EPA-560/2-76-004
                 BIOLOGICAL EFFECTS AND ENVIRONMENTAL
                       ASPECTS OF 1,3-BUTADIENE

                 (SUMMARY OF THE PUBLISHED LITERATURE)
                               MAY 1976


                             FINAL REPORT
                    ENVIRONMENTAL PROTECTION AGENCY
                      OFFICE OF TOXIC SUBSTANCES
                        WASHINGTON, D,C,  20460

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
    CRT NO.        I
    EPA 560/2-76^004
                              2.
                                                            3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
    Biological Effects and  Environmental Aspects of
    1,3-Butadiene (Summary  of the Published  Literature)
             S. REPORT DATE
                Hay 1976
             6. PERFORMING ORGANIZATION CODE
7. AUTMOR(S)
    T.B.  Parsons
    Glynda  E. Mil kins
                                                            8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
                                                            10. PROGRAM ELEMENT NO.
    Radian  Corporation
    8500  Shoal Creek Blvd.
    Austin, Texas  78766
             11. CONTRACT/GRANT NO.

                68-01-3249, Task  #7
12. SPONSORING AGENCY NAME AND ADDRESS
    Office of Toxic Substances
    U.S.  Environmental Protection Agency
    Washington, D.C.  20460
             13. TYPE OF REPORT AND PERIOD COVERED
                Final  	   •  •	
             14. SPONSORING AGENCY CODE
19. SUPPLEMENTARY NOTES
 This  task was initiated  because of a reported  increased incidence of leukemia  among
 workers  in certain styrene-butadiene synthetic rubber manufacturing plants.	
16. ABSTRACT
     This  report is a summary of the literature on the biological  effects and
     environmental aspects  of 1,3-butadiene  and was prepared  from  articles and
     abstracts identified through a search of the technical literature.  The report
     contains information on  the effects of  11,3-butadiene in  environmental samples
     and on  the reactivity  of 1,3-butadiene  in environmental  media.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                              COSATl Field/Group
     1,3-butadiene
13. DISTRIBUTION STATEMENT
 Document  available to the  public through
 the National  Technical Information Service
 Springfield,  Virginia  22151
19. SECURITY CLASS (ThisReport)
                                                                          21. NO.
20. SECURITY CLASS (Thispage)
 Unclassified
EPA Form 2220-1 (9-73)

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EPA-560/2-76-004
                      BIOLOGICAL EFFECTS AND ENVIRONMENTAL

                            ASPECTS OF 1,3-BUTADIENE


                      (Summary of the Published Literature)



                                  Final Report
                                   Prepared by

                                  T.B. Parsons
                                Glynda E. Mil kins
                         Contract No. 68-01-3249, Task 7

                                Frank Letkiewicz

                                 Project Officer
                           Office of Toxic Substances
                       U.S. Environmental Protection Agency
                             Washington, D.C.  20460
                                    May 1976

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                                   NOTICE
     This report has been reviewed by the Office of Toxic Substances,  EPA,
and approved for publication.   Approval  does not signify that the contents
necessarily reflect the views  and policies of the Environmental  Protection
Agency, nor does mention of trade names  or commercial  products constitute
endorsement or recommendation  for use.
                                     : b

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                    •   TABLE OF CONTENTS


                                                           Page

1.0       INTRODUCTION ............... ....  1

2 . 0       BIOLOGICAL EFFECTS .......  ..... ....  2
          2.1  Plant Studies .......  ......  ...  2
          2.2  Animal Studies ............ ..••'•  3
               2.2.1  Organs and Systems ..........  4
                      2.2.1.1  Reproductive System. ....  4
                      2.2.1.2  Circulatory System  .....  5
                      2.2.1.3  Hematopoietic Organs,
                               Formed Elements ,  and
                               Plasma ......... . .   •  *
                      2.2.1.4  Liver ......... ...  9
                      2.2.1.5  Kidneys. .  ...... .  .   .10
                      2.2.1.6  Respiratory System .   ...   . 10
                      2.2.1.7  Skin ........   .... 11
                      2.2.1.8  Nervous System ..... '  ... 11
                      2.2.1.9  Gastrointestinal Tract ... 12
               2.2.2  Various Metabolism Disturbances ... 13
          2.3  Observed Effects on Humans  ......... 14
               2.3.1  Circulatory System .......... 14
               2.3.2  Hematopoietic Organs,  Formed
                      Elements, and Plasma ...... ... ..   .16
               2.3.3  Liver ................. 18
               2.3.4  Kidneys  .......... ....... 19
               2.3.5  Respiratory System .......... 19
               2.3.6  Skin ................... 20
                               ii

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                 TABLE OF CONTENTS (Continued)
               2.3.7  Eyes.  .  ,	   21
               2.3.8  Nervous  System	   22
               2.3.9  Gastrointestinal Tract.  ......   23
               2.3.10 Endocrine System. .	   24

3.0       ENVIRONMENTAL ASPECTS 	  .....   25
          3.1  Occurrence	25
          3.2  Reactivity ...........  	   28

4.0       BIBLIOGRAPHY	33

5.0       ADDITIONAL REFERENCES	   49
                              111

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1.0      Introduction

         This literature summary was prepared by Radian Corporation
for EPA under task 7 of contract number 68-01-3249, Information
Concerning Selected Chemicals.  According to the task statement,
abstracts concerning biological properties, environmental effects
and analytical methods for butadiene were to be collected using
several abstracting indices.  A narrative summary of literature
describing biological and environmental aspects was to be pre-
pared.  The literature search and summary were to be completed
within a two-week time period.

         Literature describing biological aspects of butadiene
is summarized in Section 2.0.  Plant, laboratory animal, and
human studies are described.  The majority of published infor-
mation on biological aspects was written in Russian, and many
of the references were unavailable in full text English trans-
lations.  Information from these sources was obtained from the
abstracts.   If an abstract rather than a full text article was
the source of information, the abstract number was given in the
literature citation.  If the full text was consulted, the liter-
ature citation contains the author's name and the year of
publication.

         Information on environmental occurrence and reactivity
of butadiene is summarized in Section 3.0.  Most of the infor-
mation on this subject was available in full text in English.

         References cited in the text are listed in the Bibli-
ography in  Section 4.0.  Some references were not  available  in
full  text in time to be described in the  summary.   Some abstracts
did not contain the information of interest.  References in  these
two categories were not described in the  literature  summary but
are expected to contain useful information.  These  additional
references  are listed separately in Section  5.0.

                              -1-

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2.0       Biological Effects

          This section contains a summary of responses of plants,
animals, and humans to 1,3-butadiene and to mixtures of ,1,3-
butadiene with other substances as reported by various researchers
in the technical literature.

2.1       Plant Studies

          A summary of the available literature concerning effects
of 1,3-butadiene and mixtures of 1,3-butadiene with atmospheric
components on plant life is included in this section.   Only three
reports of plant studies of this type were found.

          The effects of hydrocarbon gases representative .of the
Ci- Ci» range on plant growth and development were individually
examined by Heck and Pires (1962).   Fumigation with 1000  ppm
of.1,3-butadiene produced some indication of injury in cotton,
cowpeas, and tomatoes, although the symptoms were too  slight
to be identified.  No effect was reported on coleus, sorghum,
and soybean.  Further fumigation experiments at 10 and 100 ppm
(v/v) gas in air for 3-week periods  produced no easily recognizable
effect from 1,3-butadiene on cotton, cowpeas, and tomatoes.   It
was therefore eliminated from further studies.  (Heck and Pires,
1962).

          Abeles and Gahagan (1968)  examined the role  of  ethylene
and ethylene analogs in bean plant abscission acceleration studies.
Of the seven test gases studied, 1,3-butadiene was least  active
in accelerating abscission and only displayed a 10% stimulation
at 10,000 ppm exposure for four hours.
                               -2-

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          Research conducted by Haagen-Smit,  et al.  (1951) in
trying to duplicate symptoms induced by smog on plants in the
Los Angeles area indicates both typical and atypical injury to
plants from exposure to a mixture of butadiene with ozone for
five hours.  The typical symptoms used for diagnosis were
silvering of leaves on spinach, endive, and beet .along with
speckled necrosis on oats and alfalfa.  Atypical damage encoun-
tered was wilting, the formation of large necrotic areas, tip
burning, chlorosis, bleaching, or minute pitting of leaves.
Further experimentation with mixtures of N02  and butadiene
showed typical smog damage symptoms at 5 ppm butadiene and 7 ppm
NO2 in the absence of sunlight or UV irradiation.  Lower con-
centrations of 0.5 ppm butadiene and 4.5 ppm N02 without sunlight
or UV irradiation resulted in no symptomatic response.  Results
of experiments with butadiene, NOX and UV irradiation or sunlight
were not reported.  The authors concluded from their work that
the plant damaging species were oxidation products of unsaturated
hydrocarbons (Haagen-Smit, et al, 1952).

          The three articles summarized in this section support
the hypotheses that 1,3-butadiene itself may have little effect
on plants.  However, conditions and substances present in the
atmosphere may result in the formation of reactive compounds
causing plant damage.

2.2       Animal Studies

          This section describes the effects of 1,3-butadiene
on laboratory animals.  Reported observations of the effects on
several organs and systems and metabolism are included.

          Exposure to 1-3 butadiene either alone or in combina-
tion with a-methylstyrene, toluene, N-phenyl-B-naphthylamine, iso-
prene and toluene was accomplished most often by inhalation of
                               -3-

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vapors, although a few studies utilized oral administration.
The laboratory rat was the most often used animal; guinea pigs,
rabbits, mice and cats were also utilized.

2.2.1     Organs and Systems

          In an effort to facilitate reading and utilization of
reported data concerning effects of 1,3-butadiene and mixtures
of 1,3-butadiene with other substances on animals, the informa-
tion was organized by organ or system.  The categories included
are the reproductive system; the circulatory system;  hematopoietic
organs, formed elements, and plasma; liver; kidneys;  respiratory
system; skin; the nervous system; and the gastrointestinal system.

2.2.1.1   Reproductive System

          Female                                 .    .

          During the first month of exposure by an unspecified
method to 1,3-butadiene and a-methylstyrene, a decrease in the
number of primordial cells and maturing follicles is  noted.
Large numbers of corpora lutea are preserved in the active state.
If poisoning by 1,3-butadiene and a-methylstyrene continued for
2-3 months, adaptation occurred  (CA75:96902t).   Another survey
(CA72: 30037w) describing effects of administering butadiene
and toluene by inhalation  reported prolongation of estrous
caused by both chronic and acute poisoning.  A normal cycle was
reestablished in 507» of the rats within five months after
cessation of chronic poisoning.

          Male      _   :•                                           •

          Chronic vapor inhalation of a-methylstyrene and 1,3-
butadiene by rats resulted in inhibited spermatogenesis with
                              -4-

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dysplastic and necrotic changes noted.  Signs of adaptation and
restoration of spermatogenesis did occur more than 24 days after
cessation of the 60 to 90 day course of poisoning (CA75:  96900r).

2.2.1.2   Circulatory System

          Hemodynamic disturbances with increased permeability
of vessel walls were the result of chronic exposure of rats to
1,3-butadiene for 81 days at concentrations of 30 mg/ra3
(CA75: 107774f).  Chronic vapor inhalation by rats of
a-methylstyrene and 1,3-butadiene resulted in disturbed permea-
bility of testicular veins with accumulation of blood proteins
in vein walls and testicular stroma (CA75: 96900r).   Chronic
exposure in another study of the same two substances resulted in
vascular dystonia in respiratory structures (CA78: 106680x).
During long-term administration of 1,3-butadiene and a-methylstyrene
by inhalation, an initial .toxic reaction observed was increased
permeability of blood vessels in rat lung.  Later, sclerotic
processes developed in perivascular and peribronchial zones,  and
blood vessel permeability decreased (CA75: 107749b).  Chromotropic
compounds accumulated in blood vessel walls of rats subjected to
chronic exposure by inhalation of a-methylstyrene and 1,3-butadiene
mixtures.  After 90 days of poisoning, chromotropic compounds
were found in perivascular connective tissue.  Again, signs of
sclerosis were observed and outlasted the arrest of poisoning
(CA75: 96881k).   The chronic exposure of rats to 0.03 mg/i
1,3-butadiene for 81 days caused decreased arterial pressure
(CA66: 118540s).

          Specific histopathology described in one study of rats
ingesting 100 mg/kg 1,3-butadiene daily  (subacute) for a 2.5
month course were as follows:  cytoplasm of the heart showed
granular and hydropic dystrophy, cytolysis, neuronophagia,
homogenation of vascular walls with permeability disturbance,
                              -5-

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and lymphohistiocytic infiltration  (HEEP/72/03574).  Rabbits
subjected to chronic exposure to 1,3-butadiene  (100 mg/m3)
exhibited fragmentation of muscle fibers in the myocardium
(Batkina, 1966) .                                      ..

2.2.1.3.  Hematopoietic Organs, Formed Elements,  and Plasma

          Hematopoietic Organs and  Formed Elements

          A 120-day test exposing rats to vapors  of 5 mg 'a-methyl-
styrene/m3 air and 100 mg 1,3-butadiene/m3 produced disturbances
in the tissues and cells of the bone marrow, lymph glands, and
spleen, which began to normalize at 90-120 days.  Protein metab-
olism changes were noted in lymphocytes, normoblasts, and unripe
granulocytes during the experiment.  The results  point to the
myelotoxic effect of the combination of the two compounds
(CA75:116947s).

          A change in the cell distribution in rabbits was observed
with the administration,  in an unspecified manner, of 200 mg/i
of 1,3-butadiene.  The ratio of erythroblasts to granulocytes was ,
increased (CA74:97300m).

           A separate study using inhalation of 99.8 mg 1,3-
 butadiene and 5.2 mg of  a-methylstyrene per m3  demonstrated  a
 decreased level of leukocytes in rats  (CA78:  106680x).   The
 effect was  also reported (CA75:  107786m)  with specific reference
 to decrease in neutrophils.   Hypochromic  anemia was also observed,
 indicating inhibited hemopoiesis.   Leukopenia was found in mice
 exposed to fumes from heated butadiene rubber.   The fumes con-
 tained 0.012 mg/& N-phenyl-B-naphthylamine and 0.339 mg/I
 1,3-butadiene (CA71:  41988n).   Another study (CA66:118541t)
 performed on rats exposed by inhalation of butadiene for 81  days
 also  resulted in erythrocytosis  and leukocytosis with a
 neutrophilic shift to the left.

                               -6-

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          A study of both acute and chronic poisoning of
experimental animals was reported by Batkina, 1966.  Acute
poisoning of rats and rabbits caused leukocytes is with neutropenia
and relative lymphocytes is along with changes in protein distri-
bution in the serum.  Chronic poisoning of rats with concentra-
tions of 2200 mg/m3 caused a tendency toward leukopenia along
with an increase in the number of pseudoeosinophils and in
lymphopenia.  In rats and rabbits an inhibition of phagocytic
activity of neutrophils developed earlier in the animals
subjected to chronic dosages of 2200 mg/m3 than in those subjected
to dosages of 100 mg/m3.  Rabbits subjected to chronic exposure
exhibited an increase in erythrocyte sedimentation rate and a
decrease in blood hemoglobin content as well as hyperplasia of
the spleen pulp  (Batkina, 1966).

          Chronic exposure of rats to butadiene and a-methylstyrene
supressed phagocytic activity of leukocytes  (CA78: 106680x), but
this activity was increased in macrophages of rats exposed to
butadiene (CA75: 107773e).

          Additionally, chronic exposure of rats to concentrations
of 1,3, and 30 mg of 1,3-butadiene per m3 of air resulted in
structural changes in hematopoetic organs (especially the spleen)
and thinning of  nuclear endothelium.  Also noted was a decrease
in the content of nucleic acid of splenic cells and disintegration
of red blood cells in the pulp of the spleen (CA75: 107773e).

          A study of marrow smears from rats exposed to mixtures
of a-methylstyrene and 1,3-butadiene by inhalation was made over
a period of 10-120 days.  Changes were observed in immature
granulocytes and in slightly differentiated cells.  SS and SH
groups in erythrocytes decreased in the initial period, increased
in the intermediate period,  and decreased again later.  Changes
observed in nucleoproteins,  anino acids, and functional proteins
were a function of dosage (CA73:129116d).
                             -7-

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          Chronic exposure of rabbits to a combination of toluene
and 1,3-butadiene for a 2 month period of time caused an increase
in the albumin/globulin ratio of the bone marrow with a decrease
in total protein (Faustov and Lobeevay 1970) .
                                                            /
          A statistically reliable reduction in hemoglobin con-
centration in rabbits resulted from oral administration of 40 mg
1,,3-butadiene in vegetable oil/kg over a 7-month course (BA52:69712)

          Plasma

          An increased level of total SH groups in the blood was
reported as a result of inhalation of 99.8 mg  1,3-butadiene  and
5.2 mg a-methylstyrerie/m3 air in rats (CA78:  106680x).   However,
another study using oral administration to rabbits of  40 mg/kg
1,3-butadiene in vegetable oil over a 7-month course did not change.
the number of free SH groups (BA52: 69712).

          An increase in cholesterol content in the blood of 84
rats, particularly cholesterol esters,  was noted after 120 days
of inhalation of 1,3-butadiene and/or a-methylstyrene.   An
increase from 29.3 to 64.9 mg% was observed (CA75:  96903u).
          Exposure to 1,3-butadiene and a-methylstyrene resulted
in a decrease in total serum protein, but an increase in the a2-
globulin fraction (CA75:107786m).   Changes in the immunological
state were observed after an 81-day course of inhalation of 1.0,
3.0,  and 30 mg/m3 1,3-butadiene/m3 air (CA75:107777J) in experi-
mental animals which can be related to changes in globulin/albumin
levels.
                             -8-

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2.2.1.4   Liver

          Decreased liver metabolism was noted with chronic
exposure of rats to 1,3-butadiene and a-methylstyrene by inhala-
tion.  Decreased levels of ascorbic acid and thiamine in the
liver were found (CA78: 106680x).   Also indicated was disturbed
metabolism of carbohydrates, fats, and proteins.   In another
study specific disturbance of lipid and carbohydrate metabolism
was observed in rats, especially a decrease in glycogen and
accumulation of lipids in hepatic areas after a 60-120 day course
of inhalation of a mixture of 0.05 mg 1,3-butadiene and 0.005 mg
a-methylstyrene/Jl.   Chronic inhalation of a-methylstyrene and
1,3-butadiene affected lipid metabolism and increased the
cholesterol contents of rat livers from 119 to 246.2 mg7»
(CA75:107720k).   Redistribution of total proteins and ribo-
nucleoproteins in liver cells is noted with decreases in protein
content in the cytoplasm of vacuolated cells (CA75: 107780e) of
rats subjected to chronic exposure by inhalation of butadiene
and a-methylstyrene.  Hepatic ATP content increased as did the
ratio of ATP to ADP with acute inhalation poisoning (Oura and
Reiha, 1966).

          Chronic inhalation of a mixture of 1,3-butadiene  (0.05
mg/H) and a-methylstyrene (0.005 mg /a) caused disturbances  in
the lipid and carbohydrate metabolism in rats, evidenced by  a
decrease in glycogen and an increase in lipids in hepatic cells
(CA75:107779m).

          Chronic exposure of rabbits to 1,3-butadiene  (100  mg/m3)
produced granular dystrophy in the liver (Batkina,  1966).  Specific
histopathologic changes noted in the liver are similar  to those
previously described for the heart  (BA53:5577).
                              -9-

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2.2.1.5   Kidneys

          Chronic inhalation exposure of rats to mixtures of 1,3-
butadiene and a-methylstyrene caused symptoms similar to protein
dystrophy (CA75:107797r).   During the course of the experiment
renin granules disappeared from the epithelioid cells but later
reappeared (CA75:107797r).   Increased concentrations of urinary
hippuric acid are noted in rats exposed to fumes of heated butadiene
rubber containing butadiene and N-phenyl-B-naphthylamine
(CA71: 41988n).

          Other researchers report changes in the urine composition
of rats exposed to butadiene and a-methylstyrene by inhalation.
Decreased thiamine levels and urinary excretion of riboflavin,
coporphyrins, and ascorbic acid were reported (CA78: 106680x).

          Morphologic changes in the kidneys are similar to those
described for liver and heart (BA53:5577).  Small round cell
infiltrations and congestion in the kidneys were reported in
rabbits chronically exposed to 100 mg/m3 1,3-butadiene levels
(Batkina, 1966).

2.2.1.6  Respiratory System

         Chronic exposure of rats  to 100 mg/£ 1,3-butadiene  and
5.27 mg/£ a-methylstyrene vapors initially  altered bronchial
epithelium,  caused proliferation of beaker  cells, and  increased
permeability of blood vessels.  Later,  this  significant  hyper-
secretory state in the.connective  tissue structures  of  the  lungs
resulted in  reactive cell production.   Toward the end  of the
experiment,  sclerotic processes developed in the perivascular
and peribronchial zones with a decrease in  the permeability  of
blood vessels.  Irritation of the  respiratory tract  was  noted
                               -10-

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in mice exposed by inhalation to mixtures of butadiene and
N-phenyl-3-naphthylamine.  Morphologic changes noted with oral
administration of 100 rag/kg 1,3-butadiene daily for 2.5 months
included thickening of the interalveolar septa and minor lympho-
histiocytic infiltration (BA53.:5577) .

         A study of chronic exposure of rats to .butadiene vapor
concentrations of 3 mg/in3 for 81 days caused some changes in the
epithelium of the mucous membranes of the lungs and nose (CA69:12741e)

         Chronic exposure of rabbits to 1,3-butadiene (100 mg/m3)
resulted in pulmonary vessel congestion, pronounced emphysema,
and inflammatory small-cell infiltration around the bronchi.
(Batkina, 1966).

2.2.1.7   Skin

          Changes in epidermis, connective tissue,-hair, glands,
and neuron fibers of rat skin caused by inhalation of butadiene
and a-methylstyrene disappeared 30-60 days after discontinuation
of treatment  (CA81: 100372p).

2.2.1.8   Nervous System

          Histological changes occurred in rats given 100 mg/kg
1,3-butadiene for 2.5 months.  The cytoplasm of the cells of
the brain and sympathetic ganglia showed granular and hydropic
dystrophy, cytolysis, neuronophagia, homogenatipn of the vascular
walls and disturbances of their permeability (HEEP/72/03574).

          A study conducted by Shugaev published in 1969 related
toxicity of various hydrocarbons, including butadiene, to brain
concentrations in rats, mice, and cats.  Acute atmospheric
exposure at levels of 270 mg/fc for mice and 280 mg/£ for rats
                              -11-

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was the method of administration.  In cats the butadiene was
found to concentrate in the white nervous tissue.  The author
recommends that toxicity criteria be based on minimum lethal
concentrations in the medulla oblongata.  This recommendation
is based on the fact that death during acute intoxication is
a result of the hydrocarbon concentration in this organ inducing
respiratory arrest (Shugaev, 1969).  Another study reported by
Shugaev (CA69: 50596u) reports higher concentrations of 1,3-
butadiene in the medulla oblongata than in the cerebellum or
cerebral cortex.  Chronic inhalation by laboratory animals of
1,3, and 30 mg/m3 butadiene in air resulted in functional
disturbances of the central nervous system (CA75: 107777J).
Rabbits anesthetized repeatedly with 20 to 25% butadiene in air
reportedly regained balance and muscular control in about 2
minutes.  No tissue changes were noted (Anonymous, 1963).

          Chronic exposure by inhalation of 5 mg a-methylstyrene
and 100 mg butadiene per m3 air caused a decrease in cholinesterase
activity in experimental animals.  Acetylcholinesterase activity
in rabbits administered butadiene orally for 7 months at concen-
trations of 0.4 mg, 4 mg, and 40 mg per kg in vegetable oil was
not affected (BA52: 69712).

          Acute exposure of mice to 50,000; 100,000; and 200,000
mg 1,3-butadiene per m3 produced changes in the nervous system.
Chronic exposure of rats and rabbits at concentration levels of
2200 mg/m3 and 100 mg/m3 also produced nervous system disorders
(Batkina,  1966).

2.2.1.9  Gastrointestinal Tract

         No alteration of gastric  functions was  reported.   One
study (BA53:5577) reported  lyniphohistiocytic  infiltration of the
gastrointestinal tract after a 2.5 month  course  of  oral  adminis-
tration of 100 mg 1,3-butadiene/kg daily.
                              -12-

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2.2.2     Various Metabolism Disturbances

          Disturbances in vitamin metabolism were noted in one
study of rats subjected to butadiene (99.8 mg/m3) and
a-methylstyrene (5.2 mg/m3).  The ascorbic acid level in the
blood, liver, and brain was low as was the thiamine level in
the liver and urine.  Urinary excretion of riboflavin and
ascorbic acid were noted (CA78: 106680x).

          Rabbits given oral doses of 40 mg 1,3-butadiene per
kg in vegetable oil showed an increase in fructose 1,6-diphosphate
aldolase activities (BA52:  69712).
                              -13-

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 2.3       Observed Effects on Humans

          Industry workers are exposed to mixtures of butadiene,
 styrene,  chloroprene, dimethyl dioxane, ct-methyl styrene, cata-
 lysts, hydrogen sulfide, carbon monoxide, aerylonitrile, acrolein,
 aromatic  amines, ammonia and/or mixtures of saturated or unsat-
 urated hydrocarbons, through either direct contact or inhalation.
 Thus, observed effects cannot usually be attributed solely to
 butadiene.  Observed effects on humans are described in terms
 of organs and organ systems in this section.

 2.3.1     Circulatory System

          Workers exposed to butadiene, styrene, and ethylbenzene
 for eight years exhibited dyatrophic changes in the myocardium
 affecting contractile activity, symptoms of hypotension, and
 changes in capillary resistance (CA81:140347r).   A hypotensive
 effect was also noted in workers exposed to a butadiene-styrene
 mixture under clinical and subclinical conditions (CA61:1169h).

          Persons working with styrene, ethylbenzene, and 1,3-
 butadiene showed symptons of an increase in capillary permeability
 and a high resistance to blood flow as compared to control sub-
 jects (CA70:80662a).   A study of 60 persons employed in the syn-
 thetic' rubber industry showed that prolonged contact with styrene,
 butadiene, and ethylbenzene decreased capillary stability.
 Changes were noted in pictures obtained with a capillaroscope
 (CA81:67974m).   Sixty butyl rubber workers in contact with buta-
 diene, styrene, and ethylbenzene were studied using electro-
 cardiograms and ballistocardiograms.   The results were compared
with those for a group of persons having no contact with the
hydrocarbons.   A deviation in the heart contraction function
was noted in the rubber workers as compared to those in the
                              -14-

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the control group; however, the deviations did not exceed
physiological norms.  Changes were noted in the phase structure
of the systole, but no changes were noted in contraction of the
myocardium (CA81:67973k).

          Functional disorders of the cardiovascular system re-
sulted from prolonged exposure to a-methylstyrene and butadiene
in rubber production workers (CA81:140388e).   Sixty petroleum
industry employees having prolonged contact with styrene, buta-
diene, and ethylbenzene were compared to a group having no hydro-
carbon contact.  Oscillograms were obtained and analyzed to
determine hydrocarbon effect on vascular tonus.  The tonus of
the peripheral vascular system was lower in exposed persons
than for the control group and was distinctly unsymmetrical in
exposed persons  (CA81:67971h).

          Batkina studied synthetic rubber workers in the buta-
diene, separation and purification area who had been exposed to
more than 100 mg/m3 of butadiene vapor for prolonged periods.
Other unsaturated hydrocarbons were present in insignificant
concentrations.  One hundred workers were given periodic medical
examinations over a 10-15 year period.  A tendency toward hypo-
tension was noted (Batkina, 1966).

          Three hundred sixty-five persons employed for three
years in a chemical factory were exposed to the combined effects
of benzene, cyclohexane, and butadiene.  The toxicity of the
chemicals was studied with attention to the age of the workers.
They were described in three age groups:  Group 1 was comprised
of 67 subjects aged 18 to 21; group 2 had 122 members aged 22
to 25; and group 3 had 176 members aged 26 to 35.  Toxic effects
were ascribed to the presence of benzene because its MAC was
exceeded most frequently.   Butadiene concentration was con-
siderably below its MAC.  Low blood pressure and changes in
                              -15-

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vascular tone were noted with a larger percentage of cases
being reported among group 1 workers than in other groups
(Doskin, 1971).

          Angina was prevalent among workers in synthetic
rubber production (CA80:63401d).

2.3.2     Hematopoietic Organs, Formed Elements,  and Plasma

          Workers in a vulcanization plant were exposed to
vapors containing 32 to 40 mg/tn3  of butadiene mixed with styrene,
oil aerosol, formaldehyde, methanol, sulfur dioxide, acrolein,
aromatic amines, ammonia, acrylic acid nitrile, and carbon
monoxide.  Vulcanization operators performed heavy'work under
conditions of high air temperature, radiant heat, and noise.
Investigation of these workers showed decreases in hemoglobin,
red blood cell count, reticulocytes, and thrombocytes in peripheral
blood.  These changes were ascribed to the presence of styrene
and "other components of the mixture" (Volkova and Bagdinov, 1969).

          Toxic effects on the blood of chemical plant workers
in three age groups described in Section 2.3.1 were studied in
detail.  Again, the effects were ascribed to benzene rather than
to butadiene or cyclohexane which were present in lower concen-
trations .  Blood counts and tests of the functional state of
circulating leukocytes and medullary hematopoiesis were performed.
Healthy new employees provided hematological- data for the control
group.  Noted hematological disturbances included thrombocytopenia,
disturbed erythropoiesis, and nonnochromic anemia with a tendency
toward hyperchromia after one year of employment.  When benzene
concentrations were reduced to the MAC, normal to high RBC
levels occurred.
                              -16-

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          White blood cell changes included leukocytosis followed
by leukopenia, lymphocytocis,  and disturbed phagocytic capacity
of neutrophils (deterioration in functional capacity of granulo-
cytes).

          Investigations of medullary hematopoiesis indicated
an intensified proliferation of medullary elements (myelokaryo-
cytes).  The content of reticular cells and lymphocytes was
high in the marrow tissue.  Again, hematological alterations
occurred most frequently among group 1 (younger) workers
(Doskin, 1971, CA74:57085p).

          The butadiene production workers studied by Batkina
who were exposed to butadiene concentrations greater than 100
mg/m3 with insignificant amounts of other hydrocarbons showed
blood changes.  Leukopenia, an increase in erythrocyte sedi-
mentation rate, and decrease in hemoglobin were reported.  De-
creases in phagocytic activity of neutrophils were also noted
(Batkina, 1966).

          The blood of rubber production workers exposed to
styrene and butadiene concentrations exceeding the MAC was
found to contain increased cholesterol and lecithin.  The con-
tent of B-proteins was increased while that of a-lipoproteins
was decreased.  The fraction of globulin was increased, while
blood serum albumins were decreased (CA81:67970g, CA80:40675g).
A drop in blood albumins and an increase in y- and 8-globulins
were also noted in clinical studies with styrene-butadiene
mixtures.  Styrene-butadiene rubber workers showed changes in
peripheral blood including leukopenia, lymphocytosis, throtnbo-
cytopenia, and reticulocytosis (CA61:1169h).

          The toxic effects of 1,3-butadiene and ot-methylstyrene
in peripheral blood of 1406 synthetic rubber production
                              -17-

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workers have been studied.  Results were compared with a control
group of 200 civil engineering employees having no chemical con-
tact.  Noted changes included increased hemoglobin and erythro-
cytes, decreased color index, leukocytosis,  eosinophilia,
neutropenia, relative lymphocytesis, monocytosis, both increased
and decreased thrombocytes,  and a decrease in intracellular
content of glycogen, lipids, and peroxidase in leukocytes
(CA78:88310v).

2.3.3     Liver

          Clinical studies of the chronic effect of a mixture
of butadiene and styrene on healthy workers indicated that 35
percent showed liver enlargement and a decrease in functional
tests (CA61:1169h).   Workers employed in synthetic rubber pro-
duction showed positive reactions for antihepatic antibodies
indicating pathological changes which can be used for diagnoses
of early toxic liver disorders (CA80:633902).

          The relationship between the excretory function of the
liver and the secretory function of the .stomach in workers ex-
posed to butadiene and styrene in synthetic rubber production
was investigated.  While marked suppression of liver function
was noted, there was no parallelism between liver test factors
and stomach secretory function (CA80:148759b).

          Liver and bile duct diseases were observed among
workers in synthetic rubber plants where styrene and butadiene
concentrations were from 20 to 100 and 85 to 93 mg/m3,  respectively,
in 1960.  Both concentrations were reduced to below 20 mg/m3 by
1970  (CA80:136939x).  Volkova and Bagdinov reported that styrene
and butadiene "have a selective effect" on diseases of the liver
and bile duct.  The incidence of such diseases was found to be
                             -18-

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7.6 cases per 100 workers exposed to vulcanization gases con-
taining butadiene, styrene, and many other impurities (Volkova
and Bagdinov, 1969).

2.3.4     Kidneys

          Kidney malfunctions were reported to be prevalent
in workers involved in monomer production and in isolation of
synthetic rubber from reaction products.   Catalysts were reported
to produce such toxic effects (CA80:63401d).

2.3.5     Respiratory System

          Butadiene-styrene mixtures were reported to cause
lariyngotrachyitis and sometimes bronchitis among healthy workers
studied under clinical conditions (CA61:1169h).   Acute catarrh
of the upper respiratory tract occurred often among workers in
a synthetic rubber plant with chronic exposure to butadiene and
styrene (CA80:63401d).  Chronic exposure produced increasing
tendency toward pathological changes in the upper respiratory
tract (CA80:136939x).

          An investigation of chemical hazards in the braided
hose department of Gates Rubber Company was performed.  The
study included sampling and analysis of ambient air for 1,3-
butadiene.  Sampling was.conducted on two days,  and the con-
centration of butadiene was below the detection limit of the
gas chromatographic method used.  Other chemicals in use in-
cluded styrene, isocyanates, resorcinol, vinyl pyridine, and
formaldehyde.  Approximately 2200 types of hose are produced in
small lots in the work area and 540 chemicals are employed.  A
medical evaluation of employees included completion of a question-
naire by seventeen persons.  A significant number of respondents
reported cough, runny nose and sore throat.  It was concluded
                             -19-

-------
that there was sufficient evidence to indicate a hazard for
upper respiratory tract irritation most likely associated with
styrene, butadiene,  vinyl pyridine, resorcinol or a combina-
tion of these (Gunter.and Lucas,  1973).

          Medical examinations of vulcanization workers exposed
to butadiene, styrene and numerous other contaminants were per-
formed.  Investigations indicated that 26.6 percent of diseases
resulting in absenteeism involved influenza and catarrh of the
upper respiratory tract and 10.9  percent involved tonsillitis.
Thirty-three percent of the workers examined exhibited sub-
atrophic mucosal changes in the nose, throat and larynx.   The
extent of such disorders was related to length of employment.
Olfactory perception was altered  and a high incidence of hyposmia
(decreased sensitivity to odors)  was noted (Volkova and Bagdinov,
1969).

          A statistical treatment of medical records of rubber
plant workers indicated a marked  rate of increase in respiratory
diseases with years of service (CA82:47351y).

2.3.6     Skin

          The vulcanization workers described previously (Volkova
and Bagdinov, 1969) had abnormally dry palms with superficial
cracks.  Pyoderma was noted in 15.2 percent of workers due
partly to constant friction of skin against rubber articles.

          Three cases of urticaria were noted among the workers
in the braided hose department of Gates Rubber Company.  The
incidence was thought to be abnormally high.  The possibility
that it resulted from chemical substances in the working environ-
ment was acknowledged.  Nearly half of the employees related
problems of subsiding dermatitis  (Gunter and Lucas, 1973).
                              -20-

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          Medical records of 679 workers in a synthetic rubber
plant were analyzed in two groups.   One group contained workers
in contact with styrene, butadiene, butane, butylene, benzene,
H2SO.», and catalysts.  The other group contained workers with
no contact with chemicals.  Group 1 had 21.7 percent skin dis-
eases and tuberculosis, while the second group had only 3.3
percent (CA82:47350x).

          Workers in a synthetic rubber plant exposed to air
containing a-methylstyrene, dodecylmercaptan, Neozone D, and
butadiene in concentrations exceeding the MAC were affected
with dermatosis (CA81:110878x).

2.3.7     Eyes

          Sensitivity of the human eye was investigated in
studies to determine the upper limit for a single exposure to
butadiene.  Increased sensitivity was noted at concentrations
of 4.0 mg/m3 but not at 3.6 mg/m3 (CA69:12741e).

          Workers in the braided hose department of Gates Rubber
Company are routinely exposed to numerous chemicals, one of
which is butadiene.  Burning, itching, red eyes were job-related
symptoms indicated in employee questionnaires.  Viral or allergic
conjunctivitis and corneal ulceration were observed, but it is not
clear that these problems were caused by exposure to butadiene.
Industrial hygienists concluded that a hazard responsible for
eye irritation existed in the work area (Gunter and Lucas, 1973).

          Conjunctivitis was noted as an effect of exposure to
butadiene and styrene mixtures in clinical tests on healthy
workers in synthetic rubber production (CA61:1169h).
                              -21-

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2.3.8     Nervous System

          In a study of vulcanization workers exposed to styrene,
butadiene,  oil fog ,• formaldehyde..,,; methano.lv -hydrogen sulfide,   ,   -
                  -. /        "      '        ' ''       '              •
acrolein, aromatic hydrocarbons, ammonia, aerylonitrile, and
carbon monoxide, styrene vapor was found to be the product most
frequently present in concentrations exceeding the MAC in breath-
ing zones.   The increase in time expenditure and the percentage
of errors in the execution of tests attested to the effect of
the "complex of unfavorable factors" on the state of the central
nervous system (the attention function).   The effect was more
pronounced in the case of workers who had been employed for a
longer time.  Studies of workers exposed to complex mixtures con-
taining 30-40 mg/m3  of butadiene and 10-20 mg/m3 of styrene and
working under conditions of high temperature suggested strain on the
thermoregulatory system and disturbances in the function of the
olfactory analyser.   Raised olfactory thresholds and a high
incidence of hyposmia were reported.  Diseases of the peripheral
nervous system inlcuding radiculitis, neuralgia, and lumbago
caused 17.6 percent of the cases of absenteeism among the
vulcanization operators in 1966 (Volkova and Bagdinov, 1969).  .

          Doskin studied chemical plant workers exposed to
benzene levels exceeding the MAC and butadiene and cyclohexane
at concentrations below the MAC.  He reported that workers in
the youngest of three age groups had most frequent complaints
of neurological disorders such as asthenovegetative syndrome
(Doskin, 1971).

          In tests to determine the upper limit for a single
exposure of butadiene, the odor threshold value was found to be
4 mg/m3.  Electroencephalograms showed an effect at concentra-
tions of 3 mg/m3  (CA69:12741e).
                              -22-

-------
          Clinical data on 679 synthetic rubber plant workers
for a ten-year period were analyzed to determine disease rate.
Diseases of the nervous system were found in 44.5 percent of
workers exposed to butadiene, styrene, butane, butylene, benzene,
H2SOi» and catalysts.  Only 26.7 percent of plant workers having
no contact with the compounds had nervous system diseases
(CA82:47350x).

          Synthetic rubber production workers exposed to buta-
diene and styrene, styrene alone, chloroprene, mixtures of
saturated and unsaturated hydrocarbons, dimethyl dioxane, and
ct-methylstyrene manifested symptoms of narcosis on a background
of asthenic and neurasthenic reactions (CA61:1169h).

          Workers in shops producing latex and in shops recover-
ing SKMS-30 rubber were exposed to 1,3-butadiene and a-methyl-
styrene.  An adverse effect on the nervous system was noted,
but the type of effect was not described in the abstract.
Workers reacted differently to the action of the gas and some
showed asthenia.  Changes were observed to be transient  (CA78:
88318d).

2.3.9     Gastrointestinal Tract

          A significantly higher incidence of diseases of the
digestive organs was reported in a study of synthetic rubber
plant workers in Russia exposed to styrene, butadiene, butane,
butylene, benzene, H2SOi», and various catalysts when compared
to workers not having contact with those substances.   The group
studied included a total of 679 workers.  Digestive system
disease occurred in 66.6 percent of the exposed group as opposed
to 33.3 percent in the group not exposed (CA82:47350x).
                              -23-

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          An antacid condition which was resistant to histamine
treatment was noted by Russian researchers in 68 of 130 subjects
exposed to butadiene and styrene.  Five of thirty control sub-
jects exhibited antacid conditions which responded readily to
histamine treatment.  Significant stomach disorders are at-
tributed to exposure to these hydrocarbon substances (CA74:138804z)

          Russian researchers unsuccessfully attempted to relate
liver test factors to stomach secretory function in synthetic
rubber workers exposed to butadiene and styrene.  Hypoacidic,
normacidic, and hype.racidic stomach conditions were mentioned
with no indication of frequency of occurrence or cause of the
conditions (CA80:148759b).

          Observations of healthy synthetic rubber plant workers
under clinical and subclinical conditions revealed a hypotensive
effect causing alterations in the gastrointestinal tract in- the
form of hypacid and anacid gastritis (CA61:1169h).

2.3.10    Endocrine System

          Functional changes in the endocrine glands of 70
workers in the synthetic rubber industry have been attributed
both to the prolonged effect of butadiene and styrene and to an
upset in the nervous control of endosecretion.  Functional
changes occurred primarily in the adrenal, thyroid, and pancreas
of workers with a history of upsets of the endocrine system
(CA73:107692m, CA72:11080p).
                              -24-

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3.0       Environmental Aspects

          This section summarizes information concerning re-
ported environmental levels of 1,3-butadiene and the chemical
behavior of the compound in air and water.

3.1       Occurrence

          Table 1 summarizes data on the occurrence and reported
levels of butadiene in environmental samples.  The abstracts of
sources in Russian provided data on butadiene levels in work
areas.  These were often described in terms of the maximum allow-
able concentration (MAC) which was 100 mg/m3 in 1966.  However,
a study published in that year indicated that 10 mg/m3 would be
a more effective MAC (Batkina, 1966).  From Table 1 it is appar-
ent that the butadiene concentration in the air in work areas in
Russian factories without emission controls exceeded 100 mg/m3.
Butadiene levels in the air in the braided hose department of
the Gates Rubber Company were reported in 1973 to be below 1000
ppm on two occasions on which sampling occurred (Gunter and
Lucas, 1973).

          Data on levels of butadiene in point source emissions
were not found.  An abstract describing combustion gases from
burning butadiene copolymers did not mention the presence of
butadiene.  Butadiene is present in cigarette smoke (Osborne,
1956) and gasoline vapors (Stephens and Burleson, 1967).  Quan-
titative data on butadiene concentration in automobile exhaust
were not found; however, Altshuller described the rate of buta-
diene disappearance in irradiated exhaust samples (Altshuller
et al, 1962).

          Table 1 shows that butadiene levels in urban ambient
air are well described in the literature.  The concentration
                             -25-

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                     Table 1.  REPORTED OCCURRENCE AND LEVELS OF 1,3-BUTADIENE  IN THE  ENVIRONMENT
Sample Descriptions

Cigarette Smoke

Stack gases from laboratory
combustion of copolymers
containing butadiene

Air in factory containing
emissions from polymer-modified
concrete (SKS-65GP latex)

Air in shoe factories in areas
where SKS-30 latex materials
are worked

Ambient air at sites located
2000 to 8000 meters from
synthetic rubber plant
Air in synthetic rubber
rubber plants

Air in dimethyl terephthalate
manufacturing facility in winter

Air in rooms with butadiene-
styrene rubber floor covering

Butadiene separation and puri-
fication facility in synthetic
rubber plant

Ambient air in Santiago, Chile
Early morning ambient air in
Riverside, California
Reported Butadiene
  Concentration
          -2
0.1-0.3x10   cc/puff
Butadiene concentration
exceeded maximum allowable
concentration (MAC) by a
factor of 5 to 10.

85-93 mg/m3 in 1960
5-20 mg/m3 in 1970
0.7 to 1.7 mg/m3

The butadiene concentration
was found to be above the MAC
>100 mg/m
Remarks
                                     Butadiene was not
                                     mentioned in the
                                     abstract
                                     Butadiene was present
                                     Butadiene was observed
The MAC was not given
in the abstract
                                     Butadiene was not
                                     present
Reference
                           Osborne,  1956
                           CA60:69398
                           CA77-.029900
                           CA78:47439a
2-9 ppb
CA80:40656b

CA80:136939x



CA81:175496r


CA76:76122f



Batkina, 1966


CA62:15336d
                           Stephens  and
                           Burleson, 1967

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                     Table 1 (Continued).   REPORTED  OCCURRENCE AND LEVELS OF  1,3-BUTADIENE IN THE ENVIRONMENT
   Sample Descriptions

   Ambient air during air pollution
   episode in afternoon

   Ambient air in Los Angeles,
   California

   Air  in workshops where polyester
   resins are used as binders in
   plastic production

   Air  in vicinity of synthetic
   rubber plant

to
^
!   Air  in working premises of plants
   for  production of butadiene-
   acrylonitrile rubber

   Air  in working areas at a plant
   for  manufacturing SKMS-30 rubber
   Air  in working areas of butadiene-
   a-methylstyrene  rubber plant
Reported Butadiene
  Concentration
up to 0.7 ppb

0.004 ppm
0.01 to 0.0009 mg/1
Butadiene concentration
exceeded the MAC by a factor
of 1.5 to 3.0
Remarks
                                     Butadiene concentra-
                                     tion was.measured but not
                                     reported in the abstract

                                     Butadiene was monitored.
                                     The concentration was not
                                     reported in the abstract
                                     Butadiene was measured.
                                     Specific results were not
                                     given in the abstract.
                                     The MAC was exceeded for
                                     some compounds in 40% of
                                     the samples
Reference

S tephens and
Burleson, 1967

Glasson and
Tuesday, 1970
                           CA81:175460z
                           CA82:76697w
                           CA55:23883a
                                                                                                         CA75:112601b
                                                                                                         CA76:37127s
   Ambient  air  in  downtown Los Angeles
   and  Azusa, California

   Gasoline vapor
1-2 ppb (avg)

0.001 ppm
                           Altshuller, et al, 197

                           Stephens and Burleson
                           1967

-------
depends on the time of day and is generally below 10 ppb.  Buta-
diene levels in ambient air near a rubber manufacturing plant
have been measured (CA80:40656b) but not reported in English.

3.2       Reactivity

          At ambient conditions butadiene is a colorless gas.
It is easily liquefied and is stored under pressure or at temper-
atures below 35°F.  Butadiene is soluble in organic solvents.
The solubility in water is 735g/106g water (McAuliffe, 1966).
The compound is highly reactive, and both gas and liquid are
highly flammable.  Inhibitors must be added to the pure material
to prevent polymerization and explosive peroxide formation.
Flammable and explosive limits in air are described in the lit-
erature (Osugi, et al, 1965; Hawley, 1971).  Table 2 gives some
physical properties.
        Table 2.  PHYSICAL PROPERTIES OF 1,3-.BUTADIENE
          Boiling point                   -4.41°C
          Specific gravity of              0.6211
            liquid at 20°C
          Vapor pressure at 0°C           17.65 psia
          The chemcial behavior of butadiene in the atmosphere
is well described in the literature.  However, very little data
were found describing its presence and reactivity in aqueous
waste streams.  Recent studies on pollution control in the
                              -28-

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synthetic rubber industry contained no data on the concentra-
tion of butadiene in aqueous waste streams (Sittig-, 1975).   A
high chemical oxygen demand (COD) level was noted for raw waste
from the industry, while biochemical oxygen demand (BOD) was
reported to be much lower.  Organic constituents in the waste-
waters were reported to be resistant to biological oxidation
(Sittig, 1975).

          Wastewaters from the Hiils Chemical Works, at which a
variety of chemicals were produced, were reported to contain
butadiene and other organics (CA49:11216b).  The aqueous wastes
could not be treated biologically.  Wastes containing butadiene
were steam treated and filtered through flue ash in a test pro-
gram.  Color and odor were removed and the permanganate demand
was reduced.  It was reported that soot contained in the ash
promoted butadiene polymerization.  The polymerization rate was
enhanced by the addition of lime.  A butadiene removal method
was devised consisting of steam treatment, mixing of the waste
with another waste stream containing lime, and addition of soot
sludge.  Effluent from this treatment method contained no buta-
diene.

          Table 3, which describes waste from a butadiene pro-
duction plant, contains data on total organic carbon (TOC) and
COD.  Both of these parameters could be a measure of the level
of butadiene in the wastewater.  However, butadiene concentra-
tions were not reported.
                               -29-

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    Table 3.  COMPOSITION OF WASTE FROM A BUTADIENE PLANT3
                    (Gloyna and Ford, 1970)
          pH                           8-9
          TOD                        100 - 200 g/m3
          filtered COD               200 - 375 g/m3
          suspended solids           200 - 500 g/m3
          total solidsb             3000 - 4000 g/m3
    a Flow rate 0.417 m3/Mg (100 gal/ton of product)
      Mostly sulfates and chlorides
          Butadiene reactivity in the atmosphere has been studied
because hydrocarbons are involved in the production of the
strongly oxidizing compounds which are the constituents of photo-
chemical smog.  Hydrocarbons react with nitric oxide and oxygen
species in photochemical reactions which produce peroxyacetyl
nitrates, nitrogen dioxide, ozone, and oxidized forms of the
hydrocarbons  (EPA, 1975).  Hydrocarbons vary in their degree of
reactivity in atmospheric oxidation reactions,  depending on their
chemical structure.  Olefins are the most reactive followed by
aromatics, paraffins, and naphthenes (CA59:8038f).   Olefins are
so reactive that their residence time in the atmosphere is short
(CA62:15336d; Stephens, 1966).  Reaction occurs at the double  ,
bond to form oxidation products such as aldehydes.   Glasson and
Tuesday measured the photooxidation rate of nitric oxide in the
presence of various hydrocarbons using.long-path infrared spec-
trophotometry.  Mixtures of N2, 02, NO, N02 and butadiene were
irradiated and the rate of N02 formation was monitored.  The NO
photooxidation rate at 79°F in the presence of butadiene was
                              -30-

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4.3 ppb/tnin.  Other olefins were more reactive than butadiene
(Glasson and Tuesday, 1970b).

          In another study published in 1970, Glasson and Tuesday
described the effects of NO and butadiene concentration on the
rate of NO thermal oxidation at 29°C.  The rate constant for NO
thermal oxidation in the presence of butadiene was 0.44 x 10"3/
ppm min.  Acrolein and formaldehyde were identified as NO-
butadiene reaction products.  The reaction of N02 and butadiene
was also studied.  The rate of decrease of N02 concentration in
a butadiene-air mixture was measured.  The rate constant for the
N02-butadiene reaction was 0.4 x lO'Vppm min.

          Olefin photooxidation has been studied in laboratory
experiments using irradiated automobile exhaust-air mixtures.
The rate of decrease of olefin concentration was measured using
a wet chemical analysis (Altshuller, 1962)..  The rates and pos-
sible mechanisms of reactions  of olefins with oxygen atoms,
ozone and nitric oxide have been described (Stephens, 1966a and
1966b).

          Stephens and Burleson collected air samples, subjected
the samples to irradiation, and measured changes in hydrocarbon
concentrations.   Samples were acquired in early morning hours
before natural photolysis occurred.  Table 4 summarizes analyti-
cal results for butadiene.  The butadiene concentration de-
creased to zero with UV irradiation of the sample but remained
constant in the dark.  Samples collected during afternoon pol-
lution episodes contained butadiene concentrations less than
0.7 ppb (Stephens and Burleson, 1967).
                              -31-

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      Table 4.  RESULTS OF UV IRRADIATION OF AMBIENT AIR
                CONTAINING BUTADIENE
                    	Butadiene Concentration in ppb	

                              After 24 hr UV           After 24 hr
                    Original   Irradiation    Original   in Dark
Sample
Description

Ambient air,
3/10/66, 7:50-
8:00 PST, heavy
haze, 55-608F

Ambient air,
12/22/65, 7:40-
8:00 PST, light
haze, 45-50°F

Ambient air,
3/3/66, 8:05-
8:25 PST,
moderate haze,
40-458F
                       2.6
                       9.0
                       2.4
0.
2.8
             2.0
2.6
           2.0
          Altshuller, et al, described how olefins disappeared

more rapidly in ambient air than other hydrocarbons due to their

faster rate of photolysis.  The butadiene concentration in

ambient air was reported to decrease by a factor of three from

morning to mid-afternoon (Altshuller, et al, 1971).
                            -32-

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 4.0      BIBLIOGRAPHY

 Abeles,  F.B.  and H.E.  Gahagan III,  "Abscission:   The Role of
     Ethylene,  Ethylene Analogs,  Carbon  Dioxide,  and Oxygen",
     Plant.  Physiol.  £3 (8),  1255-58 (1968).


 Altshuller, Aubrey P.,  Lois  J. Lage,  and  Stanley F.  Sleva,
     "Determination of Olefins in Combustion  Gases and in the
     Atmosphere",  Am.  Ind.  Hyg. Assoc. J.  23,  289-95 (1962).


 Altshuller, Aubrey P.,  et  al.,   "Hydrocarbon Composition of  the
     Atmosphere  of the  Los  Angeles Basin - 1967",   Environ. Sci.
     Technol.  5_ (10),  1009-16  (1971).


Anonymous, "1,3-Butadiene  (Erythrene, Vinylethylene).  Hydrogen
    Sulfide",    Am.  Ind. Hyg. Assn.  J.  24, 91-94  (1963).


Batkina, I.E.,  "Maximum Permissible Concentration of  Divinyl Vapors
     in the Air  of Work Areas",   Gig. Sanit. _31  (12),  18-22 (1966).


Doskin, V.A.,  "Significance of Age  in the Reaction of the Organism
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CA 6_9:12741e  Ripp, G. Kh. ,   "Hygienic  Basis  for  the Permissible



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CA 7_5: 96881k  Bul'Bakov, K.S., "Pathomorphology of the Heart During



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CA 21:107720k Chukreev ,. E.F., "Effect of the Long-term Action of



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CA 75/107777J   Ripp, G.Kh., "Toxicohygienic Characteristics of



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                              -43-

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                                                                               1;
                                                                               •-4
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CA 78:88310v
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CA 80:63390z
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CA 81:67970g
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