PB80-146418
Status Assessment of Toxic Chemicals:  Polynuclear Aromatic  Hydrocarbons
Monsanto Research Corp,  Dayton,  Ohio
Prepared for
Industrial Environmental Research Lab-Cincinnati,  Ohio
December 1979
                     U.S.  DEPARTMENT OF COMMERCE
                  National Technical  Information Service

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&EPA
wiiv it wi«tiiotiuJi r
Agency
                                December iy-/9..
                     Cincinnati OH 45268
          Research and Development
Status
Assessment of
Toxic Chemicals
           Polynuclear Aromatic
           Hydrocarbons

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                RESEARCH  REPORTING SERIES

Research reports of the Office of Research and Development. U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. 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 V
      9.  Miscellaneous Reports                      .

This report has been assigned to the  ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved .technology-required for the control and treatment
of pollution-sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia  22161.

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                                  ' TECHNICAL REPORT DATA'
                            (Please read Instructions on the reverse be-fore completing)
1. H-gP.ORT NO.     ••••..-
    EPA-.600/2-79-210L
                       'S ACCESSIO
                              "
4. TITLE AND SUBTITLE
 Status Assessment of Toxic  Chemicals:  Polynuciear  •
                                     Aromatic  Hydrocarbons
              >. REPORT:OA-TE
               December  1979 issuing date
             6. PERFORMING ORGANIZATION CODE
7! AUTHOH(S)  •   : ' •'•   .••.,-.
 T.R. Blackwood, S.R, Archer
 G.E. Wiltons
             $. PERFORMING tSHtSAWZATIOT* RE.TORT NO.
9. PEHFORX/H-Nq ORGANIZATION NAME ANO;AC-OR4ES$   ' '     ' -•'• • • :   ' v
 Monsanto  Research Corp         Radian Corp
 1515 Nichols Road              8500 Shoal Creek Blvd
 Dayton, Ohio   U5UOT           P.O. Box 99^8
                                 Austin, Texas  T8T66
              1O. PROGRAM 6X6MENT NO.
                1AB60U
              TV. CONTRACT/GRANT

                68^03-2550
12' SPONSORING AGENCY NAME' AND ADOReSS     '        :
 Industrial Environmental Research Lab. T Cinn,  OH
 Office  of Research and Development
 U,S.. Environmental Protection Agency
 Cincinnati, Ohio   J+5268       • .'  •
             13. TVPt OF REPORT AND PERIOD'COVEREP
                Task Final  11/77 - 12/77 .
14.
                                cooe
                      EPA/6.00/12,
15. SUPPUE'lvrENTARY NOTES
 IER|TCi  project leader'for this report  is  Dr.  Ghar.les Frank,
16. ASST.RA'OT
              This report  identifies the origins ^ .applications,  environmental  ..
              effect's,' and health effects  of polynuciear- aromatic hydrocarbons.
              Ways to  reduce polynuciear aromatic hydrocarbon; (PNA) .emissiorisr and - ".
              problems associated with PNA derived effluents  in the dye industry
              are discussed. 'Finally, various regulatory actions are listed
              and. recommendations are made for further areas  of study.      ..
17.
                                   WORDS ANQ.OOCUMENT ANALYSIS
                  DESCRIPTORS
^IDENTIFIERS/OPEN ENDED TERMS  C. ' COSATI Field/Group
 Polynuciear hydrocarbons,  triphenylene,
 Aromatic Polycyclic Hydrocarbons,...Aromatic
Toxic  chemicals, Poly- •
nuclear Aromatic Hydro--"
 Hydrocarbons, Hydrocarbons, Unsaturated
 Hydrocarbons, Anthracen-e,  Biben-tyl, Bi-'
 phenyl,  Fluorenes, Methylcholanthrene,  Aliihat'lc'.; pqlycyc'iic-
carbons,  Aromatics, Chry-
sene   ••  •  •         ••"  '
                    68A
                    68D
                    68G
                   Hydroca roons
 Naphthalene, Phenanthrene, PolyphenyLHydro<
arbons,. Benzanthracenes,
 pyrenes, stilbenes.,. terphenyls, acenaphthyienes, Unsaturated Organic
              lapthacenes,
              Compounds
13. DISTRIBUTION STATEMENT  " •

         Release to  Public
 $. .SECURIT-Y •OUASS./TVrif Repvrt>
  Unclassified
                                                                          2V. NO. DF
                                               20. SECURITY Ct_ASS 
                                                 Unclassified
                                                                          23. PRICE
EPA Form 2230-1 (3-73)
                                                                     u i oovBiiuiwr mutaeam*-. i«o-657-146/5519

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                                      EPA-600/2-79-210L
                                      December 1979
    STATUS ASSESSMENT OF TOXIC CHEMICALS;

      POLYNUCLEAR AROMATIC. HYDROCARBONS
                S. R. Archer
               T. R. Blackwood
       Monsanto Research Corporation
             Dayton, Ohio  45407

                     and

                G. E. Wilkins
             Radian Corporation.
            Austin, Texas  78766
           Contract No, 68rQ3-.2S50
•••--.     ... •     Project Officer

	••• ..   ,   •  '   David- L. -Becker •
    Industrial Pollution Control Division
Industrial Environmental Research Lalporatory
         , .Cincinnati, .Ohio  452-68
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
           CINCINNATI,' OHIO  45268

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                           DISCLAIMER
This report has been reviewed by the Industrial Environmental
Research Laboratory - Cincinnati, U.S. Environmental Protection
Agency, and approved for publication.  Approval does not signify
that the contents necessarily reflect the views and policies of
the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or
recommendation for use.

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                             FOREWORD


      When energy and material resources  are extracted,  processed,
 converted,  and used,  the related pollutional impacts  on our
 environment and even on our health often require that new and
 increasingly more efficient pollution control methods be used.
 The Industrial Environmental Research Laboratory - Cincinnati
 (IERL-Ci)  assists in developing and demonstrating new and
 .improved methodologies that will meet these needs both  effi-
 ciently and economically.

.    .  This  report contains a status assessment of the  air
 emissions,  water pollution, health effects,  and environmental
 significance of ,trio (2,3 dibromopropyl)  pho-s^feafee.  This study
 was conducted to provide a better understanding of the  distri-
 bution and characteristics of this pollutant.   Further  informa-
 tion on this subject may:be obtained from the Organic Chemicals
 and Products Branch,  Industrial Pollution Control Division.      .
      Status  a/ssessment reports  are used by IERL-Ci to communi-
 cate  the  readily available information on selected substances  to
 government, /industry,  and persons  having specific needs  and
 interests. /These reports are based primarily on data from open
 literature /sources, " including government reports,  They  are
 indicative/rather than exhaustive.
                                   David G.  Stephan
                                       Director
                     Industrial Environmental  Research Laboratory
                                      Cincinnati

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Polynuclear aromatic hydrocarbons (PNA's) enter the environment
from natural and anthropogenic (man-made) sources.  The main
PNA's of commercial significance are phenanthrene, chrysene, and
anthracene, which are refined from coal-derived chemicals.  The
1974 capacity of ph«nanthren-e, anthracene, and other PNA produc-
tion facilities was 3.63 x 105 metric tons/yr.

Sources of anthropogenic PNA emissions include, combustion or
pyrolysis of fuels, processing of fuels', and manufacturing spe-
cialized organic Chemicals., The majority of PNA emissions pro-
bably arise as pyre-lysis products formed during combustion or
heating of fossil fuels or natural prbducts.  Arithmetic mean
concentrations of PNA's in air have been calculated as
0.4 yg/1,000 m3 and 3 yg/1,000 m3 for nonurban and urban loca-
tions, respectively, showing that urban concentrations, tend to
be much greater than nonurban concentrations.

Reduction of atmospheric PNA emissions from combustion sources
can be achieved by proper control of combustion.  Secondary com-
bustion devices.for flue gases could also reduce emissions.
Since the major mode of transportation for PNA's appears to be
adsorption onto particulates; control can be achieved by conven-
tional particulate control devices, such as mechanical collectors
or eletrostatic precipitators.  indications show that chlorina-
tion and ozonation of water supplies destroys PNA's, however,
byproducts formed by chlorinatibn may result in more toxic
compounds.

Limitation of carbon monoxide and hydrocarbon emissions from
motor vehicles have simultaneously and dramatically reduced PNA
emissions.  Similarly, compliance with existing regulations for
incinerators, open burning, coal combustion, and coking opera-
tions could have corresponding benefits.

PNA derivative* employed as the basic structures  in a number of
important dyes and pigments represent a major source of water
pollution,  large quantities of brines containing organic,
highly colored materials are produced as wastes.  Further
information is needed on the magnitude of this problem and on
the most effective controls.

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Sased upon the information presented in this report, several
items need to be considere4 for further studies.  Production
quantities and sites of producer and use facilities should be
identified.  Effluents from organic dye and pigment manufacturing
processes needs to be characterized and PNA concentrations
quantified to determine the most effective controls.  Transport
methods in air and water should be studied so that the most
effective controls may be achieved.  Effects of long-term expo-
sure of low^level PNA cpncentrations on humans should be deter-
mined and the associated population at risk identified.  Finally,
chlorination and psonatioh of wastewaters should be reviewed for
control efficiencies and for identification of possible toxic
byproducts.

This report was submitted in partial fulfillment of Contract
68-rQ3-2550 by Monsanto Research Corporation under the sponsorship
of the U.S. .Environmental Protection Agency.  This repc-rt covers
the period November 1, 1977 to December 31, 1977.  The work was
completed as of January 20,

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                             CONTENTS


Foreword  	  ..... 	   iii
Abstract	    iv
Tables	  viii
Conversion Factors  and Metric; Prefixes	......     x
Acknpwledgement.	,	    xi;

   1.   Introduction.  .................  ...  ...    1
 . .,2.   Summary  .  .  .  .  .',  .................  ""'•'• -2
   •3."  Source, Description.  .  ,  .   • •  •  •. •  r  •  .•  •  .•••'•..••-. •  .? r.   3
          Chemical  and physical properties  .  .  ...... ,  .    ,3
   .       Production  and  use of polynuclear aromatic  hydr-o-r
   -         carbons	     8
   4.   Environmental  Significance arid Health  Effects  ....    12
          Environmental significance  ............    12
          Health  effects  .  .  ,  ,..."',  ............    24.
  .5.   Control Technology.	    27
    .    .  Stationary  .sources .  .   . .  .  ..*....  ~.  .  . .  .    27
          Mobile	  28.
   6.   Regulatory Action	~.	    30

References  .	    31
   Preceding page blank

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                             TABLES
Number
   1    Polynuciear Aromatic Hydrocarbons .........   3
   2    Names and Synonyms for 12 PNA's .... ......   6
   3    Physical Properties of Six PNA's ..........   7
   4    Vapor Pressure and Vapor Concentration of Selected
          PNA's at 25°C .  ............ .....   7
   5    Coal T-ar Resin -Producers. *";'*...• .......   8
   6    Steel Companies Expanding PNA Production. .....  11
   7    Major Uses o£ Three PNA's ...... ^ .....  .  11
   8   .Estimates of Annual Benzo (a)pyrene Emissions from
          Various Sources . .  *  . .....  .......  i  13
   9    Emissions of PNA From Coal-fired Plants ......  .14
  10    Emissions Of • PNA From Coal-fired Residential
          Furnaces*  . ..... .  .  . .  . . . .  . ........  .  14;.
  11    Emissions of PNA From Intermediate-sized Coal-
          fired Units . *  i ........... .....  14
  12    Emissions of PNA. From Intermediate and Small-sized
          Oil-fired Units ...... ........ ...  15
  13    Emissions of PNA From Intermediate and Small-sized
             -^ fired Units with Premix Burners .......  15
  14    Emissions of PNA From Incineration and Open
          'Burning ...... i  ......... .....  15
  15    Emissions of PNA From Motor Vehicles ........  15
  16    Emissions of PNA From Petroleum Refining ......  16
  17    Emissions of PNA From Catalyst Regeneration in
          Petroleum Catalytic Cracking ...........  16
  18    Concentration of PNA in Partieulates in Air Near
          Steel and Coke Plant ...............  17
  19    Emissions of PNA From Asphalt Blowing .......  17
  20    Emissions of PNA From Asphalt Hot^-Road Mix Plants  .  18
  21    Concentration of PNA in Partic-ulates in Air Near
          Carbon Black Plant ..... ...........  18
                              viii

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                       TABLES  (continued)

Number                                           .            Page
  22    Miscellaneous Industrial Sources of PNA's  	   19
  23    Atmospheric Concentration of PNA's in Several
          Cities	20
  24    Variations of PNA Concentration with Traffic.  ...   20
  25    PNA's in Organic Particulate Matter from Six Cities   20
  26    Carcinogenic PNA Concentrations in Water Sources.  .   21
  27    PNA Concentrations, in Water  . _•.... ...........  .21
  28    Concentrations of PNA in Various Soils.  ......   21
  29    PNA Concentrations in Cereals and Potatpes	22
  30    PNA Cpncentratipns in. Vegetables and Fruits  ....   23
  31    PNA Concentrations in. Cooked, Smoked, and Processed
          Foods . . ..',-. .  ,  .'. '.'. ...  . .  '.  .  .  .  .' ,  .   23
  32    PNA Concentrations in Beverages	   24
  33    Fossil Fuel and Its. Deriyative.s  .  . .  .....  .  ........   24
  34    Toxicity of Some PNA1 s.  .	25
  35    Automotive Benzo (a) pyrene Emission Factors	29
                               IX

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             CONVERSION FACTORS AND METRIC PREFIXES3

                       CONVERSION FACTORS
  To convert from         ,.  .   ., to	. . ,          Multiply by

Degree Celsius  (°C)    Degree Fahrenheit         t|, = 1.8 t° + 32
Kilogram  (kg)          Pound-mass  (pound-mass
                         avoirdupois)                        2.204
Kilometer2  (km2).  .     Mile2                          3.860 x 10"1
Meter3 (m3)            Foot3                           3.531 x.101
Meter3 (m3)  ...   ,      -Gal-Ion  (U.S;  liquid)            2.642 x 102
Metric ton       .     -Pound-mass                      2.205 x 103
Pascal (Pa)          :  Pound-force/inch2 (psi)        1.450 x 10"1*


                         METRIC PREFIXES


  Prefix  Symbol  Multiplica tjon. ;factor        . Example	

   Kilo     k             103             1 kg = 1 x 103 grams
   Milli  .. m          .   1:0.~3.   .  •      .1 mm = 1 x 10~3 meter
 Standard for Metric Practice.  ANSI/ASTM Designation:
 E 380-76e, IEEE Std 268-1976, American Society for Testing and
 Materials, Philadelphia,  Pennsylvania,  February 1976.  37 pp.

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                         ACKNOWLEDGMENT


This report was assembled for EPA by Radian Corporation, Austin,
TX, and Monsanto Research Corporation, Dayton, OH.  Mr. p. L.
lecker served as EPA Project Officer, and Dr. C. E. Frank, EPA
Consultant, was principal advisor and reviewer.
                                XI

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                     EPA 600/2-79-210L
                       ERRATA SHEET
                          2/11/80
Plaaia chatig* the ' following:




page iii, paragraph 2, line 3, from  "tris(2,3i-dibr6mopropyl)'"



to "pblynuclear aromatic liydrocarbons".

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                            SECTION 1

                          INTRODUCTION


Polynuclear aromatic hydrocarbons  (PNA's) enter the environment
from natural and man-made sources, including combustion or
pyrolysis of fuels, processing of fuels, and manufacturing spe-.
ciali±ed organic chemicals.  Increased levels of PNA's in urban .
air, in water, and i*1 foods have caused rising concern due'to"
the carcinogenic, mutagenic, and teratbgenic properties pf
several PNA1s.

There is a need to define the various sources from which PNA's
may enter the environment, to establish consequent health and
environmental effects, and to examine possible control strategies
and current regulatory actions.  This report provides a brief
overview describing these items, with emphasis on PNA emission
sources and resulting environmental levels.

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                            SECTION 2

                             SUMMARY
Polynuclear aromatic hydrocarbons (PNA's)  enter the environment
from natural and man-made sources.   These compounds occur natu-
rally in plants and food, and are present in coal tar and creo-
sote, which are derived from the breakdown of coal.  The main
PNA's of commercial significance, which are refined from coal-
derived chemicals, are phenarithrene,  chrysene, and anthracene.
Essentially all commercial PNA's are used as reagents in organic
synthesis.  Table 1 highlights available information regarding
PNA's.

PNA's are high melting, high boiling solids with low vapor pres-
sures and low solubilities in water.   Anthracene and phenanth-
rene can be refined from creosote,  a distillation product of coal
tar.   The 1974 capacity of anthracene, phenanthrene, and other
PNA production facilities was 3.63 x 10^ metric tons/yr, and
this capacity is expected to increase 10% by 1981.

Probably arising as pyrolysis products formed during combustion
or heating of fossil fuels, PNA's are found in living plant and
animal tissue, sediments, soils, air, and surface waters.  Other
man-made emission sources include.processing of fuels and manu-
facturing .specialized organic chemicalsi  Combustion sources are
the largest contributors to PNA emissions.

There are many compounds derived from PNA's manufactured as
specialty chemicals for Use in organic dye and pigment manufac-
ture.  Although specific effluent rates are unknown for this
industry, a problem exists in the area of liquid waste disposal
since large quantities of brines containing organic, highly
colored materials are produced as waste.  In plants manufacturing
PNA-based dyes, some of the organic materials present in the
waste brines are probably PNA compounds.

PNA's seem to be transported in water and the atmosphere adsorbed
on particulates and bacteria.  Urban concentrations of PNA's in
air tend to be 10 to 100 times greater than nonurban concentra-
tions,  with arithmetic mean concentrations of 0.4 yg/1,000 m3
for nonurban locations and 3 yg/1,000 m3 for urban locations.
Essentially insoluble in water, PNA's may exist in water in
association with other organic matter or colloids, such as those
formed by detergents.

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                                 TABLE  1.    POLYNUCLEAR  AROMATIC  HYDROCARBONS
                                               Extent of problem
        Emission source
                                   Air emission
                                    quantity3
                                 (metric tons/yr)
     Population exposed
                                                                                         Control method
                                                                                                                       Regulatory action
Combustion

  Coal                                 376.1
  Oil                                    1.4
  Gas                                    1.1

Refuse burning                           18.5

Catalytic cracking of petroleum          17.1

Asphalt road mix                     9.07 x  10'6

Asphalt air blowing                 <4.35 x  10~5

Motor vehicles                           16.7

bye and pigment manufacture               -
Indication of widespread
  exposure because PDA's
  exist in all phases of the
  environment.  Urban con-
  centrations are 10 to 100
  times.greater than non-
  urban concentrations.
  Persons working with or
  using fossil fuel-derived
  products are exposed to
  high PNA levels.
PDA's from combustion
  sources may be controlled
  by .increasing air-to-fuel
  ratios or ..using secondary
  combustion devices on flue
  gases.  Conventional
 ..particulate control methods
  could help reduce PNA
  transport.

Chlorination and ozoaation
  Of water supplies are
  believed .to destroy PNA's
  but mote toxic byproducts
  could be formed.
Compliance with existing
  regulations for  inciner-
  ators, open burning, coal
  combustion and coking
  operations could
  significantly reduce emis-
  sions.  Specific control
  regulations are  not believed
  to be warranted  or practical.

One-hundred and twenty-nine
  chemicals including 13 PNA's
  •have recently been-designated
  priority pollutants under the
  Federal Water Pollution Con-
  trol Act.
 Emissions  given in metric tons/yr of benzo(a)pyrene.

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 Air  emissions  of  PNA's  from  combustion  sources  can  be  reduced  by
 increasing air-to-fuel  ratios, or with  secondary  combustion
 devices  for flue  gases.  Particulate matter, which  appears to  a
 method of  'transport  for PNA's  in the environment, may  be  con-
 trolled  by conventional methods, such as mechanical collectors or
 electrostatic  precipitators, thus aiding in reducing PNA  emis-
 sions.   Indications  are that chldrination  and ozonation of water
 supplies destroys PNA's; however, byproducts much more toxic than
 the  original compounds  may be  produced  in  chlorination.

 Limitation of  carbon monoxide  and hydrocarbon emissions from
 motor vehicles has simultaneously and dramatically  reduced PNA
 emissions  from these sources.  Control  regulations  designed
 specifically for  PNA's  are not considered  practical, but  compli-
.ance with  existing regulations for incinerators,  open  burning,
 coal combustion,  and coking  operations  could significantly
 reduce emissions* Consideration is being  given to  establishing
 revised  standards for coke oven emissions  under the Clean Air
 Act.  Documentation  of  physical and chemical behavior, health
 and  environmental effects, and sources  ahd environmental  levels
 for  65 chemicals  and classes*  including PNA's,  was  scheduled to
 be published by July 1977.   Subsequently,  appropriate  water-
 quality  criteria, effluent guidelines,  toxic pollutant standards,
 and/or pretreatment  requirements will be established under the
 Federal  Water  Pollution Control Act in  accordance with a  court-
 approved schedule.

 Based upon the information presented in this report, the  follow-
 ing  items  need to-be considered for future studies:

    * Production quantities and ••locations of user  and manufac-
     turer facilities should be identified for  all  major  PNA's.

    • Effluents irom  Organic  dye and pigment manufacturing pro-
     cesses should be characterized and PNA concentrations
     quantified to determine the most effective controls.

    • PNA transport methods should be studied so that efficient
     emission  and effluent pollutant control may  be realized.

    • Human health effects of long-term, low-level exposure
     should be determined.

    • Population risking exposure to PNA's  should  be quantified.

    • Chlorination and bzbnation of wastewaters  should  be
     reviewed  for control efficiencies  and for  identification  of
     possible  toxic  byproducts.

    • PNA atmosphere  and environmental persistence.

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                            SECTION 3

                       SOURCE DESCRIPTION


Polynuclear aromatic hydrocarbons  (PNA's) enter the environment
from natural and anthropogenic  (man-made) sources.  EN-A's are
not manufactured as synthetic organic chemicals.' These compounds
occur naturally in plants.and food,'and are present in coal  tar
and creosote,.which are derived from the breakdown of coal.
Since the form of PNA's in coal is unclear, it is not known
whether it is .anthropogenic or natural..in- origin.  Phenanthrene,
chry.sene, and anthracene, which are refined from coal derived
chemicals, are. the main PNA's of commercial significance.
Essentially all commercial PNA's are us.ed as reagents in- organic
synthesis.

CHEMICAL AND PHYSICAL PROPERTIES

Chemical nomenclature for 12 selected PNA.'s is .listed ,in Table 2 ,
(1, 2).  Polynuclear aromatic hydrocarbons are all high melting,
high boiling solids.  Tables 3 and 4 summarize specific proper-
ties of selected PNA's (3-9) .. As shown in Table 4, vapor
(1)  Radding, S. B., T. Mill, C. W. Gould, D. H. Liv, H. L. John-
     son, D. C. Bomberger and V. C. Fpjo.  The Environmental Fate
     of Selected Polynuclear Aromatic Hydrocarbons.  EPA 560/5-
     75-009,'U.S. Environmental Protection Agency, Washington,
     D.C., February 1976.'  131. pp.         .

(2)  Patterson, A. M., L. T. Capell, and D. F. Walker.  The Ring
     Index.  A List of Ring Systems Used in Organic Chemistry.
     American Chemical Society, Washington, D.C., 1960.  1425 pp.

(3)  International Agency for Research on Cancer, "Monograph on
     the Evaluation of Carcinogenic Risk of the Chemical to Man:
     Certain Polycyclic Aromatic Hydrocarbons and Heterocyclic
     Compounds," World Health Organization, Geneva, Switzerland,
     1973, 'Volume 3.      !
.(.4)  Hansch, ..C... .  (1975) , private communication, Pomona College,
     Pomona, California.           -

(5)  Fieser, L.'F, and A. M. Seligman  (1935), "The Synthesis of
     Methycholanthrene," J. Amer. Chem. Soc. 57, 942-46.

(6)  "Handbook .of Chemistry and Physics," 45th Ed., Chemical
                                5                      (continued)

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TABLE  2.    NAMES  AND SYNONYMS  FOR  12  PNA's   (1,  2)
                  Common name
                                            Synonyms
              Benzo (a) pyrene
              Benzo (a)anthracene

                 CoTSToT
              Methylcholanthrene
3,4-Benzpyrene
BP
BAP
3,4-Benzopyrene

1,2-Benzanthracene
Benzanthrene
Benzo(b)phenanthrene
2,3-Benzophenanthrene
Tetraphene
1,2-Benz(a)anthracene

Cholanthrene, 3-roethyl-
20-MC  ••
MC
3-MC
20-Methylcholanthrene
3-Methylcholanthrene

1,2-Benzphensnthrene
                                      Paranaphthalene
                                      None
              Benzole)pyrene
              Benzo(ghi)perylene
              Fluoranthene
4,5-Benzopyrene
1,2-Benzopyrene
                                      Dibenz(de,kl)anthracene
1,12-Benzoperylene
                                      Dibenzo(def,mno)chrysene
                                      Dibenzolcd,jk)pyrene
                                      Dibenzo(ghi,pgr)perylene
                                      Benz(a)acenaphthylene
                                      1,2-Benzoacenaphthylene

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           TABLE 3.  PHYSICAL PROPERTIES  OF SIX PNA's
Mol.
PNA formula
Benzo (a) pyrene czoHl2
Benzo (a) anthracene Ci3H12
Methylcholanthrene C21H15
Chrysene C18Hu
Anthracene CII»HI
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pressures are extremely low.  Solubilities of PNA's in water
generally.appear to be less than 10*10 molar.  These compounds
undergo the reactions Of. simple aromatics, in addition to some
reactions peculiar to PNA's as a class.  They are subject to
oxidation and yield quinones, diols, peroxides, and ring cleav-
age products.  Alkylated PNA's are more reactive toward electro-
philic agents, with reactivity increasing with ring number  (1).

PRODUCTION-AND USE OF POLYNUCLEAR AROMATIC HYDROCARBONS

Anthracene is the only PNA of.commerce refined from fossil fuel
sources.  While quantities refined were not found, several coal
tar resin producers, who may refine anthracene, are presented in
Table 5 (10).

             TABLE 5.  COAL TAR RESIN PRODUCERS (10)
   Chemfax, Inc.                     Gulfport, MS
   The Goodyear Tire & fcubber Co.
     Chem. Div.                      Beaumont, TX
   Hercules, Inc.
     Organic* Dept.                  Baton Rouge, LA
                                    . Clairton, PA
                                     West Elizabeth, PA
   Neville Chem. Co.                 Anaheim, CA
                                     Neville Island, PA
   Northwest Indust., Inc.,
     Velsicoi Chem. ...Corp.,
      subsidiary                     Marshall, IL
   Reichhold ChemS., Ihc*
     Newport Div.        .            Gulfport, MS
   Schenectady Chems., Inc.           Rotterdam Junction, NY
Anthracene and phenanthrene can be refined from creosote, which
is produced by distillation of coal tar.  A number of distillate
oils are produced in the distillation of coal tar and creosote
is a mixture of these oils.  Creosote production may be repre-
sented by the schematic shown in Figure 1 (11).  Creosote is
(10) 1977 Directory of Chemical Producers.  Stanford Research
     Institute, Menlo Park, California.  1977.  p. 782.
(11) von Rumker, R*, E. W. Lawless, and A. F. Meiners.  Produc-
     tion, Distribution, Use and Environmental Impact Potential
     of Selected Pesticides (PB 238 795).  Council on Environ-
     mental Quality, Washington* D.C., March 1974.  439 pp.

-------
           AMMONIA
   COAL GAS
            CARBOLIC OIL
           NAPHTHALENE OIL
LIGHT OIL  (OTHER PRODUCTS)
                    COAL TAR
                                           WATER
                                   DISTILLATION
                                        CREOSOTE-
                                      PITCH
            COKE
       Figure 1.  Production schematic for creosote  (11).      .

then washed with water, and solid crude anthracene is separated.
in filters and centrifuges as shown i:n Figure 2  (12).  The crude
product is then recrystallized from furfural.  Solids separation
and drying steps produce refined anthracene product.

In 1974, the capacity of phenanthrene, anthracene, and other PNA
production facilities was 3.63 x 10s metric tons/yr and  this
capacity is expected to'increase 10% by 1981  (13).  Actual cur-
rent production data were -not. available.  However, since the
majprity of PNA's are produced at steel making facilities, eight
steel companies planning to expand s.te-el production by 1981 at
11 sites are listed in Table. 6 (13) .
(12) Development Document for Effluent Limitations Guidelines and
     New Source Performance Standards for the Major Organic Pro-
     ducts Segment of the Organic Chemicals Manufacturing Point
     Source Category, EPA 440/l-r74-<-OQ9-a, U.S. Environmental
     Protection Agency, Washington, D.C.., 1?74.
(13) Cooper, F. D.  Coke and Coal Chemicals.  In:  Minerals Year-
    . book 1974, Volume 1.  Metals, Minerals, and Fuels.  U.S.
     Government Printing Office, Washington, D.C., 1976.- p 447.

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   CREOSOTE
   WATER
DIRECT CONTACT
t

3
-
e
j


1
















•'•




1
Oil
- 1
CENTR



                                         WASTEWATER
                                                                                     REFINED
                                                                                    ANTHRACENE
WASTEWATER
                  WASTEWATER
                      Figure  2.   Anthracene  refining  flow diagram  (12).

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     TABLE 6.   STEEL  COMPANIES EXPANDING PNA PRODUCTION  (13)
                Company
                  Location
 Approximate
   start-up
    date
     Armqo Steel Corp.
     Bethlehem Steel Corp.
     Inland Steel Co.
     Jone? & Laughlin steel Corp•

     Lykes-Youngstown Corp.
     Republic Steel Corp.

     United States Steel Corp,

     Wheeling-rPittsbvurg Steel Corp.
              Middletown, OH
              Bethlehem, PA
              East Chicago, IN
              Ali<3uippa, PA
              Aliquippa, PA
              Indiana Harbor,
              Cleveland, OH
              Warren, OH
              Gary, IN
              Gary, IN
              Foilansbee, WV
July 1976
Mid-1975
1978 '
Mid-1975
Not contracted
Mid-1977
1976
1978
Late 1975
Late 1976
Mid-1977
Table  7  presents a partial list of  uses for three of the .most
important PNA's  (14).

             TABLE 7.   MAJOR USES OF THREE ENA's  (14)
      Compound
                     Uses
    Anthracene
Dyes;  alizarin;' phenahthrene;
  carbazole; anthraquinone; calico
  printing;  component of smoke  screens;
  scintillation counter crystals; reagent
  in organic semiconductor research
Organic  synthesis
Dye stuffs;,  explosives;, drug synthesis;
  biochemical research.; phenanthrene-
  quinone
    Chyrsene
    Phenanthrene
(14) Hawley,,. Qessaer,  G, , Ed./' The Condensed  Chemical Dictionary,
  ..-  8th'Ed.',  New York,  Van ;Nostrand Reinhqld Co., 1971.
                                  11

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                            SECTION 4

          ENVIRONMENTAL SIGNIFICANCE AND HEALTH EFFECTS
ENVIRONMENTAL SIGNIFICANCE

PNA's are widely distributed in the environment.  They are found
in living plant and animal tissue, sediments, soils, air, and
surface waters.  The majority of PNA's probably arise as pyroly-
sis products formed during combustion or heating of fossil fuels.
The major environmental transport mode is as particulate in air
or water, due primarily to low vapor pressures and virtual
insolubility in water.  Presently used methods of analysis for
estimating airborne concentrations of PNA's however, may seri-
ously underestimate the concentrations of some relatively vola-
tile PNA's such as pyrene, anthracene, and benzo(a)anthracene  (1)

Sources

PNA's enter the environment from natural and anthropogenic
sources.  Anthropogenic PNA emissions may occur from combustion  ,
or pyrolysis of fuels, processing of fuels, and manufacturing of
specialized organic chemicals.

Several potential sources of PNA emissions have been monitored.
Emission estimates for these sources are presented in Table 8
(15).  Combustion sources are the largest contributors to PNA
emissions.  Sampling and analysis data for these combustion
sources are presented in .Tables 9 through 15  (15).

PNA emissions from petroleum refining .sources have been studied;
sampling and analysis results are presented in Table 16  (16).
Table 17 lists emissions of PNA from catalytic regeneration in
petroleum catalytic cracking  (15).
(15) Hangebirauck, R. P., et al. , Sources of Polyniiclear Hydrocar-
     bons in the Atmosphere, 999-AP-33, Public Health Service,
     1967.

(16) Samedov, i. G. and A. S* Kurbanov, "Pollution of the Air
     with Carcinogenic Substances by Baku Petroleum Refineries,"
     Azerbaydzhanskiy Medit. Zh. 28  (11), 62-67  (1971) .

                                12

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     TAPLE 8.  ESTIMATE? OF ANNUAL BEN?O(a)PYRENE
               EMISSIONS- FROM VARIOUS SOURCES  (15)
               Source
£gtimated annual
    emission
 (metric tons)
Coal combustion
  Residential
    Hand stoked
    Underfeed
  Commercial
  Industrial
  Power plants

Oil combustion

Gas combustion

Refuse burning

  Municipal incineration
  Commercial incineration       : -
  Open burning-municipal
  Grass, leaves
  Auto components

Catalytic cracking of petroleum.

  FCC  - no carbon monoxide boiler
  FCCu r with carbon monoxide boiler
  HCC  T no carbon monoxide boiler
  HCC  •- with carbon monoxide boiler
  TCC  -r air lift *• no carbon monoxide
           boiler
  TCC  - air lift T with carbon
           monoxide boiler
  TCC  f bucket lift - no carbon
           monoxide boiler

Asphalt road mix

AsphaLt air blowing

Motor vehicles
  Gasoline automobiles
  Gasoline tr-ucks
  Diesel
    362.9
      8.8
      2.5
      0.5
      1.4
      1.1
      0.1
      4:4
      4.4
      4.4
      5.2
      0.19
      0.010
      5.1
      0.0022

     '11.8

     <0.0026

      0.0037

   9.07 x lO'6

  <4.35 x 10-5


      7.8

      1.8
 •Fluid catalytic cracking.

 Houdriflow catalytic cracking.

 Thermofor catalytic cracking.
                          13

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        TABLE  9.    EMISSIONS  OF  PNA  FROM  COAL^FIRED  PLANTS  (15)
                                                            Emissions in ug/103 j
         •Type of unit
                             Benzo(a)-
                              pyrene	Pvrenc
                  Beneo(e)-  Pery-
                   pyrene   lene
Benzolghi)- Anthan-          Phenan- Fluoran-
 perylene   threne   Coronene threne   thene
Pulverized coal (vertically-fired,
  dry-bottom furnace)

Pulverized coal (front-wall-fired,
  dry-bottom furnace)

Pulverized coal (tangentially-
  fired, dry-bottom furnace)

Pulverized coal (opposed-, down-
  ward inclined burners; wet
  bottom furnace)
1-8 - 123   70 - 216
16 - 20  152 - 190
  123
          133
                      52
                      80
                            67
Crushed coal (cyclone-fired,
  wet-bottom furnace)

Spreader stoker (traveling
  grate)                     <14 - S3
20 - 133   37 - 1-14    68 - 398


72 - 351  237 - 1,706  104 - 645   32
         20 - 56
                      SB
   79                            80 - 389


   13                       190   12 - 152


  142       4.6        6.7     30     370



142 - 1,042         7.7-88        52 - 199


 34 - 341              10           42 - 104
                                                         9.0
NOTE:  Blanks indicate data not available.
                                                                    20 - 56
                  TABLE  10.   EMISSIONS  OF  PNA  FROM COAL-FIRED
                                   RESIDENTIAL  FURNACES  (15)
• • . Emissions, uq/loS J fuel
Firing
Underfeed
method
stokers
Benzo(a)-
pyrene
3,600 - .
76,780
Pvrene
7,300 -'
284,360
Benzole )-
pyrene
• 5,120.- ..
55,920
Pere-
lene
407 -
7,490
Benzol ghi )-
perylene
550 -•
57,800
Anthan-
threne
1,230 -
5,780
Coronene
1,140 -
3,690
Anthra-
cene
1,230 -
66,350
Phenan-
threne
. 27,500 -
578,200
Fluoran-
thene
44,550 -
312,800
Hand stoked
                379,150 -  568,720 -  94,800 -  56,870 -
                3,127,960  8,625,600  1,421,800 331,750
                      284,360 -  85,300 -  28,440 -  379,150 -  947,900 -  947,900 -
                      2,085,300  464,500   91,950    2,748,800  7,109,000  10,426,500
NOTE:  Blanks indicate data not available.
               TABLE  11.    EMISSIONS  OF  PNA  FROM  INTERMEDIATE-
                             .   SIZED  COAL-FIRED  UNITS  (15)
•• • . . . Emissions ,. uo/109 J fuel
Firing method
Pulverized
Chain grate stoker
Spreader stoker
Underfeed stokers

Benzo(a)-
• py*«ne.
30
35
25
114 -
9,200
Benzole )' Fere- B«nzo(ghi)- Anthan-
pyrenc. Byxene. lent pervlene : threne
227
370
560
1,610 -
15,160
87
123
330
216 - 1,516 4,260 275
7,500
Anthra- Phenan- Pluoran-
Coronene cene • threne thene
350
25
313 805 948
9,480
645
340
3,030 -
36,000
 NOTE:  Blanks indicate data not available.
                                                  14

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           TABLE  12.    EMISSIONS  OF PNA  FROM  INTERMEDIATE AND
                          .SMALL-SIZED  OIL-FIRED  UNITS  (15)
                                '• •'Emissions,
                                                               J -fuel
          Firing method
             BenzoU)-          'Sense (ghi) •?    •  V '•"•' , ' Anihan-  'Shenan-
              pyrene	Pyrene    perylene   Coronene  threne   threne    thene •
   Steao atomized           «19-45    46-284
   Low pressure air Atomized   853      5,780
   Pressure atomized         <38-<57    14-1,700
   Vaporized                  <95      1,140
                                                             1.700   53-256
                                   285       1,990    3,700    3.320     1,800
                                                             3,440   72-4,470
                                                                     14,200
   NOTE:  Blank? indicate data not available.

   TABLE  13.   EMISSIONS OF  PNA FROM  INTERMEDIATE  AND SMALL-SIZED
                  GAS-FIRED UNITS  WITH  PREMIX .BURNERS  (15)
                                Emissions,  yg/109' J fuel
Ben2o(a)r '';•       ;\
 pryene     Pyrene
pyrene
                          perylene
                                                      threne,
                                            ;.  .   Flu- Anthan-' -.         ftathra-  Phenan-  Pluoran-
      of vehicle  pyrene   Byrene  pyrane    lane   parylene   threna   Coronena  ,cena    threne   thene
  Automobiles
  Trucks
 1.8 -
.,20.8
 >1.6 -
 TO .
                       8.0 -
                       212
   2.9 *
   19.6
                       255 -  >2.2 .-
                       930     65
                                  0.17 -  4.2 - 90    0.19 -
                                  2.2              2.83
                                  0.52- -   5-7 T 300   0 - 73
                                :  12
              2.S -  0.65 -
              39.7   7.9
                                   24 -
                                   ISO
                                          4 - US
2.7 -
57
162 -
640
4.2 -
145
137 -
610
                                           15

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     TABLE 16.  EMISSIONS OF PNA FROM PETROLEUM REFINING  (16)

, : . Process. . ..•••:
Straight run distillation
Pyrolysis
Asphalt production
Petroleum coke production
Petroleum products
purification
Emissions
Benzo(a)-
. , pyrene
0.015
0.30-
0.74
25.5

0.024
, vg/ioo m3a
Benzo ( ghi ) -
perylene
0.11
0.170
1.58
0.4
h


            Mean values of multiple samples.

            Not available.
     TABLE  17.   EMISSIONS OF PNA FROM CATALYST REGENERATION
                 IN PETROLEUM CATALYTIC  CRACKING (15)

Type of unit • • •
rcc:8
Regenerator outlet
Carbon monoxide boiler outlet
HCCrb
Regenerator outlet • .
TCC = C
Air lift, regenerator outlet
TCCi
Brucket lift, regenerator outlet
NOTE: Blanks indicate data not tm
. • • • - F1"* qeione , uc/»3 oil charges
Benxo(a)- Benzole)- Pery- Benxo(ghi)- ftnthan- _ Anthra- Phenan- Fluoran-
pyrene -Pyrene • pyrene> lene- pervlene threne ~coronene cene threne thene' •
0.7 - 73 6.4 - 1.7 - 572 24 - 67 63.560 7.0 - 3,180
4,450
1.7 - 3.4 3.9 - 26 2.9 - 3.3 6.8 330 3.2 - 13

.32,600- 20,700- 20,800- 5,400 47,700- 2,380- 1,780- '146- 3,340-1,320-
36,700 20,800 60,400 60,400 2,860 4,130 318 4,600 1,810

8.900 - Jl.OOO - 8,900 - 875 - 7,000 - 205 - 57 1,640 - 52,500 - 1,685 -
19.100 41,300 19,100 1,590 11,450 700 1,685 56.000 4,610

5 46 - 57 IS 9-17
lilfble.
 bHoudriflow catalytic cracking.

 CThen»for catalytic cracking.
PNA's, in the  form of partieulates, can be  emitted to the atmos-
phere from coking  operations.  Particulate  matter collected from
the air in the vicinity of a coke oven and  steel  mill has-been
analyzed and the results are shown in Table 18  (15).   The major
sources of atmospheric emissions from the coke  and steel industry
are slot-type  coke ovens and oxygen-lanced  open hearth furnaces.
Beehive ovens  have higher emission rates, but they are seldom
used in the industry.   PNA's are also found in  coal  tars (17).
(17) Lowry, H. H.,  Ed.,  Chemistry of Coal Utilization,  2 Vols.
     and supplementary volume,  N.Y., Wiley,  1945,  1963  (supple-
     mentary volume).

                                16

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        TABLE  18,   CONCENTRATION OF PNA IN PARTICULARS IN
                   AIR NEAR'STEEL AND COKE PLANT (15)

                   '"-"''     ^ v ;.-•== •  - ^Concentration,
                	Compound	   g/1,000 m3 air

                Benzo(a)pyrene            8.6
                Pyrene                    6.6
                Benzo(e)pyrene            4.1
                Perylene                  1.0
                Benzo(ghi)perylene        7.1
                Anthanthrene             .0.83     .  .
                Coronene                  0.44
                Anthracene                2.4
                Fluoranthene              3.2
 Processing  of  coal tar could result in PNA emissions in both
 gaseous  and liquid or semi-liquid form.

 Asphalt  blowing and hot-mix asphalt plants are potential PNA
 emission sources..  The results of a sampling and analysis program
 for  these two  sources are shown in Tables 19 and 20  (15).  Carbon
-black  plants are also potential emitters of PNA1s (15, .18).
 Table  21 .presents an analysis of collected particulate matter in
 the  vicinity of a carbon black "plant (15).

       TABLE 19.   EMISSIONS OF PNA FROM ASPHALT BLOWING (15)
              ''•••    ::;-'!:'  '"•"•••'   Emissions, ug/1,000 m^
                  Compound	 (211.1°C, 1 x 105 Pa)

              Pyrene                  3,100/000
              Benzo(a)pyrene             <4/000
              Anthracene                220,000
 (18)  Todd,  Robert G.,  Direct Identification of Polycyclic Aro-
      matic  Hydrocarbons from Carbon Black, Masters Thesis, Uni-
      versity of  Oklahoma,  Norman,  Oklahoma, 1970.

                                17

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TABLE 20.  EMISSIONS OF PNA FROM ASPHALT HOT-ROAD MIX PLANTS  (15)
                              Emissions, pg/1,000 m3
                . Compound ..     (.211.1°C,-.l, x. .105 Pa)

             Pyrene                    3,000
             Ben-zo (a-) pyren-e             
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      TABLE 22 r  MISCELLANEOUS INDUSTRIAL SOURCES  OF PNA'S

• -! • '  "•	••••••..-•••    •  - •   ...        ....    • •  •  •:   • ...-  •   Refer-*
        Industry  	              Emissions               enc.e

Foundry (casting                     1 -r 3 mg BaPa/103m3      19
  operations)

Aluminum plant                            10 kg  BaPa/day      20
                                     0.26 mg BaPa/m2-?day

Fiberbpard works-pitch     0.2. mg BaPa/103m3 on  premises      21
  boiling plant               0.1 mg BaPJ|/103m3  at 100 ra
                             0.05 mg BaP /103m3  at 500 m

Carborundum                            0.08 mg BaP /103m3     21

Vinyl phonograph records .               5'. 2 mg BaP /103m3     21
  plant                         .    .                    .  .     .'

Rubber products plant           0.05 r 0.02 mg BaPa/103m3.    21
                                 (dependent on distance)


 Benzo(a)pyrene                               '.

Environmental  Levels

Air—               •
Urban concentrations of  PNA's in air  tend, to be  10 to 100 times
greater than nonurban  concentrations.  An  arithmetic mean concen-
tration has been 'determined:  6.4  yg/1,000  ra3  for nonurban  loca-
tions, 3  yg/1,000 m3 for urban locations  (20).   winter levels are
usually higher than summer levels.  This  phenomenon may be  due to
both lower photo-oxidation rates and  increased use of fossil
fuels for space heating.  Table  23  contains some data for atmos-
pheric levels  of  PNA's as a  function  of  season  (3, 20).   Traffic
variations also cause  variations in PNA  concentrations.   The
range .in  values corresponding to traffic variations is shown in-
Table' 24  (3).'  Traffic contributes  from  5%  to  42% to the level
o.f PNA's  in air (22) .
 .(continued)
 •(21)  "Basic  Industrial  Sources of the Carcinogenic Hydrocarbon;
      BenzotaJpyrene," Med.  Zh. Uzb.  No.  11, 51-4.
 (22)  Sawicki,  E.   (1967),  "Airborne  Carcinogens and Allied
      pounds,"  Arch.  Environ.  Health  14 (.1) , 46-53.

                                19

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 TABLE 23.  ATMOSPHERIC CONCENTRATION OF PNA'S IN SEVERAL CITIES


Benzo(a)pyrene


Chyrsene
Benz (a) anthracene



Winter ,
yg/1,000 .m3
0.6 - 104
26
(14 U.S. Cities)
20 - 361
94
(Siena)
361
(Bochun)
Summer,
..... ug/1,000 m3
0.03 - 4
1.9
(14 U.S. Cities)
2.5 - 3.6
1.6
(Siena)
136
(Pittsburgh)
Refer-
ence
3
20

3
3




   TABLE 24.  VARIATIONS OF PNA CONCENTRATION WITH TRAFFIC (3)

.... . ... PNA ,. , . ..
Benzo (a) pyrene
Chrysene
Benz (a) anthracene
Concentration ,
yg/1,000 -in3
2.5
1.8
0.6
- 6.5
- 13.3
- 13. -7

PNA's seem t6 be transported in the atmosphere adsorbed on
particulates and bacteria.  An analysis of particulate matter
from six cities is given in Table 25 (3)>

TABLE 25*  PNA'S IN ORGANIC PARTICULATE MATTER FROM SIX CITIES  (3)
                                   Concentration,
                      .PNA
               Behio(a)pyrene
               Chrysene
               Benz(a)anthracene
110 - 670
150 - 490
 43 - 280
Water"
PNA's are essentially ihsoluble in water.  They may exist in
water in association with other organic matter or colloids, such
as those formed by detergents.  They are probably transported to
the waterways adsorbed on particles or bacteria.  Table 26 pre-
sents concentrations of carcinogenic PNA'S found in water systems
(23).  Another study of water contamination by three specific
PNA's resulted in the data shown in Table 27  (3).
                               20

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      26.  CARCINOGENIC PNA CONCENTRATIONS IN WATER SOURCES  (23!


       '   '• '''';:'-'••'-'"''   Sguree    '  : '  ..."'''"'.''       mg/m3

       Ground water                            0.001 -r 0.1
       Treated river and  lake  water             0.01 -r 0.025
       Surface water                           0.025 - 0.100
       Surface water/ strongly contaminated      >0.100
           TABLE 27.  PNA  CONCENTRATIONS IN WATER (3)

         :  ''"•  ^""'Orinking water,'" 'Surface water,
               PNA	     mg/m3  	     mg/m3

       Benzo(a)pyrene       0,0-001  - 0,023    0.0006 - 0.114
       Chrysene  '           '•'    '  -a         0.0118 - 0.038
       Ben?(a)anthracene     0.001  - 0.023    0.0043 7 0.185


       aNpt available.                                .   •

Soils-»-    • •    •       ...-.,...           - •   .  .       ••'•••
Levels of  three PNA's found in  soils from different locations are
presented  in Table  28  (3).   The PNA compounds may settle on the
soil where they are absorbed by microorganisms or plants or are
decomposed-by  bacteria.  There  is  a natural background level of
PNA's in soil, probably due to  production by plants and micro-
organisms ,

      TABLE 28.  CONCENTRATIONS OF PNA IN VARIOUS SOILS (3)
                              (yg/kg)


Soil source
Forest
Nohindustrial
Towns and vicinities
Soil near traffic
Near oil refinery
Near airfield
Polluted by coal tar. pitch
V •'..-. . . • • • • : - • .- i ; - -.•
Data not 'available.

Benzo(|i) f
pyrene
<1,300
0 - 127
0 -r 939
<2,000
200,000
785
650,000




Chrysene
a
a
a
"a
a
"a
600,000



Benz'(a)r
anthracene
5 - 206
a
a
1,500
_a
"a
2,500,000


 (23) Andelman, J.  B.,  M.  J.  Suess (1970),  "Polynuclear Aromatic
     Hydrocarbons  in the  Water. Environment," World Health Organi-
     zation 43,  479-5081                '
                               21

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Plants > Food, and Beverages-*
The concentration of benzo (a) pyrene is 10 yg/kg to 50 yg/kg in
plants, 2 yg/kg to 10 yg/kg in dried bacteria, and 103 yg/kg to
270 yg/kg in tobacco leaves  (1) .

PNA's have been determined in many foods; some of the concentra-
tions found are listed in Tables 29, 30, and 31 (3, 23-28).
Table 32 contains concentrations of PNA's as determined in
beverages (3, 25) .

      TABLE 29.  PNA CONCENTRATIONS IN CEREALS AND POTATOES
                             (yg/kg)
   _ PNA   ... .  _  Cereals _ Potatoes _ ence

   Benz (a) anthracene     In general            .a           3
                          0.4 - 6.8
   Chyrsene              In general            a           3
                          0.8 - 14.5
   Benzo (a) pyrene        In general      Peelings 0.36    24
                         0.25 - 0.84     Tubers 0.09
                     Barley, Wheat, Rye             .      25
                          0.2 - 4.1


    Not available.
(24) Shabab, L. M. and V. L. Cohan (1972), "Contents of Benzo(a)-
     pyrene iii Some Crops," Arch. Geschwulstforsch. 40  (3), 237-43.

(25) Grimmer, G.  (1968), "Carcinogenic Hydrocarbons in the Human
     Environment," Deut. Apoth.-Ztg.   108 (16),529-33.

(J>6) Grimmer, G. ,  A. Hildebrandt (1965b) , "Content of Polycyclic
     Hydrocarbons in Different Vegetables. III.  Hydrocarbons in
     the Human Surroundings," Deut. Lebensm.-Rundschau 61(8), 237-9.
(27) Gorelova, N.  D., P. P. Dikun,  L. D. Kostenko, 0. P. Gret-
     skaya, and A. V. Emshanova  (1971) , "Detection of the Possible
     Presence of 3,4-benzopyrene in Fresh Fish," Novosti Onkol.,
     8-12.

(28) Wierzchowski, j. and R. Gajewska (1972) ,  "Determination of
     3,4-benzopyrene in Smoked Fish," Bromatol. Chem. Toksykol.
     5(4), 481-6.

                               22

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      TABLE 30.   PNA CONCENTRATIONS  IN VEGETABLES AND  FRUITS
                                (yg/kg)
PNA Cabbage
Benz (a) anthracene

Chyrsene

BenzoU)pyrene 24.5 (26)



Kale
43.6 -
230
58.5 -
395
12.6 r
24.5 (25)
12.6 r
48.1 (3)
Spinach
16.1 (3)

28.0 (3)

7.4 (23)

7.4 (3)

iettuoe Tomatoes
0.3 (3)

0.5 (3)

2.8 - 0.22 (25)
12.8 (23)
0.2 (3)

Otber
Fruits Salad
4.6
15.
5.7
26.
2-8 (3)

2.8
5.3
,.
4 (3)
-
5 (3)


-
(3)
NOTE:  Blanks indicate data not available.
             TABLE 31-  PNA CONCENTRATIONS IN  COOKED,
              .   '    '    SMOKED,'AND  PROCESSED  FOODS
                                 (yg/kg)
PNA
Benzp ( a ) py rene




Cbrysene



Benz (a) anthracene


Refined oils
or fats
0.9 - 15 (3)
Margarine
0.2 - 6.8 (3)
Coconut oil
43.7 (3)
• Coconut fat
62 (3)

0.5 - 129 13)



0.5 - 13.5 (3)
Coconut oil
98 (3)
Coconut fat
125 (3)
•Fresh fish"' • •' '
frozen gr Broiled meat
salted or fish
<0.1 (.27) Meat and
Sausages (3)
0.17 - 0.63

BBQ meat (3)
2.6 - 11.2
Pish 0.9 (3)
8.7 - 27.2 (29)
Ham (3)
0.5 - 2.6
Pish 4.3 (3)
Heat and
.sausages (3)
0.5 r 2.6
BBQ meat (3)
0.6 - 25.4
Meat and
sausages (3)
0.2 - 1.1
Charcoal
broiled (3)
1.4 - 31

Smoked meat
Smoked fish sausages
1.0 - 78.0 (23) 0.02 - 107 (3)
37 (23)
0.1 - 0.8 (25)
Traces - 2.1 (3)


0.3 - 173 (3)


Ham <12 (.3)
0.02 - 189 (3)

NOTE:  'Blanks indicate data not available.
(29)- Shirotori,  1972.
                                  23

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           TABLE  32.   PNA CONCENTRATIONS IN BEVERAGES
                              (mg/m3)

: PNA. .
Benzo (a)pyrene

Roasted coffee
0.3 -
0.1 -
0.5 (25)
4 (3)
3.7
3.9
Teas
- 3.9 (25)
- 21.3 (3)
Whiskey
0.04 (3)
*
       Chrysene
             Green teas (3)
             0.5 - 16
0.6 - 19.1 (3)  4.6 - 6.3 (3)
       Benzta)anthracene  0.5 - 14.2 (3)
0.04 - 0.06 (3)
0.04 - 0.08 (3)
       aData not available.

Fossil Fuels--
Levels of  PNA's occurring  in some fossil fuels and fuel fractions
are shown  in Table  33  (3).   PNA's are more concentrated in fuel
byproducts  formed under  high temperature conditions.

Population  Exposed

There is indication of widespread exposure to PNA's from natural
and anthropogenic sources.   They occur in all phases of the
environment.  PNA's are  more concentrated in urban areas where
large population densities  exist.  Persons working with or using
products derived from fossil fuels are potentially exposed to
very high  levels of PNA's.                 .

         TABLE 33.  FOSSIL  FUEL AND ITS DERIVATIVES (3)
    :                          (vg/kg)
PNA
Benio(a)pyrene
Chrysene
Benz (a ) anthracene
Coal
300 - 1*000
«*
'**,•
Coal tar .
30,000
<2,860
<6.980
Coal tar Petroleum
pitch asphalt
12,500 0.1 - 27
<10,000 <0.4 - <34
<12,500 <35
Creosote
, ...oil '•
0.00014 -
0.0002
<1,340
<2,940

  Data hot available.

HEALTH EFFECTS

PNA's are part of a  group  of  known carcinogens that are present
in the particulate phase of polluted air.  The extent of the con-
tribution of these agents  to  the incidence of human lung cancer,
however, is unknown  (30).  The  majority of health effects data

(30) Committee of Biologic Effects of Atmospheric Pollutants,
     National Research  Council.   Particulate Pdlycyclic Organic
     Matter.  ISBN 0-309^02027-1 (PB-212 940), National Academy
     of Sciences/ Washington, D.C., August 1972.  375 pp.

                                24

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regarding  PNA's  is  concerned with  their  carcinogenicity,  muta-
genicity and  teratogenicity.    Table  34 summarized  the  low  toxic
doses  of selected  PNA's   (31)                     .    :
TABLE  34,   TOXICITY  OF
                                                             PNA's   (31)
         Combound'
 Anthracene

 Benzo(a)pyrene


 Chrysene


 Phenanthrene


 Benz (a)anthracene





 3-methycholanthrene
 Benzo(k)fluoranthene

 Pyrene
 2,3-o-phenylenepyrene

 1,2,5,6-dibenzanthracene
                                                          ("route,  anjmal,~
        18 g/kg, oral,  rat, carcinogenic
        3,300 rag/kg, subcutaneous,  rat, neoplastic effects
        2 ug/kg skin, mouse, carcinogenic
        250 ug/kg, subcutaneous, rate, neoplastic effects
        200 mg/kg, subcutaneous, mouse, carcinogenic
        99 mg/kg for 31 weeks, intermittent,  skin, mouse, neoplastic
        700 mg/kg, oral, mouse, LD50
        71 mg/kg, skin, mouse, neoplastic
        240 mg/kg for 5 weeks, skin, mouse,  carcinogenic
        2 mg/kg, subcutaneous, mouse, carcinogenic
        10 mg/kg, intraveneous, mouse, lowest lethal dose
        3 mg/kg, parenteral, mouse, carcinogenic
        80 mg/kg, implant, mouse, carcinogenic

        280 mg/kg, oral, rat, carcinogenic
        34 mg/kg fpr 25 weeks,,, intermittent,  skin, fat, neoplastic '.
        18 mg/kg, subcutaneous, rat, carcinogenic              .
        39 mg/kg for $ days, intraveneously,  rat, neoplastic
        3 mg/kg, parenteral, rat, carcinogenic
        100 mg/kg for 5 weeks, intermittently, intratracheal, rat, carcinogenic
        800 ug/kg, implant, rat, carcinogenic
        40 mg/kg for 20 days of pregnancy, oral, mouse, neoplasties
        2,300 mg/kg for 90 days continuously, oral, mouse, carcinogenic
        13 mg/kg for 42 weeks, intermittently, skin, mouse, carcinogenic
        100 mg/kg for intraperitoneal, mouse, lowest lethal dose
        1,600 mg/kg for 20 weeks intermittently, intraperitoneal,  mouse, neoplastic
        312 ug/kg, subcutaneous, mouse, carcinogenic
        120 mg/kg for week, intermittently,  intratracheal,' mouse;  carcinoienic
        80 mg/kg, implant, mouse, neoplastic
        40 mg/kg, implant, dogt, neoplastic           .
        100 mg/kg for 9 weeks, intermittently, intrapleural, rabbit, neoplastic
        132 mg/kg for 12 weeks, intermittently, intratracheal, rabbit, carcinogenic
        4 mg/kg intraperitoneal, guinea pig,  carcinogenic
        40 mg/kg for 15 days, subcutaneous,  guinea pig, carcinogenic
        36 mg/kg, intraveneously, guinea pig, neoplastic
        2,075 mg/kg for 17 weeks, intermittently, oral, hamster, carcinogenic
        3,320 ug/kg for 40 weeks, skin, hamster, neoplastic
        4,150 gg/kgr subcutaneous,  hamster,  neoplastic
        58 mg/kg, implant, hamster, carcinogenic
        4,500 ug/kg for 8 weeks, intermittently, intraperitoneal, chicken, carcinogenic
        27 mg/kg, intratracheal, duck, carcinogenic
        11 mg/kg, intrarenal, frog, lowest lethal dose

        72. mg/kg for 9  weeks, «kin, mouse, carcinogenic
        10 ug/kg for 3  weeks, intermittently, skin, mouse, neoplastic
        72 mg/kg for 9  weeks, intermittently, subcutaneously, mouse, carcinogenic

        500 ug/kg, subcutaneous, rat, carcinogenic
        360 mg/kg for 22 .weeks, continuously, oral, mouse, carcinogenic
        6 ug/kg, skin,  mouse, neoplastic
        76 ug/kg, subcutaneous, mouse, carcinogenic
        10 mg/kg, intraveneously, mouse, lowest lethal dose
        80 mg/kg, implant, mouse, neoplastic
        30 mg/kg, intraveneously, guinea pig, neoplastic
        11 mg/kg, intramuscularly,  pigeon, carcinogenic
        8 mg/kg, intrareneally, frog, carcinogenic
  Some observed doses are expressed as dependent on time.
 (31)  Christensen,  Herbert E.,  Ed.,  Registry of  Toxic  Effects of
        Chemical  Substances,  1976  Edition,  Rockville,  Md.,  U.S.
        Department of  Health,  Education  and  Welfare,  1976.    1245  pp.
                                              25

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The American Conference of Governmental Industrial Hygienists has
adopted an eight hour work day limit of 200 pg/m3 for coal tar
pitch volatiles  (benzene fractions containing compounds such as
anthracene, benzo(a)pyrene, phenanthrene, acridine, chrysene, and
pyrene) (1).  The World Health Organization has recommended
0.2 mg/m3 of PNA's as a maximum permissible concentration for
human consumption.   This is calculated a-s the sum of six com-
pounds.  The recommended benzo(a)pyrene limit for the sum was
0.0075 mg/m3, and the recommended limit for all PNA's was
0.03 mg/m3 (1).
                               26

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                            SECTION 5

                       CONTROL TECHNOLOGY


Indications are that chlori.na.tion and ozonation of water supplies
destroy PNA's (1); however, byproducts may be produced that are
much more toxic when they are "destroyed" by chlorination.  An
assessment of the degradation products formed and their toxicity
appears to be mandatory.

Emissions of PNA's from combustion sources can be reduced by.
increasing airrto-fuel ratios.  Secondary combustion devices for
flue gases would also reduce emissions.  Paxticulate matter seems
to be'a method of transport for PNA's in.the environment; thus,
particulate controls should help in reducing emissions-

STATIONARY SOURCES

Benzo(a)pyrene (BaP) is chosen to be a typical PNA emission for
the purposes of this section, since BaP emissions represent the
most completely characterized PNA emission.  The most important
contributors of BaP emissions in heat and power generation are
hand-fired coal furnaces and wood burning; thus, the preferred
choice of control would be by alternative fuel sources.  One
might argue that substitution is the only means of control for
these two sources., as neither is amenable to better engineering
controls.

In regard tp refuse burning., efficient incinerators are being
installed for municipal, commercial, industrial, and apartment
building sources.  Relative contributions from these sources are
diminishing in comparison to coal refuse banks.  Existing burn-
ing began spontaneously.  Federal regulations have been proposed
for all burning coal refuse piles which will eliminate most
emissions as these regulations are implemented.

BaP emissions from catalytic cracking in the petroleum industry
apparently are receiving necessary action through utilizing car-
bon monoxide (CO) waste boilers for effective control  (see
Table 8).  From Table 8 it is clear that CO waste-heat boilers
have significant beneficial effects on BaP emissions and, thus,
on other PNA emissions.

Much of the BaP produced at byproduct coke ovens quite likely
could be removed in the byproduct stream, except for that

                               27

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 escaping  from a  leaky  system.   However,  BaP  emissions  from most
 coke  processing  still  appear  to be quite high,  whether they
 originate from charging or  leaks or directly from the  gas  stream.

 Some  possible approaches  to controlling  BaP  from coke  ovens are
 under investigation  by EPA  and  industry  groups;  two  demonstration
_.projects _for particulate  control ..from—coke o-vens -are .in- progress,
 and BaP sampling is  being done  simultaneously (32).

 Sampling  results indicate that  about  90% control of  particulates
 is achieved  (32) .  With this  level of particulate control,  a
 similar degree of reduction in  BaP emissions was expected.   Pre-
 liminary  evaluation  of the  BaP  fraction  of the  particulate from
 the controlled versus  the noneontrolled  larry car (vehicle that
 drops coal into  the  oven) indicates that approximately 85% to 90%
 control is achieved  (32).   If these results  are obtained for
 other types  of particulate  control, a reduction of PNA's should
 result.   These results confirm  previous  expectations of control
 engineers that particulate  control will  significantly  reduce BaP
 emissions.           .               .

 MOBILE

 Before the current concern  for  reducing  vehicle emissions  was
 instigated by the Clean Air Act, most vehicles  operated with
 fuel-rich carburetion  to .-promote smooth  performance  and quick
 power response.   Preliminary  modifications prior to  the 1970
 Clean Air Amendments resulted in leaner  fuel-aix mixtures  and
 lower BaP. emissions*

 Emission  control devices  will affect  control of BaP  concomitantly,
 as indicated in  Table  35.   Data to support this view are based
 on current exhaust sampling techniques.   If  such a high degree
 of control is achieved in actual practice, mobile source pollu-
 tion  caused  by BaP will assume  a much less significant role.  At
 any rate,  one may logically expedt a  reduction  of BaP  emissions
 from  light-duty  vehicles  as a result  of  the  EPA motor  vehicle
 control activityi  A higher degree of uncertainty exists for
 other transportation sources; e.g., buses, heavy diesel trucks,
 or aircraft.
 (32)  Preferred  Standards  Path  Report  for Polycyclic Organic
      Matter.  Draft  report,  U.S. Environmental Protection Agency,
      Durham,  North Carolina, October  1974.   107 pp.

                               28

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   TABLE 35.  AUTOMOTIVE  BENZO(a)PYRENE EMISSION FACTORS  (32)

    •••••"   '•• ••' "" •'"""'   ;   ' "•. • '""    Benzo 
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                            SECTION 6

                        REGULATORY ACTION
Limitation of carbon monoxide and hydrocarbon emissions from
motor vehicles has simultaneously and dramatically reduced the  .
emissions of PNA's.  A 1974 analysis of stationary source pro-
blems concluded that control regulations designed specifically
for benzo(a)pyrene or polynuclear aromatic hydrocarbons were not
warranted or practical.  It did note that compliance with exist-
ing regulations for incinerators> open burning, coal combustion,
and coking operations cbuld significantly reduce emissions.
Additional efforts to document stationary source emissions,
atmospheric chemistry, and human exposure have been initiated
on a limited scale.  Consideration is being given to establish
revised standards for doke oven emissions under the Clean Air
Act.

One hundred and twenty-nine chemicals including 13 polynuclear
aromatic hydrocarbons, have recently been designated as priority
pollutants for study.  Physical and chemical behavior, health
and environmental effects, and sources and environmental levels
are to be documented.  Appropriate water quality criteria, efflu-
ent guidelines, toxic pollutant standards, and/or pretreatment
requirements will be established under the Federal Water Pollu-
tion Control Act in accordance with a court-approved schedule
(33).
(33) Identification Of Selected Federal Activities Directed to
     Chemicals of Near-Term Concern.  EPA 560/4-76-^007, U.S.
     Environmental Protection Agency/ Washington, D;C.,
     September 1976.  21 pp.

                               30

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                           REFERENCES3
 1.  Radding, S. B., T. Mill, C. W. Gould, D. H. Liv, H. L. John-
     son, p. C. Bomberger and V. C. Fojo.  The Environmental Fate
     of Selected Polynuclear Aromatic Hydrocarbons.  EPA 560/5-
     75-OQ9, U.S. Environmental Protection Agency, Washington.,
     D.C., February 1976.  131 pp.

 2.  Patterson, A. M.,  L. T. Capeil, and D. F. Walker.  The Ring
     Index.  A List of Ring Systems Used in Organic Chemistry.
     American Chemical Society/ Washington, P.C., 1960.  1425 pp.

 3.  International Agency for Research on Cancer, "Monograph on
     the Evaluation of Carcinogenic Risk of the Chemical to Man:
     Certain Polycyclic Aromatic Hydrocarbons and Heterocyclic
     Compounds," World Health Organization, Geneva, Switzerland,
     1973, Volume 3.

 4.  Hansch, C.   (1975), private communication, Pomona College,
     Pomona, California.

 5.  Fieser, L. F. and A. M. Seligman (1935), "The Synthesis of
     Methycholanthrene," J. Amer. Chem.. Soc. 57, 942-46.

 6.  "Handbook of Chemistry and Physics," 45th Ed., Chemical
     Rubber Co.., Cleveland, Ohio, 1964.

 7..  Leo, A., C. Hansch, and D. Elkins (1971), "Partition Coeffi-
     cients and Their Uses," Chem. Rev.  71(6), 525-616.

 8.  Pupp, C., R. C. Lao, J. J. Murray,  and R. F. Pottie (1974),
     "Equilibrium Vapor Concentrations of Some Polycyclic Aro-
     matic Hydrocarbons, Arsenic Trioxide  (Asi+Oe) and Selenium
     Dioxide, and the Collection Efficiencies of these Air
     Pollutants," Atmos. Environ. 8(9),  915-25.

 9.  Jordan,. T. E., "Vapor Pressures of Organic Compounds,"
     Interscience Publishers, Inc., New York, 1954.  •

10.  1977 Directory of Chemical Producers.  Stanford Research
     Institute, Menlo Park, California.   1977.  p. 782.
References 3-9 and 19-29 are reported as cited by author of
 Reference 1.
                               31

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  11.  vbn Riimker, R. , E. W. Lawless, and A. F. Meiners.  Produc-
       tion, Distribution, Use and Environmental Impact Potential
       of Selected Pesticides (PB 238 795).   Council on Environ-
       mental Quality, Washington, D.C., March 1974.  439 pp.

  12.  Development Document for Effluent Limitations Guidelines and
       New Source Performance Standards for the Major Organic Pro-
       ducts Segment of the Organic Chemicals Manufacturing Point
       Source Category, EPA 440/1-74-009-a,  U.S. Environmental
       Protection Agency, Washington, D.C.,  1974.

  13.  Cooper, F. D.  Coke and Coal Chemicals.  In:  Minerals Year-
       book 1974, Volume 1.  Metals, Minerals, and Fuels.  U.S.
       Government Printing Office, Washington, D.C., 1976.  p 447.

  14.  Hawley, Gessner G., Ed., The Condensed Chemical Dictionary,
       8th Ed., New York, Van Nostrand Reinhold Co., 1971.

  15.  Hangebrauck, R. P., et al., Sources of Polynuclear Hydrocar-
       bons in the Atmosphere, 999-AP-33, Public Health Service,
       1967.

  16.  Samedov/ I. G. and A. S. Kurbanov, "Pollution of the Air
       with Carcinogenic Substances by Baku Petroleum Refineries,"
       Azerbaydzhanskiy Medit. Zh. 28  (11),  62-67  (1971).

  17.  Lowry, H. H., Ed., Chemistry of Coal Utilization, 2 Vols.,
       and supplementary volume, N.Y., Wiley, 1945, 1963 (supple-
       mentary volume)...       .          .                •

  18.  Todd, Robert G., Direct Identification of Polycyclic Aro-
       Matic Hydrocarbons from Carbon Black, Masters Thesis, Uni-
       versity of Oklahoma, Norman, Oklahoma, 1970.

  19.  Zdrazil, J. and P. Picha  (1965), "Carcinogenic Hydrocarbons,
       Especially 3,4-benzopyrene, in the Atmosphere of Foundries,"
       Slevarenstvi 13, 198-9 •.

  20.  Olsen, D. A., J. L* Haynes  (1969), "Air Pollution Aspects of
       Organic Carcinogens," Report No. PB-188 090, 131 p.

  21.  Bolotova, M. N., Ya. S. Davydov, and N. G. Nikishina  (1967),
       "Basic Industrial Sources of the Carcinogenic Hydrocarbon;
       Benzo(a)pyrene," Med. Zh. Uzb. No. 11, 51-4.

  22.  Sawicki, E.  (1967), "Airborne Carcinogens and Allied Com-
       pounds," Arch. Environ. Health 14  (1), 46-53.

^23.  Andelman, J. B. , and M. J. Sxiess (1970), "Polynuclear Aromatic
       Hydrocarbons in the Water Environment," World Health Organi-
       zation 43, 479-508.
                                 32

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24.   Shabab,  L.  M.  and Y.  L.  Cohan (1972),  "Contents of Benzo(a)-
     pyrene in S6me Crops," Arch.  Geschwulstforsch.  40 (3),  237-43.

25.   Grimmer, G. (1968),  "Carcinogenic Hydrocarbons  in the Human
     Environment,"  Deut.  Apoth.-Ztg.   108(16),529-33.

26.   Grimmer, G.,  A. Hildebrandt (1965b)/ "Content of Polycyclic
     Hydrocarbons  in Different Vegetables.  III.  Hydrocarbons in
     the Human Surroundings," Deut.  Lebensm.-Rundschau 61(8), 237-9

27.   Gorelova, N.  D., P.  P. Dikun, L.  D.  Kostenko, 0.  P.  Gret-
     skaya, and A.  V. Emshanova (1971),  "Detection of the Possible
     Presence of 3,4-benzopyrene in Fresh Fish," Novosti Onkol.,
     8-12.

28.   Wierzchowski,  J. and R.  Gajewska (1972),  "Determination of
     3,4-benzopyrene in Smoked Fish,"  Bromatol. Chem.  Toksykol.
     5(4), 481-6.

29.   Shirotori,  1972.

30.   Committee of  Biologic Effects of Atmospheric Pollutants,
     National Research Council.  Particulate  Polycyclic Organic
     Matter.   ISBN 0-309-02027-1 (PB-212  940),  National Academy  ..
     of  Sciences,  Washington, D.C.,  August 1972.  375 pp.

31.   Christensen,  Herbert E., Ed., Registry of  Toxic Effects of
     Chemical Substances,  1976 Edition,  Rockville, Md., U.S.
     Department of Health, Education and  Welfare, 1976.  1245 pp.

32.   Preferred Standards  Path Report for  Polycyclic  Organic
     Matter.   Draft report, U.S. Environmental  Protection Agency,
     Durham,  North Carolina,  October 1974.   107 pp.

33.   Identification of Selected Federal Activities Directed to
     Chemicals of  Near-Term Concern.   EPA 560/4-76-007, U.S.
     Environmental Protection Agency,  Washington, D.C.,
     September 1976.  21  pp.
                               33

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