U.S. DEPARTMENT OF COMMERCE
                       National Technical Information Service
                       PB-257 524
Review of Selected
Literature on  Ethylene
Dibromide  (EDB)
Environmental Protection Agency
Jun 76

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EPA-560/8-76-001
           REVIEW OF SELECTED LITERATURE
                      ON
             ETHYLENE DIBROMIDE (EDB)
                  5SS2
\
 CD
                    JUNE 1976
          ENVIRONMENTAL PROTECTION AGENCY
            OFFICE OF TOXIC SUBSTANCES
              WASHINGTON, D,C,  20460

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EPA-560/8-76-001
                     REVIEW OF SELECTED LITERATURE

                                  ON

                       ETHYLENE DIBROMIDE  (EDB)
                               Prepared  by   .
                      Office  of Toxic  Substances
                     Envi ronmental. Protect!on  Agency
                        Washington,  D.C.  20460
                                June  1976

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
'•1. REPORT NO. 2.
EPA-560/3-76-001
4. TITLE AND SUBTITLE
Review of Selected Literature on
Ethyl ene Di bromide (EDB)
7. AUTHOR(S)
Frank D. Kover
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Office of Toxic Substances
U.S. Environmental Protection Agency
j Washington, D.C. 20460
12. SPONSORING AGENCY NAME AND ADDRESS
i • .
3. RECIPIENT'S ACCESSION>NO.
5. REPORT DATE
June 1976
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
                                                              PRICES SUBJECT TO CHANGE
1S. ABSTRACT

 Ethyl ene di bromide (synonyms - 1,2-d1bromoethane; ethylene bromide;" and EDB} is  a synthetic orga'nic
 chemical used 'mainly as a lead scavenger in leaded gasoline antiknock preparations to  volatilize
 the lead so that it is not deposited on engine surfaces during combustion.

 Annual  production of ethylene dibromide averaged about 300 million pounds in the period 1969  to 1974.
 A decrease in production to 280 million pounds occurred in 1970 and 1971..  An upward trend  is appar-.
 ent from the preliminary figures for 1972 (315 million pounds) and 1973 (331  million pounds).  Esti-
 mated consumption as a fuel additive is about 80 percent of production.  A relatively  small amount,   :
 about 1.5 to 2 million pounds, are accounted for as pesticides.  As a result of  the expected  decline
 in the  use of lead in gasoline, and use of EDB as a lead scavenger is also expected to decline.

 Animal  experimentation demonstrates that ethylene dibrWide is a highly toxic material with anesthetic
 and strong irritant properties.  Under chronic exposure liver and kidney involvement is observed.
 Carcinogenic activity has been reported for two species after chronic oral  exposure.   Mutagenic poten-
 tial has also been associated with EDB under certain test regiments.   Reproductive effects  in bulls
 have been noted after oral exposure.  Adverse effects on egg production are observed in laying hens
 fed EDB treated grain.

 The. principal use of EDB is consumptive and amounts entering the environment cannot be readily.esti-
 mated.  Very limited and preliminary air monitoring data suggest EDB is present  in ambient  air at very
 low concentrations.
17. . KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
ethylene dibromide
lead scavenger
fuel additive
antiknock fluid
fumigant
13. DISTRIBUTION STATEMENT
Document is available to public through
the National Technical Information Services
Springfield, Virginia 22151
b.lDENTIFIERS/OPEN ENDED TERMS
- physical properties
- chemical properties
- carcinogens is
- environmental exposure
19. SECURITY CLASS (This Report)
unclassified
20. SECURITY CLASS (This page)
unclassified
c. COS ATI Field/Group
06/F,J,PJ
07/A,C,D
21. NO. OF PAGES
22. PRICE
EPA Form 2220-1 (9-73)
                                                    ±C(

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Abstract

     Ethylene dibromide (synonyms - 1,2-dibromoethane;  ethylene bro-
mide;, and £DB) is a synthetic organic chemical  used mainly as a lead
scavenger in leaded gasoline antiknock preparations to  volatilize the
lead so that it is not deposited on engine surfaces during combustion.

     Annual production of ethylene d1bromide averaged about 300 mil-
lion pounds from 1969 to 1974.  A decrease in production to 280 mil-
lion pounds occurred in 1970 and 1971. .An upward trend is apparent
from the preliminary figures for 1972 (315 million pounds) and 1973
(331 million pounds).  Estimated consumption as a fuel  additive is
about 80 percent of production.  A relatively small amount* about 1.5
to 2 million pounds, are accounted for as pesticides.  As a result of
the expected decline in the use of lead in gasoline, and use of EDB as
a lead scavenger is also expected to decline.

     Animal experimentation demonstrates that ethylene  dibromide is a
highly toxic material with anesthetic and strong irritant properties.
Under chronic exposure liver and kidney involvement is  observed.
Carcinogenic activity has been reported for two species after chronic
oral exposure.  Mutagenic potential has also been associated with EDB
under certain test regiments.  Reproductive effects in  bulls have been
noted after oral exposure.  Adverse effects on egg.production are
observed in laying hens fed EDB treated grain.

     The principal use of EDB is consumptive and amounts entering the
environment cannot be readily estimated.  Very limited  and preliminary
air monitoring data suggest EDB is present in ambient air at very low
concentrations.

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Properties

     Ethylene dibromide (EDB) is a colorless,  heavy, nonflammable liquid with a
sweet odor. The odor is detectable at 10 ppm (NIOSH, 1975).

     Chemical and physical data are shown in Table 1.

Table 1 (Merck Index, 8th Ed.)
Empirical formula:
Molecular weight:   187.88
Boiling point:      131-132°C
Appearance:         colorless liquid
Vapor pressure:     17.4 mm Kg @ 30°G
Specific Gravity: d — = 2.172
                    25
Solubility :      miscible with most solvents; .slightly soluble in water

Uses

     EDB's major use is as a gasoline additive (SRI estimates 80 percent
of production).  It serves as a lead scavenger in leaded gasolines either
alone or in combination with ethylene dichlorid.e (EDC).  Lead antiknock
compositions containing ethylene dihalides as scavenging agents typically
contain enough to supply one atom of halogen for each atom of lead. Halogen-
containing compounds typically cause a decrease in the octane number of
leaded gasolines.  EDB and ethylene dichloride are used because they are
the least expensive organic halides which do not reduce the antiknock
effectiveness of lead alkyls.  At present the trend is to increase the
ethylene dichloride in the mixture.  The cost of ethylene dichloride is
about one third that of EDB.  While automotive gasoline contains both
EDB and ethylene dichloride, aviation gasoline contains EDB alone.  Ethy-
lene dichloride is not used alone probably due to a lower functional
efficiency than EDB.
                                 - 2 -

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     Over 124 pesticides containing EDB are registered with EPA.   About
1.5 to 2 million pounds of EDB are used annually for agricultural  pur-
poses, such as a fumigant on many crops, particularly grains and  fruits
(EPA, 1975).  Many EDB containing fumigants also contain ethylene dichlo-
ride, carbon tetrachloride or methyl bromide.  Soil fumigant nematocides
containing EDB usually also contain methyl bromide.

     Ethylene dibromide is also used as an intermediate in the synthesis of
dyes and Pharmaceuticals, and as a solvent for resins, gums and waxes.  A
minor use of EDB with considerable growth potential is as a chemical pre-
cursor for vinyl bromide.

Production

     Ethylene dibromide is prepared commercially by reacting bromine
with ethylene gas.  The major U.S. producers are Ethyl, Dow, PPG,
Northwest and Great Lakes.  Four EDB manufacturing sites are located
in Arkansas with one in Texas and another in Michigan.  Salient
statistics available for ethylene dibromide are shown in Table 2.

Environmental Aspects

     Fresh water toxicity data for EDB  is reported in ENVIRON (1974).
The 48-hour TLm for bluegill and largemouth bass are 18 and 15 ppm,
respectively.   (TLm (tolerance limit median) represents the dose that
kills 50 percent of the animals for the time period indicated).

     In studies on the behavior of EDB  in soils McKenry (1972) observed
that EDB did not degrade to any great extent after a two week period.
But, Castro and Belser (1968) found that  in soil-water culture (ster-
ilized soil that was inoculated) EDB at 5.75 X 10"4M converted
almost completely, and quantitatively in about two months (see Figure  1).
                                 - 3 -

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Table 2 - Ethylene dibromide production,  imports, sales
Production3                        Million Ibs
1969                                  309.9
1970                                  296.8
1971                                  280.0
1972                                  315.5
1973                                  331.1
1974                                  332.1

Imports5                           Million Ibs.

1966              -                   0.519
1967                                  0.185
1968                                  0.002
1969                                  0.058
1970                                  0.084 (last year reported)

Sales3

1969                                    -
1970                                  145.6
1971                                  173.7
1972                                  173.4
1973                                  169.3
1974,                                 170.8
a)  International Trade Commission Reports (formerly U.S. Tariff Commis-
    sion Reports)
                                 - 4 .

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Figure 1
     BrCH2CH2Br         "2>      CH2=CH2 + 2 Br
                      pH 7.0

     Some very limited and preliminary air monitoring data shows air
concentration values of 0.07-0.11 ug/m3 (about 0.01 ppb) in the vicinity
of gasoline stations along traffic arteries in three cities (Phoenix,
Los Angeles, and Seattle), 0:2-1.7 yg/m3 (about 0.1 ppb) on the property
of an oil refinery in Kansas City, and 90-115 yg/m3 (10-15 ppb) at
EDB manufacturing sites in Arkansas.  This suggests that EDB is present
in ambient air at very low concentrations.  Concentrations on the order
of 1 ppb of EDB were found in two samples from streams of water on
industrial sites (EPA, 1975a).

Sampling and Analysis Methodology

     The EDB air monitoring data was obtained with an adsorbent
                        fa
technique using Tenax-GC5' traps cooled with dry ice; recovery after
two hexane extractions was about 95 percent.  After collection, samples
were stored in a freezer at -13°C.  Analysis was by 6C-ECD on Carbowax
20M.  Additional columns were used for confirmation of identity.
Water samples were extracted with hexane and stored in a freezer
until analysis by GC-ECD  (EPA, 1975a).

     Methods for determining EDB content of gasoline engine exhaust
have not been developed.  However, methods developed, for determination
of halide scavengers  in gasoline may be adaptable.  GC with fame
ionization detection  has  been used  (Soul ages, 1966; 1967).  Ai other method
is based on the quantitative conversion of EDB to  vinyl bromide plus potas-
sium bromide after reaction with alcoholic KOH (Esposito, 1972).
                             *         -            r              •
EDB Emission Estimates

     EDB's major use  as a gasoline  additive  is considered to  be consumptive
so that attention has been focused  on  EDB's  potential for entry into the
environment from evaporative and refueling losses  and from  its other uses.
               ''    ;".             - 5 -,

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     Possible emission factors from lead scavenger uses include refueling
and evaporative losses as well as automotive exhaust emissions.  A "worst-
case" and "most-likely-case" analysis was prepared by EPA's Office of Mobile
Source Air Pollution Control.  The estimated emission factors are contained
in Table 3.  Total amounts of EDB emitted can be approximated by multiplying
the table values by the lead content (in gm/gal) of gasoline to obtain the
EOB factor per gallon of fuel dispensed and then multiplying by the number
of gallons of gasoline being dispensed.

     .In 1973 approximately 100 billion gallons of gasoline were consumed
for highway use (CEH, 1975).  The "worst-case" estimates reflect the
fact that the exhaust emission factor for EDB is not well established
experimentally; thus the assumption for those estimates was that 70 per-
cent of the EDB in gasoline is emitted in the exhaust (EPA, 1975b).

Biological and Toxicological Considerations

     EDB acute oral toxicity is moderate.  Some reported LDgQ values
(Rowe e_t al_., 1952) are:

     Mice (F)            420 mg/kg
     Rats (M)            148 mg/kg
     Rats (F)            117 mg/kg
     Guinea pigs         110 mg/kg
     Chicks               79 mg/kg
     Rabbits  (F)         55 mg/kg
     Acute inhalation studies in rats  (Rowe e_t al_.,  1952) revealed
immediate CNS depression (anesthesia, usually followed by death).
Also observed was congestion, edema, hemorrhage* and inflammation of
the lungs; swelling and necrosis of the liver and  congestion and edema
of the kidneys.  Rats and guinea 'pigs survived for only a few  hours at
200 ppm.  Higher concentrations caused death in less than one  hour.

     Chronic inhalation studies (Rowe ejt al_., 1952) with rats  and rabbits
(7 hr/day for 5 days/wk for 6 mo.) at 100 ppm resulted in some deaths in
less than 2 weeks.  At 50 ppm about 50% of the rats  died from  pneumonia
and upper respiratory infections due the effects of  EDB.  At 25 ppm rats,

                                - 6 -

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Table 3.
AUTOMOTIVE EDB EMISSIONS
          (EPA, 1975b)
                       Controlled Vehicle,,
                    9/gPb/gal.     g/mile1'
                    0.000047
                    0.000047
                    0.000063
                    0.00014
             0.000005
             0.000005
             0.000007
             0.000016
                            Uncontrolled Vehicle ,,
                            g/gPb/gal.     g/mile-'
0.000047
0.000047
0.000063
0.00063
0.000005
0.000005
0.000007
0.000042
Refueling Losses
  Spillage
  Entrainment
  Displaced vapor

Evaporative Losses
  Tank
  Carburetor
    Most Likely
    Worst Case

Exhaust Emissions
    Most Likely
    Worst Case

Total Emissions
    Most Likely
    Worst Case

]_/  Assumes average regular gas lead content of 1.90 grams per gallon and
     16 miles per gallon.
0.0016
0.0043
0.0065
0.3
0.008397
0.304597
0.00019
0.00051
0.000771
0.035625
*
0.000997
0.036170
0. 0028
0.0076
0.019
0.3
0.022317
0.308117
0.00532
0.000902
0.002256
0.035625
0.002650
0.036588
                                - 7 -

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guinea pigs, rabbits and monkeys generally tolerated the exposure
without evidence of adverse effect as judged by general appearance and
behavior, growth, final body and organ weights, blood urea nitrogen
values, results of periodic hematological examination, and results of
gross and microscopic examination of tissues; the highest mortalities
were observed in rats due to pneumonia and upper respiratory infections.

     A dose of 1.1 g/kg applied to the skin of rabbits killed 5 of 5
animals after a 24 hour contact period.  Fourteen of fifteen animals
survived a dose of 0.21 g/kg. (Rowe et_aj_., 1952).

     Laying hens fed 10 ppm EDB in grain resulted in gradual diminution
of egg size and egg number.  Alumot and Harduf (1970) in some isotope
studies observed impaired passage of proteins from blood serum to
ovarian follicles in EDB treated hens and indicate that this may be
related to the decreased egg size observed in laying hens exposed to EDB
in their diet.

     Calves administered a single oral dose  (gelatin capsule) of 10 or
25 mg/kg EDB suffered no ill effects.  At 50 mg/kg EDB the calf died in
three days, after signs of anorexia and prostration.  Necropsies were
inconclusive regarding gross lesions (Schlinke, 1969).  Similar results were
observed with sheep at the same dose levels.  However, one sheep suc-
cumbed at the 25 mg/kg EDB dose (Schlinke, 1969).

Human Toxicity

     Direct contact with EDB causes irritation and injury to the skin
and eyes.  Exposure to the vapor has caused  the development of respiratory
tract inflammation along with anorexia and headache with recovery after
discontinuance of exposure.
       •
     Weakness and rapid pulse have been associated with EDB exposure as well
as cardiac failure leading to death.   (Von Oettingen,  1958 cited in
NIOSH, 1975).

                                 - 8 -

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     A case of accidental poisoning with 4.5.  ml EDB in a 45 year old
woman fatal after 54 hours.  Primary pathological findings were liver
necrosis and kidney tubular damage (01 instead,  1960).        :

     To date, there have been no published reports of any association
between EDB and cancer in humans.

Mutagem'c Potential
 i
                                              *
     Several studies have shown EDB to have mutagenic potential.  In a
host-mediated assay in mice reported by Buselmaier ejtal., 1972, EDB was
described as distinctly mutagenic at 500 mg/kg  (subcutaneous dose).

     In an ochre mutant, induced by hydroxylamine, Tessman (1971) ob-
served a 7-fold increase in the number of reverse mutants over the
background level after treatment with EDB.  A study of AD-3 mutants from
Neurospora crassa after treatment with EDB in solution of 10% DMSO
(dimethyl sulfoxide) for 3 hours resulted in 1139 AD-3 mutants compared
to 7 with 10% DMSO alone.  (De Serres, 1970).  Mutagenesis assays (Ames
method) of a series of haloalkanes using Salmonella, typhimirium showed
EDB to be mutagenic.  in addition, DNA-modifying effects were implied
when EDB was shown to preferentially  inhibit the growth of DMA polyermase-
deficient  (pol A-1) Escherichia coli  (Brem et aV.,  1974).  Mutagenic
activity as a result of EDB treatment has also  been observed in Drosophila
melanogaster (Vogel and Chandler,  1974).

Reproductive Effects

     A study of sperm smears prepared from different  parts of the genital
tract of bulls after oral  treatment with EDB  (4 mg/kg on  alternate
days, for  12 and 21 days)  showed a distribution of  abnormal  sperma-
tozoa, which indicated the EDB affected the spermatozoa during sperma-
togenesis and during maturation  in the epididymis  (Amir,  1973).
                                  r  9  -

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Carcinogenic Activity

     Gastric intubation of EDB to rats (40 and 80 mg/kg/day) and mice
(60 and 120 mg/kg/day) 5 times per week resulted in a high incidence of
squamous cell carcinomas of the stomach in both species as early as 10
weeks after initiation of treatment.   The tumors originated locally
in the forestomach, invaded locally, and eventually metastasized
throughout the abdominal cavity.  No squamous cell carcinomas were
observed in controls (Olson e_t al_., 1973).  The "memorandum of alert"
(10/4/74) by Page of NCI apparently describes the same study, charac-
terizing the results which indicate strong carcinogenic activity as pre-
liminary (see Appendix A).  This document indicates that further tabulation
and analysis of the data will be forthcoming after completion in November 1974.

     Recent discussion with the National Cancer Institute  (NCI) revealed
that it will be several months before the final technical  report on this
study is issued.  However, it was indicated that in fact the data are the
same as that previously reported by Olson ejt al_.  (NCI, 1975).

     NCI has developed the protocol for an inhalation carcinogenesis bio-
assay of EDB.  The protocol specifies administration of EDB at the Maximum
Tolerated Dose (MTD) and a fraction of the MTD.  This study is presently
in the planning stage (NCI, 1975).

Human Exposure-Occupational

     The National Institute of Occupational Safety and Health has
developed estimates of the worker population exposed to EDB (see Table
4).

Regulations

     Many food tolerances have been established for inorganic bromide
residues resulting from the use of EDB as a soil fumigant  (40 CFR
120.126) and as a commodity fumigant'(40 CFR 120.126).  Food additive
                                - 10 -

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Table 4.  Estimated number of workers Exposed to
               Ethylene Dibromide by Industry* (Lloyd, 1975)

               Industry                      No. Exposed

               Fumigators and Exterminators       8,897
               General Merchandising                110
               Chemical Manufacturing                76
               Petroleum and Products Manufacturing  28

               Total                              9,111**
*Projections based on preliminary data from the National Occupational
Hazard Survey, Hazard Surveillance Branch, Office of Occupational Health
Surveillance and Biometrics, NIOSH.  This ddes not include exposure
to trade name products.

**Does not include approximately 650,000 persons employed in service
stations with potential exposure to leaded gasoline.
                                - 11 -

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tolerances of 125 ppm have been established for inorganic bromide
residues in all processed food except for dried eggs (400 ppm) roquefort
and parmesan cheese (325 ppm) and tomato products and dried figs (40
CFR 121.1020 and 121.270).

     Use of EDB as a fumigant can also result in organic bromide residues.
 The quantities found are variable and dependent on many factors.  In
comparison studies with other fumigants EDB was found (in grains) in a
range from less than 0.01 ppm to 6.10 ppm.  The lower volatility of EDB
compared to other commonly used compounds seems to account for the
disproportionately higher residues.  There is an exemption from the
requirement of tolerance for organic bromide residues from EDB (40 CFR
120.1006) for the postharvest use on grains. The exemption was based on
the conclusion that no residues of EDB results in food as consumed and
that any residues are expelled by cooking (McMahon, 1971).  However a
Dutch study of EDB residues in wheat, flour, and bread, showed about
2-3 ppm EDB in flour from wheat fumigated with an EDB-containing fumigant
13 weeks earlier.  Bread from this flour contained about 0.02-0.12 ppm
EDB (Wit ert al_., 1969).  EDB has been measured as a residue in fumigated
commodities (Malone, 1971).

     The current OSHA standard is 20 ppm EDB for an eight-hour-time
weighted average with a 30-ppm acceptable ceiling concentration and
an acceptable maximum peak of 50 ppm for a maximum duration of 5 minutes
during an eight-hour shift. This is based on ANSI standard - Z.37.31
(FR 37 (202) p. 22139).

EDB Substitutes

     Ethylene dichloride  (EDC) is at least a partial substitute for
EDB as a lead scavenger.  The typical scavenger mix contains both
EDB and EDC.  EDB is considered to be functionally more efficient
than EDC.  The feasibility of EDC as a total substitute is uncertain.
                                - 12 -

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     Some toxicity information is available on EDC.  The oral LD5Q
in rats is 0.68 g EDC/kg (McCollister et al_., 1956).  Health effects
observed in guinea pigs after inhalation exposures to EDC were prin-
cipally congestion and edema of the lungs.  The kidneys showed conges-
tion and degenerative changes (Sayers e_t al_., 1930).  At doses of
3000 ppm EDC in rats, pathological changes in the liver and adrenals
were also observed (Spencer et,al_., 1951).

     Chronic inhalation studies in rats at 200 ppm (151 exposures
7 hrs/day for 5 days/week for 212 days) showed no adverse effects.
Similarily at 100 ppm, rats, guinea pigs, rabbits and monkeys were given
120 exposures for 168 days without apparent effect (Spencer e_t al_.,
1951).

     A few fatal human cases have been reported which were associated
with occupational situations and one case of accidental ingestion resulted
in death (reviewed by Browning, 1965).

     EDC is a potent mutagen in Drosophila  (Shakarnis  (1969) cited in
Vogel and Chandler, 1974).
                                   *

    - Substitution for pesticidal applications such as methyl bromide
may be feasible in some cases.  However, for certain import and export
commodities available substitutes are not acceptable (USDA, 1975).
                                -13 -

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                         REFERENCES

Alumot (Olomucki), E. and Z. Harduf (1970)" Impaired Uptake of Labeled
Proteins By the Ovarian Follicles of Hens Treated with Ethylene Di-
bromide", Comp.  Biochem.  Physiol. 39B, 6.1-68.

Amir, D. (1973), Sites of Spermicidal Action of Ethylene  Dibromide in
Bulls", J. Reprod. Fert. 35_  (3): 519-525,

Brem, H., Stein, and H.S. Rosenkranz (1974), "The Mutagenicity and DNA-
modifying effect of Haloalkanes", Cancer Research, 34_, 2576-2579.

Browning, E.  (1975), Toxicity and MetaboTtsm of Industrial Solvents,
Elsevier, Amsterdam p. 251-252.

-Buselmaier, W. et al. (1972)," Critical Considerations on the Host-
Mediated Assay, A Method for Detection of Chemically  Induced Mutations",
Biol. Zentralbl. 9J_, 311-325.

Castro, C. E. and N. 0. Belser (1968),"Biodeh:alogenati6n. Reductive
Dehalogenation of the Biocides Ethylene Dibromide, l,2-Dibromo-3-
chloropropane, and 2,3 Dibromobutane in Soil", Env. Sci,  and Tech, 2_
(10), 779-783.

DeSerres, F.  and Mailing  (1970),"Genetic Analysis of  the  AD-3 Mutants of
Neurospora Crassa Induced by Ethylene Dibromide-A Commonly Used  Pesticide",
Newsletter Env. Mutagen Soc. 3:  36-37.

ENVIRON  (1974) 011 and Hazardous Materials  Technical  Assistance  Data
Systems File   (OHMTADS).

EPA (1975) EDB pesticidal use estimates-Office of Pesticide  Programs.

EPA (1975a) Preliminary monitoring  data  (Sampling and Analysis  by  MRI)  -
Office of Toxic Substances,  EPA  560/6-75-001.

EPA (1975a) EDB emmission estimates-Mobil Source Air  Pollution  Control
Office.

Esposito, G.G.  (1972) Final  Report, Analytical Method for Ethylene
Dibromide Depletion  in Aviation  Gasoline U.S. Army, Aberdeen Research
and Development Center, Coating  and Chemical  Laboratory:  Aberdeen
Proving Ground, Maryland  (NTIS-AD  746,  250).


Lloyd, J. W.  (July 7, 1975)  "Background  Information on Ethylene Dibromide",
Office of Occupational Health Surveillance  and  Biometrics,  NIOSH.

Malone,  B.  (1971), "Analytical Methods  for  the  Determination of Fumigants",
Residue  Reviews 38,  p. 24.

McCollister,  D. D. R. L.  Hollingsworth,  F.  Oyen,  and  V.  K.  Rowe (1956),
"Comparative  Inhalation Toxicity of Fumigant Mixtures",  A.M. A.  Arch.
Ind. Health V3, 1-7.

                                 -  14  -

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McKenry, N.V. (1972), "The Behavior Pesticides containing 1,3-Dichlor-
opropane and 1,2-^Dibromoethane in Soils", Diss. Abstr. Int. 34 (7)
3034B, 1974.
McMahon, B. M. (1971)," Analysis of Commercially Fumigated Grains for
Residues of Organic Fumigants", JAOAC, 54,  964.
Nachtomi, E., E. Alumot and A. Bondi (1972)," Metabolism of Halogen
Containing Fumigants in Mammalians and Birds", Proc.  Int. Cong. Pest.
Chem., 2nd (1971) vol.6, 495-501.

NCI, (1975) - Personal communication with Dr. C. Cueto.
Olmstead, E. V. (I960)," Pathological Changes in Ethylene Dibromide
Poisoning", Arch of Ind. Health, 21., 525-27.
Olson, et al. (1973),"Induction of the Stomach Cancer in Rats and Mice
with Halogenated Aliphatic Fumigants", J. Nat. Cancer Inst.  51 (6),
1993-1995.
Rowe, V. K. et al_. (1952), "Toxicity of  Ethylene Dibromide determined on
Experimental~"A~himals", AMA Arch, of Ind. Hyg. and Occup. Med. 6_, 158.
Sayers, R.R., W.P. Yant, C.P. Waite, and F. A. Patty  (1930) Public
Health Reports. Reprint.No. 1349.
Schlinke, J. C. (1969) "lexicological Effects of Five Soil Nematocides in
Cattle and Sheep", J. Am. Vet. Med Assoc: 155  (8),  1364-1366.
Shakarnis, V.F., Genetica 5, 89  (1969).
Soulages, N.L.  (1966) "Simultaneous Determination of  Lead Alkyls and
Halide Scavengers in Gasoline by Gas Chromatography with Flame lonization
Detection". Anal. Chem. 38_ (1), 28-33.
Soulages, N.L.  (1967)" Determination of  Methyl Ethyl  Lead Alkyls and
Halide Scavengers in Gasoline by Gas Chromotography and Flame lonization
Detection", Anal. Chem. 39_ (11), 1340-41.
Spencer, H.C., V.K. Rowe, E.M. Adams, D.D.  McCollister, and D.D.  Irish
(1951), A.M.A. Arch. Ind. Hyg. Occupational Med. (4)  482.
SRI- Stanford Research Institute-personal communication.
Tessman, I.  (1971), "Induction of Transversions and Transitions by  1,1-
dibromoethane", Newsletter Environ. Mutagen Soc. 4: 33.
                                                                •
The Chemical Economics Handbook, Stanford Research  Institute, 1975.
The Merck  Index, 8th Edition Merck & Co., Inc.  1958.
The U. S. Tariff Commission Reports, 1969-1972.
                                - 15 -

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Vogel, E. and J.L.R.Chandler (1974),"Mutagenicity Testing of Cyclamate
and Some Pesticides in Drosophi 1 a Melanogaster"t Experientia, 3Qi (6),'
621-623.

Von Oettingen, W. F. (1958) "The Halogenated Hydrocarbons: Toxicity and
Potential Dangers", Public Health Service Reports No. 414, p.152.

Wit, S. L. A.F.H. Besetner, H.A. Das, W. Goedkoop, F.E. Ldosjes, and E.K.
Mappelink (1969), "Results of an investigation on the regression of three
fumigants (carbon tetrachloride, ethylene dibromide, and ethylene
dichloride) in wheat during processing to bread", Report* 36/69 Tox,
National Institute of Public Health, Utrecht, The Netherlands.
                                - 16 -

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                 APPENDIX A
NCI Memorandum of Alert - Ethylene D1bromide

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                                                                         /*^y • i

                                                      PUBLIC HEALTH SERVICE
*ra" ."'":• Chairman of DREW Committee to Coordinate
           Tbxioology and Belated Programs
         Through:  Director for DCCP, NGI
                                                    DATE: October 16, 1974 *
FROM
Associate
for CaTrrfjy?ggi«=>gi3/ DCCP, NCI
         Memorandum of Alert - Ethylene Dzbroatide
         1.  The Director of our Bioassay Operations Segment has informed me of    ./,_
         preliminary findings in bioassays in which ethylene dibronide is being
         tested for carcinogenicity.  These preliminary results suggest a strong'
         carcinogenic activity both in rats and in mice.  The main tumor response
         is represented by sguamous cell carcinomas of the stomach.

         2.  Ethylene dibromide is an industrial chemical having significant
         camcrcial production.  The total capacity in the United States is
         estimated to be approximately 350,000,000 pounds a year.  Its major uses
         are as a lead scavenger in motor fuels, an agricultural furaigant, a solvent,
         and an intermediate in the prDchic*"'"n of dyes and Pharmaceuticals.
        ,3.  I am bringing this infornatdon^tqjyj^niri-attention since I think it is
         important that the appropriate agencies'be inade aware of our concerns with
         this matter and so that we may give it our attention in advance of the
         conclusion of the studies and the compilation of a detailed report for
         publication.

         4.  It must be emphasized that the^ Information* transM%ted to you represents
         only a statement of concern and that no definite conclusions as to the
         carcinogenicity of the substance may be reached until all of the data from
         histopathology examinations has been received and evaluated.  It is expected
         that such a final report will be available to you in the near, future. . .  v—  :.
                                                          /   „  -h,
                                                         <*/f.j//y
                                                         ,i.'.'  ? '' )
         Enclosure:  Memo of 10/4/74

         cc:
         Dr. Kraybill
         Dr. Mehlman
         Dr. Page
         Dr. Bauscher
                                            Qnberto Saffiotti, M.D.

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 *0
                                                        _ __ .

                                                      MTIMMfc
                                                                  0V
                                                                   10/4/74
""
        1.  Preliminary results of the carcinogenesis testing of ethylene
        dibromide, CAS No.  106-93-4, indicate strong carcinogenic activity
        in both rats and mice.   The predominant tumors  are  squamous  cell
        carcinomas of the stomach.


        2.  Ethylene dibromide,  synonyms -  (a)  1,2-dibromoethane;  (b) ethane,
        1-2-dibromo-; and (c) ethylene bromide has been tested by gastric
        intubation in both sexes of Osborne Mendel rats and B6C3F1 mice.
       Details are presented in the attached information sheet.

       3.  The results of these studies are being tabulated and analyzed  at
       this time.   It is expected that an  official report will be available
       within a few weeks.   Additional  details  will  be  *><><*•* -—-•*-«-•
       request.
      Enclosure
                                          Norbert P. Page, D.V.M

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•jr f
                                            15IOASNA* INiTiUMATlDN .'JIII.LT
                                           t:          r        "      •
                                 Carcinogen Bioasscy and Program Resources Branch
                                            Lanclow ik.Dding, Room C325
                                             National Cancer Institute
                                                Bethesda, Md. 20014  .
      Chemical   Ethvlene Dibtomide
                               CAS Mo.   106-93-4
COPS
CQQ522
»•• ; - . '• ; .;
J .»
Group Size
.
Route of Administration
Dose Levels
Frequency of Administration
i
Duration of Treatment*
; i *
Duration of Observation
Total Length of Test*
Expected Date of Completion
- J - • - jj —
Hat ( Osborne Mendel 1
Hale
50
ORAL
80 mg/kg/day
AO mg/kg/day
5 days/wk
•
' 18 mo
6 mo
24 mo
November 1974
Frrp;-;le
50
,
ORAL
80 mg/kg/day
40 mg/kg/day
5 days/wk
18 mo
6 mo
24 mo
.
November 1974
F'ou so ( B6C3F1 ' )
»Plo
50
ORAL
»
120 ng/kg/day
60 mg/kg/day
5 days/wk
18 mo
3 mo
21 mo
November 1974
F«n«l o
50
ORAL
120 mg/kg/day
60 mg/kg/day
5 days/wk
18 mo
3 mo
21 mo
November 1974
  ..I
  ,
Oi
        * Planned :*• studies wAr« terminated early due to early carcinogenic response.

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