
well as for some of the transition elements such as  Zn and Zr.
     SSMS results for analyses of the coal and coke  samples are presented in
Table 15.
GASEOUS EMISSIONS
     The light hydrocarbons and inorganic components detected in the flask
samples for Test No.  1 and 2 are presented in Table  16 and 17,  respectively.
These results are calculated on a dry basis;  the amount of water detected is
shown at the bottom of each table.   Water was much higher for Test No. 2 re-
sults which might be due to the fact it rained during this test.
     For compounds present at concentrations lower than the sensitivity of the
analysis technique, values are reported as less than 0.1  ppm or less than 50
ppm of the component was present.   In the first instance  a more sensitive
                                   52

-------
             TABLE 10.   TLC QUANTITATION RESULTS  FOR  BaP
Sample                            pg                        mg/hr
 A1F                             710                          5.0
 A2F                             440                          4.0
 A3F                             700                          2.7
 A4F                             540                          1.1
 A5F                             230                          .35
                               53

-------
     TABLE  11.  LOW VOLTAGE MASS SPECTROMETRIC  RESULTS  OBTAINED
                ON FIBER SAMPLES
Major Structural Type,
Including Alkyl Derivatives
({i-Naphthalenes
6-Ring Peri
3-Rings
1 , 12-Benzoperylenes
Benzonaphthothiophenes
5-Ring Cata
Acenaphtyhlenes + Fluorenes
5-Ring Peri
Dibenzothiophenes
<|>- 3-Rings or Binaphthyls
4-Ring Cata
4-Ring Peri
Coronenes
Dinaphthothiophenes
AIF
8.8
.3
16.5
1.3
2.0^
1.6
8.6
8.3
3.5^
3.5
10.7
17.9
.2
-
Total lonization, percent
A2F A3F A4F A5F
8.5
1.7
10.0
4.0
2.2^
3.9
5.4
15.1
2.2^
4.9
12.1
17.8
.5
-
9.6
.4
12.4
2.0
2.3
2.2
4.5
11.6
2.5
4.2
13.4
23.7
-
.6
9.2
.9
7.4
3.2
2.3
3.2
2.9
13.4
1.9
5.1
20.8
19.4
.2
-
8.2
1.9
4.2
4.8
2.2
3.1
4.5
16.0
1.6
4.5
18.1
21.4
.5
-
(a)   Percent total ionization assumes  equal  sensitivity for all
     components.   Valid for comparison of similar samples.
(b)   Confirmed by HRMS.
(c)   Not confirmed by HRMS.
     Note:   3-Ring compounds are  anthracene  and  phenathrene
            4-Ring peri compounds are  pyrene and fluoranthene
            4-Ring cata compounds are  chrysene,  3.4-benzphenanthrene,
                 tetraphene, and  tetracene
            5-Ring peri compounds are  perylene,  benzo(a)pyrene,
               benzo(e)pyrene
            5-Ring cata compounds includes 11 5-ring compounds
            6-Ring peri compounds includes 11 6-ring compounds
                             54

-------
       TABLE 12.   LOW VOLTAGE MASS SPECTROMETRIC RESULTS OBTAINED ON
                   ADSORBER SAMPLES

Benzenes
Indanola/Benzothiophenes
(((-Naphthalenes
Phenols
3-Rings
Acenaphthylenes + Fluorenes
5-Ring Cata
Acenaphthenes + Biphenyls
Dibenzofurans
Naphthalenes
Dibenzothiophenes
Indenes
4-Ring Cata
Indans/Tetralins
Benzofurans
4-Ring Peri
5-Ring Peri
Al
3.4
2.4
.9
9.9
6.3
8.5
.1
4.3
3.2
42.1
1.0
7.0
.6
3.2
2.7
1.7
-
A2
4.6
1.6
.3
19.5
4.1
5.3
-
3.9
-
42.2
.5
6.9
-
1.8
2.0
1.0
-
Total
M
11.7
1.7
.4
17.6
2.6
3.6
-
2.6
-
39.5
.2
11.6
-
2.8
3.7
.9
-
(a)
lonization, percent
A4_ A5_ A6
4.2
2.8
.5
18.1
3.0
5.4
-
4.0
-
44.7
.2
8.3
.2
2.2
2.7
1.6
-
4.5
3.1
.6
16.4
4.0
6.1
-
4.4
-
47.0
.3
7.4
.2
2.1
1.1
1.7
.1
(a)   Percent total ionization assumes  equal  sensitivity  for  all
     components.   Valid for comparison of similar  samples.
 Note:  See note on Table 11.
                                55

-------
      TABLE 13.   HIGH RESOLUTION MASS  SPECTROMETRIC  RESULTS
Sample Identification
m/e Formula
228 C10H, .
18 12

252 C_-H10
20 12

254 ConHn/
20 14

256 C20H16

267 C.-H.-N
20 13


268 C21H16

278 C.-H,,
22 14

279 C01H10N
21 13


302 Cn,E..
?4 14

Al
A

•
A

•
A

G
A
O
A

G

L
0
A

r\
^^
A

O

A

o
A2
A

O
A

L.;
A

O
A
O
A

U

A
G
A

0
A

0

A

o
A3
/.

0
A

0
A

O
A
O
A

•u

A
O
A

O
A

O

A

o
A4
A

•
A

O
A

O
A
O
A

O

A
0
A

O
A

0

A

o
A5
A

9
A

G
A

0
A
O
A

G

A
O
A

O
A

O

A

o
A6
A

(._)
A

vJ
L

O
A
O
A

G

A
G
A

O
A

O

A

o
Sample Identification
A1F
A

*
A

a
A

0
A
©
A

O
a
A
O
A

&
A

C
D
A

O
A2F
A

G
A

O
A

O
A
O
A

O
B
A
O
A

C
A

G
n
A

O
A3F
A

e
A

G
A

6
A
©
A

O
B
A
G
A

©
A

O
a
A

G
A4F
A

O
A

O
A

G
A
G
A

O
•
A
O
A

O
A

0
o
A

G
A5F
A

O
A

O
A

O
A
O
A

O
•
A
O
A

O
A

O
a
A

O
O - Detected by HRMS  (photoplate)




O - Not  detected by HRMS  (photoplate)




B - Detected by HRMS  peak  matching




D - Not  detected by HRMS peak  matching




A - Detected by HRMS  (computer run)  data  system




A - Not  detected by HRMS  (computer run) data  system
                           56

-------
TABLE 14.   SSMS ANALYSIS OF FILTER SAMPLES
Element

LI
Be
F
Na
Kg
Al
P
S
K
Ca
'Jr. •
7i
y
Or
M.T
Te
(Jo
N.i.
Cii
i'.n
C;,
Ce
As
r,e
?,c
Kb
Sr
Y
Zr
Mb
Mo
Ru
Kh
ra
AS
Cd
A1F

1.5
<10

<0.15
<0.058
<0.058
<0.15
<0.15
A4F

<0. 00010
<0.52
<0.10
<7900
<260
<370
<2.6
<520
<1000
<1600
<1.0
<2.6
<0.52
<0.52
<0.52
26
<0.52
<1.6
0.52
I--2
'0.52
<] .0
<1.0
<0.52
<0.52
<] .6
±1.6
<0.052
<1.0
<0.052
<0.52
<0.26
<0.1
<0.1
<0.26
<0.26
A5F

<0.
<350
<0.
<25,000
<870
<1,200
<8.
<1,700
<3,500
<5.200
<3.
<3.
<1.
1.

-------
                                             TABLE 14.  SSHS ANALYSIS OF  FILTER SAMPLES (Continued)
Ln
CO
Element

In
Sn
Sb
Te
I
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
PC
Au
Hg
Tl
Pb
Bi
Th
U
B
A1F

<5
500
<10
<1
0.5
<1
<500
50
100
<1
<3
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<1
<2
1
<1
<1
<1
<1
<1
<1
<1
1,000
15
<0.5
<0.5
<2,000
A2F

<5
<20
<10
<1
<0.5
<1
<500
<1
<1
<1
<3
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<1
<2
<1
<1
<1
<1
<1
<1
<1
<1
<100
5
<0.5
<0.5
<2,000
A3F
US
<5
<20
<10
<1
<0.5
<1
<500
<1
<1
<1
<3
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<1
<2
<1
<1
<1
<1
<1
<1
<1
<1
<100
<0.5
<0.5
<0.5
<2,000
A4F

<5
<20
<10
<1
<0.5
<1
<500
<1
<1
<1
<3
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<1
<2
<1
<1
<1
<1
<1
<1
<1
<1
<100
<0.5
<0.5
<0.5
<2,000
ASF

<5
<20
<10
<1
<0.5
<1
<500
<1
<1
<1
<3
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<1
<2
<1
<1
<1
<1
<1
<1
<1
<1
<100
<0.5
<0.5
<0.5
<2,000
A1F

<0.079
7.9
<0.16
<0.016
<0.0079
<0.016
<7.9
0.79
1.6
<0.016
<0.047
<0.031
<0.031
<0.031
<0.031
<0.031
<0.031
<0.031
<0.031
<0.031
<0.031
<0.016
<0.031
0.016
<0.016
<0.016
<0.016
<0.016
<0.016
<0.016
<0.016
16
0.24
<0.0079
<0.0079
<31
A2F

<0.16
<0.64
<0.32
<0.032
<0.016
<0.032
<16
<0.032
<0.032
<0.032
<0.095
<0.064
<0.064
<0.064
<0.064
<0.064
<0.064
<0.064
<0.064
<0.064
<0.064
<0.032
<0.064
<0.032
<0.032
<0.032
<0.032
<0.032
<0.032
<0.032
<0.032
<32
0.16
<0.016
<0.016
<64
A3F
Pg/g
<0.15
<0.58
<0.29
<0.029
<0.015
<0.029
<15
<0.029
<0.029
<0.029
<0.087
<0.058
<0.058
<0.058
<0.058
<0.058
<0.058
<0.058
<0.058
<0.058
<0.058
<0.029
<0.058
<0.029
<0.029
<0.029
<0.029
<0.029
<0.029
<0.029
<0.029
<29
<0.015
<0.015
<0.015
<58
A4F

<0.26
<1.0
<0.52
<0.052
<0.026
<0.052
<26
<0.052
<0.052
<0.052
<0.16
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.052
<0.10
<0.052
<0.052
<0.052
<0.052
<0.052
<0.052
<0.052
<0.052
<52
<0.026
<0.026
<0.026
<100
ASF

<0.87
<3.5
<1. 7
<0.17
<0.087
<0.17
<87
<0.17
<0.17
<0.17
<0.52
<0.35
<0.35
<0.35
<0.35
<0.35
<0.35
<0.35
<0.35
<0.35
<0.35
<0.17
<0.35
<0.17
<0.17
<0.17
<0.17
<0.17
<0.17
<0.17
<0.17
<17
<0.087
<0.087
<0.087
<35

-------
      TABLE 15.  MASS SPECTROGRAPHIC ANALYSES OF COAL & COKE
                                                            (b)
Element
Li
Be
B
F
Na
Mg
Al
Si
P
S
Cl
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se(a)
Br
Rb
Sr
Y
Zr
Nb
Mo
Ru
Rh
Pd(a)
Ag
Cd
In(a)
Sn
Coal
30
5
100
5
3000
5000
-v5%
VLO%
300
3000
100
500
2000
30
5000
100
100
300
^5%
20
20
30
30
30
2
10
<5
10
5
2000
100
200
2
10
<2
<1
<1
0.5
10
<0.5
1
Sample
Coke
Designation
Element
10 ppm Sb
3
100
5
3000
2000
^3%
VLO%
300
5000
200
2000
^2%
30
3000
50
20
300
M.%
20
100
30
50
20
20
20
<20
20
10
3000
100
200
10
20
<5
<1
<10
5
10
<2
100
Te
I
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Hg
Tl
Pb
Bi
Th
U








Coal
<0.5
<1
<1
1
100
10
20
1
10
3
<1
1
<1
3
<0.5
<1
<1
<1
<2
<3
<2
<1
<1
<2
<3
<5
<2
<5
<2
1
<1
<3
<1








Coke
2 ppm
3
5
20
1000
300
200
100
200
10
3
10
1
10
1
5
<1
5
0.5
<1
<2
<2
<1
<5
<3
<5
<2
<5
<2
10
<1
5
3








(a)   Memory from previous sample.
(b)   Total weight of sample analyzed 100 mg.
                               59

-------
TABLE 16.  OVEN NO.  41 "A" GAS PHASE, TEST NO. 1


Sample No. & (Hrs )
Component
Nitrogen
Oxygen
Argon
Carbon dioxide
Carbon monoxide
Hvdrogen
Methane
Acetylene & ethene
Ethane
Propene
Propane
1-Butene
Iso-Butane
n- Butane
Benzene
Toluene
Total low MW hydrocarbons
Water
a. Number of hours into the
* Less than 0.1 ppm.

1 (0.5)
% ppm
77.40
20.60
.95
.09
.10
.44
3200
200
200
50
20
8
2
6
100
62
3848
<•!
run is shown

Results Reported as Volume Percent & Volume ppm, Dry Bases
2 (1.5) 3 (3) 4 (6) 5 (10) 6 (13)
% ppm % ppm % ppm % ppm % ppm
77.8 79.4 78.0 78.0 78.0
20.9 19.4 20.8 20.9 20.9
.95 .99 .96 .96 .95
.08 .06 .05 .05 .05
.03 .004 .02 .01 .005
.16 <.l .08 .04 .03
900 60 400 100 31
50 3 200 2 .6
30 2 9 2 .4
9 .3 .4 .2 *
3 .1 .2 .1 *
1 ft * * *
*****
.5 * * * *
** ** ** ** *ft
ft* ft* *ft ft* ft*
993.5 65.4 609.6 104.3 32
.2 .2 .6 .3 .2
in parenthesis.


-------
                               TABLE 17.   QVEN  NO.  41  "A"  GAS  PHASE,  TEST NO.  2

Results Reported as Volume Percent & Volume
Sample No. & (Hrsa)
Component
Nitrogen
Oxygen
Argon
Carbon dioxide
Carbon monoxide
Hydrogen
Methane
Acetylene & ethane
Ethane
Propane
Propane
1-Butene
Iso-Butane
n-Butane
Pentene
Pentane
Hexane
Benzene
Toluene
Carbonyl sulfide
Carbon disulfide
Total Low MW hydrocarbons
Water
a. Number of hours into the
* T.PRQ t-Vian 0.1 nr>m .
1 (0.5)
% ppm
76.3
20.5
.95
.24
.16
.81
.69
.16
.08
.02
84
67
12
32
7
16
3
3
A
10
1
9724
3.8
run is shown

2 (1.5)
% ppm
82.9
15.9
1.03
.13
.003
<.l
<2
A
A
A
A
A
A
A
A A
AA
AA
AA
AA
AA
AA
<2
0.5
in parenthesis.

3 (3)
% ppm
81.7
16.9
1.00
.16
.03
.07
30
60
50
60
30
0.3
A
A
AA
AA
AA
AA
AA
AA
AA
230
4.6


4 (6)
% ppm
80.4
18.3
.98
.17
.02
.11
.04
9
20
2
0.8
0.4
A
A
AA
AA
AA
AA
AA
AA
AA
432.2
2.2


ppm, Dry Bases
5 (10)
% ppm
80.5
18.2
.99
.17
.02
.07
.04
40
7
0.3
0.3
A
0.4
0.7
AA
AA
AA
AA
AA
AA
AA
448.7
0.5



6 (13)
% ppm
79.3
19.5
1.0
.07
<0.3
<.l
.01
0.1
A
A
A
A
A
A
AA
AA
AA
AA
AA
AA
AA
.1
0.4


Less than 50 ppm.

-------
analytical technique was used; the technique used for those components re-
ported as less than 50 ppm is not capable of detecing a specific quantity less
than 50 ppm.  Sample No. 1 of Test No. 2 was concentrated which made it pos-
sible to detect much lower concentrations of C5 to Cy hydrocarbon and other
inorganic gases, but few additional compounds were detected.
     The gas analysis results support the contention that much greater leakage
occurred around the oven door in Test No. 2 compared to Test No. 1.  The data
for analysis of gaseous grab samples reported in Tables 16 and 17, showed
generally higher hydrocarbon contents for Test No. 2 samples compared to Test
No. 1 samples.  The inorganic products of combustion (carbon dioxide, carbon
monoxide, and hydrogen) showed approximately twice the amount for Test No. 2.
During Test No. 2, the oxygen content of the gas dropped as low as 15.9 volume
percent (Sample 2) and gradually increased to 19.5 percent by the end of the
run.  This low oxygen content (20.9 percent in normal air) was evident in
spite of air addition of about 68 m^/hr (40 cfm).   This is in contrast with
Test No. 1 which showed a lower oxygen content of 19.4 percent for Sample 3
with Samples 2, 4, 5, and 6 having an oxygen content close to normal air.  In
all cases of low oxygen (except Sample 1) for Test No.  2,  the inert components
of the air (nitrogen and argon) increased above normal which indicates pro-
ducts formed from the oxygen consumption were high molecular weight compounds,
or the filter coated with tars and/or the adsorber were removing more of the
volatile components before they reached the flask sample.
     During the running of Test No.  1, the total light hydrocarbon content de-
creased with time (as expected since the volatile components should be driven
off earlier in the run).   Sample 3 was the only exception in this trend.
During Test No.  2, Sample 2 showed no hydrocarbons despite the high oxygen
consumption and Sample 6 showed less than Sample 4 and  5.   It would appear
that some of the hydrocarbons were removed from these samples before reaching
the flasks,  probably by adsorption on a caked filter or in the adsorption
bulb.
     A partial list of compounds that could be detected by the gas analysis
techniques used but not found in the coke oven samples  are listed below.   The
lower limit of detection for these compounds for the concentrated sample
(Sample 1, Test 2) is 0.1 ppm,  and 50 ppra for the  other samples.
                                   62

-------
     Sulfur dioxide             Hydrogen cyanide
     Hydrogen sulfide           Nitrogen oxides
     Hydrogen chloride          GI to C3 alcohols
     Methyl chloride            Acetone
Quantifying Gaseous Emissions
     The quantifying of gaseous emissions cannot be done precisely for the
coke oven samples.  The reason that such quantitation cannot be done is ap-
parent disagreement between gas flow data and the results of the gas analyses.
     For example, field test data for Test No. 1 show that the air flow into
the hood (as measured at the rotameter) ranged from 15 to 35 scfm, and was
mostly between 27 and 35 scfm.  Flows out of the hood were 41 to 47 scfm at
the orifice and 27 to 30 scfm at the Hi-Vol filter.  By addition, the total
flow out was about 68 to 77 scfm.  Subtracting the air flow into the hood, 27
to 35 scfm, would leave estimated leakage values of 33 to 50 scfm.  Thus, the
leakage is calculated to be 100 to 150 percent of the inlet air flow.
     However, examining the gas analyses, the high values for oxygen and
nitrogen (averaging 20.6 and 78.1, respectively) suggests that the flask
samples consisted of mostly air.  This suggests  that the leakage  rate
through the oven door may have been much lower than the rate of air  flow
into the hood via the compressor and any leakage at the hood seals.
     The best estimate that can be made of gaseous emissions can be made by
assuming that the total gas flow out (via the orifice and the Hi-Vol sampler)
was measured fairly accurately.  Then, by using the flow rate and the gas
analysis data, estimates of gaseous emissions can be made.   This has been done
                           *
and is reported in Table 18 .
RESULTS OF BACTERIAL MUTAGENESIS ANALYSIS
     Table 19 shows the results of the average of two experiments with the
tester strains on samples A1F, A3F, and ASF.   In these assays,  the number of
*  Because the gas flow rate data was not taken simultaneously with the gas
   samples, average gas flow rates for the entire test were used to calculate
   gaseous emissions.
                                  63

-------
TABLE 18.  GASEOUS EMISSION ESTIMATES
Test No.
Total Estimated Gas
Flow Out, scfm
Total Estimated Gas
Flow Out, Nm^/min
Sample Number
Emission, mg/min
Carbon monoxide
Methane
Acetylene
Ethane
Propene
Propane
1-Butene
Iso-Butane
n-Butane
Benzene
Toluene
Pentene
Pentane
Hexane
Carbonyl sulfide
Carbon disulfide
1
73.0

2.06
1 2 3 A 5 6
2,392 717 96 478 239 120
4,382 1,233 82 548 137 42
462 115 7 462 51
513 77 . 5 23 5 1
180 32 1 1 1
75 11 <1 1 <1
38 5
10
30 2
787
488





2
72.2

2.04
1
3,790
9,361
3,659
2,033
712
313
318
59
157
20

41
98
22
51
6




23456
71 711 474 474 <1
<3 41 543 543 136
137 21 91 <1
127 51 18
213 7 1
112 3 1
1 2
2
3








-------
                                    TABLE 19.  EPA COKE OVEN SAMPLES
                                                                    (5)
     Compound
Metabolic
Activation
Negative control


Positive controls
      g-Prop!olactone
      2-Anthramine


Coke-oven sample A1F
 Microli ters
  of Sample
(in 50 ul of
     DM SO)
                                                                     Average of  Two  Experiments
                    0 ,05
                    0 .01
                    0 .Ul

                    0 .01
                    0 .05
                    0 . 10
                    0 .50
                     1.0
                     2. 5
                     5.0

                    0 .01
                    0 .05
                    0 . 10
                    0 .50
                     1.0
                     2.5
                     5.0
Histidine-Posi tive Revertants per
TA1535
22
19
201


9
16
19
14
23
31
32
10
28
22
24
16
48
54
TA1537
4
4

4
130
1
2
3
S
8
6
20
4
6
15
45
63
74
135
TA153S
10
13

15
1563
9
8
8
9
17
30
35
9
14
17
86
116
144
226
TA98
18
17

32
1371
14
17
17
42
81
96
117
21
26
46
153
243
373
415
Pla te
TA100
86
77
234


08
65
59
61
7-1
68
88
92
88
84
120
158
1GG
228

-------
                            TABLE 19.  EPA COKE-OVEN  SAMPLES     (Continued)
      Compound
Metabolic
Activation
Negative control


Positive controls
      (3-Propiolactone
      2-Anthramine


Coke-oven sample A3F
                                                 Microliters
                                                  of Sample
                                                (in 50 p,l of
                                     Average of Two Experiments
                                    +
                                    +
                   0 .05
                   0 .01
                   0 .01

                   0 .01 ,
                   0 .05
                   0 .10
                   0 .50
                    1.0
                    2.5
                    5.0

                   0 .01
                   0 .05
                   0 .10
                   0 .50
                    1.0
                    2.5
                    5.0
Histidine-Positive Revertants per Plate
TA1535
22
19
201


13
17
20
15
20
22
17
17
17
20
..19
19
34
40
TA1537
4
4

4
130
2
3
2
7
6
5
10
1
6
8
32
53
56
94
TA1538
10
13

15
1563
6
9
8
13
10
9
17
10
13
9
45
71
135
152
TA98
18
17

32
1371
22
17
24
28
37
27
69
25
27
37
91
159
183
293
TA100
86
77
234


64
68
76
83
81
79
74
95
71
86
117
144
146
156

-------
                         TABLE 19.
    EPA COKE-OVEN SAMPLES(5)   (Continued)
      Compound
Metabolic
Activation
Negative  control


Positive  controls
      g-Propiolactone
      2-Anthramine


Coke-oven sample A5F
 Microli ters
  of Sample
(in 50 (j.1 of
   DMSO)
                                                                      Average  of Two Experiments
                    0.05
                    0.01
                    0.01

                    o.oi'
                    0.05
                    0.10
                    0. 50
                    1.0
                    2.5
                    5.0
                   10.0

                    0.01
                    0.05
                    0. 10
                    0.50
                    1.0
                    2.5
                    5.0
                   10.0
Histidine-Positi ve Revertnnts per Plate
TA1535
25
24
213


22
30
34
27
25
19
17
22
13
13
21
17
16
•41
15
35
TA1537
6
3

4
199
6
7
5
6
9
7
15
toxic
7
5
10
13
30
33
54
toxic
TA1538
11
10

15
2029
6
5
12
9
17
10
23
29
9
7
13
21
34
49
85
99
TA98
23
29

33
1924
14
25
18
19
42
57
115
119
18
25
29
44
81
128
22G
172
TA100
98
104
263


91
68
71
82
. 74
60
93
71
103
101
7S
89
103
116
172
127

-------
revertants per plate was increased ten-fold over the negative control in
strains TA1537, TA1538, and TA98, and two-fold in strain TA100.  Metabolic
activation (rat-liver homogenate) increased the number of mutants above that
observed without activation.  The results suggest that coke oven samples A1F,
A3F, and A5F are moderately mutagenic and that a frame-shift mutation occurred
since TA1535, which is  reverted by baser-pair substitution mutagens, was not
affected.  Mutagenic activity was enhanced when the metabolic activitation
system was added to the test.  The relative order of mutagenic activity was
A1F >A3F >A5F.
     Table 20 presents the results of the experiments with ^. typhimurium on
samples Al, A3, A5, and A6.  In the first experiment, 0.1 ml of each sample
was removed and dissolved in 0.9 ml of DMSO (50 yl = 5 yl of sample).  Dilu-
tions were then made so that each dose was in 50 yl of DMSO.  In the second
experiment, 0.4 ml of sample was dissolved in 1.6 ml DMSO (50 yl = 10 yl of
sample) for samples A5 and A6.
     Samples Al, A3, and A5 were weakly mutagenic on strains TA1537, TA1538,
TA98, and TA100 when a metabolic activation system was added.  In the first
experiment, the number of histidine revertants per plate increased 2-4 fold
over the control plates.  In the second experiment, only strain TA100, with
metabolic activation, had a 2-fold increase in revertants.   These samples
also appear to cause frame shift mutations.   Sample A6 was not mutagenic in
either of the tests.
RESULTS OF MAMMALIAN CELL CYTOTOXICITY STUDIES
     Due to the nature of the filter samples,  it was not possible to quanti-
tate the dose or concentration of effluent material the cells were exposed  to.
Control filters were not available for testing.   The edge of the filter did
not appear to have been exposed to the coke  oven emissions  and was found not
to be toxic to the alveolar macrophages.   The  center of the filters A1F, A2F,
A3F, A4F, and ASF all caused a significant reduction in cellular viability.
     In each case, between 5-30 mg of filter was utilized in the cytotoxicity
test.   It was not possible to quantitate the cytotoxic response or compare
relative toxicity of these samples since the emissions were not evenly dis-
tributed on the filters and the amount of emissions present in the test was
no t known.
                                     68

-------
                                    TABLE  20.  EPA COKE-OVEN SAMPLES
     Compound
Metabolic
Activation
Negative control
Positive controls
    g-Propiolactone
    2-Anthramine
Coke-oven sample Al
 Microli ters
  of Sample
(in 50 ul of
  DMSO)
                    0 .05
                    0 .01
                    0 .01

                    0 .01
                    0 .05
                    0 . 10
                    0 .50
                     1.0
                     5.0

                    0 .01
                    0 .05
                    0 . 10
                    0 . 50
                     1.0
                     5.0
                                                               Hlstidine-Positive Revertants  per Plate
TA1535
22
19
329


28
19
31
16
23
24
11
7
14
15
14
12
TA1537
7
3


201
8
8
3
6
14
5
5
13
8
7
9
47
TA1538
15
6

16
1625
9
10
17
11
15
8
12
12
9
14
20
68
TA9S
29
34

29
1705
23
16
16
12
15
9
23
26
39
33
28
124
TA100
107
128
360


82
92
80
88
58
115
77
81
105
82
95
162

-------
                                   TABLE 20.  EPA COKE-OVEN SAMPLES (Continued)
      Compound
Metabolic
Activation
Experiment 2

  Negative control


  Positive controls
      AF-2
      2-Anthramine


•  Coke-oven sample Al
 Microliters
  of Sample
(in 50 ul of
     DM SO)
                                                                Histidine-Positive  Revertants per Plate
TA1535   TA1537  TA1538
TA98   TA100


0 .005
0 .01
0 .01
0.1
0.5
1.0
2.5
5.0
10.0
0.1
0.5
1.0
2.5
5.0
10.0
14
13
408
20
387
19
22
11
8
8
7
12
16
10
10
12
7
9
8
694
21
543
6
3
1
5
5
6
15
12
6
10
20
18
9
14
1915
17
876
16
12
7
4
11
6
20
18
32
26
18
20
17
22
1007
28
697
13
9
10
9
12
1
13
27
19
12
17
toxic
110
118
624
139
880
115
102
105
91
115
100
150
154
155
159
253
245

-------
                        TABLE 20. EPA COKE-OVEN SAMPLES  (Continued)
    Compound
Metabolic
Activation
Negative control

Positive controls
    P-Propiolactone
    2-Anthramine


Coke-oven sample A3
                                  -f
Microliters
 of Sample
(in 50 p,l of
    DMSO)
                                                              Histidine-Posi ti.ve Revertants per Plate
                    0 .05
                    0 .01
                    0 .01

                    0 .01
                    0 .05
                    0 . 10
                    0 .50
                    1.0
                    5.0

                    0 .01
                    0 .05
                    0 .10
                    0 .50
                    1.0
                    5.0
TA1535
22
19
329


29
29
31
24
25
16
5
10
16
10
7
15
TA1537
7
3


201
1
2
6
6
5
5
7
5
5
10
7
10
TA1538
15
6

16
1625
8
9
15
12
0
9
10
12
13
14
16
28
TA98
29
34

29
1705
19
If)
1<>
20
12
18
2iJ
26
27
34
33
62
TA100
107
128
360


83
84
79
89
72
67
8-1
82
85
90
74
116

-------
                             TABLE 20.  EPA COKE-OVEN SAMPLES (Continued)
      Compound
Metabolic
Activation
Experiment 2

  Negative control
  Positive control
      AF-2
      2-Anthramine
  Coke-oven sample A3
Microliters
  of  Sample
 (in  50  p,!
.  of  DMSO)
                   0.005
                   0.01
                   0.01

                   0.1
                   0.5
                   1.0
                   2.5
                   5.0
                  10.0

                   0.1
                   0.5
                   1.0
                   2.5
                   5.0
                  10.0
Histidine-Positive Revertants per Plate
TA1535
14
13
408
20
387
27
18
20
12
11
7
15
13
8
7
10
15
TA1537
9
8
694
21
543
11
9
5
4
9
6
11
10
5
13
12
77
TA1538
9
14
1915
17
S7G
6
7
4
5
3
10
19
14
26
21
26
35
TA9S
1"
->2
1007
28
697
9
20
23
18
17
12
29
21
27
38
53
40
TA100
110
118
624
139
880
131
110
98
126
85
91
122
128
177
164
198
211

-------
                               TABLE 20.  EPA COKE-OVEN SAMPLES (Continued)
Positive controls
    p-Prop!olactone
    2-Anthramine
Coke-oven sample A5
                                  +
                                  +
0.05
0.01
0.01

0.01
0.05
0.10
0.50
1.0
5.0

 .01
 .05
 .10
 .50
1.0
5.0
Histidine-Posi tive Revertcints per Plate
TA1535
22
19
329


14
17
23
27
19
14
14
5
10
7
18
7
TA1537
7
3


201
2
5
5
6
G
toxic
4
5
6
11
5
18
TA1538
15
6

17
1625
18
11
9
7
10
4
12
18
15
IS
22
40
TA98
20
34

29
1705
23
19
16
27
13
1-1
17
24
27
25
31
73
TA100
107
128
3fiO


77
78
88
82
7f>
68
86
80
88
62
9-1
123

-------
                                            TABLE  20.   EPA  COKE-OVEN  SAMPLES  (Continued)
              Compound
                             Metabolic
                             Activation
 Microliters
  of Sample
(in 50 ^1
 of DMSO)
—i
.p-
        •Experiment 2

          •Negative control
          Positive controls
             AF-2
             2-Anthramine
Coke-oven sample A5
    0.005
    0.01
    0.01'

     0.1
     0.5
     1.0
     2.5
     5.0
    10.0

     0.1
     0.5
     1.0
     2.5
     5.0
    10.0
                                                                        Histldine-Positive Revertants  per Plate
TA1535
14
13
408
20
387
19
24
15
14
toxic
7
17
23
14
9
toxic
TA1537
9
8
694
21
543
16
G
11
5
toxic
13
11
11
7
4
toxic
TA1538
9
14
1915
17
876
17
14
11
13
toxic
14
18
25
19
18
toxic
TA9S
17
22
1007
28
697
30
11
10
toxic

15
14
29
toxic


TA100
110
118
62-1
139
880
161
142
139
96
toxic
131
191
210
193
107
toxi c

-------
                              TABLE 20.   EPA COKE-OVEN SAMPLES  (Continued)
     Compound
Metabolic
Activation
Negative control
Positive controls
     p-Propiolactone
     2-Anthramine
Coke-oven sample A6
 Microli ters
  of Sample
(in 50 ,_,!
 of DMSO)
                                   4-
                    0 .05
                    0 .01
                    0 .01

                    0 .01
                    0 -05
                    0 .10
                    0 .50
                     1.0
                     5.0

                    0 .01
                    0 .05
                    0 .10
                    0 . 50
                     1.0
                     5.0
                                                               His tidine-Posi tive Revertcmts per  Plate
TA1535
19
20
280


22
15
22
14
9
16
15
6
15
20
9
14
TA1537
5
8
375


5
5
6
3
4
2
8
4
5
7
4
12
TA1538
12
20

14
1545
3
8
10
10
10
9
7
9
6
16
3
13
TA98
22
31

32
16G1
22
28
30
20
18
6
27
16
28
30
24
22
TA100
137
104
315


IDS
77
102
73
SO
62
98
105
81
126
90
100

-------
                                  TABLE 20.   EPA COKE-OVEN  SAMPLES  (Continued)
     Compound
Metabolic
Activation
Experiment 2
  Negative control
  Positive control
     g-Propiolactone
     2-Anthramine
  Coke-oven sample A6
Mlcrpliters
 o'f Sample
(in 50 p. 1
 of DMSO) .
                    0 .05
                    0 .01
                    0 .01
                        t
                    0 .10
                    0 .50
                    1.0
                    2.5
                    5.0
                   10.0
                                                   0
                                                   0
                                                    1.
                      10
                      50
                     .0
                    2.5
                    5.0
                   10.0
                                                                Histidine-Ppsitive Revertants per Plnte
TA1535
27
28
97


20
17
15
14
17
18
29
27
31
. 15
28
26
TA1537
5
3

4
196
2
3
4
3
2
2
4
2
4
2
4
8
TA153S
7
15

14
2432
7
7
4
7
5
13
9
8
5
7
16
6
TA98
17
24

36
2143
26
16
18
12
16
9
31
17
22
15
27
20
TA100
8S
80
166


74
60
64
60
58
40
59
53
60
63
67
64

-------
DISCUSSION OF RESULTS
     As would be expected during devolatilization of organic materials, such
as coal, the rate at which materials are emitted is high initially and then
decreases with time.  Figure A and Table 5 shows that this phenomena was
observed at the coke plant - particulate emissions were greater than 1000
mg/min during the first hour and decreased to less than 1 mg/min near the
end of the coking cycle.  Thus, even though filters and adsorbent columns
were changed more frequently during the early part of the test, the filters
and adsorbent columns used during the early part of the coking cycle were
much more heavily loaded than those used later in the cycle.
     The large variation is mass emission between the two tests raises
questions concerning using results of a small number of runs to determine
emission factors or emission estimates for these sources.
     Highly complex sample mixtures such as coke oven effluents are ex-
tremely difficult to analyze qualitatively, even more so quantitatively.
The Level-1 analytical strategy followed here has enabled a semi-quanti-
tative determination of the predominate classes of organic components
present in the samples obtained.
     Infrared analysis of the Level-1 fractions failed to detect any
significant differences in the composition of the emissions during the
coking cycle.  However, the LC fractions obtained in the Level-1 analysis
remain highly complex and, therefore, not easily amenable to detailed in-
frared analysis.
     GC-MS analyses were conducted on representative fractions, as deter-
mined by infrared analysis; these analyses also proved difficult due to
the highly complex nature of the fractions yielding insufficient GC re-
solution.   In many cases, the mass spectral data obtained for these unre-
solved GC components proved too complex for adequate interpretation.
Nevertheless, the predominate classes of organic components that were
identified by infrared analysis were subsequently identified by GC-MS.
     HRMS further confirmed the presence of many components identified
by GC-MS.   In addition, HRMS detected dibenzothiophenes and a C  H  N
component which were not observed using GC-MS.
                                   77

-------
     Bioassay results for the total sample are of limited value, since
infrared and GC-MS confirmed the presence of a large number of known
hazardous species such as polynuclear aromatic hydrocarbons present in
these samples.  Since many of such compounds are mutagenic and/or cyto-
toxic, we would clearly expect the positive bioassay results obtained in
this study.
RECOMMENDATIONS
     Further studies which involve the chemical analysis and bioassay of
coke emissions should include provisions for obtaining higher resolution
fractionation of the samples.  This would include HPLC size and class
separation which would yield fractions which were more amenable to success-
ful infrared and mass spectral analyses.
     Bioassay tests should be conducted after the LC or, preferably, HPLC
fractionation.  They would then give an indication as to which fractions
merit further analysis, giving a more complete overview of such coke oven
emissions.
                                   78

-------
                                 REFERENCES

1.  B. Commoner.  Chemical Carcinogens in the Environment.  Chapter 4 in
    Identification and Analysis of Organic Pollutants in Water.  Ed. by
    L. H. Keith, Ann Arbor Science Publ., Ann Arbor, MI, 1976.

2.  Jones, P. W.,  Graffeo, A. P., Detrick, R., Clarke, P. A., and
    Jakobsen, R. J.  Technical Manual for Analysis of Organic Materials
    in Process Streams.  EPA-600/2-76-072.  U.S. Environmental Protection
    Agency, Office of Research and Development, Washington, D.C.,
    March, 1976.

3.  Kier, L. D., Yamasaki, E., and Ames, B. N.  Detection of Mutagenic
    Activity in Cigarette Smoke Condensate.  Proc. Nat.  Acad. Sci. USA.
    71:4159-4163,  1974.

4.  Ames, B. N., McCann, J. and Yamasaki.  Methods for Detecting Carcinogens
    and Mutagens with the Salmonella/Mammalian-Microsome Mutagenicity Test.
    Mut.  Res., 31:347-364, 1975.

5.  Simmon, V. F., Poole, D.   In Vitro Microbiological Mutagenicity, Studies
    of Seven Coke-Oven Samples.  Stanford Research Institute Report No.
    LSU-3493.  Submitted to EPA, Research Triangle Park, NC, January 6, 1977,

6.  Waters, M. D., et al.  Environmental Research,  9:32-47, 1975.
                                      79

-------
            APPENDIX A
THERMAL ANALYSIS OF COKE OVEN DOORS
                80

-------
               SUMMARY REPORT
                      on
     THERMAL ANALYSIS OF COKE OVEN DOORS
      (Contract No. 68-02-1409, Task 16)
                     to
    U.S. ENVIRONMENTAL PROTECTION AGENCY
                June 12, 1975
                     by
G. R. Whitacre, S. E. Miller,  and J.  B.  Purdy
                  BATTELLE
            Columbus Laboratories
               505 King Avenue
            Columbus, Ohio  43201
               Franklin County
                     81

-------
                           TAPiLli OF CONTENTS


                                                                    Pa.qe


INTRODUCTION  	  1

SUMMARY AND CONCLUSIONS	4

DISCUSSION OF THE PROGRAM	8

  Test Setup	•. . . .   .  8

  Results of Test Runs	14

  Theoretical Analysis  	 20

       Calculation Procedure 	 20
       Results	23



                            LIST OF TABLES
Table 1.  Summary of Results of Heat Transfer Analysis 	  7
Table 2.  Ambient Temperature in Portsmouth Area During Period
          of Coke Oven Door Temperature Measurements (April 24-25,
          1975) as Recorded by Huntington, West Virginia,
          Weather Service	13
Table 3.  Average Door Temperatures During Empty Oven Period and
          Over a Complete 15-Hour Coking Cycle 	 15
                            LIST OF FIGURES
Figure 1.  Sampling Hood Installed on Coke Oven No. 6 with Recorder
           Showing on Top of Battery Above Hood	2
Figure 2.  Thermocouple Locations, No. 6 Coke Oven Door	  5
Figure 3.  Closeup of Thermocouples No. 4 and 8 Showing Leads to
           Recorder, and Section of Purge Air Pipe .	9
Figure 4.  Closeup of Thermocouple No. 2 Showing Detail of Quick
           Disconnect Plug in Thermocouple Lead	9
Figure 5.  No. 6 Coke Oven Showing Eight Thermocouple Locations. .  . 10
Figure 6.  Top Plate of Sampling Hood Installed on No.  6 Coke Oven
           Showing Thermocouple Leads and Purge Air Pipe in Place.  . 10
Figure 7.  Twelve Point Recorder Installed on Top of  Battery Above
           No. 6 Oven	12
Figure 8.  Closeup of Temperature Recorder 	 12
Figure 9.  Temperature Record of Four Thermocouples,  Right Side of
           No. 6 Coke Oven Door, Approximate 15-Hour  Cycle,
           April 24-25, 1975	16
                                  82

-------
                            LIST OF FIGURES (Cont'd)
Figure 10. Temperature Record of Thermocouples No. 5, 7, and 8,
           with Sampling Hood in Place Followinj.; No. 6 Oven
           Push, April 25, 1975	19
Figure 11. Calculated Maximum Door Temperature Versus Purge
           Gas Flow Rate	24
Figure 12. Calculated Maximum Hood Temperature Versus Purge
           Gas Flow Rate	25
Figure 13. Total Heat Flux Dissipated and Division of Heat Flux
           Between Purge and Ambient Air	26
                                    83

-------
                            SUMMARY REPORT
                                  on
                  THERMAL ANALYSIS OF COKE-OVEN DOORS
                                  to
                  U.S. ENVIRONMENTAL PROTECTION AGENCY
                                 from
                               BATTELLE
                         Columbus Laboratories
                                  by
             G. R. Whitacre, S. E. Miller, and J. B. Purdy
                             June 6, 1975


                             INTRODUCTION

          As part of a study of concepts for minimizing emissions from
coke-oven doors (Contract No.  68-02-1439), a system was developed at
Battelle for measuring the emissions escaping from oven doors.  Figure 1
shows the hood used to capture emissions from around the oven door.
In its original form,  the hood had a natural aluminum shiny surface on
both inside and outside,  and the outside surface was covered with a 1-inch
thickness of glass fiber backed on its outside surface with aluminum
foil.  The system was  tested on a Koppers oven at Empire-Detroit Steel
in Portsmouth, Ohio.  The system performed satisfactorily.  However, with
the hood installed on  the oven buckstays, and natural convection over
the oven door cut off, the surface temperature of the door rose about
65 C (150 F)  above a similar spot temperature on a nearby door.  The
comparison door was charged 10 to 15 minutes later than the test door.
          The temperature rise caused by installation of the hood was
undesirable for two reasons:   (1)   uncontrolled temperature rise might
cause damage to an oven door,  and (2)  excessive temperature above normal
could result in abnormal  samples of  emissions collected for analysis
through expansion of leakage  cracks  or through thermal  change  of leakage
products.
                                   84

-------
FIGURE 1. SAMPLING HOOD INSTALLED  ON
          COKE OVEN
                  85

-------
          It was proposed thai: certain control steps be taken  to control
temperature rise, and that normal door temperature levels be established
by a test run over a complete normal coking cycle.  Proposed control
steps were:
          (1)  Remove glass fiber insulation from the hood
          (2)  Increase the amount of purge air released beneath
               the hood
          (3)  Blacken both sides of the hood to increase heat
               radiation
          (4)  Remove hood for a cooling-off period when oven
               door temperatures rise to a predetermined point.
          In order to determine the effectiveness of the proposed modifi-
cations for control of door temperature, EPA authorized Task 16.  This task
provided for measurement of door temperatures throughout a normal col:ing
cycle.   It also authorized a heat-transfer analysis to provide the following
information:
          (1)  Quantification of heat flux, under normal operating
               conditions, identifying the proportion of heat loss due
               to convection and radiation
          (2)  On a theoretical basis, determine what the increase
               in door temperature would be with the testing hood
               installed in the original test condition.  Compare
               these calculations to conditions actually observed.
          (3)  Theoretically determine the temperature effect that
               darkening the inside of the shield and removing the
               insulation will have without increasing the purge-gas
               flow rate.
          (4)  Show the temperature effect, including the above modi-
               fications,  of increasing the purge-gas flow rate
               throughout the range of 30 cfm to 90 cfm.  A graph of
               gas flow rate versus total heat dissipation is expected.
          (5)  On a theoretical basis, show the temperature effect of
               intermittent removal of the hood indicating approximate
               rate of door temperature decrease after removal.
                                    86

-------
          A  meeting  to  1:0.view  1 h J r;  work  war,  held  on June  3  with  Mcsrs.
Richard  Rovang  and Norman  Plakt:  of  I1!PA.   Two suggestions  were  made  by
Mr.  Pinks that  might Further  improve  heat transfer  and reduce  door
temperatures when  the sampling hood is  in place.  Thus,  a sampling  run
might  be made over an entire coking cycle with  door temperatures remaining
close  to those  of  a  normal  coking cycle.   The suggestions were:
          (1)   Install  small fins  (about 1/4 inch high)  in  a vertical
                position on  the inside and possibly  on  the outside of
                the hood sections  to aid  in heat transfer
          (2)   Provide  air  circulation  in back  of the  hood  by  use of
                several  fans or blowers.
          It was agreed that a brief  study of these approaches would be
made prior to any  extensive sampling  program, to  determine  the degree of
improvement  they may provide and  to help in  design  and placement of
the fins.  Also, it  was  agreed that this  brief  investigation should be
made a preliminary part of  any sampling  program.
          Door  temperatures were measured  by eight  thermocouples  through-
out one 15-hour coking cycle.  Figure  2  is a schematic  illustration  of  the
door size and the relative locations of  the thermocouples.
          The No. 7  thermocouple,  267  cm  (105  inches)   from  the bottom
of the door, registered the highest peak and average  temperatures.  The
peak temperature recorded was about  213 C  (416 F) and  the  average
temperature value for No. 7 thermocouple was 206 C  (403 F).
          Following  one complete coking cycle with  recorded  temperatures,
the sampling hood was installed for a  period of 2 hours and  20  minutes.
As shown by Figure 1, the insulation had been removed  from the hood  and
its surfaces were, painted black.  Purge air was  fed under  the hood  at
a rate of 1.7 m /rain  (60 ft /m.i.n) .  Temperature  on No.  7 thermocouple  rosi
from 204 C  (400 F) to 241 C (465 F), an increase rate of 0.26 C/min (0.46
                                     87

-------
             ?f>  -in.
                      ••']
          7/4
           •

         R a
              33  cm

             "13  in'J
                  JL-,  OH
                  »f/ irui
                 _>.  . .
                     vD-D
           #1
                                O  -H
                                oo  m
                                ro  r-i
                                E   c
                                O  -i-l
                                CM
                                   OO
»
                                 E  C
                                 O -H
                                    /
                                 E  C
                                 O  -H


                                CM  OO
                                CM  
-------
F/min) .  The hood wan  then ruuoved .-md  in 1 hour  the  temperature had de-
creased  to  271 C  (430  10, a rate of decrease oC 0.67  C/min  (0.58 F/min).
          From Lcmpera l.vires recorded during the test  run  on  the coke
oven door,  a theoretical heat analysis  was made.   It  consisted of:
heat loss due to  convection and radiation, door temperatures  with  various
hood emissivities and  purge air  flows,  and  the  door  temperatures  with
insulation  on the hood.
          Table 1 summarizes the temperatures and heat  flux  calculated
                                         3                        3
under  conditions  of 0.85, 1.70, and 2.5 m /min  (30, 60, and  90 ft  /min) air
flow in combination with emissivities  (e) of 0.9  and  0.2  on  both  sides of
the hood.   Calculations were also made  for an air flow  of 1.7 rrr/min
       3
(60 ft /min] with emissivities of 0.9 and 0.2 applied to  the  inside and
outside surfaces  of the hood respectively, and  then 0.2 and  0.9 applied
to the inside and outside surfaces, respectively.
                                                    3
          The door temperature calculated with  1.7 m  /min purge air flow
and with both sides of the hood painted black (e  = 0.9) was  248 C  (478 F);
this temperature  as measured during the test run  after  2 hours and 20 minutes
was 241 C (465 F).  At 241 C the hood was removed with  the  temperature
still slightly on the  rise.  Therefore, the calculated  door  temperature
of 248 C (.478 F)   appears to be reasonable.
          Calculations show that the total heat dissipated  by convection
                         3           3
levels off  at about 2.5 m /min (90 ft /min) of  purge  air.  Calculated
door temperature  with  insulation on the outside surface was  399 C  (750 F).
Over the purge air range of 0.85-2.5 m  /min (30-90 ft /min),  calculated
door temperatures vary from 343 C (650  F) to about 306  C  (582 F) with
shiny aluminum surface on both sides of the hood;  by  painting only the
outside surface black, door temperature is lowered only about 1.7  C (3 F).
Painting the inside surface black and leaving the outside shiny drops
the door temperature 54 C (97 F), and painting  both inside  and outside
surfaces black lowcrr;  door temperature  66 C (119  F) .
          Hood temperature is less affected than  door temperature  by
cmiss ivity  change duo  to p.'iinting both  hood surfaces  black.   At a  purge -
                  3           3
air flow of 0.85  m /min (30 ft /min), hood temperature is  141 C (286 F)
                                  89

-------
                  TABLE  i.  SUMMARY OF RESULTS OF HEAT TRANSFER ANALYSIS
Air Flew.
m3/-in
and
ft" /-in sin eout
O.S5 0.9 0.9
30
1.7 0.9 0.9
60
2.5 0.9 0.9
50
O.S5 0.2 0.2
30
1.7 0.2 0.2
60
2.5 0.2 0.2
90
1.7 0.9 0.2
60
1.7 0.2 0.9
60
With Insulation on Hood:
0.85 0.2 0.2
30
^door ,
Degrees ,
C and F
261.0
502.0
248.0
478.0
239.6
463.3
343.1
649.5
314.0
597.0
306.0
582.0
260.0
500.0
201.0
594.0

393.0
740.0
^air ,
Degrees ,
C and F
101.8
215.2
69.1
156.5
54.2
129.5
128.0
263.0
85.4
185.8
64.0
148.0
77.0
170.5
79.0
175.0

172.5
342.5
^hood,
Degrees ,
C and F
127.0
260.5
134.1
237.3
106.2
223.1
141.4
286.5

242.0

222.0
148.1
298.5
89.7
193.5

284.2
543.5
^insulation Heat
Outside
Surface q to
Degrees , purge
C and F air
1078.7
341.9
1389.1
440.3
1556.0
493.2
1394.2
441.9
1770.9
561.3
1902.8
603.1
1574.3
499.0
1632.1
517.3

75.3 1917.3
167.5 607.7
pi,... /w/m and
FlaX I.BU;/ft2hr
q to
ambient
air
1687.3
534.8
1422.0
450.7
1276.5
40 4 . 6
1111.2
352.2
826.6
262.0
722.8
229.1
1191.6
377.7
969.8
307.4

425.3
134.8
Total q
2766.3
876.8
2808.6
£90,2
2S34.4
S9S.4
2505.4
794.1
2598.1
823.5
2624.6
831.9
2769.8
877o9
2603.5
825.2

2345.4
743.4
c = emissivity factor;
Cubic feet x 0.0283 = cubic
  T = temperature,  C and F;       q = heat flux,  w/m2 and Btu/ft2hr.
meters;             Heat flux,  Btu/ft2hr x 3.155 = w/m2 .

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 \v.r:ui.s  ] !'.7  C  ('.'OH I-')  v.-licn  belli  riidc.s  oC Ihc hood .-ire pai.ntcd.  An purge
 air  flow is increased,  hood  temperature under the two cnu'ssivity condi-
                                             3           3
 ti.onr;  becomes  more nearly  equal  and at 2.5 ni /mi n (90 ft /inin) it is equal
 tinder  the  two  purge-air flow conditions.
          The  tests  and theoretical analyses show that removal of hood
 insulation  and increased emissivity from  paintiny both sides of the
 hood black  are effective1, in  lowering  door temperature.  Although normal
 door temperature  is  not maintained  by these steps alone, theoretical
                             3
 analysis shows that  at  1.7 m /rnin purge-air flow door temperature should
 be about 248 C 0478  F).  The actual test  run of over 2 hours made on
 April  25 verifies this  calculated temperature;  a maximum temperature of
 240 C  (464  F)  was recorded with  indications that the temperature was
 starting to stabilize.   A  run of 3  hours' duration under these test condi-
 tions  could undoubtedly be completed,  and the test just completed shows
 that hood removal results  in a  rapid  lowering of door temperature.  The
 increase in door  temperature of  36  to 42  C (65  to 75 F)  that would
 probably result from  the type of test run just  completed, would not, In
 the opinion of Battelle  chemistry analytical authorities, have a harmful
 effect on samples obtained.   Metallurgical experts advise that this
 much temperature  rise in this temperature range will not be harmful to
 the oven door.
          It is possible that further improved  heat dissipation such as
 from fins on the  hood may  enable a  run to be made over a complete cycle
without removing  the hood.
                      DISCUSSION  OF  THE  PROGRAM

                              Test Setup

          Eight thermocouples,  numbered  and  located  as  shown in Figure 2,
were installed on the door of No. 6  coke oven  at  the Koppcrs battery of
Empire-Detroit, Portsmouth, Ohio.  Figures  3,  4,  and 5  show details of
                                    91

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FIGURE 3. CLOSEUP OF THERMOCOUPLES NO.  4 AND 8 SHOWING LEADS TO
          RECORDER, AND SECTION OF PURGE AIR PIPE (UPPER RIGHT CORNER)
    FIGURE 4. CLOSEUP OF THERMOCOUPLE NO. 2 SHOWING DETAIL OF
              QUICK "DISCONNECT PLUG IN THERMOCOUPLE LEAD

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                                                 FIGURE 5. NO. 6 COKE OVEN SHOWING
                                                           EIGHT THERMOCOUPLE LOCATIONS
FIGURE 6. TOP PLATE OF
          SAMPLING HOOD
          INSTALLED ON NO.  6
          COKE OVEN SHOWING
          THERMOCOUPLE LEADS
          AND PURGE AIR PIPE
          IN PLACE
                                     93

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thermocouple  Jnr; tallal'ions.  The  couples  were  20  gage  Chromel-alumel
wires joined  by  a welded beau.  At  the  point on  the  door  where temperature
was to be read,  a small hole about  0.3  cm (1/8 inch) deep was  drilled.
A thermocouple was  Inserted in  the  hole and  the  bead was  peencd with a
center punch  so  as  to  fill the  hole and make the  couple secure.  To
further secure the  couple  a spot  several  inches  from the  couple bead
was cleaned by abrasion and a stainless steel  foil strap  was welded over
the insulated couple wires.  In Figures 3, 4,  and 5, the  cleaned spots
can be seen as bright  strips.   Best detail appears in  Figure 4 which
also shows in good  detail  the disconnect  plug  that enabled thermcouple
lead wires to be quickly pulled up  out of  the way when the door had to
be removed to push  the oven.
          Figure 6  shows thermocouple leads passing  up through the  gas
exit in the sampling-hood  top plate.  Figure 7 is a  general view of the
12 point Honeywell  recorder in  position on top of the  battery.  Figure  8
is a closeup  of  the recorder that shows the general  trace of temperatures
being recorded.  Since only eight temperature  points were being measured
in the door,  the re;;;.:rJning four (Nos. 9,  10, 11,  and 12)  were  shorted
in the back of the  recorder; thus,  they recorded  air temperature in the
back of the recorder.
          A record  of  ambient temperature  in the  area  was obtained  from
the Huntington, West Virginia,weather service, located 30 miles east
and 23 miles  south  of  the  Portsmouth, Ohio,coke-oven battery.   Table 2
summarizes these temperatures from  1:00 p.m., April  24, through 1:00 p.m.
on April 25.
          The thermocouple installation was completed  on  No. 6 oven door
the morning of April 24.   The push  on No.  6 oven was completed at 2:07  p.m.
and the door was back  in place  at 2:U8 p.m.  Thermocouple leads were
reconnected and  recording was started at  2:15  p.m., April 24.   The  oven
was charged at 2:28 p.m. and tin.1; charge  was pushed  at 5:35 a.m.  on the
morning of April 25.
          Although  door temperature measurements with  the hood in place
were not a previously  plannr-.d part  of this pros'.r.'iw,  time  and ccjuipiiicnt
                                     94

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FIGURE 7. TWELVE POINT RECORDER INSTALLED OK
          TOP OF BATTERY ABOVE NO.  6 OVEK
  FIGURE 8.  CLOSEUP OF  TEMPERATURE  RECORDER

-------
    TABLE 2.  ANCIENT TEMPERATURE IN PORTSMOUTH AREA DURING
             PERIOD OF COKE-OVEN DOOR TEMPERATURE MEASUREMENTS
             (APRIL 24-25,  1975) AS RECORDED BY IIUNTINGTON,
             WEST VIRGINIA,  WEATHER SERVICE(a)
Time
Thursday, April 24 1:00 p.m.
2:00 p.m.
3:00 p.m.
4:00 p.m.
5:00 p.m.
6:00 p.m.
7:00 p.m.
8:00 p.m.
9;00 p.m.
10:00 p.m.
11:00 p.m.
12:00 a.m.
Friday, April 25 1:00 a.m.
2:00 a.m.
3:00 a.m.
4:00 a.m.
5:00 a.m.
6:00 a.m.
7:00 a.m.
8:00 a.m.
9:00 a.m.
10:00 a.m.
11:00 a.m.
12:00 p.m.
1:00 p.m.
Temperature,
C
17.2
17.2
17.2
17.2
17.8
17.2
17.2
16.7
16.7
16.7
15.6
14.4
13.3
13.3
12.8
12.8
13.3
13.3
13.9
14.4
15.0
16.1
16.1
15.6
17.2
Temperature,
F
63
63
63
63
64
63
63
62
62
62
60
58
56
56
55
55
56
56
57
58
59
61
61
60
63
(a)   Located  30 miles  east and 23 miles south of coke oven battery.
                               96

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 were available  so several  hours  of  temperature measurements were made
 under sampling-hood  conditions.
           No high-volume sampler and  filters were  used  in  these  test
 runs.  Since only door  temperatures were  of interest, purge air  and
 door emissions  merely exhausted  through the hood  top  plate  to  the atmo-
 sphere.

                         Results of Test  Runs

           Table 3 presents  a  summary  of average door-temperature values,
 without  the  sampling hood,  during a 15-minute period  before charging and
 after the  door  had been put on.   It also  gives  the average  temperature
 value for  each  of the eight thermocouples during  the  complete  coking cycle
 for  the  April 24-April  25,  15-hour  period.
           Figure  9,  plotted over the  span of three pages, shows the curves
 for  temperature  plots of couples  No.  5, 6, 7, and  8.  Only  temperatures
 from the four couples on the  right side of the door were plotted because
the  right  side  of  the door  was consistently the hottest side.  Figure 9
 shows  that the hottest  spot was  at couple No. 7.   It started out at about
 199  C  (390 F),  gradually increased to a maximum of about 213 C (416 F)
 after  5 hours,  leveled  off  to 209 C (409  F) for about 1.5 hours and then
very gradually  decreased to around 199 C  (390 F) at the end of the coking
cycle.  Couple  No. 6 leveled  off and started to decline in temperature
more quickly than  No. 7.  No. 5  and No. 8 declined near the start of the
cycle  and  leveled  off after about 3.5 hours.
          Figure 10  is  a plot of  temperatures from thermocouples 5, 7,
and  8 with the sampling hood  installed and immediately after the hood is
removed.   It shows temperatures with the  hood in position for 2 hours
and  20 minutes,  and the temperature decrease over  a period of an hour
after  the hood was removed.  The plot of  No. 7 couple in Figure 10
indicates  that temperature falls more rapidly when  the hood is removed
than it rises when the hood is installed.   Theoretical analysis discussed
later shows a good correlation between the 241 C (465 F) maximum temperature
recorded with the hood in place and the calculated value of 248 C (478 F)
at a purge air rate of 1.7 m /min (60 ft  /min).

                                   97

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            TABLE 3.  AVERAGE DOOR TEMPERATURES WITHOUT HOOD
                     DURING EMPTY OVEN PERIOD AND  OVER A
                     COMPLETE 15-HOUR  COKING CYCLE
Period
Covered
Average Temperature, C and F
Thermocouple Number
12345678
4/24/75, 2:15
 2:30 p.m.:
 Empty Oven
181
357
181
357
189
373
182
360
182
360
191
375
201
394
171
340
4/24, 2:28 p.m.-
 4/25, 5:35 a.m.:
 Complete 15-Hour
 Coking Cycle
170
339
172
342
195
383
174
345
171
340
186
368
206
403
162
324
                                   98

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                                                       ^
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April 24, 1975 ; . ' I » 1 I I
i, . , ; , '...i — ; 	 : — : — ! — i — i 	 : _j — :,. , ,•.
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                                                             5:00 p.m.
6:00 p.m.
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	j


 8:00  p.m.
                                  FIGURE 9. TEMPERATURE RECORD OF FOUR THERMOCOUPLES,

                                            WITHOUT HOOD,  RIGHT SIDE OF NO.  6 COKE-OVEN

                                            DOOR, APPROXIMATE 15-HOUR CYCLE, APRIL  24-25, 1975

-------
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                                                 FIGURE 9.  (Continued)

-------
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                             Th co ret.ic.-11 An •'ij_)^ji_s^

           A  parametric  analysis was  conducted  to determine  the  effectiveness
 of  potential modifications  to reduce the  temperature  of  the  coke-oven door
 with  the  hood  in  place.  However,  first it was  necessary  to  determine the
 thermal condition of  the door under  normal operating  conditions.  Using  the
 temperature  data  obtained in the  field test, the proportion  of  heat  loss
 due to natural convection and radiation and  the thermal  resistance of the
 door  were  determined.   Quasi-steady-state, one-dimensional,  thermal  analyses
 were  then  performed with the hood  in  place to determine  the  predicted
 increase  in  door  temperature with  the original  testing hood.  Finally, the
 effect on  temperature and heat flux  was determined parametrically over a
 range of  purge-gas flows and emissivities with  the insulation removed.  A
 theoretical  analysis of the  transient behavior  of the door  following hood
 removal was  not conducted due to potential complexity.  However, the transient
 behavior was determined by an additional  test conducted  following the normal
 operation  cycle and is described elsewhere in this report.

 Calculation  Procedure

           In order to keep the analysis essentially one-dimensional, it was
necessary  to chose a location on the door at which the calculations  would be
performed.   (An alternate procedure would be to  use averages over the entire
door,  but  this was rejected  as combining and masking too many different
effects such as purge gas temperature rise and  end effects.)  The location used
was thermocouple  location No. 7 which is 2.67 meters  (8-3/4  feet) from the
 bottom of  the door.  This was chosen because it was farthest from end effects
 and away  from latches which  act as cooling fins  and further  complicate the
 analysis.   Thus,   it was the maximum  temperature  recorded.  In addition,  it
had the best defined flow because the upward flow at that location had been
unobstructed for approximately 1.2 meters  (4 feet)  below.
            In order to be quasi-stcady-state,the average of the temperature
at location No. 7 over the entire cycle,  206 C  (403 F),  was  used as  the
                                      103

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basis for the normal operation calculations.  From this temperature and
an average ambient temperature, 15.6 C (60 F) , the normal operation heat
fluxes at this location were calculated using accepted heat-transfer correla-
                 f ~\
tion from McAdams^ ' .  The natural convection heat flux from a vertical
                  2            -2-1
plate was 1379 w/m  (437 Btu ft   hr~ ) and was in the turbulent regime so
that the characteristic length cancelled out of the correlation.  The
radiation using a door emissivity of 0.6 and a view factor of 1.0 was
1562 w/m2 (495 Btu ft"2 hr"1) .  This gave a total heat flux of 2941 w/m
(932 Btu ft"2 hr"1).
            To calculate the effect of the hood installation and other
changes, it was assumed that the average inside wall surface temperature
would not be affected by the changes since it is essentially fixed by the
process.  To determine this steady-state inside-surface temperature, the one-
dimensional  thermal resistance of the door was calculated from available
thermal conductivity data.  The door consisted of 34.3 cm (13-1/2 in.)  of
first quality silica firebrick with a thermal conductivity of 190 w/m
(1.10 Btu ft"  hr   F  ) plus 5.1 cm (2 in.) of H.B. #28 castable refrac-
tory with a conductivity of 0.38 w/m K (0.22 Btu ft"  hr"  F" ) for a total
                             2-1             2_    -1
thermal resistance of 0.3146 m Kw   (1.785 hr ft F Btu  ).  This gives a
calculated inside-surface temperature of 1131 C (2067 F) which was held
fixed for all subsequent calculations.  This wall surface temperature is
                                                                     (c)
within the range of 1010 to 1149 C (1850 to 2100 F) given by Preston
for typical coking operation.
            For all calculation with the hood in place, steady-state heat
balances were performed on the hood and at the door surface.  The heat
transferred through the door was convected to the purge air and radiated
to the hood.  The heat received by the hood was radiated and convected to
the outside ambient air as well as some additional convection to the purge
air.  Then insulation was added on the hood, inside and outside hood
(a)  McAdams, W. H., Heat Transmission, 3rd Edition, McGraw-Hill, New York,
     1954.
(b)  w = watts; m = meter; K = degrees Kelvin.
(c)  Preston, E., "Carbonization of Coal and Gas Making", Mechanical Engineers'
     Handbook. Edited by L. S. Marks, 5th Edition, McGraw-Hill, 1951, p 817.
                                     104

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 temperatures  were  calculated  and  the  temperature difference determined  by
 the  heat  flux to  the  ambient  and  the  thermal  resistance  of the  insulation.
 The  purge air temperature  rise was  also  calculated using total  heat  convected
 to the  purge-air  from the  inlet to  location No. 7.  The  temperature  differ-
 ences at  location  7 were used in  this calculation.  Although  the door wall,
 hood, and air temperatures  all decrease  in  the direction of the inlet at
 the  bottom,  the  temperature differences  should remain  nearly  constant,  so
 use  of  location  7  temperature differences is  a reasonable approximation.
 Iterations were  performed  on  the  various  temperatures  until all the  heat
 balances  and  other conditions were  satisfied.
           The convection  to the purge air flow was a combination of  natural
 and  forced convection.  The Reynolds  number for the purge air flow in  the
 unobstructed  passage  was  1800 to  6100 which is in  the  transition regime
 from laminar  to  turbulent  flow.   Therefore, the transition correlation  of
                      (a)
 Kroll given  in McAdams  was used.   However, the natural  convection heat
 transfer  coefficient  for vertical surfaces was always  much larger  than  the
 forced  convection  coefficient.  For combined  natural and forced convection
 in laminar flow, Martinelli and Boelter   derived and  confirmed a  relation-
 ship of the  form
                       h   , .   ,  =   3/ h3      . +  h]
                       combined         natural —   forced

This  relationship was  used  to  combine the  convection  in  the  present  calculations
although  the  flow was  in  the transition regime.   Because  the natural convection
h was larger  than the  forced h,  the  effect  on h directly  of  increasing  purge
air flow  was  quite small.   However,  the increased  air  flow decreased the  air
temperature rise which did  increase  the temperature difference  and the  natural
convection h  so that there  was an effect of  purge-gas  flow rate.
(a)  McAdams,  loc.  cit.,  p.  240.
(b)  Mart.inclli,  R.  C.  and  Boelter,  L.M.K.,  University  of  California  Publication
    in  Engineering,  Vol. 5,  No.  2,  Berkeley,  1942,  pp.  23-58.
                                     105

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Results

            Table 1 shows a summary of results of the various cases calculated.
The emissivity of 0.2 is representative of the aluminum hood or aluminum foil
used with the original hood..  The emissivity of 0.9 is representative of
black paint  on the aluminum hood.  All the results apply to thermocouple loca-
tion No. 7 and, therefore, are approximately the maximum to be expected.  The
total heat flux as well as the division between the heat transferred to the
purge air and the ambient are also given.  All the various terms in the
heat balances were calculated and are available in the detailed calculation
sheets.
            Figure 11 shows the calculated maximum door temperature versus
purge-gas flow rate for the various cases.  It does not appear possible to
decrease the door temperature to the normal operating temperature of 260 C
(403 F) by increasing the purge-gas flow rate or the emissivity of the
surfaces.  Painting the outside only has little effect on decreasing the
door temperature.  On the other hand, painting the inside only  has a
significant effect.  The predicted value of 248 C (478 F) for both sides
painted and a purge-gas flow rate of 1.7 m /min (60 cfm) is close to the
value of 241 C (465 F) measured in the test of the No. 7 thermocouple
which had not yet quite reached its quasi-steady-state value after about
2 hours with the hood on.
            Figure 12 shows the calculated maximum hood temperature versus
purge-gas flow rate for the same cases.  With equal emissivity the maximum
hood temperature is not very dependent on purge-gas flow rate or the
emissivity itself.  However, there are significant changes with unequal
emissivities.
            Figure 13 shows the total heat flux dissipated and the division
between heat transfer to the purge air and to the ambient for the cases with equal
emissivities of 0.9 only.  The total heat flux has decreased very little from  the
normal operation value of 2953 w/m^ (936 Btu ft'^hr"^-) and is nearly indepen-
dent of purge gas flow rate.
                                      106

-------
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     288
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     2209
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                      Total  Heat Diasipcitc-d
                                                          e Inside = 0.9
                                                          e Outside = 0.9
                     1.132      1.415        1.698       1.981        2.264
                       40         50           60          70           80

                            Purge Gas Flow Rate, m3/min  and  ft3/min
2.547
  90
             FIGURE 13. TOTAL HEAT FLUX DISSIPATED  AND  DIVISION OF
                        HEAT FLUX BETWEEN PURGE AND AMBIENT AIR
                                          109

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          APPENDIX B
HEAT TRANSFER ANALYSIS FOR HOOD
           110

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        SUMMARY REPORT
              on
  EFFECT OF FINS ON COKE-OVEN
      HOOD HEAT TRANSFER
              to
ENVIRONMENTAL PROTECTION AGENCY
        October 9, 1975
              by
        G. R. Whitacre
           BATTELLE
     Columbus Laboratories
        505 King Avenue
     Columbus,  Ohio  43201
            111

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                               SUMMARY REPORT
                                     on
                         EFFECT OF FINS ON COKE-OVEN
                             HOOD HEAT TRANSFER
                                     to
                      ENVIRONMENTAL PROTECTION AGENCY
                                    from

                                  BATTELLE
                            Columbus Laboratories
                                     by
                               G. R. Whitacre

                               October 9, 1975
                                INTRODUCTION

          To permit sampling of emissions from coke-oven doors, a hood must
be used to contain the emissions.  The addition of a hood in the vicinity of
the coke-oven door serves to reduce heat loss from the door and, thus, in-
creases the door temperature.  It has been proposed that fins might be added
to the hood to increase heat loss from the hood and thereby, reduce the
temperature of the hood and of the door.  A thermal analysis was conducted to
determine the effectiveness of hood fins and whether they should be placed
on the inside or outside of the hood.  In addition, optimum fin spacing and
heights were determined.

                              CALCULATION PROCEDURE
          The analytical thermal analysis techniques described in a
previous report"' were used to predict steady state maximum door and
••'"Whitacre, G.R., Miller,  S.E.,  and Purdy,  J.B.,  "Thermal  Analysis  of
 Coke Oven Doors", Summary Report to EPA,  June 12,  1975.
                                   112

-------
 hood temperatures.   Only the  modification  and  additions  necessary  to  in-
 clude the effect of the  fins  and  optimize  their  spacing  and height are
 discussed here.   There are  two  limiting analysis procedures available  to
 handle  natural  convection  fin heat  transfer.   One limit  applies  to small
 fins which are  spaced  far  enough  apart  that  the  boundary layers  which  form
 around  one fin  do not  interact  with  the boundary layers  from  the adjoining
 fins.   In addition,  it is assumed  (for  vertical  fins)  that the heat transfer
 coefficient on  the  fin surfaces including  the  corners  is the  same as  the
 coefficient on  the  plane base surface.   This heat transfer coefficient  is
 determined from  a Grashof number correlation based on  vertical hood height.
 The  only  effect  of  the fins is  to increase the surface area for  heat  transfer.
 However,  the  fin surface area is multiplied  by the fin effectiveness  due
 to heat conduction  in  the  fin before this  product is added to the
 remaining base area  to obtain the effective  total area for heat  transfer.
 For  aluminum  fins with the same gage  as  the hood  (16)  the fin effectiveness
                                               *
 was  over  99 percent  for all the cases analyzed.   Therefore, fin thickness
 could be  changed  with practically no  effect on fin effectiveness.
           For this  limiting case of  small  fins with no interaction, the
 natural convection  is in the  turbulent  regime on  both  sides of the hood.
Although  the purge  flow on the  inside of the hood enclosure is provided at
               3           3
 a rate of  1.7 m /min (60 ft /min), natural convection  is still the dominant
mode of heat transfer and the procedure used in combining the forced and
 natural convection  is described in the previous report.  Essentially the
heat transfer coefficient is  determined by the turbulent natural convection
but  the purge air temperature rise affects the heat transfer by  reducing
 the available temperature difference.  The analysis procedure used to
determine  the fin effectiveness  for this limiting case is identical to
                                      **
 that described in the previous report.    The surface area on both the in-
side and outside  of the hood was increased in steps representing the
*
  Fin effectiveness is defined as the ratio of the amount of heat dissipated
  by the fin. surface to that which would be dissipated if the fin surface
  were held at the temperature of the fin base.
**
  Ibid.
                                    113

-------
 addition  of  fins,  and new wall, hood,  and  air  temperatures were  determined
 by performing  iterative calculations until the  energy  (heat balance)
 equations were  satisfied.
          The  other  limiting  case  for  vertical  natural convection  fins  is
 to consider  the  flow between  the fins  as flow  in an enclosure with  con-
 stant wall temperature.   (For aluminum fins  the high fin effectiveness
 is equivalent  to a constant wall temperature.)  This case has been  well
 analyzed  both  experimentally  and analytically by Elenbaas for both  parallel
      *                                                        **
 plates  and  for  enclosures of various  shapes and aspect ratios.     In
 addition  Elenbaas  derives an  expression to optimize the fin spacing for
 maximum heat transfer as a function of aspect ratio of the enclosure.
 This optimum results from a decrease in the heat transfer coefficient as
 the fin spacing  decreases in  competition with an increase in the surface
 area with decreased  spacing.  Treating the space between the fins as an
 enclosure, the optimum fin spacing is  given by
                                                , .
                             Grm Pr = 0.72  (YRe) /J
where
          r    =   hydraulic radius with optimum spacing

           1   =   vertical distance
                                            3
         Gr    =   Grashof number based on r
           ro                                m
          Pr   =   Prandtl nun.i. :r of fluid.
The flow resistance parameter Y Re is a function of the aspect ratio and
varies  from 24 for an infinite parallel plate to 14.225 for a rectangular
enclosure with an aspect ratio of 1.0.   The complete variation with aspect
ratio is given in the second Elenbaas paper.
          In calculating the effect of fins in the enclosure limit,
various aspect ratios were selected and the opt 'mum spacing calculated by
*  Elenbaas, W., "Heat Dissipation of Parallel Plates by Free Convection",
   Physica, Vol. 9, No. 1, January, 1942,  pp 1-28.
** Elenbaas, W., "The Dissipation of Heat  by Free Convection.  The Inner
   Surface of Vertical Tubes of Different  Shapes of Cross-Section",  Physica
   Vol. 9, No. 9, September, 1942, pp 865-873.
                                     114

-------
 the  Elenbaas  formula.   In  order  to  simulate a  full enclosure  for  this
 limiting  case,  the  aspect  ratio  was  assumed to be equal  to  the  ratio of
 twice  the  fin height  to the  distance between the fins.   Physically, this
 assumption  is equivalent to  the  actual  fins with no  leakage flow  in or out
 past the  plane  of the  fin  tips.  Also,  the hydraulic  radius as  used by
 Elenbaas  is twice the  cross-sectional area divided by the wetted  perimeter.
 This hydraulic  radius  is twice the value normally used in classical treat-
 ments  of  flow in enclosures.
          After the optimum  fin  spacing was calculated for  the  various
 aspect  ratios the heat-transfer  coefficient was determined  from the Elenbaas
 correlation at  the optimum point.  The correlation is

                               hr                 1 ,
                         Nu  = -r21-  = 0-385 (Y Re) '
                           m     k
where
          Nu    =   is the Nusselt number at the optimum spacing
            h   =   is the heat transfer coefficient and
            k   =   is the thermal conductivity of the fluid.
The heat transfer rate obtained in this manner is based on the temperature
difference between the fin and the inlet air temperature and the effect
of the air temperature rise in the flow direction is included in the
derivation and verification of the correlation.  Because of the small
spacing between fins and the interaction between boundary layers the flow
remains in the laminar flow regime so the correlation and all the results
calculated for the enclosure limit are for laminar flow.
          Using the heat-transfer coefficients and optimum spacings cal-
culated for the various aspect ratios, the heat balance iterations previously
formulated were repeated with the various fin arrangements on both sides
of the hood.  For the fins on the outside, the procedure was essentially
the same as described, but several changes were necessary for the fins placed
on the inside.  Because it was assumed that there was no flow through the
plane of the fin tips the inside flow was divided into two parts.  In order
                                    115

-------
 to  calculate  the  flow  between  the  fins  the  theoretical  solution  of  Bodoia
 and Osterle   was  used  since  it  included  a prediction of the amount  of  flow
 and also  showed good agreement  with  the  experimental data of Elenbaas.
 The heat  transfer by convection from the door  surface was determined using
 only the  difference between  the total purge air  flow and flow between  the
 fin since only this flow was available  to cool the door directly.
          The fins also affect  the radiation heat transfer by increasing
 the effective emissivity of  the  surface  through  the cavity effect.  This
 increase  in emissivity was included  using the data from Sparrow  and Gregg.


                                  RESULTS

          Table 1 shows a summary of results for the various fin configura-
 tions considered.  All of these  results  were obtained for an assumed purge
                  3           3
 air flow  of 1.7 m /min (60 ft /min) and  a hood emissivity of 0.9 (painted
 black) on both sides.  The first line in the table repeats the results
 obtained previously (June 12, 1975 Summary Report) for  the  case without
 fins.  Where  an aspect ratio is  given, the calculation procedure was based
 on  the enclosure  technique and  the fin spacing is the optimized  spacing
 (second limiting case discussed).  Where no aspect ratio appears, no
 interaction was assumed and  the area ratio  was used  to  increase  the appropriate
heat transfer surface (first limiting case discussed).   The  total heat flux
as well as the division between  the heat transferred to the  purge air and
 the ambient environment are also given.   All the  various terms in the  heat
balances were calculated and balanced by iteration and  are  available in
detailed calculation sheets.
          Figure  1 shows the calculated  maximum door temperatures for
various fin configurations.   Somewhat surprisingly,  the fins on the inside
   Bodoia, J. R.,  and Osterle, J. F., "The Development of Free Convection
   Between Heated  Vertical Plates", Journal of Heat Transfer,  Trans.  ASME,
   Series C, Vol.  84, No. 1, February, 1962, pp 40-44.
.,„,, Sparrow, E. M., and Gregs, J. L. ,  "Radiant Emission from a  Parallel-
   Walled Groove", Journal of Heat Transfer, Trans ASME, Series C, Vol. 84,
   No. 1, February, 1962, pp 40-44.
                                     116

-------
TABLE 1.  SUMMARY OF RESULTS OF HEAT TRANSFER ANALYSIS
Total Area Fins
B.ise Area Location
1 . 0 None

1.5 Inside

2.0 Inside

3.0 Inside

2.40 Inside

2.86 Inside

4.68 Inside

1.5 Outside

2.0 Outside

3.0 Outside

1.95 Outside

2.86 Outside

4.68 Outside

Spacing
cm
in
-

2.54
1.0
2.54
1.0
2.54
1.0
2.36
0.93
2.18
0.86
1.93
0.76
2.54
1.0
2.54
1.0
2.54
1.0
?..72
1.07
2.16
0.85
1.91
0.75
Height
cm
in
-

0.64
0.25
1.27
0.5
2.54
1.0
1.65
0.65
2.03
0.80
3.56
1.40
0.64
0.25
1.27
0.5
2.54
1.0
1.30
0.51
2.01
0.79
3.51
1.38
Enclosure Door
Aspect C
Ratio F
247.8
478.0
246.9
476.4
246.1
475.0
245.3
473.6
1.5 244.0
471.2
2.0 244.3
471.8
4.0 248.6
479.5
244.3
471.7
241.7
467.0
238.1
460.5
1.0 251.7
485.0
2.0 248.3
479.0
4.0 244.2
471.5
Door
C
F
114.1
237.3
111.3
232.3
109.6
229.2
106.9
224.4
105.0
221.0
102.6
216.6
96.7
206.0
102.9
217.3
94.1
201.4
81.7
179.0
124.2
255.5
208.5
240.5
102.8
217.0
f w/m
lBtu/ft Hr
q to
PUTRC Air
1389.1
440.3
1429.5
433.1
1464.6
464.2
1520.1
481.8
1564.2
495.8
1607.8
509.6
1701.2
539.2
1331.4
422.0
1290.1
408.9
1234.9
391.4
1430.8
453.5
1395.8
442.4
1330.8
121.8
q to
Ambient
1122.0
450.7
1381.6
437.9
1347.5
427.1
1295.8
410.7
1257.3
398.5
1211.5
384.0
1103.0
349.6
1486.6
471.2
1537.4
487.3
1607.5
509.5
1365.2
432.7
1407.8
446.2
1487.6
471.5
Total
q
2811.1
891.0
2811.1
891.0
2812.1
891.3
2815.9
892.5
2821.5
894.3
2819.3
893.6
2804.2
888.8
2818.0
892.3
2827.5
896.2
2842.4
900.9
2796.0
886.2
2803.6
888.6
2818.4
893.3

-------
00
               460
                                    2.0                  3.0                 4.0
                                      AT/AB, Ratio of Total  Area to Base Area
               FIGURE I.  CALCULATED MAXIMUM DOOR TEMPERATURE FOR VARIOUS FIN CONFIGURATIONS

-------
 had  very little  effect  on  the maximum door  temperature.  In fact, practically
 all  of the  slight  decrease  shown  for fins on  the inside with turbulent
 natural convection,  i.e.,  the no  interaction  limit, was a result of the in-
 crease in effective  emissivity  caused by the  cavity effect.  As the ratio
 of the areas  increases,  the actual door temperature should switch from the
 no interaction limit curve  to the laminar flow enclosure curve.  The poor
 performance of fins placed  on the inside of the hood can be explained by
 a combination of factors.   First, the heat  transfer from the door to the
 hood  is  radiation  dominated and convection  is only secondary.  Second, the
 inside  fins do increase  the heat transfer to  the purge air and decrease
 the hood temperature as  shown in Table 1.  However, because of the interactions
 between  the hood,  wall,  and purge air heat balances there is a detrimental
 effect  of the lower hood temperature which balances the heat transfer gain
 and can  even result in an increase in door  temperature.  This gives a
 significantly lower heat transfer rate to the ambient both by radiation
 and natural convection from the outside of  the lower temperature
hood.  In addition, the  increased flow and heat transferred in the en-
 closure between fins reduces the available purge air flow and resulting
natural convection directly from the door to the purge air.   Thus, it
appears that fins placed on the inside of the hood are not worth the cost
and effort and may even be detrimental.
          The results for fins placed on the outside of the  hood are quite
different, however.  For the no interaction assumption with  turbulent
natural convection, there is a beneficial effect of decreasing door
temperature with increasing fin area.  There are no major counterbalancing
effects although the heat flux to the purge air does decrease due to the
lower wall and hood temperatures.   This effect of outside fins with  tur-
bulent natural convection does not come close to reducing the door tempera-
ture  to its normal operating temperature of 206 C (403 F)  however.
          When the limiting analysis of a laminar flow enclosure is  applied
to the outside fin case there  is a significant shift in results with an
increase in wall  temperature (compared  with  the no  fin case,  A /A   = 1)
for area ratios less than about 3.   This is  caused  by  a much  lower heat-
transfer coefficient inside the  enclosure with laminar natural  convection
                                   119

-------
 than  exists  on  a  vertical  surface with  turbulent  natural  convection.   This
 lower coefficient is not offset  by  the  increased  surface  area until an
 area  ratio of 3 is  reached.  This decrease  in heat-transfer coefficient
 would be  a real effect as  the.  interaction of the  flow between fins in-
 creases.  The actual wall  temperature curve probably leaves the  turbulent
 curve somewhere between an area  ratio of 2  to 2-1/2 and should blend into
 the laminar  flow  enclosure curve somewhere between an area ratio of 3  to
 4 as  shown by the shaded area  in Figure 1.  This  transition is only an
 estimate  so  it appears that short fins with an area ratio no greater than
 2.0 to minimize flow interaction and maintain turbulent flow are most
desirable.   The optimum spacing  for an area ratio of 2 is approximately
 2.54  cm (1.0 in)  resulting in a  fin height of 1.27 cm (0.5 in).
                                  *
          A  recent paper by Pnueli  indicates that an improvement in heat
 transfer  can be achieved by a moderate inclination from vertical for natural
 convection fins.  The initial decrease in length  for a number of fins
 terminating  in the vertical edge increases the heat-transfer coefficient
enough to more than offset the cosine law decrease in Grashof number.   How-
                                                                        -1/4
ever,  this effect is based on a heat-transfer coefficient varying with 1
which is  true for laminar natural convection.   For turbulent natural con-
vection we are trying to insure in the present case the coefficient is
independent of L and thus there is no gain (only  the cosine law loss)
by inclining the  fins.
                                CONCLUSIONS

          The conclusions from the heat transfer analysis on the effect
of fins on coke oven door heat transfer are as follows.
          Vertical fins placed on the inside of the sampling hood are
not effective in reducing door temperature.
          Short vertical fins placed on the outside of the sampling hood
can reduce the door temperature by a maximum of approximately 6 C out of
 •
 Pnueli, David, "Optimization of Inclined Convcctive Fins", Journal of Hont
 Transfer, Trans ASME, Series C, Vol. 96, No. 4, November, 1974, pp 545-547,
                                     120

-------
a total temperature rise of 42 C from the normal operating condition as
indicated in the June 12, 1975, Summary Report.
          Deep vertical fins on the outside can actually cause an increase
in the door temperature because of the trapping of flow between fins and
the resulting transition to laminar flow.
          If fins are used on the outside of the hood they should be
approximately 1.27 cm (0.5 in) high on 2.54 cm (1.0 in) spacing and can be
the same gage as the hood.
          For this case, inclination of the fins from vertical provides
no increase in heat transfer.
                                     121

-------
                   APPENDIX C
        FIELD DATA AND CALIBRATION SHEETS

(Copies of field  data and  calibration sheets may be
 obtained from R.C.  McCrillis MD-62,  US  Environmental
 Protection Agency,  Research Triangle Park,  N.C.   27711)
                        122

-------
                         APPENDIX D
RECONSTRUCTED GAS CHROMATOGRAMS.  ELECTRON IMPACT IONIZATION
    MASS SPECTRA. AND METHANE IONIZATION MASS SPECTRA  OF
               EMISSIONS FROM COKE OVEN DOORS
                          123

-------
1 «"•"'
d Q
3   :
  Q T
  fi
  S
  »-*'
  B

  ff
         10   20   3(1   10   SO   GO   70  80   30   ICCl
         I     i     I  __(_	I	^t	__?._   I     I     I
                       -- Tetra hydronaphthalene
                                                Methyl naphthalenes
                 --  Biphenyl/acenaphthrene
               --  Biphenyl/acenaphthrene
                     Fluorene/methyl acenaphthrene/methyl biphenyl
                  --  Anthracene
            Methyl  anthracenes
Fluoranthene

Pyrene
                 FIGURE D-l.   RECONSTRUCTED GAS CHROMATOGRAM; GC-MS ANALYSIS OF
                              COKE OVEN DOOR EMISSIONS, SAMPLE A5-2
                                     124

-------
        SPECTRUM   3 -   2
            OVEN R5-2
£P
»c^^
UJO

-------
     SPECTRUM   8 -   7
8
«r«

8.
          OVEN flS-2
   10   S3   60   70  80   90   100  110  120  130  140  150  160  170  1«J
        M/E
                            126

-------
       SPECTRUM  19-22
 8-
 8-
|Pu
18.

!8-
 8.
       COKE OVEN RS-2
in.|m.(l).MIM,|i>ll|lnl|inl(l)).|MMl.|l|)ln.|
10   SO   60   70   80   90
     M/E
                                   .|M,....,...|	I
                                  103  110  120  133  110  193  163  170  183  19C
                               127

-------
       SPECTRUM
             -  30
bRu
I*.
  8.
  8.
       COKEWEH RS-2
             tfr
                               *
40  S3  60   70   80  90
    M/E
                              100  110 120  130  1
-------
      SPECTRUM 35-34
          OVEN RS-2
  a.
  8.
^p
fr f^» —
UJO
EG? -
bR.
**_
  8_
    10  SO  60  70  80  90  100 110 120 130  HO  150  160  170  180
        h/E
                           129

-------
       SPECTHUM  16 - 18
  8
  Rj
  8
 jP
 IS
            OVEN PE-2
bR
I*
 Is
 •
 8
 o
                                                         Ttf
       •'""I
   "'I " '• "I' '•
93   63    70
M/E
                        80  90   103  110  120  130  110   1S0  160  170  180  19C
                               130

-------
        SPECTRUM  SB -  SB
        COKE OVEN flS-2
^C CD
BC ^^



UJO

ft*® -



bR_
                                                                         J—Ih
       •'""I
          S3   60  70   80   90

          M/E
100  110  120  130  110  ISO  160  170  180  13?
                                 131

-------
      SPECTRUM  64 -  62
  8
      COKE OVEN flS-2
£P
HL^^ —•
UJO
QW _
bR.
fcj
 »8.
  8.
  o
    *3  SB  60  70   80   90   100  110  120  130  1*3  ISO  160  170 180 19C
        M/E
                           132

-------
      SPEOHLM 83-81
8
a.
      CONE OVEN
   •W   S3   63   7CT  83   93   133  113  123  133  140  1SB  168  173  183   13C
        M/E
                              133

-------
       SPECTRUM  71 -



       COKE OVEN RS-2
VJFJ
CL ^^ ^--

ujo
8  -


bR.


fc.


 8.
    10   SO   60  70  80  30   100  110 120  130  110  ISO  160 170  180  13G

         M/E
                             ' 134

-------
      SPECTRUM 123 - 127
8
           OVEN FS-2
              tfr
**T
   10   50   60   70   80  90   100  110  120  130  110  153  160  170  163  13C
        M/E
                                135

-------
Mi;'
il
7J '•
"r "
f. ;:-
  '
        c:
rMethyl pyrenes
 Methyl fluoranthenes
i Dimethyl pyrenes
' Dimethyl fluoranthenes
 Benz(c)phenanthrene
   	=:= -- Chrysene
               •) Methyl chrysenes
               J Methyl benzanthracenes
                     =-.-=— -- Benzofluoranthenes
                ~^r^=^ -- Benzo pyrenes
              Methyl benzpyrenes
              Methyl benzfluoranthenes
               -- Indenopyrene
               -- Benroperylene
             " Dibenzoanthracene
              -- Coronene
                    FIGURE D-2.   RECONSTRUCTED GAS CHROMATOGRAM;
                                 GC-MS ANALYSIS OF COKE OVEN DOOR
                                 EMISSIONS,  SAMPLE A5F-2
                      136

-------
      SPECTRUM 211 - 205
g
8.
      CDKE OVEN El FS-F2
4r"4
f
                                            \\
JH,
    TTTJ.TTTJTTTMrTr.|,»'|"" iTM™Mp'1|nT1|rTTTrT*Y"N""|"'M"
-------
       SPECTRH 223 - 216
  8
  8.
       CCKE OVEX El FE-F2
feS.
  8J
  o
     70   80  90   100  110  120  130  ItO  150  160  170  180  190  200 210
         M/E
                            138

-------
      SPECTHJM H9 - 115
       CCKE 0\e< El PS-F2
 IP-
I*.
 !«..
 •
 s^
 o
                        1
    SO   60   70  80  90   100  110 120  130  110  ISO  160  170  1:

         M/E
                   139

-------
       9PECTRJM 239 - 237
  8
        CCKE ON/EN El flS-F2
 :P
 18-
fe8
i«
  s
  o




     iWTTWTtTTmTTtTI
                            ,,„..,„„,

     170  180  190 200  210  220  230

          M/E
                             140

-------
      SPECTFLM 212 - 215
 8
 8.
      COKE CMEN El PG-F2
 O
 CD _
18.
    170  180 190  200  210 220  Z30

        M/E
                            141

-------
       SPECTFLM 219 - 2SO
       COKE OVEN El F&-FZ
fc8_
«,
 8.
 8-
    170  180  193  203  210  220 230 2*3 2SS
         M/E
                         142

-------
      SPECTPLM 270-267
3
      CCKEOVEN El  R5-f2
   190  200  210  220  230  210  293  26O
        M/E
                            143

-------
        SPECTRUM 281 - 277
  8
        COKE OVEN El FS-F2
I
     180  198  238  218  223  233  213
          M/E
                              144

-------
               283-287

           OVEN El
oj _
w _j
o
13.
          .^^^..-T^TT^^rV^J. ,,-, ,^TTT,.TTT^
   200  210  220  230  2-W  250   260
        r
-------
       SPECTRUM 382 - 297
  g
       COKE OVEN El RS-F2
 iP-
bs.
tt!»
  8_j
    210  223  233  2*3 233 260  270
         M/E
                           146

-------
     SPECTRUM 329 - 32S
8
     CCKEOVEN El R5-F2
JlUp^pJll
                      u
   210 220  230  2-K3 233  260 270
       M/E
                         147

-------
      SPECTPLh 338 -
3
      CDKE CNEN El flS-FZ
                 A
   210  220 230  2-H3  2SO 260 270  280
        M/E
                            148

-------
      SPECTRA 391 -
g
8.
      COME OVEN El RS-F2
   2SO  263 273  280  290  303
        M/E
                          149

-------
                 -383
 8
 8-
      CC3KEOVEN El RS-F2
i8_
•
R.
   250  273  288 233 303  310
        M/E
                         150

-------
a

#}

aj

8]

»-«~
8-
-
2
»-••
2

s:
»-•"
a
  -f
81
        10   20   30   10   LO-   GO  TO   CO   90   ICO
                J	J	I	I	I     I	I	I
                                         C3  Phenol
                                                    n
                               f C2  Benzaldehydes


                           -- Methyl allyl  phenol
                                                    Methyl naphthols
                                                 -- Hydroxy  fluorene
                                         --  Benz  enthrone
                   FIGURE D-3.   RECONSTRUCTED GAS CHROMATOCRAM; GC-MS ANALYSIS

                                OF  COKE  OVEN DOOR EMISSIONS, SAMPLE A1F-4
                                 151

-------
      SPECIRH  18 -  IS
g
      El OKE OVEN
8-
8.
i^
fC
.
0
V J ••
o
0 _
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    FIGURE D-4.   RECONSTRUCTED GAS CHROMATOGRAM; GC-MS
               .   ANALYSIS  OF COKE OVEN DOOR EMISSION,
                  SAMPLE A1-3
                                 167

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                                TECHNICAL REPORT DATA
                         (Please read Inductions on ilic reverse before completing)
I. REPORT NO.
  EPA-600/2-77-213
                           2.
                                                      3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
 Sampling and Analysis of Coke-oven Door Emissions
                                5. REPORT DATE
                                 October 1977
                                                      6. PERFORMING ORGANIZATION CODE
7. AUTHORIS)
                                                      8. PERFORMING ORGANIZATION REPORT NO
 R.E.Barrett, W.L.Margard, J.B.Purdy, and
    P E
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Batte lie-Columbus Laboratories
  505 King Avenue
  Columbus, Ohio  43201
                                 10. PROGRAM ELEMENT NO.

                                 1AB604C
                                 11. CONTRACT/GRANT NO.

                                 68-02-1409, Task 34
12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and  Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC  27711
                                13. TYPE OF REPORT AND PERIOD COVERED
                                 Task Final:  8/75-8/77
                                14. SPONSORING AGENCY CODE
                                  EPA/600/13
,5. SUPPLEMENTARY NOTES iERL_RTp pr0ject officer for this
 Mail Drop 62, 919/541-2733.
                              report is Robert C. McCrillis,
  . ABSTRACT
          Tne rep0rt gives results of extensive tests of selected fractions of samples
 of emissions generated by leakage from a coke oven door during a 16-hour  coking
 cycle.  The tests included: particulate emissions  determination; trace metal analyses;
 gas analyses; organic analyses by IR spectroscopy ,  GC-MS, TLC, and HRMS on
 entire samples or on LC fractions of the samples; and bioassay analyses of bacterial
 mutagenesis and mammalian cell cytotoxicity. The particulate mass  emission deter-
 mination showed that coke oven emissions can vary considerably from cycle to cycle.
 The bioassay analyses confirmed that the samples were mutagenic, as implied by
 the chemical analyses.  A sealed hood was fabricated to fit over the coke oven door,
 so that gases leaking past the door during the coking cycle would be contained and
 representative samples could be obtained.  Additional criteria for the  hood  included
 not severely altering the normal door leakage and not interfering with coke oven
 operation.  Initial tests of one hood design suggested modifications  which were incor-
 porated into the final design. The final  hood was  used for conducting  two sampling
 runs at an operating coke oven.
17.
                             KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
                    b.IDENTIFIERS/OPEN ENDED TERMS  C.  COSATI i K'ld/CrO'.i|)
 Air Pollution
 Coking
 Ovens
 Leakage
 Sampling
 Analyzing
Organic Chemistry
Bioassay
Air Pollution Control
Stationary Sources
Coke Oven Doors
Particulate
13B
13H
13A
07C
06A
iy. DISTRIBUTION STATEMENT

 Unlimited
                    19. SECURITY CLASS i/iiij Kcporn
                    Unclassified
                        21. NO. ul' I'AdES
                             17S
                    20. SECURITY CLASS (This
                    Unclassified
                                             22.
EPA Form 2220-1 (9-73)
                                        172

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