United States
Environmental Protection
Agency
Office of Exploratory
Research
Washington DC 20460
Research and Development
EPA-600/S8-82-020 SepJ. 1982
Project Summary
Environmental Implications of
Changes in the Brominated
Chemicals Industry
Lawrence W. Margler
I
In light of the large-scale changes
occurring within the bromine-based
chemicals industry, the U.S. Environ-
mental Protection Agency (EPA)
commissioned a study to investigate
the potential for adverse environmen-
tal effects that might result from such
changes. In particular, EPA was
interested in learning if the existing
excess capacity to produce bromine
and ethylene dibromide has or would
stimulate the industry to seek alternate
uses for bromine that could result in
new environmental concerns.
To accomplish the objectives of the
study, an extensive literature review
was conducted, followed by personal
contacts with knowledgeable individ-
uals and by independent analysis.
Efforts were concentrated on present
and future markets, exposure potential,
and risk assessment.
The greatest potential environmen-
tal hazard is not with bromine emis-
sions, but rather with exposure to
chemicals that may be carcinogenic or
teratogenic, such as ethylene di-
bromide, vinyl bromide, and "tris."
Many gaps exist in the information
available on the bromine-based chem-
icals industry. Where necessary,
assumptions were made to temporarily
bridge the gaps. In most cases, the
analyses indicate that filling the data
gaps should not be a high priority in
light of other pressing issues that EPA
faces. In general, the environmental
effects are relatively minor or the
problems are already recognized and
are being addressed by EPA. However,
several areas do require further atten-
tion: the brominated flame retardants
industry; the effect of methyl bromide
on stratospheric ozone; the lack of
carcinogenteity and food-residue data
for methyl bromide; and the environ-
mental effects of bromine chloride
utilization.
This Project Summary was devel-
oped by EPA's Office of Exploratory
Research, Washington, DC, to an-
nounce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).
Introduction
Because of changing market condi-
tions, much of which is attributable to
various environmental considerations,
substantial alterations in existing
production and consumption patterns of
bromine compounds have occurred. At
the outset of the study, Winzler and
Kelly were aware that several factors
were acting to reduce the level of
bromine compound demand:
• Lead phase-down. EPA's phase-
down of the lead content of gaso-
line has already resulted in sub-
stantial reductions in lead use (and
hence ethylene dibromide use) in
gasoline.
• DBCP ban. EPA suspended nearly
all uses of the pesticide dibromo-
chloropropane on 29 October
1979. Future use of DBCP appears
to be very limited, if not nil. DBCP is
also controlled by OSHA.
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• Ethylene dibromide regulation.
Ethylene dibromide is under con-
sideration by EPA for regulation
under Section 112 of the Clean Air
Act (NESHAP). Such regulation
would result in an emission stan-
dard for ethylene dibromide, or,
where this is infeasible, design,
equipment, work practice, or op-
erational standards may be im-
posed. The effect of such regula-
tions on ethylene dibromide con-
sumption is unclear. Vinyl chloride
is under NESHAP regulation, and
its domestic production and con-
sumption remain very high.
• Tris ban. Tris (2,3-dibromopropyl)
phosphate, a flame-retardant used
in textiles, is no longer used for this
purpose because of its carcinogen-
icity and exposure potential.
• PBB contamination. The contam-
ination of animal feed with poly-
brominated biphenyls (a group of
fire retardants) in 1973 in Michigan
heightened the public's aware-
ness of this group of chemicals,
and their use has nearly stopped
since then.
• Ethylene dibromide replacement
in some fumigation. The tech-
nology for using gamma radiation
for fruit fumigation has been devel-
oped, and this could replace ethyl-
ene dibromide for this purpose.
However, the investigators were also
aware of other market factors increasing
the demand for bromines:
• Greater use of BrCI for water disin-
fection. The trend toward reducing
the residual chlorine demand in ef-
fluents appears to be resulting in a
strong demand for bromine chlo-
ride.
• Calcium bromide use in drilling
fluid. The use of calcium bromide
in well-drilling fluid is expanding
very rapidly.
• Fire retardants. The use of bromi-
nated compounds as fire retardants
represents a strong market.
• Ethylene dibromide as fumigant.
The use of ethylene dibromide as
an agricultural crop and seed fumi-
gant is increasing.
• Flame retardant not found to be
carcinogenic. No carcinogenic re-
sponse was observed in rats ex-
posed to dibromoneopentyl/gly-
col, a reactive flame retardant
widely used in uns'aturated poly-
ester resins and polyurethane
foam.
The very dynamic nature of the
bromine market is of interest to EPA
because of the potential for new or
expanded uses for bromine, which in
turn might result in environmental
problems from specific compounds. The
objective of the proposed study was to
evaluate this potential and to assess the
implications for EPA's regulatory mis-
sion.
The approach to achieving the objec-
tives of the study included the following
major elements where desirable and
practical:
• Identification of significant bro-
mine compounds, their producers
and users, and the quantities in-
volved.
• Identification of future trends in
production and use.
• Estimation of emission rates.
• Characterization of environmental
fate of bromine compounds, in-
cluding estimates of ambient con-
centrations.
• Review of pertinent toxicological
data, with emphasis on carcino-
genicity and teratogenicity.
• Identification of pollution-control
technologies and analytical meth-
ods.
• Rough assessment of carcinogenic
and non-carcinogenic risk.
• Evaluation of likelihood and mag-
nitude of potential problems and
the likely regulatory pathway and
control strategies.
First, a literature review based upon
an extensive computerized bibliographic
search was conducted. The literature
review was followed by a campaign of
personal contacts by telephone with
individuals working in industry, govern-
ment, and academe, the purpose of
which was to clarify the literature and to
fill some of the major information gaps in
the literature. Then, the tasks mentioned
above were completed, and independent
assumptions and calculations were
made where needed. The most impor-
tant compounds received the greatest
attention.
Results
The major uses for bromine in the
United States are for manufacturing
ethylene dibromide, flame retardants,
calcium bromide, methyl bromide, and
bromine chloride. Despite the declining
usage of ethylene dibromide (EDB) in
gasoline, EDB is still responsible for
nearly half of the total domestic bromine
demand. At least 76 brominated organic
chemicals were listed by the U.S. Inter-
national Trade Commission as being
produced commercially during 1978.
The salient features of the 1979
domestic bromide industry according to
the U.S. Bureau of Mines were:
• The United States produced 65
percent of the world's bromine.
• U.S. exports were far greater than
imports.
• Nearly half of the U.S. demand for
bromine was supplied as the gaso-
line additive ethylene dibromide
(48 percent), followed by fire re-
tardants (29 percent), sanitation
preparations (16 percent), and
other uses (6 percent).
Several significant changes have oc-
curred in the bromine industry over the
last several years, the most important of
which has been the decline in ethylene
dibromide utilization as a gasoline addi-
tive.
Since the EPA's gasoline lead phase-
down program began in 1973, and its ban
against the use of leaded gasoline in
automobiles equipped with catalytic
converters began some time later, the
use of ethylene dibromide as a combus-
tion-exhaust lead scavenger has de-
clined substantially — roughly 25%
between 1974 and 1979 — resulting in
60 x 106 Ib less bromine being used for
EDB production in 1979 than in 1974.
This situation, plus the addition of 200 x
106 Ib bromine production capacity
(nameplate) during 1975 and 1976, left
the bromine industry with a large
excess production capacity for ethylene
dibromide and bromine. No other
sizeable products exist for which the
excess EDB capacity can be used.
Bromine-based fire-retardant chem-
icals have shown a moderately strong
and steady increase in demand, over the
years. However, great uncertainty exists
regarding the actual rates of production
and consumption. Because of the
increasing demand for fire retardants,
the virtual elimination of the production
and use of the brominated flame
retardants "tris" and polybrominated
biphenyls in the United States during
the 1970's did not cause a dip in the
overall demand for fire retardants.
The demand for calcium bromide has
grown tremendously since its introduc-
tion as a well-drilling fluid in 1972.
Since 1976, domestic production in-
creased from nearly zero to over 100 x
106 Ib (42% bromine content) in 1978.
This increased demand stems from the
oil and gas industry's efforts to increase
production.
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"Sanitation preparations," a group
designation of the Bureau of Mines that
includes bromine chloride and ele-
mental bromine used as water disin-
fectants and methyl bromide and
ethylene dibromide used as fumigants,
experienced a diminishing demand until
1979, when domestic demand increased
73 percent over the 1978 level. Virtually
all of the "sanitary preparations" group
can be accounted for by the fumigants
methyl bromide and ethylene dibromide
through 1978. In 1979, a new facility
with a production capacity for bromine
chloride of 30 x 106 Ib/yr (21 * 106 Ib
bromine per yr) began operating,
helping to account for the large increase
in demand.
The historical data show a gradual
increase in production and demand for
bromine; a widening in the difference
between production and demand,
indicating increased exports in the
1970's; a moderately high increase in
the demand for fire retardants and a
decrease for EDB; and sharp increases
in production capacity during 1975 and
1976.
A crude forecast of EDB demand
between 1973 and 1979, assuming that
leaded gasoline consumption had not
been diminished by EPA regulations,
indicated that there would likely have
been only a small excess bromine
production capacity by 1979, rather
than the large excess that exists now.
Domestic bromine demand is expected
to increase at a rate of 2 to 5 percent
annually (compounded annually) to
1985, driven by demand increases for
flame retardants (4 to 8%/yr), bromine
chloride (15%/yr), calcium bromide
(15%/yr), and methyl bromide (4 to
5%/yr). Demand for ethylene dibromide
will continue declining, perhaps at a
rate of 15 percent per year. The overall
demand for bromine will depend heavily
on the demand for calcium bromide.
While bromine production in the
United States has increased modestly
over the years, production in Israel has
more than doubled since 1976, although
U.S. production was still five-fold
greater than Israel's in 1979. Moreover,
in an effort to boost exports, Israel plans
on doubling its bromine production from
53,000 tonnes (116 x 106 Ib) in 1980 to
100,000 tonnes (220 * 106 Ib) per year
by 1984.
Imports increased greatly during
1978 and 1979, although they are still
only 1 % or less of domestic consumption.
During 1979, approximately 99% of the
accounted-for imports were from Israel.
Exports increased significantly over
1977, although declining 6% from 1978
to 1979. Exports represented approxi-
mately 18 percent of the bromine
produced in the United States during
1979. Israel is aggressively pursuing a
program of increased production of
bromine and bromine-based chemicals
for foreign markets. Because bromine in
its lead-lined shipping containers is
heavy, and therefore costly to transport,
Israel will likely be able to capture a
portion of U.S. exports to areas that are
closer to Israel than to the United
States. Nevertheless, U.S. producers
feel that their foreign markets will
remain strong. The strength of the
recent export market is thought to be
due to the approval of a lightweight
container for shipping bromine. Also, to
increase profits and safety, producers
tend to ship bromine derivatives rather
than bromine itself, according to a major
producer.
Conclusions and
Recommendations
The greatest potential environmental
hazard is not with bromine emissions,
but rather with exposure to chemicals
that may be carcinogenic or teratogenic,
such as ethylene dibromide, vinyl
bromide, and "tris."
Many gaps exist in the information
available on the bromine-based cherrv
icals industry. Where necessary, as-
sumptions were made which tentatively
bridged the gaps. In most cases, the
analyses indicate that filling the data
gaps should not be a high priority in light
of other pressing issues that EPA faces.
In general, the environmental effects
are relatively minor or the problems are
already recognized and are being
addressed by EPA. However, several
issues do require further attention:
• Better definition of the brominated
flame retardants industry and as-
sociated environmental effects is
needed. A current EPA-sponsored
study strives to achieve this goal.
• The effect of methyl bromide on
stratospheric ozone deserves great-
er attention.
• The lack of carcinogenicity and
food-residue data for methyl bro-
mide may hamper EPA's planned
review under the Federal Insecti-
cide, Fungicide, and Rodenticide
Act.
• Additional research into the envi-
ronmental effects of bromine chlo-
ride utilization would be useful to
further substantiate the evidence
that bromochlorination is less en-
vironmentally damaging than chlo-
rination.
Lawrence W. Margler is with W/nzler and Kelly Consulting Engineers, Eureka,
CA 95501.
Robert Barles is the EPA Project Officer fsee below).
The complete report, entitled "Environmental Implications of Changes in the
Brominated Chemicals Industry," (Order No. PB 82-247 594; Cost: $13.50,
subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Office of Exploratory Research (RD-675)
U.S. Environmental Protection Agency
Washington, DC 20460
0 U.S.GOVERNMENTPRimiNSOFFICE-108!-559-017/0323
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