United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
EPA-600 2-79-210n
December 1979
Research and Development
Status
Assessment of
Toxic Chemicals
Tris(2,3-Dibromo-
propyl) Phosphate
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution-sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-210n
DecemBer 1979
STATUS ASSESSMENT OF TOXIC CHEMICALS:
TRIS(2,3-Dibromopropy1) PHOSPHATE
by
S. R. Archer
T. R. Blackwood
Monsanto Research Corporation
Dayton, Ohio 45407
and
P. J. Murin
Radian Corporation
Austin, Texas 78766
Contract No. 68-03-2550
Project Officer
David L. Becker
Industrial Pollution Control Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental
Research Laboratory - Cincinnati, U.S. Environmental Protection
Agency, and approved for publication. Approval does not signify
that the contents necessarily reflect the views and policies of
the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or
recommendation for use.
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FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our
environment and even on our health often require that new and
increasingly more efficient pollution control methods be used
The Industrial Environmental Research Laboratory - Cincinnati
(lERL-Ci) assists in developing and demonstrating new and im-
proved methodologies that will meet these needs both efficiently
and economically.
This report contains a status assessment of the air emis-
sions, water pollution, health effects, and environmental signi-
ficance of lead. This study was conducted to provide a better
understanding of the distribution and characteristics of this
pollutant. Further information on this subject may be obtained
from the Organic Chemicals and Products Branch, Industrial
Pollution Control Division.
Status assessment reports are used by lERL-Ci to communicate
the readily available information on selected substances to
government, industry, and persons having specific needs and
interests. These reports are based primarily on data from open
literature sources, including government reports. They are indi-
cative rather than exhaustive.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
111
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ABSTRACT
Tris(2,3-dibromopropyl) phosphate (tris), one of six commercial-
ly significant haloalkyl phosphate compounds produced in the
United States, has been used as a flame retardant additive in a
variety of products, including cellulose acetate and polyester
fibers. Until a recent ban by the Consumer Product Safety
Commission (CPSC), tris was extensively used in material for
children's wearing apparel. Very few data are available on
post-ban uses of tris, both in type of use and in quantity used.
Tris may be produced by addition of bromine to triallyl phos-
phate or by esterification of phosphorus oxychloride with
2,3-dibromopropanol. Companies manufacturing tris prior to the
CPSC ban included Great Lakes Chemical Corporation, Velsicol
Chemical Corporation, and White Chemical Corporation; however,
the latter no longer produces tris. Production after the CPSC
ban has not been quantified. Estimated consumption in 1975 was
4,080 metric tons to 5,400 metric tons.
Little or no research has been performed to determine the en-
vironmental fate and reactivity of tris. Reactions and reaction
pathways in the environment have not been discovered or pro-
posed, and environmental levels have not been reported. Little
information is available regarding atmospheric losses during
production, but relatively low losses are expected. Tris could
potentially reach the environment from waste streams generated
in plants where it is added to fabrics and plastics, or from
the final product during its use, disposal and recycling.
Although tris has been shown to be an animal carcinogen, no
conclusive data regarding carcinogenicity and mutagenicity to
humans are available. A large population may be affected by
production and use of fibers and polymers containing tris.
Predicted incidences of cancer in children are as high as 17,000
cases/million from 1 yr of exposure to tris-treated garments.
While condensation and absorption generally appear to be the
best methods of reducing atmospheric emissions from tris manu-
facture, information concerning actual techniques is unavail-
able. A series of treatment steps for wastewater, such as fil-
tration, chemical precipitation and flocculation/filtration, and
reverse osmosis, appear to be required.
xv
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On April 8, 1977, the CPSC banned certain children's wearing
apparel and certain uncut fabric containing tris. Pursuant
to an order of a Federal district court judge, the CPSC con-
sequently banned not only certain fabric, yarn, and fiber con-
taining tris, but tris itself which is used in or intended for
use in children's wearing apparel.
Information is needed concerning the actual amount of tris pre-
sently produced; however, in view of its demonstrated toxicity
and its ban from children's garments, this may be insignificant.
Initial efforts should be made to catalog the uses of tris by
company, usage category, and quantity produced. Production pro-
cesses and sites should be studied for environmental effects and
significance, and information on emissions and effluents from
its synthesis and applications, as well as on control tech-
nologies should be obtained. A ban on other uses may be in-
dicated. Studies should be coordinated with the CPSC to avoid
duplication of effort and to coordinate regulatory action.
This report was submitted in partial fulfillment of Contract
68-03-2550 by Monsanto Research Corporation under the sponsorship
of tne U.S. Environmental Protection Agency. This report covers
the period November 1,( 1977 to December 31, 1977. The work was
completed as of January 20, 1978.
v
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CONTENTS
Foreword iii
Abstract iv
Conversion Factors and Metric Prefixes viii
Acknowledgements ix
1. Introduction 1
2. Summary 2
3. Source Description 5
Physical and chemical properties 5
Production 5
Process description 6
Uses 7
4. Environmental Significance and Health Effects .... 8
Environmental significance 8
Health effects . . 9
Population exposed 11
5. Control Technology 12
6. Regulatory Action 13
References 14
VII
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CONVERSION FACTORS AND METRIC PREFIXES
To convert from
Degree Celsius (°C)
Gram/second (g/s)
Kilogram (kg)
Meter2 (m2)
Meter3 (m3)
Meter3 (m3)
Metric ton
Pascal (Pa)
CONVERSION FACTORS
To
Degree Fahrenheit
Pound/hr
Pound-mass
(avoirdupois)
Foot2
Gallon (U.S. liquid)
Inch
Pound-mass
Pound-force/inch2 (psi)
Multiply by
tj = 1.8 t° = +32
7.937
2.205
1.076 x 101
2.642 x 102
6.102 x I0k
;
2.205 x 103
1.450 x 10~4
METRIC PREFIXES
Prefix
Kilo
Milli
Symbol Multiplication factor Example
k
m
io-3
103
1 mg = 1
1 kPa =
x 10~3 gram
1 x 10 3 pascals
aStandard for Metric Practice. ANSI/ASTM Designation:
E 380-76e, IEEE Std 268-1976, American Society for Testing and
Materials, Philadelphia, Pennsylvania, February 1976. 37 pp.
viii
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ACKNOWLEDGEMENT
This report was assembled for EPA by Radian Corporation, Austin,
TX, and Monsanto Research Corporation, Dayton, OH. Mr. D. L.
Becker served as EPA Project Officer, and Dr. C. E. Frank, EPA
Consultant, was principal advisor and reviewer.
IX
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SECTION 1
INTRODUCTION
Tris (2,3-dibromopropyl) phosphate (tris) has been used as a
flame retardant additive in acrylics, cellulose acetate, cellu-
lose nitrate, phenolics, polyester, polystyrene, polyvinyl ace-
tate, polyvinyl chloride, flexible urethane foam, paints, paper
coatings, rubber, and textile coatings. Tris, which is poten-
tially absorbed through the skin, has been shown to be an animal
carcinogen in two species and a mutagen to certain bacteria and
Drosoph-Lla. Due to its potential carcinogenicity, concern over
potential adverse health effects to the general population from
tris exposure has been expressed.
There is a need to define the various sources from which tris may
enter the environment, to establish the subsequent health and
environmental effects, and to examine possible control strategies
and present regulatory actions. This report provides a brief
overview describing these items along with a description of tris.
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SECTION 2
SUMMARY
Tris, one of six commercially significant haloalkyl phosphate
compounds, is primarily used as a fire retardant additive for
cellulose acetate and polyester fibers. Until a recent ban by
the Consumer Product Safety Commission (CPSC), tris was exten-
sively used in material for children's wearing apparel.
Companies producing tris include Great Lakes Chemical Corp. and
Velsicol Chemical Corp. White Chemical Corp. used to produce
tris prior to the CPSC ban. The compound may be produced by the
addition of bromine to triallyl phosphate or by the esterifica-
tion reaction of phosphorus oxychloride with 2,3-dibromopropanol.
Estimated consumption of tris in 1975 was 4,080 metric tons3 to
5,440 metric tons. Use of tris in children's wearing apparel
was banned by the CPSC on April 8, 1977. The full extent of
using tris in other applications is unknown.
No specific monitoring data or other information is available
regarding losses of haloalkyl phosphates from production, but
relatively low losses are expected. Table 1 summarizes high-
lighted information regarding tris. These esters are produced
in batch kettles, and since their vapor pressures are low, atmos-
pheric emissions are expected to be insignificant. Industrial
sources suggest that no solid or liquid organic wastes are
produced. Aqueous wastes could be produced from washing reaction
kettles and equipment or from workup. Tris could potentially
reach the environment from waste streams generated in plants
where it is added to fabrics and plastics or from the final pro-
duct during its use, disposal, and recycling. Potential trans-
port to the environment could occur by atmospheric emissions,
leaching, or with movement of small pieces of treated fabrics or
plastic products.
Tris has been shown to be an animal carcinogen. Conclusive data
for human exposure have not been established. Since cancers de-
velop over many years and cannot usually be linked to particular
cases, this is not unexpected.
al metric ton equals 106 grams; conversion factors and metric
system prefixes are presented in the prefatory material.
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TABLE 1. TRIS(2,3-DIBROMOPROPYL) PHOSPHATE
Extent of problem
Emission source
Emission quantity
Population exposed
Control method
Regulatory action
Production:
Great Lakes Chemical
Corp., El Dorado, AK
Velsicol chemical Corp.
El Dorado, AK
Use:
Estimated 1975 consump-
tion equaled 4,080
metric tons to 5,440
metric tons.
Atmospheric emissions are Unknown.
expected to be insignifi-
cant.
No solid or organic wastes
are reported by producers.
Aqueous wastes from equip-
ment cleanup.
Transport and storage
losses probably negli-
gible.
Washing fabric treated
with tris could result
in leaching into wash
water.
Possible ingestion of tris
by children putting
treated sleepwear in
mouths.
Estimates include:
•17,000 cases/million
for children with
1-yr exposure to
garments;
•6,000 cases/million
male population;
•25 to 5,100 cases/
million males.
Information not available. Unknown.
Condensation and absorption
appear to be best for atmos-
pheric emissions. Adsorbents
other than carbon possibly
applicable.
Aqueous wastes require a series
of steps such as filtration,
chemical precipitation,
flocculation/filtration, and
reverse osmosis.
Fugitive emission control
through improved operation
and maintenance procedures.
Use alternate fire-retardant
material.
Consumer Product Safety
Commission on April 8,
1977, banned certain
childrens' wearing
apparel containing tris.
The CPSC later banned
certain fabric, yarn,
and fiber containing
tris as well as tris
itself.
Expressed as cases of cancer per million exposed. Several assumptions were made in arriving at this estimate.
-------
Information on actual techniques used to control emissions of
tris during production is unavailable. Condensation and absorp-
tion generally appear to be the best methods for reducing atmos-
pheric emissions from production. Incineration and flaring
would produce acid contaminants, and carbon adsorption is most
desirable for nonpolar compounds. Adsorbents other than carbon
may have some application potential.
Liquid wastes require a series of treatment steps. A typical
sequence might include filtration, chemical precipitation and
flocculation/filtration, and reverse osmosis. Biological treat-
ment may also be applicable. Applicable technologies depend on
wastewaters composition.
In assessing the risk from tris-treated apparel, the CPSC con-
sidered cancer incidence projections from three studies. First
it was estimated that for 1 yr of exposure to tris-treated gar-
ments, 1.7% of the children would develop cancer (17,000 cases/
million). Second, the Environmental Defense Funds predicted
incidences as high as 6,000/million male population. Third, the
CPSC's own estimate ranged from 25 to 5,100 cases/million males.
On April 8, 1977, the CPSC banned certain children's wearing
apparel and certain uncut fabric containing tris. Pursuant to
an order of a Federal district court judge, the CPSC consequent-
ly banned not only certain fabric, yarn, and fiber containing
tris, but tris itself which is used in or intended for use in
children's wearing apparel. The CPSC is preparing an environ-
mental impact statement of the tris ban and may be studying the
appropriateness of a ban on other uses of tris.
Based on the information presented in this report, the following
items need to be considered in future studies:
• present production should be quantified; however, in
view of its ban from children's garments, this may be
insignificant.
• efforts should initially be made to catalog the uses of
tris by company, usage category, and quantity produced.
• production processes and sites should be studied for
environmental effects and significance.
• information concerning control technology should be
obtained.
• production and uses of other haloalkyl phosphates should
be determined; if significant, toxicity tests should be
conducted to determine similarity to tris.
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SECTION 3
SOURCE DESCRIPTION
Tris(2,3-dibromopropyl) phosphate (tris) is one of the six
haloalkyl phosphate compounds produced in significant commercial
quantities in the United States. Tris and three other tris
(haloalkyl) phosphate compounds, DEPP[tris(2,3-dibromopropyl)
phosphate]; CEP[tris(2-chloroethyl)phosphate]; CPP[tris(2-chloro-
p'ropyl) phosphate] ; and DCPP [tris (1,3-dichloroisopropyl) phosphate] ;
are used as fire retardants and are added to products which must
meet Federal or state fire retardancy standards (1). The major
application of tris is a fire retardant additive for cellulose
acetate and polyester fibers. Until a recent ban by the CPSC,
tris was extensively used in material for children's sleepwear.
PHYSICAL AND CHEMICAL PROPERTIES
Commercially-available haloalkyl phosphate fire retardants are
characterized as essentially odorless liquids ranging in color
from colorless to pale yellow. All the commercially significant
tris(haloalkyl) phosphate compounds are viscous liquids at
ambient temperatures, although, sometimes, the temperature must
be increased to permit their pumping in conventional manufac-
turing technology (1).
General physical properties of tris are summarized in Table 2 (1).
PRODUCTION
Companies producing tris prior to the CPSC ban included Great
Lakes Chemical Corp., Velsicol Chemical Corp., and White Chemi-
cal Corp. (2). White Chemical Corp. no longer produces tris.
Velsicol produces tris but refuses to release any information
regarding their production process (personal communication with
Fred Lavinn, Velsicol Chemical Corp., August 5, 1977). Great
(1) Lande, S. S., J. Santodonato, P. H. Howard, D. Greninger,
and D. H. Christopher. Investigation of Selected Potential
Environmental Contaminants: Haloalkyl Phosphates. EPA-560/
2-76-007 (PB 257 910), U.S. Environmental Protection Agency,
Washington, D.C., August 1976. 209 pp.
(2) 1977 Directory of Chemical Producers. Stanford Research
Institute, Menlo Park, California, 1977. 1059 pp.
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TABLE 2. SELECTED PHYSICAL PROPERTIES OF TRIS
Empirical formula
Molecular weight 697.7
Weight percentage: bromine 68.7
Weight percentage: phosphorus 4.4
Freezing point, °C 5.5
Pour point, °C -1.16
Viscosity, Pa-s (25°C) 9.2
Vapor pressure, Pa:
25°C 2.59 x 10~2
45°C 1.60 x 10"1
65°C 6.40 x 10-1
Density, metric tons/m3 (25°C) 2.27
Physical description of the Pale yellow to light
commercial material at yellow, viscous
ambient temperature liquid.
Odor of commercial product None.
Lakes Chemical Corp. refused to acknowledge when asked if they
produce tris (personal communication with Carl, Great Lakes
Chemical Corp. on August 5, 1977). The tris manufacturing
operations of both Great Lakes and Velsicol are located in El
Dorado, Arkansas. Production details for each manufacturer
(including capacities and process descriptions) are unavailable.
PROCESS DESCRIPTION
Tris(2,3-dibromopropyl) phosphate may be manufactured by the
addition of bromine to triallyl phosphate or by the esterifi-
cation reaction of phosphorous oxychloride with 2,3-dibromo-
propanol (3).
In the production of phosphate esters by esterification, phos-
phorous oxychloride is condensed with the alcohol reactant. The
reaction for tris, which usually requires a catalyst, may be
written as
3CH2BrCHBrCH2OH + POC13 —> (CH2BrCHBrCH20)3PO + 3HC1 (1)
2,3-Dibromopropanol Phosphorous Tris Hydrochloric
oxychloride acid
(3) Chemical and Process Technology Encyclopedia. D. M.
Considine, ed. McGraw-Hill Book Co., New York, New York,
1974. 183 pp.
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Hydrogen chloride is removed by a current of air or neutralized
by the addition of alkali. Glass-lined or alloy kettles are
used because the reaction mixture is highly corrosive. In the
similar esterification reactions of cresols, product purification
is achieved by flash distillation of the reaction mixture and
washing with dilute caustic. The dilute caustic neutralizes
residual hydrogen chloride and extracts unreacted alcohol and
partial esterification products. Further purification steps in-
clude caustic washing, steam stripping, permanganate treatment,
dehydration under reduced pressure, bleaching with activated
carbon, and filtration (4).
Process details were not found in the literature for the produc-
tion of tris by reacting bromine with triallyl phosphate.
USES
Tris has been used as a flame retardant additive in acrylics,
cellulose acetate, cellulose nitrate, phenolics, polyesters,
polystyrene, polyvinyl acetate, polyvinyl chloride, flexible
urethane foam, intumescent paints, paper coatings, rubber, and
textile coatings (5). The synthetic fiber and polymer (plastics
and resins) industries include numerous manufacturing facilities
which could employ tris in production operations. Flame retard-
ants are added in final mixing steps of polymer production pro-
cesses or during fiber spinning processes.
Estimated 1975 consumption of tris was 4,080 metric tons to 5,440
metric tons (1). Use of tris in children's wearing apparel was
first banned by the CPSC on April 8, 1977 (6). The CPSC compiled
a partial list of other tris applications during its investiga-
tion of tris manufacturers in preparation for the April 8 ban
(personal communication with Bob Poth, Compliance, Consumer Pro-
duct Safety Division, August 5, 1977). However, the full extent
of using tris in other applications is unknown. There are indi-
cations that this has been used extensively in the manufacture
of cellulose insulation. Due to the rising cost of energy, it is
being installed in many northern U.S. homes.
(4) Thompson, C. M. Industrial Process Profiles for Environ-
mental Use, Chapter 13: Plasticizers Industry. Radian
Corporation, for U.S. Environmental Protection Agency,
Cincinnati, Ohio, February 1977.
(5) Modern Plastics Encyclopedia, Volume 15, No. 10A. October
1974.
(6) Tris and Fabric, Yarn, or Fiber Containing Tris; Additional
Interpretations as Banned Hazardous Substances. Federal
Register 42 (105):28060-28064. 1977.
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SECTION 4
ENVIRONMENTAL SIGNIFICANCE AND HEALTH EFFECTS
ENVIRONMENTAL SIGNIFICANCE
No specific monitoring data or other information are available
regarding losses of haloalkyl phosphates from production, but
relatively low losses are expected. These esters are produced
in batch kettles, and since their vapor pressures are low, atmos-
pheric emissions are expected to be insignificant. Industrial
sources suggest that no solid or liquid organic wastes are
produced. Aqueous wastes could be produced from washing of
reaction kettles and equipment cleanup (1).
Transport and storage losses are probably negligible. Fire re-
tardants are transported in bulk carriers or sealed metal con-
tainers. All haloalkyl phosphates are usually stored in sealed
containers. Since their vapor pressures are quite low, venting
losses should be virtually nonexistent. Accidental spills and
mishandling of haloalkyl phosphates may result in some losses;
however, no specific information is available on such losses.
Tris could potentially reach the environment from waste streams
generated in plants where tris is added to fabrics and plastics
or from the final product during its use, disposal, and recyc-
ling. Potential transport to the environment could occur by
atmospheric emissions, leaching, or small pieces of treated
fabrics or plastic products.
Experimental laundering of treated fabric demonstrated that tris
can be leached into wash and rinse waters. In a 1975 study,
tris surface concentrations on dacron polyester and cellulose
acetate were measured during the course of 50 launderings. Tris
was spun into the cellulose acetate and topically applied to the
polyester. Results indicated that approximately 12% of the tris
was lost from the polyester and that most of this loss apparently
occured in the first three washings. Results also indicated
that a negligible amount of tris was lost from the cellulose
acetate. Another 1975 study estimated that in a typical home
laundering of six sheets of specified size in 0.11 m3 of water,
a concentration of 6 parts per million (ppm) of tris would be
released in the combined rinse and wash.
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HEALTH EFFECTS
Effects on Animals
Under the National Cancer Institute's carcinogen bioassay pro-
gram, which was begun early in 1974, rats and mice were fed tris
daily at two dose levels and compared to control animals which
were fed no tris. Rats were placed on diets containing 50 ppm
(low dose) and 100 ppm (high dose) tris; mice were placed on
diets containing 500 ppm (low dose) and 1000 ppm (high dose)
tris. The test mice developed tumors in the liver, kidney, lung,
and stomach; and the test rats developed tumors in the kidneys.
Thus, tris was established as an animal carcinogen (6).
In subchronic toxicity and dermal penetration studies performed
by the Consumer Product Safety Commission's Bureau of Biomedical
Science, rats receiving daily oral dose of 25 mg/kg and 250 mg/kg
developed renal nephrosis following a 13-wk period. Rabbits
receiving a weekly dermal application of 10~6 m3/kg of undiluted
tris developed renal nephrosis and testicular atrophy at the end
of a 13-wk period (6). In one study, the hydrolysis product of
tris, 2,3-dibromopropanol, was detected in the urine of a rat
following dermal application of tris, thus indicating that tris
may be absorbed through the skin. No dibromopropanol was de-
tected in the urine of a rat treated with a fabric containing
tris (7). Testing by the CPSC's Bureau of Biomedical Science
showed penetration of tris through the skins of rabbits after
dermal application of undiluted tris and of tris-treated cloth
(6).
A study by Prival, McCoy, Gutter, and Rosenkranz found tris to be
mutagenic to histidine-requiring strains of Salmonella typhimu*
rium. Fabrics treated with tris were also found to be mutagenic
to the same bacteria strains (8). Tests conducted by the CPSC's
Bureau of Biomedical Science reported no chromosome aberrations
in bone marrow chromosomes of rats which received a single or
multiple dose of tris 5d/wk for 13-wk (6). In a letter to the
CPSC, Hooper and Ames reported that tris is a potent mutagen in
Dvosophila, causing large numbers of recessive lethal mutations
in offspring.
(7) St. John, L. E., M. E. Eldefrawi, and D. J. List. Studies
of Possible Absorption of Flame Retardant from Treated
Fabrics Worn by Rats and Humans. Bulletin of Environmental
Contamination and Toxicology. 15(2), 1976.
(8) Prival, M. J., E. C. McCoy, B. Gutter, and H. S. Rosenkranz
Tris(2,3-dibromopropyl) Phosphate Mutagenicity of a Widely
Used Flame Retardant. Science, 195(4273):76-78, 1977.
-------
The National Institute for Occupational Safety and Health (NIOSH)
reports the lowest lethal dose of tris for mice to be 300 mg/kg
(direct injection of tris into the peritoneal cavity). The
lethal dose for 50% of a test group of rats (oral doses) is
reported to be 1,010 mg/kg (9).
Effects on Man
No conclusive data exist establishing that tris -has caused can-
cer in humans. Since cancers develop over many years and cannot
be easily linked to particular cases, this is not unexpected.
In banning tris from use in children's wearing apparel, the CPSC
considered the June 2, 1976 National Cancer Advisory Board
opinion that
"Demonstration that a compound is carcinogenic in
animals should be considered evidence that it is
likely to be carcinogenic in humans, unless there
is strong evidence in humans to the contrary (6).
"Liquid tris caused delayed hypersensitivity in
human subject maximization tests. It showed a
dose/response relationship and is judged a weak
sensitizer. Patch testing of presensitized subjects
using fabrics containing tris produced responses
varying with the availability of the agent at the
fiber surface (10)."
In an inconclusive test, the absorption of tris from treated
fabrics worn by male subjects was studied by observing the
presence of the hydrolysis product of tris, 2,3-dibromopropanol,
in the subjects' urine. No 2,3-dibromopropanol was detected in
the urine of a man and a boy who wore tris-treated fabrics for
up to 9 days (7).
In their letter to the CPSC, Hooper and Ames asserted that tris
is capable of causing damage to deoxyribonucleic acid (DNA) syn-
thesis in human cells in tissue culture. However, no conclusive
data exist establishing tris as mutagenic in humans (6). Another
report identifies tris(haloalkyl)phosphates as cholinesterase
inhibitors and potential carcinogens and mutagens (1).
(9) Registry of Toxic Effects of Chemical Substances 1976
Edition. Christensen, H. E., and E. J. Fairchild, eds.
U.S. Department of Health, Education, and Welfare,
Washington, D.C., June 1976. 1245 pp.
(10) Morrow, R. W., C. S. Hornberger, A. M. Kligman, and H. I.
Miabach. Tris(2,3-dibromopropyl) Phosphate: Human Contact
Sensitization, Am. Ind. Assoc. J., 37(3):1976.
10
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POPULATION EXPOSED
A large population may be affected by production and use of
fibers and polymers containing tris. At the time of the CPSC
ban in April 1977, about 40% of all children's sleepwear
(about 20 x 106 garments) in the retail industry contained tris.
About 10% to 20% of these garments had already been sold to
consumers. In addition, the CPSC's Bureau of Economic Analysis
estimated that about 5.85 x 106 m2 of tris-treated fabric was
then in inventory with fabric and garment producers (6). Pub-
lic exposure to other tris-treated products has not been re-
ported.
In assessing the risk from tris-treated apparel, the CPSC con-
sidered cancer incidence projections from three studies. Hooper
and Ames estimated that for 1 yr of exposure to tris-treated
garments, 1.7% of the children would develop cancer (17,000
cases/million). The Environmental Defense Fund predicted inci-
dences as high as 6,000/million male population. The CPSC's
estimate ranged from 25 to 5,100 cases/million males (6).
If Velsicol Chemical and Great Lakes Chemical are indeed the only
remaining manufacturers of tris, the only area affected by emis-
sions from tris production is El Dorado, Arkansas. The city of
El Dorado had a population in 1970 of about 25,000; the county
encompassing El Dorado had an estimated population in 1974 of
45,000.
11
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SECTION 5
CONTROL TECHNOLOGY
Information on actual techniques used to control emissions of
tris during production is unavailable. Condensation and absorp-
tion generally appear to be the best methods for reducing atmos-
pheric emissions from production. Incineration and flaring would
produce acid contaminants, and carbon adsorption is most desir-
able for nonpolar compounds. Adsorbents other than carbon may
have some application potential. Costs and efficiencies are
dependent on the unknown characteristics of the waste stream.
Liquid wastes require a series of treatment steps. A typical
sequence might include filtration, chemical precipitation and
flocculation/filtration, and reverse osmosis. Biological treat-
ment may also be applicable. Applicable technologies depend on
wastewaters composition.
Control of fugitive emissions is accomplished by improving oper-
ating and maintenance procedures.
Emissions from employing tris as an additive in polymer and fiber
production and from using end products containing tris can be
reduced by selecting an alternate fire-retar.dant in place of
tris.
12
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SECTION 6
REGULATORY ACTION
On April 8, 1977, the Consumer Product Safety Commission (CPSC)
banned certain children's wearing apparel and certain uncut
fabric containing tris. On May 5, 1977, pursuant to an order of
a Federal district court judge, the CPSC banned not only certain
fabric, yarn, and fiber containing tris but tris itself which is
used in or intended for use in children's wearing apparel. The
CPSC is preparing an environmental impact statement of the tris
ban and may be studying the appropriateness of a ban on other
uses of tris (personal communication with Bob Poth of Compliance,
CPSC).
13
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REFERENCES
1. Lande, S. S., J. Santodonato, P. H. Howard, D. Greninger,
and D. H. Christopher. Investigation of Selected Potential
Environmental Contaminants: Haloalkyl Phosphates. EPA-560/
2-76-007 (PB 257 910), U.S. Environmental Protection Agency,
Washington, B.C., August 1976. 209 pp.
2. 1977 Directory of Chemical Producers. Stanford Research
Institute, Menlo Park, California, 1977. 1059 pp.
3. Chemical and Process Technology Encyclopedia. D. M.
Considine, ed. McGraw-Hill Book Co., New York, New York,
1974. 183 pp.
4. Thompson, C. M. Industrial Process Profiles for Environ-
mental Use, Chapter 13: Plasticizers Industry. Radian
Corporation, for U.S. Environmental Protection Agency,
Cincinnati, Ohio, February 1977.
5. Modern Plastics Encyclopedia, Volume 15, No. IDA. October
1974.
6. Tris and Fabric, Yarn, or Fiber Containing Tris; Additional
Interpretations as Banned Hazardous Substances. Federal
Register 42 (105):28060-28064. 1977.
7. St. John, L. E., M. E. Eldefrawi, and D. J. Lisk. Studies
of Possible Absorption of Flame Retardant from Treated
Fabrics Worn by Rats and Humans. Bulletin of Environmental
Contamination and Toxicology. 15(2), 1976.
8. Prival, M. J., E. C. McCoy, B. Gutter, and H. S. Rosenkranz.
Tris(2,3-dibromopropyl) Phosphate Mutagenicity of a Widely
Used Flame Retardant. Science, 195(4273):76-78, 1977.
9. Registry of Toxic Effects of Chemical Substances 1976
Edition. Christensen, H. E., and E. J. Fairchild, eds.
U.S. Department of Health, Education, and Welfare,,
Washington, D.C., June 1976. 1245 pp.
10. Morrow, R. W., C. S. Hornberger, A. M. Kligman, and H. I.
Miabach. Tris(2,3-dibromopropyl) Phosphate: Human Contact
Sensitization, Am. Ind. Assoc. J., 37(3):1976.
14
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
. REPORT NO.
EPA-600/2-79-210n
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Status Assessment of Toxic Chemicals:
Tris (2,3-Dibromopropyl) Phosphate
5. REPORT DATE
December 1979 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
T.R. Blackwood, S.R. Archer
P.J. Murin
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corp Radian Corp
1515 Nichols Road 8500 Shoal Creek Blvd
Dayton, Ohio 1+5^07 P.O. Box 99^8
Austin, Texas 78766
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-2550
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Lab. - Cinn, OH
Office of Research and Development
US Environmental Protection Agency
Cincinnati, Ohio ^5268
13. TYPE OF REPORT AND PERIOD COVERED
Task Final 11/77 - 12/77
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
IERL-Ci project leader for this report is Dr. Charles Frank, 513-68U-UU81
16. ABSTRACT
The properties, production processes, and uses of tris (2,3-Dibromopropyl)
phosphate (otherwise known as "tris") are listed. Current control
technology is discussed along with potential sources of environmental
contamination by tris. Possible effects on children already exposed
to tris are indicated, a history of the regulation of tris is given,
and areas in which information is lacking are identified.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Phosphates, flame retar-
dants, textile treatment,
Plastics treatment, Tris,
Phosphates, Halogenated
Phosphates
68A
68D
68G
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
25
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
15
U.S. GOVERNMENT PRINTING OFFICE: 1980-6.57-146/5515
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