United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
EPA 600 2 79 210k
December 1979
Research and Development
Status
Assessment of
Toxic Chemicals
Polybrominated
Biphenyls
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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-600/2-79-210K
December 1979
STATUS ASSESSMENT OF TOXIC CHEMICALS:
POLYBROMINATED BIPHENYLS
by
S. R. Archer
T. R. Blackwood
Monsanto Research Corporation
Dayton, Ohio 45407
and
C. S. Collins
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 acrylonitrile. 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
13,1
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ABSTRACT
Polybrominated biphenyls (PBB's), no longer produced for use in
the United States, have been used commercially as flame retard-
ant additives in synthetic fibers and molded thermoplastic parts.
Michigan Chemical Corp., located in St. Louis, Michigan, was the
major U.S. manufacturer of PBB's, producing approximately 4,990
metric tons between 1970 and 1974. Also recently discontinuing
PBB production, the White Chemical Corp. of Bayonne, New Jersey,
produced approximately 454 metric tons of octabromo-biphenyl and
decabromobiphenyl from 1970 to 1973. Nine companies have been
suppliers of laboratory quantities of PBB's, each producing about
2.2 kg/yr.
The main sources of PBB's today appear to be the residues remain-
ing in and around facilities which at one time manufactured,
processed, or produced products using PBB's. Preliminary indica-
tions show that the level of PBB's in the water near a Cincinnati,
Ohio plant which processed PBB's is from 1 ppm to 20 ppm. Con-
centrations as high as 0.15 g/m3 have been detected in the
Pine River at St. Louis even after shutdown of the PBB operation,
possibly because of release of PBB's accumulated in discharge
pipes or from contact with contaminated soils. Soils collected
from bagging and loading areas at the Michigan plant were found
to have 3,500 yg/kg and 2,500 yg/kg PBB, respectively.
Effects of PBB's on humans have not been fully documented.
However, epidemiological studies are being conducted by the
Michigan Department of Health and several other studies are
underway to determine the health and ecological effects of PPB's.
The State of Michigan has been the focal point for responding
to PBB contamination because of a 1973 incident in which PBB's
were accidentally mixed into an animal feed supplement, resulting
in widespread contamination of farm animals. EPA studies to
assist the state are continuing. While residues about manufac-
turing and processing sites are the present major concern, a
potential problem exists in the plastic and textile products
still in use which contain the PBB's as flame retardants.
Regulatory action must be directed toward cleaning up residual
PBB's in the environment from past emissions. Provided that PBB
production continues, regulatory action to control emissions from
production and transportation may be required. Locations of
iv
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manufacturer- and user-facilities should be determined. Infor-
mation is needed to determine emission sources and population
potentially exposed to PBB's from their manufacture, use, and
disposal. Viable control technologies should also be identified.
This report was submitted in partial fulfillment of Contract
68-03-2550 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. This report covers
the period November 1, 1977 to December 31, 1977. The work was
completed as of January 20, 1978.
v
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CONTENTS
Foreword iii
Abstract iv
Abbreviations viii
Conversion Factors and Metric Prefixes ix
Acknowledgements x
1. Introduction 1
2. Summary 2
3. Source Description 5
Physical and chemical properties 5
Production 6
Production process 6
Uses 7
4. Environmental Significance and Health Effects ... 9
Environmental significance 9
Health effects 10
5. Control Technology 13
6. Regulatory Action 14
References 16
Appendix 18
Vll
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ABBREVIATIONS
ABS --acrylonitrile-butadiene-styrene
PPB's —polybrominated biphenyls
ppb —parts per billion
ppm —parts per million
TSCA —Toxic Substances Control Act
Vlll
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CONVERSION FACTORS AND METRIC PREFIXES
To convert from
Degree Celsius (°C)
Kilogram (kg)
Meter3 (m3)
Metric ton
CONVERSION FACTORS
to
Degree Fahrenheit
Pound-mass (pound-mass
avoirdupois)
Gallon (U.S. liquid)
Pound-mass
Multiply by
t° = 1.8 t° + 32
2.204
2.642 x 102
2.205 x 103
Prefix Symbol
Kilo
Micro
k
y
METRIC PREFIXES
Multiplication factor
103
10~6
Example
1 kg = 1 x 103 grams
1 urn = 1 x 10~6 meter
Standard for Metric Practice. ANSI/ASTM Designation:
E 380-76e, IEEE Std 268-1976, American Society for Testing and
Materials, Philadelphia, Pennsylvania, February 1976. -37 pp.
IX
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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.
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SECTION 1
INTRODUCTION
Polybrominated biphenyls (PBB's), no longer produced for use in
the United States, have been used commercially as flame retard-
ant additives in synthetic fibers and molded thermoplastic parts,
In 1973, 0.9 metric tons to 1.8 metric tons of PBB's were
accidentally mixed into an animal feed supplement and eventually
fed to cattle in Michigan, causing widespread contamination of
farm animals. Before the nature of the contamination was recog-
nized, many of the contaminated animals had been slaughtered,
marketed, and eaten, and milk of the contaminated animals was
consumed. While no official standard for exposure level has
been set, any exposure to PBB's is considered hazardous.
There is a need to define various sources from which PBB's may
enter the environment, to establish consequent health and envi-
ronmental health effects, and to examine possible control or
cleanup measures and present regulatory actions. This report
provides a brief overview describing these items with emphasis
on PBB sources of emission and resulting environmental effects.
Also discussed are PBB control techniques, and current regula-
tory actions.
31 metric ton equals 106 grams; conversion factors and metric
system prefixes are presented in the prefatory material.
1
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SECTION 2
SUMMARY
PBB's may be represented by a biphenyl molecule with up to 10
substituted bromine atoms. PBB's are quite persistent in the
environment and vaporize readily. They do not leach from thermo-
plastics in which they are incorporated.
Michigan Chemical Corp., located in St. Louis, Michigan, was the
major U.S. manufacturer of PBB's, producing approximately 4,990
metric tons between 1970 and 1974. The White Chemical Corp., of
Bayonne, New Jersey, produced approximately 454 metric tons of
octabromobiphenyl and decabromobiphenyl from 1970 to 1973. PBB
production at these locations has been discontinued. Nine
companies have been suppliers of laboratory quantities of PBB's,
each producing approximately 2.2 kg/yr.
Little information is available regarding PBB production methods.
The process involves bromination of biphenyl in the presence of
catalyst.
PBB's have been used commercially as flame retardant additives in
synthetic fibers and molded thermoplastic parts. They have been
incorporated into the plastic housings of many commercial pro-
ducts, such as typewriters, calculators, and microfilm readers,
and industrial products, such as radio and television parts,
thermostats, shavers, and handtools.
The main sources of PBB's today appear to be residues remaining
in and around plants which at one time manufactured, processed,
or produced products using PBB's. PBB emissions occurred at the
St. Louis, Michigan, plant through contamination of the cooling
water during the flaking operation. No other emission sources
during manufacture have been identified.
Preliminary indications show that the level of PBB's in the water
near an Ohio plant, which processed PBB's, is from 1 to 20 parts
per million (ppm). Concentrations as high as 150 mg/m3 (ppb)
have been detected in the Pine River at St. Louis, Michigan,
even after shutdown of the PBB operation. This may be due to
delayed release of PBB's which were accumulated in discharge
pipes or to leachate from contaminated soils. Soils collected
from bagging and loading areas at the Michigan plant were found
to have 3,500 yg/kg and 2,500 yg/kg PBB, respectively.
-------
In 1973, 0.9 metric tons to 1.8 metric tons of PBB's were acci-
dentally mixed into an animal feed supplement and fed to cattle
in Michigan, resulting in widespread contamination of farm
animals. Before the nature of the contamination was recognized,
many of the contaminated animals had been slaughtered, marketed,
and eaten. Milk of contaminated animals was also consumed.
Approximately 10,000 persons have been identified in demographic
studies as having been impacted by this incident.
Although the effect of PBB's on humans has not been fully docu-
mented, epidemiological studies are being conducted by the
Michigan Department of Health and several other studies are
underway to determine their health and ecological effects.
The State of Michigan has been the focal point for responding to
PBB contamination. EPA studies to assist in assigning the most
appropriate regulatory action are continuing. While residues
about manufacturing and processing sites are the current major
concern, a potential problem exists in the plastic and textile
products still in use containing the PBB's as flame retardants.
i
It is possible that there are no significant emission sources at
present. Since areas of concern include not only facilities pro-
ducing PBB's for export, but also any plant that has ever used
PBB's in production of thermoplastic resins or other products,
regulatory action must be directed toward cleaning up residual
PBB's in the environment from past emissions. Provided that PBB
production continues, regulatory action to control emissions
from production and transportation may be required.
Table 1 highlights information regarding PBB's. Based on the
information presented in this report, the following items need
to be considered for future studies:
• Current production statistics and locations should be
identified for facilities manufacturing PBB's in the
United States.
• Provided that PBB's are currently manufactured in the
United States, production methods should be identified
to determine emission sources.
• Population potentially exposed to PBB's from contami-
nation by previous manufacturing facilities, disposal
of PBB-containing products, and use of PBB-containing
products should be investigated.
• Information is needed regarding control technology for
disposal of environmental residues from previous PBB
manufacture. Also, control technology should be identi-
fied for emissions from PBB manufacture provided that
PBB's are currently produced in the U.S.
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TABLE 1. POLYBROMINATED BIPHENYLS
Emission source
Production:
Current
Extent of
Emission quantity
Does not appear to be a
problem
Population exposed
Control method Regulatory action
The U.S. Department of Agri-
Previous
Use:
Accidents
Synthetic fibers
Molded thermoplastic
major source of emissions.
Residues remaining in and
around plants which once
manufactured, processed,
or produced products using
PBB' s are the main sources.
Dp to 150 mg/m3 have been
detected in a river near a
Michigan chemical plant,
even after shutdown of PBB
operation. Soil samples
from the bagging area show
a concentration of
3,500 wg/kg.
Approximately 0.9 metric
tons to 1.8 metric tons
of PBB's were acciden-
tally mixed in animal
feed and fed to cattle in
Michigan in 1973, result-
ing in widespread contami-
nation of farm animals.
Fabrics treated with PBB
are a potential hazard,
but no data are
available.
PBB's do not appear to
leach from these pro-
ducts .
Stockpiles may be isolated
or destroyed; however,
environmental residues
will be more difficult to
control.
Approximately 10,000 persons
have been impacted from
the accidental use.
culture, FDA, National Cancer
Institute, EPA, Michigan
State University, and the
University of Michigan have
conducted epidemiological,
toxicological, analytical,
and other projects to assess ,
the extent of PBB contami-
nation.
The FDA has set temporary action
levels for PBB's in contami-
nated foods and feed.
None.
Replace with more expensive
decabromodiphenyl ether
or several other halo-
genated aliphatic compounds.
None. None.
Note - Blanks indicate data not available.
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SECTION 3
SOURCE DESCRIPTION
PHYSICAL AND CHEMICAL PROPERTIES
Polybrominated biphenyls (PBB's) may be represented by the
following generalized structure, where Br and Br represent one
to five substituted bromine atoms: x ^
BP-6, the highly publicized PBB that was accidentally mixed with
animal feed and fed to cattle in Michigan, is a mixture of poly-
brominated biphenyls with an average of six bromine atoms per
molecule. BP-6 has a solubility of 11 parts per billion (ppb)
in water at 25°C. It is a solid at room temperature and it
decomposes at approximately 300°C to 400°C.
PBB's are quite persistent in the environment. PBB's were de-
tected in soils from a field which had received manure from a
PBB-contaminated herd 10 mo earlier. The flame retardant which
contaminated the animals' feed contained two isomers of penta-
bromobiphenyl, four isomers of hexabromobiphenyl (one of which
was the major component), and two isomers of heptabromobiphenyl.
Only one pentabromobiphenyl showed any significant disappearance
after 24 wk in the soil (1). As evidence of this persistence,
PBB's are still found in Michigan food, although production was
halted in 1974 (2).
(1) Jacobs, L. W., S. Chou, and J. M. Tiedje. Fate of Poly
brominated Biphenyls (PBB's) in Soils. Persistence and
Plant Uptake. Journal of Agricultural Food Chemicals
24(6):1198-1201, 1976.
(2) Wheat, D., EPA Checking Area Plant Site for Possible Poi-
sons in Soil. The Cincinnati Enquirer, Cincinnati, Ohio,
August 4, 1977, p.l.
-------
Although PBB's readily vaporize, they are not used as a liquid.
They do not leach readily from the thermoplastics in which they
are incorporated (3).
PRODUCTION
Michigan Chemical Corp., located in St. Louis, Michigan, was the
major manufacturer of PBB's in the United States from 1970
through 1974. During these 5 yr, approximately 4,990 metric tons
of PBB's were produced (4). PBB production by Michigan Chemical
Corp. was discontinued on November 20, 1974 (personal communi-
cation with Frank Daniher, Director of Research, Michigan Chem-
ical Corp., Ann Arbor, Michigan). The White Chemical Corp. of
Bayonne, New Jersey, produced approximately 454 metric tons of
the closely related compounds octabromobiphenyl and decabromo-
biphenyl from 1970 to 1973 (4). However, production by this
company ceased several months ago (personal communication with
Ms. Terry Simon, White Chemical Corp., Bayonne, New Jersey). In
addition, nine companies have been suppliers of laboratory
quantities of PBB's each producing approximately 2.2 kg/yr (4).
Hexcel Corp., located in Lodi, New Jersey, has previously pro-
duced and exported PBB's; however, the status of current pro-
duction is unknown. There is no indication that this material is
imported. A summary of telephone conversations with industry
representatives regarding PBB production is presented in the
Appendix.
PRODUCTION PROCESS
Little information is available regarding PBB production methods.
The process involves bromination of biphenyl in the presence of
catalyst. While there is a slight similarity to the manufac-
turing process for polychlorinated biphenyls, the two methods are
essentially different.
Ethyl Corp. reported in 1973 that mixtures of PBB's with an
average of less than or equal to 10 bromine atoms were prepared
by brominating biphenyl with dibromomethane in the presence of
(3) Hesse, J. L., Water Pollution Aspects of Polybrominated Bi-
phenyl Production: Results of Surveys in the Pine River in
the Vicinity of St. Louis, Michigan. In: Proceedings of
the Second National Conference on Complete Water Reuse,
Water's Interface with Energy, Air and Solids. The Ameri-
can Institute of Chemical Engineers and the U.S. Environ-
mental Protection Agency Technology Transfer, Chicago,
Illinois, May 4-8, 1975.
(4) Summary Characterizations of Selected Chemicals of Near-Term
Interest. EPA-560/4-76-004 (PB 255 817), U.S. Environmental
Protection Agency, Washington, D.C., April 1976. 50 pp.
-------
aluminum chloride or aluminum bromide at 25°C to 95°C (5).
Whether this method is the commercially preferred technique is
unclear.
USES
PBB's have been used commercially as flame retardant additives in
synthetic fibers and molded thermoplastic parts (4). Used by
manufacturers in the plastic, resin, and synthetic fiber indus-
try, they are added to polymers (thermoplastic resins) in mixing
and blending steps after polymerization (6). PBB's may be added
to fiber polymers during spinning and finishing operations (7).
PBB's have been incorporated into the plastic housings of many
commercial products, such as typewriters, calculators, and micro-
film readers; and consumer products, such as radio and television
parts, thermostats, shavers and handtools (4) .
Octabromobiphenyl, produced by Great Lakes Chemical Corp., was
used as a flame retardant in acrylonitrile-butadiene-styrene
(ABS) and polyolefin resins. PBB's manufactured by White Chem-
ical Corp. were sold to manufacturers of polycarbonates, poly-
esters, polyolefins, and polystyrene (8).
Manufacturing facilities using PBB's in polymer products are
numerous. Producers of some fibers and resins number in the
hundreds and are catalogued in the available literature by pro-
duction location and products (6, 7).
(5) Mitchell, L. C. Catalytic Production of Polybrominated Bi-
phenyls, U.S. Patent 3,763,623 (to Ethyl Corporation),
October 2, 1973.
(6) Wilkins, G. E. Industrial Process Profiles for Environ-
mental Use, Chapter 10. Plastics and Resins Industry, U.S.
Environmental Protection Agency, Research Triangle Park,
North Carolina. (Submitted to the EPA by Radian Corpora-
tion, February, 1977.)
(7) Parr, J. L. Industrial Process Profiles for Environmental
Use. Chapter 11, The Synthetic Fiber Industry, U.S.
Environmental Protection Agency, Research Triangle Park,
North Carolina. (Submitted to the EPA by Radian Corpora-
ation, February, 1977.)
(8) Modern Plastics Encyclopedia.
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Table 2 lists end uses of BP-6 manufactured by Michigan Chemical
Corp. (3).
TABLE 2. INDUSTRIAL USES OP FIREMASTER BP-6a (3)
Industry type
Products
Percent
of total
production
Business machines and
industrial equipment
Electrical
Fabricated products
Transportation
Miscellaneous
Typewriter, calculator, and
microfilm reader housings.
Radio, and TV parts, therm-
ostats, and shaver and
hand tool housings.
Projector housings and
movie equipment cases.
Miscellaneous small auto-
motive parts; i.e.,
electrical wire con-
nectors and speaker
grills.
Components for industrial
equipment.
48
35
-12
1
As presented by A. Fred Kerst, Vice President of Research and
Development, Michigan Chemical Corp., to the Michigan Environ-
mental Review Board, September 23, 1974.
Among the substitutes for PBB's are the more expensive decabromo-
biphenyl oxide and several halogenated aliphatic compounds, but
the environmental significance of these substitutes is
unknown (4).
No specific information has been obtained regarding transporta-
tion of PBB's.
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SECTION 4
ENVIRONMENTAL SIGNIFICANCE AND HEALTH EFFECTS
ENVIRONMENTAL SIGNIFICANCE
Sources
The main sources of PBB's today appear to be residues remaining
in and around plants which at one time manufactured, processed,
or produced products using PBB's. In addition to the manufac-
ture sites described in Section 3, contamination was recently
found near industrial plants on Staten Island, New York, and in
New Jersey. The U.S. Environmental Protection Agency (EPA) is
currently examining a plant in Cincinnati, Ohio, which processed
PBB's in 1972, along with seven other suspected plants (2).
PBB emissions occurred at the Michigan Chemical Corp. plant
through contamination of the cooling water during the flaking
operation. No other sources of emissions during manufacture
have been identified (3).
PBB powder can contaminate the soil in bagging and loading oper-
ations and, from these, be leached to the waterways.
Environmental Levels
Preliminary indications show that the level of PBB's in the water
near the Cincinnati plant under investigation is from 1 ppm to
20 ppm (2) .
Monitoring in the Pine River near the St. Louis, Michigan,
facility where polybrominated biphenyls were produced indicated
that PBB levels diminished from 3.2 parts per billion (ppb) in
the ambient stream near the effluent discharge to 0.01 ppb 13 km
downstream. Fish obtained in this 13 km stretch contained levels
of 0.09 ppm to 1.33 ppm. Near the New Jersey plants, a level of
100 ppm was found in a sediment sample, 10 ppb to 60 ppb in
receiving water, and 1 ppm to 2.7 ppm in soils near the two pro-
ducing plants. Land-based plant samples showed 0.3 ppm to
10 ppm, and aquatic specimens had 0.3 ppm to 1 ppm. Three of
nine human hair samples contained 0.03 ppm, 1 ppm, and 2 ppm.
-------
In September 1974, an estimated 0.11 kg/day PBB's were discharged
to the Pine River at St. Louis, Michigan (3). Contamination was
found as far as 13 km below the city.
Concentrations as high as 0.15 g/m3 have been detected in the
Pine River at St. Louis even after shutdown of the PBB operation,
possibly because of release of PBB's accumulated in discharge
pipes or from contact with contaminated soils. Soils collected
from bagging and loading areas at the Michigan Chemical plant
were found to have 3,500 yg/kg and 2,500 yg/kg PBB, respectively.
Population at Risk
Assuming that Hexcel Corp. is still producing PBB's, an area
with a population of about 1,300,000 persons could be exposed.
Approximately 10,000 individuals have been identified in demo-
graphic studies as having been impacted by the Michigan feed
contamination incident (9) .
Potential population risks exist in the disposal of products
such as business machines, industrial equipment, and fabricated
parts whose plastic components may contain PBB's as fire retard-
ants. Fumes may be generated inadvertently in fires or from
burning in dumps.
At St. Louis, Michigan, and other locations, such as Cincinnati,
Ohio, where handling of the material has ceased, there is possi-
ble inclusion of PBB's into the water supply, contamination of
fish and other wildlife, and danger to persons working in the
plants.
The risk to persons using fabrics treated with PBB's has not
been investigated.
HEALTH EFFECTS
Effects on Humans
Effects of PBB's on humans have not been fully documented.
However, epidemiological studies are being conducted by the
Michigan Department of Health and several other studies are
underway to determine the health and ecological effects of
PBB's (9). A paper on the epidemiological investigation of
human exposure to PBB's was presented at the Ninth Annual Con-
ference on Trace Substances in Environmental Health, University
of Missouri, June 10, 1975. The National Institute of Environ-
mental Health Sciences confirms earlier reports that farmers
(9) Identification of Selected Federal Activities Directed to
Chemicals of Near-Term Concern. EPA-560/4-76-006
(PB 257 494), U.S. Environmental Protection Agency,
Washington, D.C., July 1976. 36 pp.
10
-------
exposed to PBB's in Michigan in 1973 are more susceptible to
disease (10).
Following disclosure in May 1974 that PBB-contamination of cattle
feed had occurred, some 90% of quarantined farms were contacted
by the Michigan Department of Public Health. Initially, it ap-
peared that over 250 persons had been exposed and that 500 others
had used products from the farms. Eventually, a sample of 165
exposed persons (quarantined farms) and 133 nonexposed (non-
quarantined farms) was selected to permit correlation of PBB
levels in the body with illness. Medical history interviews,
physical examinations, and the collection of blood specimens
were begun in October 1974. The object was to assess short-term
effects of PBB on health. Positive blood values for PBB were
found among 74 adults and 30 children on non-quarantined farms
(97% below 0.019 ppm), whereas on quarantined farms only 52% of
82 adults and 29% of 28 children showed levels below 0.019 ppm.
There were 6 adults and 7 children with levels between 0.5 and
2.26 ppm. There was no significant difference between the fre-
quencies of the conditions and complaints of the quarantined and
nonquarantined groups. It was then established that the com-
plaints of 17 adults with the highest PBB blood levels (0.1-
2.26 ppm) were no more frequent than those of the remainder of
the study group, regardless of whether they were in the quaran-
tined or nonquarantined groups. In terms of family clusters,
an interesting finding was that some of those on the nonquaran-
tined farms had had exposure to PPB. The results of physical
examinations and clinical laboratory tests failed to establish
any effect of PBB exposure. A further study of possible long-
term effects is to be carried out by the Michigan Health Depart-
ment (11) .
Any human exposure to PBB is considered hazardous; however, no
official standard for exposure level has been set (2).
Effects on Animals
PBB's accumulate in fish at 10,000 times to 50,000 times ambient
levels (3). Large amounts of PBB's are also accumulated in duck
tissues.
About 400 cows given contaminated feed for 16 days exhibited
anorexia, decreased milk production, increased frequency of uri-
nation, some lameness, abnormal hoof growth, and shrinking of
the udder. Later signs of toxic effects included bloody blebs,
(10) Toxic Materials News. L. S. Stern, ed. Business Publish-
ers, Inc., Silver Springs, Maryland. July 20, 1977.
(11) Kay, K. Polybrominated Biphenyls (PBB) Environmental Con-
tamination in Michigan, 1973-1976. Environmental Research
(13)1:74-93, 1977.
11
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malformed or dead fetuses, abcesses, weight loss, and high sus-
ceptibility to stress. Nonlactating cows died within six months,
while the lactating cows survived and gradually improved. Mas-
sive liver abcesses were found in the dead animals (4). More
information on the pathology of PBB's in cattle can be found in
the Journal of the American Veterinarians' Medical Association
and the Journal of the Dairy Society (12, 13, 14).
PBB's are immune-suppressant agents in guinea pigs. Neoplastic
liver nodules have been noted in rats exposed to PBB's.
University of Michigan Medical School Studies have shown adverse
effects of PBB's on the kidney, liver, and thyroid of rats and
mice (4).
Short-term exposure to PBB's can interfere with reproduction and
liver functions, promote nervous disorders, and react as a
teratogenic agent in tissues of rats, mice and cattle. PBB's
have produced pathological changes in the livers of rats, mice,
guinea pigs, cows, and rabbits (4).
After PBB was mistakenly substituted in a cattle feed in Michigan
in 1973, animal symptoms included brain weight loss and roughen-
ing, abnormal hoof growth, losses in weight, and milk production,
excessive abortions and still-births, loss of vitality in adults
and offspring, and in some cases death (3).
(12) Moorhead, P. D., L. B. Willett, C. J. Brumm, and H. D.
Mercer. Pathology of Experimentally Induced Polybrominated
Biphenyl Toxicosis in Pregnant Heifers. Journal of the
American Veterinarians' Medical Association, 170(3):307-313,
1977.
(13) Fries, G. F., and G. S. Morrow. Excretion of Polybrominated
Biphenyls into the Milk Cows. Journal of the Dairy Society,
58(6):947-951, 1975.
(14) Murata, L. W., M. E. Zabik, and M. Zabik. Polybrominated
Biphenyls in Raw Milk and Processed Dairy Products. Journal
of the Dairy Society, 60 (4):516-520, 1977.
12
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SECTION 5
CONTROL TECHNOLOGY
Production of PBB's does not appear to be a source of emissions
at present. At the Michigan chemical plant in 1972 before
hazards were known, emissions of BP-6 in the production area were
caused by contamination of cooling water during the flaking oper
ation. Sampling of the outfall indicated levels of 0.98 mg/m3
to 5.03 mg/m3. To solve the problem, additional shielding was
added to the flaker, and a brine chiller was added to allow
recirculation instead of disposal of the flaker cooling water.
Condenser cooling water was repiped to another outfall. The
first outfall was abandoned. In 1974, the highest concentration
detected at the second outfall was 0.11 mg/m3 (3).
Current potential emission sources of this chemical include
possible stockpiles at producer and user locations, residues in
the ambient and natural environment, and possible emissions from
use and disposal of products containing PBB's.
Stockpiles can be controlled by destruction or isolation of the
chemical. Since PBB's are similar to, but less stable than poly-
chlorinated biphenyls (PCB's), control technologies used for PCB
control and destruction such as high temperature incineration,
should be applicable to PBB's. Environmental residues will be
more difficult to control.
13
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SECTION 6
REGULATORY ACTION
The State of Michigan has been the focal point for responding to
the contamination incident. In addition, the U.S. Department of
Agriculture, the Food and Drug Administration, the National
Cancer Institute, Communicable Disease Center, EPA, Michigan
State University, and the University of Michigan have conducted
wide array of epidemiological, toxicological, analytical, and
related projects to clarify the effects of the chemical on humans
and animals and to assess the extent of contamination. The
Toxicology Coordinating Committee of the U.S. Department of
Health, Education, and Welfare is preparing a synthesis of avail-
able health effects information. EPA provides assistance in
environmental monitoring.
The Food and Drug Administration has set temporary action levels
for polybrominated biphenyls in contaminated foods and in animal
feed. The State of Michigan has issued warnings to sport fisher-
men along the Pine River.
The Environmental Protection Agency has set up a work group to
write regulations on PBB's. The group has released an informal
draft schedule in which a draft of the regulation would go to
Assistant Administrator for Toxic Substances, Steven Jellinek,
on March 1, 1978. About one month later, draft would go to, the
EPA Steering Committee, and would be submitted for Administra-
tive signature at the end of April. On May 1, the rules would
be formally proposed; a hearing would follow in July, and final
rules would be announced in September 1978. The group is seeking
comments on the following issues: 1) Should PBB's be used in any
form or should specific uses of PBB's be restricted? 2) If PBB's
are not allowed to be used in the U.S., should their manufacture
be allowed for export? 3) What is the appropriate form of con-
trol? Should control be a regulation restricting production, end
uses, etc.? 4) What will be the impact on existing state laws?
5) What type of controls, if any, should be placed on articles
containing PBB's? and 6) What type of controls, if any, should
be placed on disposal of PBB's (15)?
(15) Toxic Materials News. L. S. Stern, ed. Business Pub-
lishers, Inc., Silver Springs, Maryland. October 19, 1977.
14
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Michigan's Governor William Milliken has requested that the
Public Health Department accelerate testing of nonfarm residents
for the chemical. That department is currently developing a
scheme to accomplish that additional testing; alternatives under
consideration include setting up clinic programs or making the
testing service available through private physicians. Health
department representatives say, however, that their labs are at
peak capacity now, and more funding to allow the contracting of
commercial labs will be needed (16) .
(16) Toxic Materials News. L. S. Stern, ed. Business Publishers,
Inc., Silver Springs, Maryland. August 17, 1977.
15
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REFERENCES
1. Jacobs, L. W., S. Chou, and J. M. Tiedje. Fate of Poly
brominated Biphenyls (PBB's) in Soils. Persistence and
Plant Uptake. Journal of Agricultural Food Chemicals
24(6):1198-1201, 1976.
2. Wheat, D., EPA Checking Area Plant Site for Possible Poi
sons in Soil. The Cincinnati Enquirer, Cincinnati, Ohio,
August 4, 1977, p. 1.
3. Hesse, J. L., Water Pollution Aspects of Polybrominated Bi
phenyl Production: Results of Surveys in the Pine River in
the Vicinity of St. Louis, Michigan. In: Proceedings of
the Second National Conference on Complete Water Reuse,
Water's Interface with Energy, Air and Solids. The Ameri
can Institute of Chemical Engineers and the U.S. Environ
mental Protection Agency Technology Transfer, Chicago,
Illinois, May 4-8, 1975.
4. Summary Characterizations of Selected Chemicals of Near-Term
Interest. EPA-560/4-76-004 (PB 255 817), U.S. Environmental
Protection Agency, Washington, D.C., April 1976. 50 pp.
5. Mitchell, L. C. Catalytic Production of Polybrominated Bi
phenyls. U.S. Patent 3,763,623 (to Ethyl Corporation),
October 2, 1973.
6. Wilkins, G. E. Industrial Process Profiles for Environ
mental Use. Chapter 10, Plastics and Resins Industry, U.S.
Environmental Protection Agency Research Triangle Park,
North Carolina. (Submitted to the EPA by Radian Corpora
tion, February 1977.)
7. Parr, J. L. Industrial Process Profiles for Environmental
Use. Chapter 11, The Synthetic Fiber Industry, U.S.
Environmental Protection Agency, Research Triangle Park,
North Carolina. (Submitted to the EPA by Radian Corpora
tion, February 1977.)
8. Modern Plastics Encyclopedia.
9. Identification of Selected Federal Activities Directed to
Chemicals of Near-Term Concern. EPA-560/4-76-006
(PB 257 494), U.S. Environmental Protection Agency,
Washington, B.C., July 1976. 36 pp.
16
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10. Toxic Materials News. L. S. Stern, ed. Business Publish-
ers, Inc., Silver Springs, Maryland. July 20, 1977.
11. Kay, K. Polybrominated Biphenyls (PBB) Environmental
Contamination in Michigan, 1973-1976. Environmental
Research (13)1:74-93, 1977.
12. Moorhead, P. D., L. B. Willett, C. J. Brumm, and H. D.
Mercer. Pathology of Experimentally Induced Polybrominated
Biphenyl Toxicosis in Pregnant Heifers. Journal of the
American Veterinarians' Medical Association, 170(3):307-313,
1977.
13. Fries, G. F., and G. S. Morrow. Excretion of Polybrominated
Biphenyls into the Milk Cows. Journal of the Dairy Society,
58(6):947-951, 1975.
14. Murata, L. W., M. E. Zabik, and M. Zabik. Polybrominated
Biphenyls in Raw Milk and Processed Dairy Products. Journal
of the Dairy Society, 60 (4):516-520, 1977.
15. Toxic Materials News. L. S. Stern, ed. Business Pub-
lishers, Inc., Silver Springs, Maryland, October 19, 1977.
16. Toxic Materials News. L. S. Stern, ed. Business Pub-
lishers, Inc., Silver Springs, Maryland. August 17, 1977.
17
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APPENDIX
TELEPHONE CONTACTS BETWEEN
INDUSTRY AND RADIAN CORPORATION
Industry Contacts Telephone Number
Dr. Frank Daniher 313-994-8000
Director of Research
Michigan Chemical Corp.
Ann Arbor, MI
Michigan Chemical Corp. has not produced PBB's since Novem-
ber 20, 1974.
Ms. Terry Simon 212-421-7000
White Chemical Corp.
Bayonne, NJ
White Chemical Corp. has manufactured no PBB's "since sever-
al months ago."
Dr. Robert Ortlep 201-472-6800
General Manager
Fine Organics, Inc.
Hexcel Corp.
Lodi, NJ
A statement has already been issued to the government. Any
further inquiries should be directed in writing to Laverne
Mafinski.
Bill Blake 317-463-2511
Great Lakes Chemical
West Lafayette, IN
Great Lakes Chemical has never produced PBB's.
Jack Eadie 517-636-1000
Dow Chemical
Midland, MI
They have never manufactured any PBB's or products derived
from it.
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Velsicol Chemical Corp. 312-670-4500
Chicago, IL
Check with Howard Waster for a firm answer. One person who
couldn't be quoted said PBB's had not been produced since
November 1975. (Velsicol merged with Michigan Chemical
early this year.)
Fred Fields 504-388-7518
Ethyl Corp.
Baton Rouge, LA
Ethyl Corp. has never manufactured PBB's.
19
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-79-210k
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
Status Assessment of Toxic Chemicals:
Polybrominated
Biphenyls
December 1979 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
T.R. Blackwood, S.R. Archer
C.S. Collins
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 ^07 P.O. Box 99^8
Austin, Texas 78766
10. PROGRAM ELEMENT NO.
1AB60H
11. CONTRACT/GRANT NO.
68-03-2550
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Lab.
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio ^5268
- Cinn, OH
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, 513-684-
16. ABSTRACT
The properties, uses, production processes and history of
polybrominated biphenyls are dealt with in this report. The
health and environmental hazards associated with polybrominated
biphenyls are examined. Although no longer produced in large
quantities, regulatory action is necessary for the clean-up of
residues and for the control of any further production and use.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
Biphenyl, Diphenyl, Aromatic Hydrocarbons,
Aromatic Polycyclic Hydrocarbons, Hydro-
carbons , polyphenyl compounds, polyphenyl
hydrocarbons, Unsaturated hydrocarbons, brjominated
bromohydrocarbons, Halogenation, Bromine
organic compounds, Bromo compounds, halo-
Flame retardants, Synthe-
tics, Plastics, Textiles
68D
68G
hydrocarbons,
alromatic compounds, Bromine
h ydrocarbons
8. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)'
Unclassified
21. NO. OF PAGES
30
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
20
A U.S. GOVERNMENT PRINTING OFFICE: 1980 -657-146/5518
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