oEPA
              United States
              Environmental Protection
              Agency
              Industrial Environmental Research
              Laboratory
              Cincinnati OH 45268
EPA-600 2-79-210d
December 1979
              Research and Development
Status
Assessment of
Toxic  Chemicals
              Benzene

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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
      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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                                     EPA-600/2-79-210d
                                     December 1979
    STATUS ASSESSMENT OF TOXIC CHEMICALS:

                   BENZENE


                     by
                J.  C.  Ochsner
               T.  R.  Blackwood
        Monsanto Research Corporation
             Dayton,  Ohio  45407

                     and

                L.  D.  Zeagler
             Radian Corporation
            Austin, Texas  78766
           Contract No.  68-03-2550
               Project Officer

               David L.  Becker
    Industrial Pollution Control Division
Industrial Environmental Research Laboratory
           Cincinnati, Ohio  45268
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.
                                11

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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
(lERL-Ci) assists in developing and demonstrating new and im-
proved methodologies that will meet these needs both efficiently
and economically.

     This report contains a status assessment of the air emis-
sions, water pollution, health effects, and environmental signi-
ficance of vinylidene chloride.  This study was conducted to
provide a better understanding of the distribution and character-
istics of this pollutant.  Further information on this subject
may be obtained from the Organic Chemicals and Products Branch,
Industrial Pollution Control Division.

     Status assessment reports are used by lERL-Ci to communicate
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 indi-
cative rather than exhaustive.
                                   David G. Stephan
                                        Director
                     Industrial Environmental Research Laboratory
                                       Cincinnati
                               111

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                            ABSTRACT
Benzene, one of the most significant commercial organic chemi-
cals in the United States, is a component of gasoline and a
major intermediate in the organic chemicals industry.  Because
of its health hazards, it is also very important from an environ-
mental standpoint.  Produced in quantity second only to  ethylene,
the estimated 1977 capacity is 6.8 x 106 m3 divided among more
than 50 manufacturing plants.  Increasing demand is expected
to continue, possibly by 7.5%/yr until at least 1980.

Benzene is primarily used in the synthesis of other organic
chemicals.  Ethylbenzene, cumene, and cyclohexane production
account for more than 80% of benzene used in the United States.
Although production and process consumption is concentrated in
the Texas Gulf and Northeast areas, its presence in gasoline
gives it nationwide distribution.  In fact, the largest total
mass of emission is a result of motor vehicle operations
(456 x 106 kg/yr).  Major industrial sources of benzene emis-
sion include degreasing  (73.1 x 106 kg/yr), ethylbenzene/styrene
(9.5 x 106 kg/yr), and cyclohexane manufacture  (7.8 x 105 kg/yr).

Benzene clearly produces adverse health effects.  It has long
been recognized as a poison if ingested in large quantities, and
at nonlethal concentrations, a variety of human central nervous
system disorders are observed.  Federal standards for occupa-
tional exposure to benzene have been set, but further reduction
in allowable concentrations has been proposed.  Regulatory action
under the Clean Air Act  is awaiting results of an air monitoring
program.  Water quality  criteria are anticipated under the
Federal Water Pollution  Control Act  (FWPCA) by July 1978.  The
Consumer Products Safety Commission is considering action con-
tingent on results of an Academy of Sciences study.

The following recommended areas for further study are:  1) ambient
levels of benzene and the population exposed, 2) environmental
reactivity, 3) benzene loss due to spills, accidents, or leaks,
4) benzene emissions from fugitive sources, 5) effects from non-
lethal doses of benzene, 6) benzene's connection with leukemia,
and 7) effect of modern  motor vehicle emission controls on
benzene emissions.
                                xv

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This report was submitted in partial fulfillment of Contract
68-03-2550 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency.  This report covers
the period November 1, 1977 to December 31, 1977.  The work was
completed as of January 20, 1978.

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                            CONTENTS
Foreword	iii
Abstract	iv
Tables	viii
Abbreviations 	  ix
Conversion Factors and Metric Prefixes	   x
Acknowledgement 	  xi

   1.  Introduction 	 1
   2 .  Summary	2
   3.  Source Description 	 5
            Physical and chemical properties	5
            Production	6
            Process description 	 6
            Uses	12
            Transportation	13
   4.  Environmental Significance and Health Effects	18
            Environmental significance	18
            Health effects	18
   5.  Control Technologies	26
            Emission source control methods	26
            Control efficiencies	26
   6.  Regulatory Action	32

References	33
Glossary	36

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                             TABLES
Number
  1     Benzene	   3
  2     Producing Companies, Plant Locations, and Capacity
          of the Benzene Industry	-	   7
  3     Estimated Benzene Production  (1976)	11
  4     Benzene Consumption  (1976)  	  13
  5     Benzene Emission Sources 	  19
  6     Evaporative Emission Factors  for Benzene Storage
          Tanks Without Controls 	  21
  7     Ambient Monitoring Data for Benzene	22
  8     Toxicity Data for Benzene	25
  9     Control Devices and Reported  Control Efficiencies
          for the Maleic Anhydride Industry	30
                               viii

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                          ABBREVIATIONS
FWPCA
LD50
MRC
NIOSH
OSHA
OTS
ppb
ppm
TC,
TD
'Lo
I
Lo
-Federal  Water Pollution Control Act
-lowest reported concentration to have caused death
-calculated concentration expected to kill 50% of an
 exposed  population
-lowest reported dose to have caused death
-dose expected to kill 50% of a population
-Monsanto Research Corporation, Dayton, Ohio
-National Institute of Occupational Safety and Health
-Occupational Safety and Health Administration
-Office of Toxic Substances
-parts per billion
-parts per million
-lowest concentration reported to produce toxic effects
-lowest dose reported to produce toxic effects
                                IX

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             CONVERSION FACTORS AND METRIC  PREFIXES
  To convert from

Degree Celsius  (°C)
Gram/second  (g/s)
Kilogram  (kg)
Meter  (m)
Meter3  (m3)
Meter3  (m3)
Meter3  (m3)
Metric ton
Metric ton
Pascal  (Pa)
              CONVERSION FACTORS

             	To	

             Degree Fahrenheit
             Pound/hr
             Pound-mass (avoirdupois)
             Foot
             Barrels
             Foot3
             Gallon  (U.S.  liquid)
             Kilogram
             Pound-mass
             Pound-force/inch2  (psi)
                                  Multiply by
          = 1
                                    1.
                                    2.
                                      8 t° +
32
                  7.937
                  2.205
                  3.281
                  6.293
            3.531 x 101
            2.642 x 102
              000 x 103
              205 x 103
                                   1.450 x
Prefix

Kilo
Milli
Symbol

  k
  m
      METRIC PREFIXES

Multiplication factor

         103
         10~3
        Example
1 kPa = 1 x 103 pascals
1 mg = 1 x 10"3 gram
 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.
                                x

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

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                          SECTION 1

                         INTRODUCTION
Benzene is one of the most significant commercial organic
chemicals in the United States.  It is a component of gasoline
and a major intermediate in the organic chemicals industry-
Large quantities of benzene enter the environment and have
become the subject of increasing concern and widespread inves-
tigation.  Benzene clearly produces adverse health effects.
Its commercial significance and pervasiveness mean that regula-
tory action must be considered.  Devising a management strategy
will be a complex and difficult problem.

Much of the information needed to define regulatory action is
currently being generated by agencies outside the U.S. Office of
Toxic Substance (OTS).  The purpose of this report is to summar-
ize available information on health effects, ambient concentra-
tions, and sources of benzene.  Production methods and quantities
are described along with control techniques and regulatory action
under consideration.

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                            SECTION 2

                             SUMMARY
Benzene is a volatile, colorless, flammable liquid that is one
of the most important industrial organic chemicals produced in
the United States.  Because of its potential health hazards,
it is also very important from an environmental standpoint.
However, a general lack of data prevents any accurate predic-
tion of its environmental reactivity.

Benzene is produced in over 50 locations in quantities second
only to ethylene.  The estimated capacity for 1977 is 6.8 million
m3.  Increasing demand is  expected to continue, possibly by
7.5%/yr until  at least 1980.

The two major  sources of benzene are petroleum and coal, with
petroleum being the largest source.  Six processes are used to
manufacture benzene;  four operate on petroleum derivatives and
two operate on coal.

Benzene is primarily  used in the synthesis of other organic chem-
icals.  Ethylbenzene, cumene, and cyclohexane production account
for more than  80% of  benzene used in the United States.  Barring
any unexpected events, benzene will  remain as one of the most
important chemicals to industry.

Benzene is shipped in drums and tank cars domestically by water
 (79.6%), rail  (14.8%), and truck  (5.6%).  Most pipeline shipment
is restricted  to that which is captively used by the plant in
which it is produced.

There are several sources of benzene emissions.  The largest
total mass of  emission is from motor vehicles (exhaust fumes),
450 million kg/yr.  Major industrial sources of benzene include
degreasing and ethyl  benzene/styrene manufacture, 73.1 million
kg/yr and 9.5  million kg/yr, respectively.  About 576,000 metric
tons of benzene are released to the  atmosphere from the produc-
tion and use of benzene and products which contain it.

Information on levels of benzene in the atmosphere is sparse.
However, one study indicated high values for metropolitan areas
(Los Angeles and Toronto)  which may be primarily due to exhausts
from motor vehicles.   Benzene has been identified in the drinking

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 water  of  three  U.S.  locations  at  levels  of  2.0  ppb.    It has  also
 been identified in  subsurface  water at  levels  of  10  ppm in brine
 from one  area,  and  24  ppm  in  another  geographic area  having
 extensive  oil and gas  deposits.

 Benzene has  long  been  recognized  as a poison if ingested  in
 large  quantities.    The effects  of nonlethal  doses,  including
 long-term  illnesses,  are not  fully  understood.   Many  researchers
 have concluded  that more study  is definitely needed,  especially
 to determine  if benzene  can cause cancer.

 Control of  benzene  emissions  can  be achieved by preventing
 release of  the  pollutant or by  treating  the  waste  streams.
 Various techniques  of  implementing  these ideas  have  been  devel-
 oped and  are  summarized  in Table  1.    Also  presented  are emissions
 sources and rates,  population  exposed,  and regulatory action.

                                    TABLE  1.   BENZENE
       Emission source
                        Bnission rate,
                         10s kg/yr
                                  Extent of problem
                                      Population exposed
                                                            Control method
                                                                            Regulatory agency or action
Production:
 Catalytic reforming              2.6
 Toluene dealkylation              1.4
 Toluene disproportionation          0.04
 Pyrolysis gasoline               0.6
 Coke-oven light oil              0.2
 Coke-oven operations              0.2
Production of benzene is gen-  Incineration or vapor recovery  OSHA has proposed a reduc-
 erally localized in the
 Texas Gulf and Northeast
 systems.  Wet scrubbing in
 an absorber or a combination
 of the above. (>95% effi-
 ciency) .  Hater treatment
 generally involves primary
 separation (70% to 90% effi-
 ciency) followed by secondary
 and possibly tertiary treat-
 tion of the 10 ppm stand-
 ard to 1 ppm 8-hr weighted
 average with a ceiling of
 5 ppm over a 15-min period.
Transport and storage:
 Bulk terminal loading/storage
Industrial use:

 Ethyl benzene/styrene             9.5
 Cumene/phenol                  2.4
 Cyclohexane                    7.B
 Aniline                      0.1
 Chlorobenzenes                  2.6
 Haleic anhydride                2.0
 Detergent alkylate               0.01
 Surface coatings (paints)           3.2
 Degreasing                   73.1
 Nitrobenzene                   3.4
 Fumaric acid                   0.3
 Acrylonitrile                  0.2

Use of products containing benzenei
 Automobile tank loading            5.9
 Service station tanks             0.2
 Motor vehicles                 450
 Oil spills                   10
                                                       Modified loading procedures
                                                         (submerged or bottom loading)
                                                         in conjunction with vapor
                                                         recovery devices.  Improved
                                                         storage tank designs.
Process consumption of benzene
 is generally localized in
 the Texas Gulf and North-
 east areas.
The presence of benzene in
 gasoline gives it nation-
 wide distribution. Scarce
 data indicate that most
 Americans are probably
 exposed continuously to
 very low levels of benzene.
Incineration or vapor recovery
 systems.  Wet scrubbing in
 an absorber or a combination
 of the above. (>95% effi-
 ciency.)  Hater treatment
 generally involves primary
 separation (70% to 90% effi-
 ciency) followed by secondary
 and possibly tertiary treat-
 ment.
OSHA has proposed a reduc-
 tion of the 10 ppm stand-
 ard to 1 ppm 8-hr weighted
 average with a ceiling of
 5 ppm over a 15-min period.
Vapor recovery and modified
 loading procedures.
Catalytic converter.
Proper procedure after
 benzene-containing spill.
EPA has initiated an air
 monitoring program which
 will determine benzene
 levels in* selected areas.
 Benzene has been designa-
 ted a priority pollutant
 under the Federal Hater
 Pollution Control Act.

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Based upon the information in this report the following areas
for further study are recommended:

  • More data is needed on ambient levels of benzene and
    the population exposed.

  • More information is needed on benzene's environmental
    reactivity, for instance, its environmental residence
    time.

  • Information is lacking on the amount of benzene lost
    due to spills, accidents, or leaks.

  • The extent of benzene emissions from fugitive sources
    is unknown.

  • The effects from nonlethal doses of benzene are not
    fully understood.

  • More studies are needed to determine if there is a
    connection between benzene and leukemia.

  • The effect that modern emission controls will have on
    benzene emissions from motor vehicles is an' area for
    study.

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                            SECTION 3

                       SOURCE DESCRIPTION
PHYSICAL AND CHEMICAL PROPERTIES

Benzene is one of the most important industrial organic chemicals
produced in the United States.  Because of its potential health
hazards, it is also very important from an environmental stand-
point.  The behavior of benzene after it has been emitted to the
air or to a body of water is dependent to a large extent upon
its physical properties.  These will control its stability,
chemical reactions, and long-term ambient concentrations in the
environment.

Benzene is a volatile, colorless, flammable liquid.  Its chemical
formula is CgH6, and it has a structure represented as

                  H
                  C
         HC
              HC

                     CH
                         or
                                      or
                  H
Its important chemical properties are listed below:
Molecular weight

Vapor pressure

Boiling point

Specific gravity

Octanol/water partition
  coefficient

Physical state

Vapor specific gravity (air = 1)
Melting point
                                                       78.11
                                              13 kPa at 25°C

                                           80.1°C at 101 kPa

                                          0.8787 at 20°C/4°C


                                                        2.28

                                                      Liquid

                                                        2.77
                                                       5.5°C
Solubility
                              Slightly (1.79 x 10 3 g/m3 H20)

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Little is known about benzene's environmental reactivity. In the
atmosphere, it slowly reacts with oxidizing materials.  Benzene
is not photochemically reactive, but it is biodegradable  (1).
It is quite persistant, and due to its high vapor pressure, it
is highly mobile in the atmosphere.

Benzene has been detected in both inland and marine waters.
Because of its biodegradability, some benzene is oxidized by
microorganisms in both air and water environments.  A general
lack of data prevents any accurate prediction of the environ-
mental residence time of benzene  (2).

PRODUCTION

Benzene is one of the most significant petrochemicals in the
United States.  It is produced  in quantity second only to
ethylene.  In 1973, over 5.170  x 106 m3 of benzene were pro-
duced in the United States.  The estimated capacity for 1977 is
6.805 x 106 m3 divided among more than 50 manufacturing plants.
A list of benzene manufacturers is presented in Table 2  (3).
The flexibility of most aromatics operations enables the re-
porting of only approximate capacities.

PROCESS DESCRIPTION

The two major sources of benzene are petroleum and coal, with
petroleum supplying the largest percentage.  Six processes  are
used to manufacture benzene; four of them operate on petroleum
derivatives and two operate on  coal.  These processes are listed
in Table 3 by estimated 1976 production and number of sites.

Petroleum-derived benzene is isolated from catalytic reformate
and pyrolysis gasoline and produced directly by the dealkylation
and disproportionation of toluene.  Coal-derived benzene is iso-
lated from coke-oven light oil, a byproduct of coke manufacture.
Each of these processes is subsequently described.
 (1) Dorigan, J.  Scoring of Organic Air Pollutants:  Chemistry
    Production and Toxicity of Selected Synthetic Organic Chemi-
    cals.  Mitre Corporation, September 1976.
 (2) Ocean Affairs Board, National Research Council1.  Assessing
    Potential Ocean Pollutants.  Report No.  0-309-02325-4, U.S.
    Environmental Protection Agency and National Science
    Foundation, Washington, D. C., January 1975.  456 pp.

 (3) Directory of Chemical Producers—U.S.A.  Chemical Information
    Services, Stanford Research  Institute, Menlo Park,
    California, 1977.  1059 pp.

                                 6

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TABLE 2.   PRODUCING COMPANIES, PLANT  LOCATIONS, AND CAPACITY  OF THE BENZENE  INDUSTRY  (3)
              Company
      Location
Annual capacity,
    103 m3
      Raw material
 Amerada Hess Corp.
   Hess Oil Virgin Islands Corp.,
     subsidiary
 American Petrofina, Inc.
   American Petrofina Co. of Texas,
     subsidiary
   Cosden Oil & Chemical Co.,
     subsidiary

 Armco Steel Corp.
 Ashland Oil, Inc.
   Ashland Chemical Co., division
   Petrochemicals division

 Atlantic Richfield Co.
   ARCO Chemical Co., division
 Bethlehem Steel Corp.
 CF&I Steel Corp.

 The Charter Co.
   Charter Oil Co., subsidiary
     Charter International Oil
       Co., subsidiary
 Cities Service Co.
   Chemicals Group
     Columbian Chemicals division

 Coastal States Gas Corp.
   Coastal States Marketing, Inc.,
     subsidiary
St. Croix,  VI
Port Arthur,  TX

Big Spring,  TX
Middletown,  OH

Ashland, KY
North Tonawanda,  NY
Carson, CA
Channelview,  TX
Houston, TX
Bethlehem, PA
Sparrows Point, MD

Pueblo, CO
Houston,  TX
Lake Charles, LA
Corpus Christi,  TX
        95
        57

       170

        11


       238
        57

        45
       132
       159

        19
        57

        11
        19
        95
       265
Petroleum
Petroleum, captive

Petroleum, partly captive
Coal
Petroleum, partly captive
Petroleum

Petroleum
Petroleum
Petroleum
Coal
Coal
Coal
Petroleum
Petroleum
Petroleum, partly captive
              (continued)

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                                            TABLE  2  (continued)
                  Company
                                          Location
                      Annual capacity,
                          103 m3
                                                                                        Raw material
oo
     Commonwealth Oil Refining Co., Inc.
       Commonwealth Petrochemicals,
         Inc., subsidiary
     Crown Central Petroleum Corp.
       Chemicals division
     Dow Chemicals U.S.A.
Exxon Corp.
  Exxon Chemicals Co.,  division
    Exxon Chemicals Co. U.S.A.

Getty Oil Co.
  Getty Refining and Marketing
    Co. subsidiary
Gulf Oil Corp.
  Gulf Oil Chemicals Co.,  division
    Petrochemicals, division
      Independent Refining Corp.
      Interlake, Inc.
      Jones and Laughlin Industries, Inc.
       Jones & Laughlin Steel Corp.,
          subsidiary
      Kerr-McGee Corp.
       Southwestern Refining Co., Inc.
          subsidiary
                                    Ponce, PR
                                    Pasadena, TX

                                    Bay City, MI
                                    Freeport, TX
                                         Baton Rouge, LA
                                         Baytown, TX
                                         El Dorado, KS
Alliance, PA
Philadelphia, PA
Port Arthur, TX

Winnie,  TX

Toledo,  OH
                                    Aliquippa, PA
                                    Corpus Christi, TX
                             700
                              87

                             114
                             189
                              83
                             227
                              49
265
125
144

 11

  4
                              38
                              61
                                                                             Petroleum
            Petroleum
            Petroleum, captive
            Petroleum, captive
            Petroleum
            Petroleum, partly captive
            Petroleum, captive
Petroleum
Petroleum, captive
Petroleum, captive
Petroleum
Coal
            Coal
            Petroleum
                                                                                                (continued)

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                                        TABLE  2  (continued)
             Company
      Location
Annual capacity,
    103 m3
      Paw material
Marathon Oil Co.

Mobil Corp.
  Mobil Oil Corp.
    Mobil Chemicals Co., division
      Petrochemicals division

Monsanto Co.
  Monsanto Chemicals Intermediates
    Co.
Northwest Industries, Inc.
  Lone Star Steel Co., subsidiary
Pennzoil Co.
  Atlas Processing Co.,  subsidiary
Phillips Petroleum Co.
  Phillips Chemicals Co.
  Phillips Puerto Rico Core, Inc.,
    subsidiary
Quintana-Howel1
Shell Chemicals Co.
Standard Oil Co. of California
  Chevron Chemical Co., subsidiary
    Petrochemicals division
      Industries Chemicals
Standard Oil Co. (Indiana)
  Amoco Oil Co., subsidiary

The Standard Oil Co.  (Ohio)
  BP Oil Inc., subsidiary
Texas City, TX
Beaumont, TX
Chocolate Bayou, TX

Lone Star, TX

Shreveport, LA

Sweeney,  TX

Guayama,  PR

Corpus Christi, TX

Deer Park, TX
Odessa Park, TX
Wood River, IL
El Segundo, CA
Texas City, TX
Marcus Hook, PA
        23
        38
       284
        57


        84

       416

        27

       379
        45
       170
        87


       322


        30
Petroleum, captive
Petroleum
Petroleum, captive

Coal

Petroleum

Petroleum, captive

Petroleum, partly captive
Petroleum

Petroleum
Petroleum
Petroleum
Petroleum, captive
Petroleum, captive
Petroleum
                                                                                            (continued)

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                                      TABLE  2  (continued)
             Company
      Location
Annual capacity,
    103 m$
      Raw material
Sun Oil Co.,  Inc.
  Sun Oil Co. of Pennsylvania,
    subsidiary
  Suntide Refining Co., subsidiary
Tenneco Inc.,
  Tenneco Oil Co., division
Texaco, Inc.
Union Carbide Corp.
  Chemicals and Plastics division
Union Oil Co. of California
Union Pacific Corp.
  Champlin Petroleum Co.,
    subsidiary
United States Steel Corp.
  USS Chemicals division
TOTAL
Marcus Hook, PA
Toledo, OH
Tulsa, OK
Corpus Christi, TX

Chalmette, LA

Port Arthur, TX
Westville, NJ

Taft, LA
            a
Beaumont, TX
Lemont, IL
Corpus Christi, TX

Clairton, PA
Geneva, UT
        57
       132
        91
       132


        38

       170
       132


       189

        84
        64
        38


       170
        15

     6,805
Petroleum
Petroleum
Petroleum
Petroleum, captive


Petroleum
Petroleum, partly captive
Petroleum, partly captive

Petroleum, captive
Petroleum
Petroleum
Petroleum, captive


Coal
Coal
 Joint venture with American Petrofina of Texas,  subsidiary of American Petrofina  Incorporated.

NOTE:  Some petroleum operators also isolate benzene from purchased coal-derived light oil.

Sources:  Compiled in association with the World Hydrocarbons Program and communication with  industry.

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         TABLE 3.  ESTIMATED BENZENE PRODUCTION  (1976)


                                    Capacity,   Number of
    	Process	10 6 m3	sites

    Catalytic reforming                2.8         39
    Toluene dealkylation               1.5         16
    Toluene disproportionation         0.04         2
    Pyrolysis gasoline                 0.68        10
    Purchased coke-oven light oil      0.21         5
    Coke-oven operations               0.25         6

    TOTAL                              5.28


     More than one process per site may be performed.

Catalytic Reforming

Catalytic reforming converts the paraffins and naphthalenes in
naphtha to a higher octane reformate; the reformate contains a
high percentage of aromatics.  Reactions include cyclization of
paraffins and dehydration and dealkylation of naphthalenes.
Reformers are dedicated to production of either gasoline-blending
components or petrochemical feedstocks.   Feed to the latter
produces a reformate containing 40% to 60% aromatics.  The
aromatic fraction is separated from the reformate via solvent
extraction.  The aromatic-rich extract can then be further
separated into benzene, toluene, and xylenes by distillation.
Benzene purities of 99.9% can be obtained (4).

Olefin Production—Pyrolysis Gasoline

Ethylene and propylene (and other olefins) are produced by
cracking lower paraffins (propane or butane) or heavier stocks
(naphtha or gas oils).  A byproduct is pyrolysis gasoline, which
can contain up to 80% aromatics (4).  Purification of the gaso-
line requires hydrogenation for olefin saturation followed by
solvent extraction.  Processing details can be found in the
literature (4-6).
(4)  Parsons,  T.  B.,  et al.   Industrial Process Profiles for
    Industrial Use:   Basic  Petrochemicals Industry,  Chapter 5.
    Contract  68-02-1319,  U.S.  Environmental Protection Agency,
    Research  Triangle Park,  North Carolina,  January  1977.

(5)  Refining  Handbook.   Hydrocarbon Processing,  53(9):192,
    1974.

(6)  Petroleum Processing Handbook, Chapter 3.   W.  F.  Bland  and
    R.  L.  Davidson,  eds.  McGraw-Hill Book Co.,  New  York, New
    York,  1967.   pp.  1-152.

                              11

-------
Toluene Dealkylation/Disproportionation

Toluene is used as the feedstock for two different benzene-
producing reactions.  In the presence of hydrogen, it can be
dealkylated to yield benzene and methane.  Higher alkyl aromatics
are sometimes dealkylated to yield naphthalenes, with appreciable
quantities of benzene formed as a byproduct.  If 2 mol of toluene
are catalytically reacted, 1 mol of benzene and 1 mol of xylene
are produced  (disproportionation).  Products of all reactions
must undergo distillation for separation.  The toluene feed to
these reactions generally comes from solvent extraction of
catalytic reformate and can contain mixed xylenes as well as
toluene  (4).

Coke-Oven Light Oil

Coke manufacturing, which involves high-temperature coal carbon-
ization, produces a light byproduct containing benzene.  Further
processing of the light oil sometimes includes hydrogenation for
sulfur removal.  Standard separations techniques are employed for
benzene purification.  There is a large potential for producing
benzene from coal liquefaction processes, but these are several
years from commercialization.

USES

The primary end use for benzene is in the synthesis of other
organic chemicals.  Ethylbenzene, cumene, and cyclohexane pro-
duction account for more than 80% of the benzene used in the
United States.  A detailed breakdown is presented in Table 4  (7)
and detailed discussions of these uses of benzene are found in
Reference  8.  A chemical  tree is presented  in Figure 1  (7).

Historically, demand  has  increased  significantly because of the
market  for styrene  monomer, phenol,  cyclohexane, nitrobenzene,
and maleic anhydride.   Increasing demand  is  expected to continue,
possibly by  7.5%/yr until  at  least  1980  (9).  Barring some
 (7)  Chemical  Origins and Markets,  Fifth Edition,  G. M.  Lawler,
     ed.   Chemical Information Services,  Stanford  Research
     Institute,  Menlo Park,  California,  1977-   118
 (8)  Wilkins,  G.  E.   End Use Patterns  for Significant  Organic
     Chemicals.   Contract 68-02-1319,  U.S.  Environmental Pro-
     tection Agency,  Research Triangle Park,  North  Carolina,
     July 1976.
 (9)  Ponder, T.  C.   Benzene:  Outlook  Through 1980.  Hydrocarbon
     Processing,  55 (11) :217-218,  1976.

                                12

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            TABLE 4.  BENZENE CONSUMPTION  (1976)  (7)

Product use
Ethylbenzene
Cumene
Cyclohexane
Aniline
Chlorobenzenes
Maleic anhydride
Detergent alkylate
Miscellaneous applications
Exports
Percent
50.0
16.6
14.9
4.3
3.5
2.7
2.6
3.0
2.4

catastrophe or emergence of a less expensive raw material, ben-
zene will remain as one of the most important chemicals to
industry.

TRANSPORTATION

Drums and tank cars are standard containers for benzene.  Accord-
ing to one study (10), 79.6% of domestically shipped benzene
goes by water, 14.8% by rail, and 5.6% by truck.  Most pipeline
shipment is restricted to benzene that is used captively by the
plant in which it is produced.
(10)  Dawson,  G.  W.,  A.  J.  Shuckrow,  and W.  H.  Swift.   Control
     of Spillage of  Hazardous Polluting Substances.   Contract
     14-12-866 (PB  197  596),  U.S.  Department of the  Interior,
     Federal  Water  Quality Administration,  Washington, D.C.,
     November 1970.   96 pp.

                               13

-------



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Reproduced by permission of SRI International, Menlo Park, CA.

-------





7



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-------
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Figure 1  (continued)

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                            SECTION 4

          ENVIRONMENTAL SIGNIFICANCE AND HEALTH EFFECTS
ENVIRONMENTAL SIGNIFICANCE

Benzene is one of the major petrochemical intermediates produced
and used in the United States.  It has also been identified as a
potential hazard.  This section will examine sources of benzene
emissions, ambient levels of benzene that result, secondary
emissions formed, and the population at risk.

Sources of Emissions

There are several sources of benzene emissions.  The largest
emission source of benzene is motor vehicles (exhaust fumes).
The largest individual sources of benzene are estimated to be
from cyclohexanes, nitrobenzene and chlorobenzenes manufacture.
Table 5 shows that in 1976, an estimated 576 x 106 kg of benzene
were emitted to the atmosphere from 132 x 106 stationary and
mobile sources.  This includes an estimated 110 million kg/yr
from production, transportation, storage, and use of benzene,
456 million kg/yr from refueling and operation of motor vehicles,
and 10 million kg/yr from oil spills (private communication,
T. W. Hughes, Monsanto Research Corporation; Reference 11; and
engineering estimates as described in this section).

Production and Subsequent Processing Into Other Products—
The processes employed for benzene production are catalytic
reforming/aromatics extraction, olefin manufacture/pyrolysis gas
processing, toluene hydrodealkylation and disproportionation,
and coking of coal.  Hydrocarbons can be emitted from each of
these processes in the form of fugitive leaks; e.g. from valves
or flanges.  Although emission factors exist for fugitive hydro-
carbon emissions from oil refineries (12), no data specifically
 (11) Eimutis, E. C., and R. P. Quill.  Source Assessment:
     Noncriteria Pollutant Emissions.  EPA-600/2-77-107e, U.S
     Environmental Protection Agency, Research Triangle Park,
     North Carolina, July 1977.  113 pp.

 (12) Compilation of Air Pollutant Emission Factors, Second
     Edition  (with Supplements 1-7).  Publication No. AP-42,
     U.S. Environmental Protection Agency.- Research Triangle
     Park, North Carolina, 1973.

                              18

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                 TABLE  5.   BENZENE EMISSION SOURCES

Emission source
Benzene production:
Catalytic reforming
Toluene dealkylation
Toluene disproportionation
Pyrolysis gasoline
Coke-oven light oil
Coke-oven operations
Benzene consumption:
Ethylbenzene/styrene
Cumene/phenol
Cyclohexane
Aniline
Chlorobenzenes
Maleic anhydride
Detergent alkylate
Surface coatings (paints)
Degreasing
Nitrobenzene
Fumaric acid
Acrylonitrile
Other sources:
Automobile tank loading
Service station tanks
Bulk terminal loading/storage
Motor vehicles
Oil spills
TOTALS
1976 Estimated
benzene emis-
sion rate,
106 kg/yr (11)

2.63
1.4a
0.04a
0.6a
0.2a
0.2a

9.5a
2.4a
7.8a
o.ia
2.6
2.0a
0.01
3.2a
73.1
3.4
0.3a
0.2a

5.9
0.2
0.04
450b
10b
576
Number of
sources

39
16
2
10
5
6

12
9
8
7
7
9
5
8,745
1,300,000
9
6
6

226,500
226,500
30,900
130,000,000
787
131,800,000
Mass
emissions
per source,
kg/yr

67,000
88,000
20,000
60,000
40,000
33,000

190,000
270,000
975,000
14,000
370,000
220,000
2,700
370
56
380,000
50,000
33,000

26
80
1
3
12,000


Private communication, T.  W.  Hughes, Monsanto Research Corporation, Dayton,
Ohio.

See text,  1971 emissions estimates.
                                  19

-------
address benzene.  Processes that use catalysts undergo periodic
catalyst regeneration to burn off hydrocarbons adhering to the
catalyst surface.  Existing data on emissions from these sources
encompass only hydrocarbons in general.  There are potential
aqueous emissions from olefins/pyrolysis gasoline manufacture,
pyrolysis gas hydrotreating, coal coking, and aromatics extrac-
tion.  A sludge is produced in the extraction processes as well.,
All of these streams have the potential of containing benzene.

Benzene is a feedstock for several organic chemical production
processes .as well as a gasoline blending component.  Fugitive
hydrocarbon  (includes benzene) emission potential is as common
as the lack of emission data.  Almost all of the processes are
catalytic, and benzene could be released during solid catalyst
regeneration.   [Process units maintained at atmospheric pressure
by open vents can be sources of benzene emissions.   [In nitro-
benzene manufacture, 8.2 kg benzene/metric tona nitrobenzene can
be emitted from absorber vents  (13).]  Scrubber air from the
recovery section in maleic anhydride production can contain as
much as 107 kg benzene/metric ton of product  (13) .

Benzene is released to aqueous streams in different ways, depend-
ing on the process.  The liquid-phase ethylbenzene process dis-
charges a scrubber effluent water containing 11 kg of benzene/
metric ton water  (13).  The vapor process has spent caustic and
wash streams that contain significant amounts of benzene.  Cumene
recovery produces a wastewater stream contaminated with benzene.
Solvent extraction is employed in cyclohexane production, and
this produces a benzene-contaminated wash water.  Water washing
of the nitrobenzene product stream produces an aqueous waste
containing benzene.  Scrubbing and stripping operations in the
bromobenzene and biphenyl processes also generate aqueous benzene
mixtures.

Storage—
Benzene, a fluid  of  intermediate volatility,  is  stored  in float-
ing  roof tanks  (internal or external) or  fixed-roof  tanks having
vapor  recovery  systems.  Emissions  from these tanks  result  from
poor floating roof  seals, evaporation  from wetted walls during
emptying of  floating roof tanks, venting  of vapor recovery  units,
and  exceeding the vapor  space capacity in variable vapor space
tanks  (internal roof).  Methods for  calculating  losses  are  well
  1 metric ton equals 106 grams; conversion factors and metric
  system prefixes are presented in the prefatory material.
 (13)  Industrial Process Profiles for Environmental Use:  Chapter
      6,  The Organic Chemicals Industry, Part I (Draft).  Contract
      68-02-1320, Task 17, and Contract 68-02-1325, Task 70, U.S.
      Environmental Protection Agency, Research Triangle Park,
      North Carolina.

                                20

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documented  (14).  Storage losses account  for  significant  frac-
tions of all hydrocarbon emissions.  Table  6  presents  evaporative
emission factors for benzene storage tanks  without  controls  (12).

       TABLE 6.  EVAPORATIVE EMISSION FACTORS FOR BENZENE
                 STORAGE TANKS WITHOUT CONTROLS  (12)

Fixed roof tanks
Breathing loss,
kg/day-m3
New tank Old tank Throughput
conditions conditions loss, kg/m3
Floating roof tanks
Standing storage
loss, kg/day-m3
New tank Old tank
conditions conditions
Variable vapor
space tanks
Throughput
loss , kg/m3
       0.0094     0.011      0.27       0.0013    0.0031       0.25
Transportation—
Benzene is transported in railroad tank cars or carried on ships
or trucks in 0.21-m3 drums.  Emissions can result from spills,
leaks, loading, and accidents.  Detailed studies of hydrocarbon
losses have been performed, but little information on benzene
losses exists  (15, 16).  In a study of hazardous material spill-
age into water streams, benzene was ranked as sixth among chemi-
cals likely to cause significant water pollution due to spillage
during transport  (10).

Motor Vehicles—
Motor vehicles are sources of benzene emissions during both  fuel-
ing and operation.  Gasoline evaporation from vehicle refueling
results in 1.4 kg of hydrocarbons/m3 pumped  (12).  Loading and
unloading of trucks and underground tanks at service stations
have been estimated to transfer about 1.5 kg/m3.  The large  quan-
tities of gasoline consumed annually result in an emission of
24 million kg/yr of benzene (17); however, this estimate is based
on an assumption that 1% benzene exists in the vapor.  The vapor
contains only 0.01% (11).  Emissions of unburned hydrocarbons
from engine exhausts also present a hazard.  Approximately

(14)  Burklin, C. E., and R. L. Honerkamp.  Revision of Evapora-
     tive Hydrocarbon Emission Factors.  Radian Project
     100-086-01, Radian Corporation, Austin, Texas, June 1976.

(15)  Air Pollution Engineering Manual, Second Edition.  J. A.
     Danielson, ed.  Publication No. AP-40, U.S. Environmental
     Protection Agency, Research Triangle Park, North Carolina,
     May 1973.  987 pp.

(16)  Burklin, C. E., E. C. Cavanaugh, J. C. Dickerman, S. R.
     Fernandes, and G. C. Wilkins.  Control of Hydrocarbon
     Emissions from Petroleum Liquids.  EPA-600/2-75-042, U.S.
     Environmental Protection Agency, Research Triangle Park,
     North Carolina, September 1975.  245 pp.

(17)  Benzene from Gasoline Evaporation is "Significant Health
     Hazard," EDF says.  Environmental Report 1977, 1363.

                              21

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450 million kg of benzene were  released in hydrocarbon emissions
from motor vehicles in 1971.

Oil Spills—
The OTS has reported a possible release of  from 10 to 11 million
kg/yr of benzene due to oil spills; however,  no data have yet
been found  to  support this figure   The maximum content of
benzene in  crude oil is approximately  3.0%  (18).   If all crude
oil contained  3% benzene and if it all evaporated when the oil
spilled, approximately 0.3 billion kg/yr of oil would have to be
lost to produce 10 million kg of benzene.   Since one source
reports annual oil spillage to be about 1.8 billion kg/yr (2),
the OTS estimate is reasonable.

Environmental  Levels

Information on levels of benzene in the atmosphere is deficient.
Table 7 summarizes ambient monitoring  data  for benzene in selec-
ted areas  of the United States and shows that the observed am-
bient levels of benzene are 1 ppb to 100 ppb (volume basis).
The high values for metropolitan areas (Los Angeles and Toronto)
may be primarily due to exhausts from  motor vehicles (19).

       TABLE 7.  AMBIENT MONITORING DATA FOR BENZENE (19)
Concentrations
Geographical location
Vancouver, Canada
Near solvent reclamation plants
Los Angeles Basin
Downtown Los Angeles
Los Angeles Basin
Zurich, Switzerland
Riverside, California
Toronto, Canada
Sampling/analysis technique
Cold trap/GC-FIDa h
Grap sample/GC-MS, IR°
Cold trap/GC-FID
Grab sample/GC-FID
Cold trap/GC-FID
Charcoal trap/GC-MS,GC-F!D
Cold trap/GC-FID
Cold trap/GC-FID
Lowest
1

5
15


7

Average




15


13
, PPb
Highest
10
23
22
60
57
54
8
98
          aGC~FID is gas chromatograph-flame ionization detector.
           GC-M5, IR is gas chromatograph-mass spe
          NOTE: Blanks indicate no reported data.
GC-M5, IR is gas chromatograph-mass spectroscopy and infrared analysis, respectively.
Levels  of benzene in bodies of water  are also presented in a re-
port on potential ocean pollutants  (2) .   Benzene has been iden-
tified  in drinking water in three United States locations (from
the Mississippi and Potomac Rivers).   Levels were approximately
2.0 ppb.   In one EPA study of organic compounds in drinking water
of 10 cities,  benzene was detected  in water from four cities
 (18) Smith,  H.  M.   Qualitative and Quantitative Aspects of Crude
     Oil Composition.   Bulletin 642, U.S.  Department of the
     Interior,  Bureau of Mines, Washington,  D.C.,  1968.

 (19) Howard,  P-  H.,  and P- R. Durkin.   Sources of  Contamination,
     Ambient Levels, and Fate of Benzene  in  the Environment.
     EPA-560/5-75-005, U.S. Environmental  Protection Agency.-
     Washington, D.C., December 1974.   73  pp.

                                22

-------
at concentration levels of 1.0 mg/m3 to 3.0 mg/m3.  Benzene has
also been identified as a component of subsurface water, reach-
ing concentrations of 10.4 ppm in one subsurface brine and up to
24 ppm in another area having extensive oil and gas deposits.
Levels of light aromatics in marine waters near oil production
platforms have been reported to be in the 0.1 ppb to 0.7 ppb
range, with average levels being less than 1 ppb.  No data have
been found on levels of benzene in soil, wildlife, and fish (2).

Population at Risk

Production and process consumption of benzene are generally
localized in the Texas Gulf area and in the Northeast; however,
the presence of benzene in gasoline gives it nationwide distri-
bution.  The scarce data that currently exist indicate that most
Americans are probably exposed continuously to very low levels
of benzene.  Persons that live and work in areas of major ben-
zene production and consumption obviously are exposed to larger
concentrations.  Until definitive studies are made concerning
true ambient levels and the actual risks involved with such
exposure, no estimate should be made of the number of people
currently at risk from exposure to benzene emissions.

HEALTH EFFECTS

Benzene has long been recognized as a poison if ingested in large
quantities.  The effects of nonlethal doses, including long-term
illnesses, are not as fully understood; however, information
on benzene's effects on both humans and animals is available.

Effects on Humans

Numerous fatalities from occupational benzene poisoning have been
reported since the early 1900's.   After inhalation or ingestion,
benzene is absorbed rapidly by the blood.   At nonlethal concen-
trations, a variety of human central nervous system disorders are
observed, depending upon the extent of exposure.  These maladies
include euphoria followed by giddiness, headache, nausea and
staggering gait, as well as fatigue, insomnia, dizziness,  and
unconsciousness.  Observed damage to the human blood-forming
system includes anemia, reduction in platelet numbers, and
depression of the white blood cell count.

Oral ingestion can cause local irritation of the mucous mem-
branes, bronchitis, pneumonia, signs and symptoms of systemic
intoxication, and collapse (20).   Skin exposure may cause blis-
ters.  A scaly dermititis results from prolonged exposure.
(20)  Criteria for a Recommended Standard:   Occupational Exposure
     to Benzene.   U.S.  Department of Health,  Education and
     Welfare, Public Health Service Center for Disease Control,
     Washington,  D.C.,  1974.

                               23

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Results of several tests on humans are reported in the litera-
ture (20).  The current lowest lethal concentration  (LCLo) is
20,000 ppm for 5 min  (21).  The lowest toxic concentration
(TCLQ)  reported for humans is 210 ppm.

Chronic benzene exposure also has resulted in chromosome aberra-
tions in human lymphocytes.  As early as the 1930's, benzene was
suspected in cases of leukemia.  Available epidemiological data
indicate that the compound does induce leukemia although the
data cannot be considered to constitute unequivocal  evidence that
benzene acting alone  is leukemogenic.  There currently seems to
be no typical response in the blood to chronic exposure at low
levels  (22).  In one  study, no correlation between the extent of
exposure and the severity of the benzene poisoning was reported
to exist  (20).  Results of similar studies are also  reported in
this work.  Most recently, National Institute of  Occupational
Safety and Health  (NIOSH) studies in two Ohio rubber plants
revealed incidences of leukemia five times higher than normal
(23).  This report prompted current Occupational  Safety and
Health Administration (OSHA) emergency standards.  Although
benzene is suspected  to cause leukemia, no fully  convincing
experimental proof exists.

There are other chronic effects of exposure to benzene.  Muta-
tions in the pulmonary system and in bone marrow  have been
observed, along with  liver, kidney, and lung damage, hormone
alteration, and bone  marrow hyperplasia  (1).

Effects on Animals

Acute effects on animals are similar to those on  humans.  Acute
toxicity data currently available is summarized in Table 8  (1,
21).  Much of the work done on animals is summarized in Refer-
ence 20.

Most testing in the studies of chronic effects of benzene has
been performed on animals.  The results of carcinogenity tests
on mouse skin indicate the lowest toxic dose is 1,232 mg/kg for
a 52-wk exposure  (1).  Studies of both long- and  short-term
 (21)Markle, R. A.,  et  al.  Potentially  Toxic  and Hazardous
     Substances in the  Industrial  Organic Chemicals and Organic
     Dyes and Pigments  Industry-   Contract  68-02-1323, U.S.
     Environmental Protection Agency, Research Triangle Park,
     North Carolina,  October 1976.

 (22) Industrial Hygiene and Toxicology,  Volume II.  F. A. Patty,
     ed.  John Wiley &  Sons, Inc., New York, New York, 1962.
     2305 pp.

 (23) Benzene Emerging Standard  Set by OSHA.  Chemical &
     Engineering News,  55(19):4, 1977.


                                24

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           TABLE 8.  TOXICITY DATA FOR BENZENE  (1, 21)


      Acute
     toxicity	Dosage	 Animal	Route	

     LD50         468 mg/kg      Mouse        Intraperitoneal
                1,150 mg/kg      Rat          Intraperitoneal
                3,800 mg/kg      Rat          Oral
                4,700 mg/kg      Mouse        Oral

     LD           530 mg/kg      Guinea pig   Intraperitoneal
                1,400 mg/kg      Frog         Subcutaneous
                2,000 mg/kg      Dog          Oral

     LC50C     10,000 ppm/7 hr   Rat          Inhalation


      Calculated dose expected to kill 50% of the exposed
      population.
      Lowest reported dose to cause death.

      Calculated concentration expected to kill 50% of the
      exposed population.

inhalation of benzene vapors by dogs show that benzene concen-
trates in ,fat, bone marrow, urine, and red blood cells following
a rapid distribution through the body (20).

Attempts by the National Cancer Institute and others to induce
leukemia in animals with benzene have not been successful.
However, results of inhalation experiments with mice, the
species most susceptible to leukemia, are not yet available.
Many researchers have concluded that more study is definitely
needed  (20).
                               25

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                            SECTION 5

                      CONTROL TECHNOLOGIES


Benzene emissions can be controlled by preventing the release of
the pollutant or by treating the waste streams.  Various techni-
ques of implementing these ideas have been developed.  Applicable
control methods, their efficiencies, and the economics of their
use are briefly described.

EMISSION SOURCE CONTROL METHODS

Different control methods have been developed for different
sources of emissions.  The following are generally applicable to
any process containing emissions of benzene.

Fugitive Emissions

Most fugitive hydrocarbon emissions can be controlled only by
regular inspection, maintenance, and good housekeeping.  For
sources such as pump and compressor seals, wastewater systems,
and storage tanks, specific devices have been designed to help
control emissions.  Other sources require major equipment addi-
tions such as installing an integrated vapor recovery/flare
system for all vents and relief valves (24, 25).

Catalyst Regeneration

Several of the processes for producing or using benzene employ
solid catalysts, which require periodic regeneration.  Any
unburned benzene  (or other hydrocarbon) in the flue gas could
be removed by incineration in a heater firebox or smoke plume
burner.  These devices are not usually used due to the infre-
quency of catalyst regenerations.
(24) Rosebrook, D. D., et al.  Sampling Plan for Fugitive Emis-
     sions from Petroleum Refineries.  Radian Contract 200-144,
     Task 6, Radian Corporation, Austin, Texas, January 1977-
(25) Control Techniques for Volatile Organic Emissions from
     Stationary Sources.  Publication No. AP-68, Project 220-
     187-12, U.S. Environmental Protection Agency, Research
     Triangle Park, North Carolina.  (Draft report submitted
     to the EPA by Radian Corporation,  July 1977.)

                                26

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Vents

Benzene  can be continuously emitted through vents.  Emissions
can be eliminated by routing them to an  integrated vapor recov-
ery or incineration system, wet  scrubbing in an absorber, a  com-
bination scrubbing-incineration  system,  or an  adsorption system.

Aqueous  Discharge Prevention

Aqueous  emissions are often generated by water wash of products,
water quenches,  steam stripping.- and vacuum production using
steam ejectors and barometric condensers.  In some cases, the
initial  production of such benzene-contaminated streams can  be
prevented.  For  example, a stripping column can replace water
wash.  Vacuum pumps, surface condensers, and oily water inciner-
ators can eliminate the contaminated effluent from ejectors  and
barometric condensers (26).

Aqueous  Discharges Treatment

Aqueous  effluents from benzene processes can be treated in stand-
ard wastewater treatment units.  If benzene was the only pollu-
tant, a  covered  hydrocarbon/water separator would be sufficient
(26).  Most benzene processes are part of a large refinery or
chemical plant,  which generally has primary, secondary.- and, often,
tertiary treatment systems.  These systems are more complex  than
can be described in this document (24, 25, 26).

Organic Sludges

A benzene-contaminated sludge is often a byproduct of solvent
extraction processes for aromatics purification.  Standard prac-
tice is to dry it and use it as landfill; however, incineration
is an alternative (25, 27)   When the sludge is dried an unknown
amount of benzene could be released to the air.

Control of Storage Losses

Although not generally applied, there are several methods of
controlling emissions from benzene storage.   Replacement of old
(26) Sittig, M.  Pollution Control in the Organic Chemical Indus-
     try.  Noyes Data Corporation, Park Ridge, New Jersey, 1974.
     304 pp.

(27) Cavanaugh, E. C., J. D. Colley, P. S. Dzierlenga, J. M.
     Felix, D. C. Jones, and T. P. Nelson.  Environmental Problem
     Definition for Petroleum Refineries, Synthetic Natural Gas
     Plants, and Liquefied Natural Gas Plants.  EPA-600/2-75-068,
     U.S. Environmental Protection Agency, Research Triangle
     Park, North Carolina, November 1975.  476 pp.


                               27

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floating roof seals with newer double seals will reduce emis-
sions by 50% to 75% (28) .  Use of pressure tankage for new con-
struction is also possible as a control method since emissions
from pressure tanks are virtually negligible.  Storage emissions
control is discussed in Reference 25.

Transportation of Benzene

Losses resulting from benzene transportation are very similar to
losses resulting from gasoline transportation.  Controls can be
applied at marine terminals, tank truck terminals, and rail car
terminals.  Modified loading procedures (submerged or bottom
loading) in conjunction with vapor recovery devices are the prin-
cipal technologies available.  Detailed descriptions of such
methods are found in Reference 25.

Motor Vehicles

Benzene emissions due to gasoline evaporation at service stations
can be controlled in ways similar to those used in other loading
and unloading operations.  Both vapor recovery systems and modi-
fied loading methods can be applied to bulk handling of gasoline.
Vapor recovery units on gasoline pumps can significantly reduce
emissions  (25, 29).

Exhaust emissions of benzene are controlled primarily by carbu-
retion adjustment.  This will allow more complete combustion of
the hydrocarbons found in gasoline.

The emergence of the catalytic converter is expected to have an
impact on benzene emissions from motor vehicle exhaust.  For•
example, in exhaust sample testing the converter was able to
reduce benzo(a)pyrene emissions  (a difficult to control poly-
cyclic organic), by an order of magnitude from 1968 emission-
controlled vehicles.  Actual figures were from 2 to 6 mg/m3 down
to 0.5 mg/m3 of fuel consumed  (30).  If such a high degree of
control is achieved with polycyclic organics, reduction in ben-
zene emissions would also be expected from catalytic converters.
 (28)  American Petroleum Institute,  Evaporative Loss Committee.
      Evaporative Loss from Floating Roof Tanks.  Bulletin 2517,
      Washington, D.C.,  1972.
 (29)  Burklin, C. E.,  E. C. Cavanaugh,  J. C.  Dickerman,  and S.  R.
      Fernandes.   A Study of Vapor Control Methods for Gasoline
      Marketing Operations, Volume I.  EPA-450/3-75-046-9, U.S.
      Environmental Protection Agency,  Research Triangle Park,
      North Carolina,  April 1975.   215  pp.
 (30)  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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Oil Spills

Accidental spills of oil  (or benzene) are virtually unavoidable.
Several steps can be taken whenever a benzene-containing hydro-
carbon is spilled into a body of water (10) .  These include noti-
fying the nearest users of the water; removing the source of the
spill from the water; skimming of hydrocarbon liquids from the
surface; treating the water with activated carbon, a coagulant,
and a polyelectrolyte (where feasible); and removing the resul-
tant floe.  These techniques are generally more applicable to
inland waterways than to oceans.

CONTROL EFFICIENCIES

The efficiency of any method of controlling benzene emissions
depends on such factors as operating conditions, quality and
quantity of the waste stream, and state of repair of the system.
Table 9 lists present producers of maleic anhydride (a benzene
consumer industry), their control technology, and reported con-
trol efficiencies (31).

Incineration

Incineration is an acceptable form of controlling benzene emis-
sions from sludges and concentrated hydrocarbon liquids.  Incin-
eration can be accomplished in afterburners  (direct flame and
catalytic) and boilers.   Properly designed and operated inciner-
ators usually achieve organic vapor removal efficiencies in
excess of 95%.

Adsorption

Benzene can by physically adsorbed from a gas stream by activa-
ted carbon.  Such adsorption is usually more efficient than
incineration for removing organics in concentrations lower than
200 ppm.  Efficiencies are usually around 100% (25).

Absorption (Scrubbing)

Absorption or scrubbing involves the dissolution of certain
vapor-phase components into a liquid solvent.  Benzene is re-
moved from gas streams in such a unit operation.  When the con-
centration of benzene in the gas is low, large quantities of
absorbent and long contact times are required for adequate re-
moval.  For this reason, scrubbers are often used in series with
incinerators.
(31) Lewis, W. A. Jr., G. M. Rinaldi, and T. W. Hughes.  Source
     Assessment:  Maleic Anhydride.  Contract 68-02-1874, U.S.
     Environmental Protection Agency, Industrial Environmental
     Research Laboratory, Cincinnati, Ohio.  118 pp.

                                29

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   TABLE 9.  CONTROL DEVICES AND REPORTED CONTROL EFFICIENCIES
             FOR THE MALEIC ANHYDRIDE  INDUSTRY (31)




Company
Amoco Chemicals Corp.
Ashland Oil, Inc.

Denka Chemical Corp.

Koppers Co.

Monsanto Co .
Reichold Chemicals,
Inc.

Flaking
pelletizing,
and packaging
NR9
_b

Scrubberc

Scrubber c

Scrubber0
_b

Emission points

Product recovery
scrubber
NR
Scrubberc

Thermal incinera-
tor 93%, 95%
Thermal incinera-
tor 97%e
_f
Carbon
absorber 84%d


Storage
tank vents
NR
Floating roof
tanksc
Floating roof
tanks0
Return ventsc

Scrubber c
Scrubber,
conservation
  Tenneco,  Inc.
  U.S. Steel Corp.
                           _f
Scrubberc
                   _f
Catalytic incin-
  erator 85%"
  vents1-
Scrubber,
  conservation
  ventsc
Floating roof
  tanks0
  aNot reported.                      Hydrocarbon control efficiency.
  K                                 G
  Plant does not have the emission      Carbon monoxide control efficiency.
  P°int-                            No control.
  Control efficiency not reported.

Vapor Recovery

Benzene loss  due to fugitive emissions from pressure  relief
devices,  loading and unloading  operations, and gasoline market-
ing operations can be minimized by vapor recovery systems.
These allow the vapors to be collected and routed to  knockout
drums,  condensers, refrigeration units, absorbers, or simply  the
tank from which they came.  Control efficiencies are  between  85%
and 100%,  depending upon the source of the emissions;  gasoline
marketing emissions are the most difficult to control (25).

Alternate Loading Methods

Bulk handling of benzene-containing hydrocarbons i§ subject to
losses  due to loading and unloading.   Procedure changes in  load-
ing practices can reduce emissions by the amounts shown below.
                                 30

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         Emission source                Percent reduction

     Marine terminals                       60 to 80
     Rail and tank truck terminals          40 to 60
     Gasoline service stations
The preferred methods include vapor- freeing ballasted and empty-
ship cargo tanks at sea, slower tank loading, submerged filling,
and bottom loading.

Wastewater Treatment

Treatment of benzene-contaminated water generally involves pri-
mary separation followed by secondary and possibly tertiary
treatment.  Hydrocarbon removal efficiency for the primary sepa-
rations step is generally between 70% and 90% (24) .  No data
are known for benzene removal efficiencies in any treatment step.
Standard texts on wastewater treatment plant design are readily
available, such as Metcalf and Eddy (32) .

Storage Vessels

Installation of double seals on floating roof tanks can reduce
emissions by 50% to 75% (28) .  Construction of pressure storage
vessels would virtually eliminate emissions.
(32) Metcalf, L.,  and H. P. Eddy.  Wastewater Engineering
     Collection, Treatment, Disposal.  McGraw-Hill Book
     Company, New York, New York, 1972.  734 pp.

                               31

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                           SECTION 6

                        REGULATORY ACTION
In 1974 NIOSH  (National Institute of Occupational Safety and
Health) published a criteria document for occupational exposure
to benzene which recommended adherence to the existing Federal
standard of 10 ppm as a time-weighted average with a ceiling of
25 ppm.  OSHA has proposed a reduction of the standard to a
1 ppm 8-hr time-weighted average with a ceiling of 5 ppm over a
15-min period.  An OSHA  (Occupational Safety and Health Adminis-
tration) Emergency Temporary Standard has been stayed pending
a hearing on a request for injunction.  NIOSH is conducting
retrospective studies of benzene mortality and airborne benzene
levels in service stations; however, the OSHA regulations would
apply to sources with only 5 or more employees; thus service
stations remain unregulated.

EPA has initiated an air-monitoring program which will determine
benzene levels in selected areas.  Qualitative results obtained
to date indicate widespread low-level benzene contamination.
Studies are in progress to document the extent of hazard and the
best regulatory approach under the Clean Air Act.  EPA has con-
ducted a limited survey of drinking water supplies in which
benzene was identified in some samples and has begun a more
extensive survey which will seek out benzene as well as a number
of other pollutants.  Benzene has been designated a priority
pollutant under the FWPCA (Federal Water Pollution Control Act),
and ocean dumping is already strictly regulated.  Additional
water quality criteria for benzene are anticipated from EPA
under the FWPCA Consent Decree by July 1978.  The Consumer
Products Safety Commission is awaiting results of the National
Academy of Sciences study on the health effects of benzene to
determine if the results warrant further action.
                                32

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                           REFERENCES
 1.   Dorigan,  J.  Scoring of Organic Air Pollutants:  Chemistry
     Production and Toxicity of Selected Synthetic Organic
     Chemicals.  Mitre Corporation, September 1976.

 2.   Ocean Affairs Board, National Research Council.  Assessing
     Potential Ocean Pollutants.  Report No. 0-309-02325-4, U.S.
     Environmental Protection Agency and National Science
     Foundation,  Washington, D.C., January 1975.   456 pp.

 3.   Directory of Chemical Producers—U.S.A.  Chemical Informa-
     tion Services, Stanford Research Institute,  Menlo Park,
     California,  1977-  1059 pp.

 4.   Parsons,  T.  B., et al.  Industrial Process Profiles for
     Industrial Use:  Basic Petrochemicals Industry, Chapter 5.
     Contract 68-02-1319, U.S. Environmental Protection Agency,
     Research Triangle Park, North Carolina, January 1977-

 5.   Refining Handbook.  Hydrocarbon Processing,  53(9):192, 1974,

 6.   Petroleum Processing Handbook, Chapter 3.  W. F. Bland and
     R. L. Davidson, eds.  McGraw-Hill Book Co.,  New York, New
     York, 1967.   pp. 1-152.

 7.   Chemical Origins and Markets, Fifth Edition, G. M. Lawler,
     ed.  Chemical Information Services, Stanford Research
     Institute, Menlo Park, California, 1977.  118 pp.

 8.   Wilkins,  G.  E.  End Use Patterns for Significant Organic
     Chemicals.  Contract 68-02-1319, U.S. Environmental Pro-
     tection Agency, Research Triangle Park, North Carolina,
     July 1976.

 9.   Ponder, T. C.  Benzene:  Outlook Through 1980.  Hydrocarbon
     Processing,  55(11):217-218, 1976.

10.   Dawson, G. W., A. J. Shuckrow, and W. H. Swift.  Control of
     Spillage of Hazardous Polluting Substances.   Contract
     14-12-866 (PB 197 596), U.S. Department of the Interior,
     Federal Water Quality Administration, Washington,  D.C.,
     November 1970.  96 pp.
                               33

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11.  Eimutis, E. C., and R. P. Quill.  Source Assessment:  Non-
     criteria Pollutant Emissions.  EPA-600/2-77-107e, U.S.
     Environmental Protection Agency, Research Triangle Park,
     North Carolina, July 1977.  113 pp.

12.  Compilation of Air Pollutant Emission Factors, Second
     Edition  (with Supplements 1-7).  Publication No. AP-42,
     U.S. Environmental Protection Agency, Research Triangle
     Park, North Carolina, 1973.

13.  Industrial Process Profiles for Environmental Use:  Chapter
     6, The Organic Chemicals Industry, Part I.  (Draft).  Contract
     68-02-1320, Task 17 and Contract 68-02-1325, Task 70, U.S.
     Environmental Protection Agency, Research Triangle Park,
     North Carolina.

14.  Burklin, C. E., and R. L. Honerkamp.  Revision of Evapora-
     tive Hydrocarbon Emission Factors.  Radian Project 100-
     086-01,  Radian Corporation, Austin, Texas, June 1976.

15.  Air Pollution Engineering Manual, Second Edition.  J. A.
     Danielson, ed.  Publication No. AP-40, U.S. Environmental
     Protection Agency, Research Triangle Park, North Carolina,
     May 1973.  987 pp.

16.  Burklin, C. E., E. C. Cavanaugh, J. C. Dickerman, S. R.
     Fernandes, and G. C. Wilkins.  Control of Hydrocarbon
     Emissions from Petroleum Liquids.  EPA-600/2-75-042, U.S.
     Environmental Protection Agency, Research Triangle Park,
     North Carolina, September 1975.  245 pp.

17.  Benzene  from Gasoline Evaporation is "Significant Health
     Hazard", EDF says.  Environmental Report 1977, 1363.

18.  Smith, H. M.  Qualitative and Quantitative Aspects of Crude
     Oil Composition.  Bulletin 642, U.S. Department of the
     Interior, Bureau of Mines, Washington, D.C., 1968.

19.  Howard,  P. H., and P. R. Durkin.  Sources of Contamination,
     Ambient  Levels, and Fate of Benzene in the Environment.
     EPA-560/5-75-005, U.S. Environmental Protection Agency,
     Washington, D.C., December 1974.  73 pp.

20.  Criteria for a Recommended Standard:  Occupational Exposure
     to Benzene.  U.S. Department of Health, Education and
     Welfare, Public Health Service Center for Disease Control,
     Washington, D.C., 1974.

21.  Markle,  R. A., et al.  Potentially Toxic and Hazardous
     Substances in the Industrial Organic Chemicals and Organic
     Dyes and Pigments Industry.  Contract 68-02-1323, U.S.
     Environmental Protection Agency, Research Triangle Park,
     North Carolina, October 1976.
                                34

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22.  Industrial Hygiene and Toxicology, Volume II.  F. A. Patty,
     ed.  John Wiley & Sons, Inc., New York, New York, 1962.
     2305 pp.

23.  Benzene Emerging Standard Set by OSHA.  Chemical  &  Engineer-
     ing News, 55 (19):4, 1977.

24.  Rosebrook, D.  D., et al.   Sampling Plan for Fugitive Emis-
     sions from Petroleum Refineries.  Radian Contract 200-144,
     Task 6, Radian Corporation, Austin, Texas, January 1977.

25.  Control Techniques for Volatile Organic Emissions from
     Stationary Sources.  Publication No. AP-68, Project 220-187-
     12, U.S. Environmental Protection Agency, Research Triangle
     Park, North Carolina.  (Draft report submitted to the EPA
     by Radian Corporation, July 1977.)

26.  Sittig, M.  Pollution Control in the Organic Chemical Indus-
     try.  Noyes Data Corporation, Park Ridge, New Jersey, 1974.
     304 pp.

27.  Cavanaugh, E.  C., J. D. Colley, P. S. Dzierlenga, J. M.
     Felix, D. C. Jones, and T.  P- Nelson.  Environmental Problem
     Definition for Petroleum Refineries, Synthetic Natural Gas
     Plants, and Liquified Natural Gas Plants.  EPA-600/2-75-068,
     U.S. Environmental Protection Agency, Research Triangle
     Park, North Carolina, November 1975.  476 pp.

28.  American Petroleum Institute, Evaporative Loss Committee.
     Evaporative Loss from Floating Roof Tanks.  Bulletin 2517,
     Washington, D.C., 1972.

29.  Burklin, C. E., E. C. Cavanaugh, J. C. Dickerman, and S. R.
     Fernandes.  A Study of Vapor Control Methods for  Gasoline
     Marketing Operations, Volume I.  EPA-450/3-75-046-9, U.S.
     Environmental Protection Agency, Research Triangle Park,
     North Carolina, April 1975.  215 pp.

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

31.  Lewis, W. A. Jr., G. M. Rinaldi, and T. W. Hughes.   Source
     Assessment:  Maleic Anhydride.  Contract 68-02-1874, U.S.
     Environmental  Protection Agency, Industrial Environmental
     Research Laboratory, Cincinnati, Ohio.  118 pp.

32.  Metcalf, L., and H. P. Eddy-  Wastewater Engineering
     Collection, Treatment, Disposal.  McGraw-Hill Book
     Company, New York, New York, 1972.  734 pp.
                               35

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                            GLOSSARY
aromatic:  Designating any of a series of benzene ring compounds,

fugitive emission:  Gaseous or particulate emissions from
     industry-related operations that escape to the atmosphere
     without passing through a primary exhaust system.

miticide:  Material used primarily in the control of plant-feed-
     ing mites, especially spider mites.

olefin:  Any series of unsaturated open-chain hydrocarbons con-
     taining one double bond.

pyrolysis:  Decomposition of a compound by the action of heat
     alone.
                               36

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
1. REPORT NO.
  EPA-600/2-79-210d
                              2.
                                                            3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE

 Status Assessment of Toxic  Chemicals:  Benzene
                                     5. REPORT DATE
                                      December  1979
issuing date
                                                            6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
 T.R. Blackwood, J.C.
 L.D. Zeagler
                                                            8. PERFORMING ORGANIZATION REPORT NO.
Ochsner
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Monsanto  Research Corp       Radian Corp
 1515 Nichols Road            8500 Shoal Creek  Blvd
 Dayton, Ohio   1+5^07         P.O. Box 99kQ
                               Austin, Texas   78766
                                     10. PROGRAM ELEMENT NO.
                                       IAB6oh
                                     11. CONTRACT/GRANT NO.

                                       68-03-2550
12. SPONSORING AGENCY NAME AND ADDRESS
 Industrial Environmental Research Lab.  - Cinn,  OH
 Office  of Research and Development
 U.S. Environmental Protection Agency
 Cincinnati, Ohio   1*5268
                                     13. TYPE OF REPORT AND PERIOD COVERED
                                       Task Final    11/77 - 12/77
                                     14. SPONSORING AGENCY CODE
                                           EPA/600/12
15. SUPPLEMENTARY NOTES
 IERL-Ci  project leader for this report is Dr.  Charles Frank, 513-68U-U^8l.
16. ABSTRACT
              Benzene is one  of the most ubiquitous  organic chemicals,  widely
              employed as a solvent, as a fuel  component, and for the  synthesis
              of other organic  chemicals.  This  report details the  emission of
              benzene from industrial sources and  from the largest  source of all,
              the operation of  motor vehicles.   Descriptions of the health hazards
              of benzene exposure are included,  and  both current and anticipated
              regulations are listed.  The report  is concluded with recommendations
              of areas for further study.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                       b.lDENTIFIERS/OPEN ENDED TERMS  C. COS AT I Field/Group
 Aromatic  Hydrocarbons, Aromatic Monocyclic
 Hydrocarbons, Hydrocarbons, Unsaturated
 Hydrocarbons, Chlorobenzenes
                         Organics,  Organic
                         Chemical  Synthesis
   68A
   68D
   68G
18. DISTRIBUTION STATEMENT
  Release to Public
                                               19. SECURITY CLASS (ThisReport)
                                                Unclassified
                                                   21. NO. OF PAGES

                                                        49
                       20. SECURITY CLASS (This page)
                         Unclassified
                                                                          22. PRICE
EPA Form 2220-1 (Rev. 4-77)   PREVIOUS EDITION is OBSOLETE
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                                              iUS GOVEBIIIIENT PRINI1NG OfflCE 1980-657-146/5510

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