EPfl 56O/6-77-O17
mflftKET INPUT/OUTPUT STUDIES
TflSK IV
POLYBROmiNflTED BIPHENYLS
JULY 1977
U.S. ENYIRONmENTPL PROTECTION RGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 2O46O
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EPA-560/6-77-017 • AAI 2378/2379-104-TR-3
Market Input/Output Studies
Task IV
Polybrominated Biphenyls
M. Lynne Neufeld
Marcus Sittenfield
Kathryn F. WoIk
August 1977
Final Report
Contract No. 68-01-1996
Project Officer
Vincent DeCarlo, Ph.D.
Prepared for:
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
Document is available to the public through the
National Technical Information Service, Springfield,
Virginia 22151
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NOTICE
This report has been reviewed by the Office of Toxic Substances, Environ-
mental Protection Agency, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and policies of
the Environmental Protection Agency. Mention of tradenames or commercial
products is for purposes of clarity only and does not constitute endorse-
ment or recommendation for use.
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TABLE OF CONTENTS
PARAGRAPH TITUE PAGE
SECTION I. STATUS OUTLOOK AND SUMMATION
1.1 TECHNICAL AND COMMERCIAL HISTORY OF POLYBROMINATED
BIPHENYLS 1
1.1.1 Manufacturing History 4
1.1.2 Distribution and Consumption History 6
1.1.2.1 Former Consumption Sites and Uses 9
1.1.2.2 General Consumption Process Chemistry for the Main
Commercial Uses 12
1.1.2.3 Potential Use Categories for PBBs 13
1.1.3 Disposal and Ultimate Fate 20
1.1.4 Market Factors 22
1.2 SUMMARY OF MANUFACTURING PROCESSES AND END PRODUCTS .... 24
1.2.1 Patented Manufacturing Processes 24
1.2.2 By-Products and End Products 28
1.2.3 Imports and Exports 28
SECTION II. CURRENT MATERIAL BALANCE
2.1 ' NATURAL SOURCES 29
2.2 MANUFACTURING 29
2.3 IMPORTERS 30
2.4 CONSUMPTION AND USERS 30
2.5 EXPORTERS ; 30
2.6 FINAL DISPOSAL AND ENVIRONMENTAL FATE 31
2.7 AREA MASS BALANCE 32
SECTION III. MANUFACTURING PROCESSES STUDY
3.1 PURPOSEFUL MANUFACTURING 34
3.1.1 Manufacturing Sites 34
3.1.2 Manufacturing Processes by Site 36
3.1.3 Transportation and Handling 41
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TABLE OF CONTENTS (CONTINUED)
PARAGRAPH TITLE PAGE
3.1.4 Current Environmental Management Practices 41
3.1.4.1 Losses or Disposal via Air, Water and Solids 41
3.1.4.2 Reclamation 43
3.1.4.3 Pollution Control Practices and Technologies 43
3.2 CHEMICALS PRODUCED WITH PBB AS AN ACCIDENTAL IMPURITY
BY-PRODUCT 45
3.2.1 Accidental Impurities in the PBB Product 46
3.2.2 Accidental By-Product Impurities in Waste Streams from PBB
Manufacture 47
SECTION IV. CONSUMPTION PATTERNS
4.1 IMPORTERS 48
4.2 EXPORTERS 49
4.3 TRANSPORTATION AND HANDLING 50
SECTION V. SUMMARY OF CHEMICAL LOSSES
5.1 AIR EMISSION FROM MANUFACTURING PLANTS, PROCESSING PLANTS
AND OTHER USERS 51
5.2 SOLID WASTE DISPOSITION OF POLYBROMINATED BIPHENYLS .... 53
5.3 LIQUID EFFLUENT EMISSIONS 55
5.4 GENERAL ENVIRONMENTAL POLLUTION BY POLYBROMINATED BIPHENYLS 56
5.5 POTENTIAL FOR INADVERTANT PRODUCTION OF PBBs IN OTHER
INDUSTRIAL PROCESSES AS A BY-PRODUCT 58
5.6 POTENTIAL FOR INADVERTANT PRODUCTION OF PBBs IN THE
ENVIRONMENT 60
SECTION VI. FUTURE PROJECTIONS 61
SECTION VII. USE ALTERNATIVE ANALYSIS
7.1 ALTERNATIVE CHEMICALS AS REPLACEMENTS TO PBBs IN EXISTING
PROCESSES AND PRODUCTS 63
7.2 ALTERNATIVE PROCESSES AND PRODUCTS WHICH COULD BE USED
AS A REPLACEMENT FOR PBB 64
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TABLE OF CONTENTS (CONTINUED)
PARAGRAPH TITLE PAGE
7.3 ALTERNATE PRODUCTS 65
7.4 ALTERNATIVE FINAL USE PRODUCTS 71
7.5 TRANSPORTATION AND HANDLING 71
7.6 CURRENT ENVIRONMENTAL PRACTICES 72
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LIST OF ILLUSTRATIONS
FIGURE TITLE PAGE
1-1 General Structure of Polybrominated Biphenyls 2
2-1 Estimated Input/Output, U.S. Manufacture of PBB as
Decabromobiphenyl Equivalent for 1976 33
3-1 Flow Diagram for Typical Recovery of Hydrogen
Bromide, Bromine, and Solvent 44
LIST OF TABLES
ABUED TITLE PAGE
1-1 TOTAL COMMERCIAL DOMESTIC PRODUCTION OF POLYBROMINATED
BIPHENYLS, 1970-1976 5
1-2 DOMESTIC USES FOR HEXABROMOBIPHENYL •. • • • 8
1-3 MAJOR FORMER CONSUMPTION SITES 10
1-4 POTENTIAL USE CATEGORIES FOR POLYBROMINATED BIPHENYLS . . 14
1-5 PATENT ASSIGNMENTS BY COMPANY 18
1-6 BROMINATION OF BIPHENYL 27
3-1 COMMERCIAL DOMESTIC PRODUCTION AND ESTIMATED PRODUCTION
CAPABILITIES FOR POLYBROMINATED BIPHENYLS, 1976 35
3-2 DOMESTIC PRODUCERS OR SUPPLIERS OF LABORATORY QUANTITIES
OF BROMINATED BIPHENYLS, 1976 37
3-3 PHYSICAL DATA FOR BIPHENYL AND BROMINATED BIPHENYLS ... 39
3-4 SUMMARY OF THE MANUFACTURING PROCESS FOR PBBs 40
3-5 TYPICAL AIR EMISSIONS DURING PBB MANUFACTURING 42
4-1 POTENTIAL SOURCES OF PBB IMPORTS TO THE U.S 50
7-1 ALTERNATIVE FLAME RETARDANT CHEMICALS AND THEIR
APPLICATIONS 66
7-2 COST OF ALTERNATE FLAME RETARDANTS. 71
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SECTION I. STATUS OUTLOOK AND SUMMATION
1.1 TECHNICAL AND COMMERCIAL HISTORY OF POLYBROMINATED BIPHENYLS
Polybrominated biphenyls (PBBs) are industrial compounds
that were used as flame retardants in various plastic materials from
1970 to 1974, about 40 years after the introduction of their
chlorinated analogues, the PCBs. The PBBs produced domestically
f f or commercial use included hexabromobiphenyl (marketed as Firemaster
BP-6 by Michigan Chemicals), octabromobiphenyl and decabromobiphenyl.*
*
*The polybrominated biphenyls discussed in this report refer to the
commercial products.
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Br
n
n + m = 6 Hexabromobiphenyl
n + m = 8 Octabromobiphenyl
n + m =10 Decabromobiphenyl
Figure 1-1. General Structure of
Polybrominated Biphenyls
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The bromine content of these products ranges from about 77% for
Firemaster BP-6 to about 82% for the decabromobiphenyl. Several
structural isomers of each of these brominated biphenyls are
possible and may be present in the product. The composition of
Firemaster BP-6 has been given as follows:
Hexabromobiphenyl 63%
Heptabromobiphenyl 14%
Pentabromobiphenyl 10%
Tetrabromobiphenyl 2%
Other bromobiphenyl 11%
In addition to the various PBBs present in Firemaster BP-6, the
presence of brominated naphthalenes (tetrabromo to hexabromo) has
also been detected (O'Keefe, 1977).
An analysis of Bromkal 80, (Norstrom, 1976) manufactured by
Chemische Fabrik Kalk, Germany, showed the following composition:
Hexabromobiphenyl 1%
Heptabromobiphenyl 27%
Octabromobiphenyl 72%
Nonabromobiphenyl Trace
Three octabromobiphenyl isomers were found to be present at 14%, 16%
and 42%.
In 1973, Firemaster BP-6 was accidentally mixed with
cattle feed, which, in turn, was distributed to a large number of farmers
in Michigan. The extent of the hazard to the health of the Michigan
farmers and consumers of dairy products has not yet been fully eval-
uated, but the livelihood of hundreds of farmers has been disrupted
and thousands of farm animals have been quarantined and destroyed
(Hecht, 1977; Chem. Eng. News, 1975).
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It is against this background that considerable interest
in PBBs has been aroused among environmental chemists and biologists.
This interest is based on both the severe accidental poisoning des-
cribed above, and the structural similarity of PBBs to the well
known pollutants polychlorinated biphenyls (PCBs). The purpose of
this study, undertaken for the Office of Toxic Substances of the
Environmental Protection Agency, was to define the routes and sites
through which the chemical is entering the environment.
1.1.1 Manufacturing History
During the period 1970 to 1976, approximately 13.3 million
pounds of polybrominated biphenyls were produced in the U.S. About
11.8 million pounds of this total were Firemaster BP-6 and FF-1, the re-
maining 1.5 million pounds consisted of octabromobiphenyl and
decabromobiphenyl. The sole U.S. producer of hexabromobiphenyl,
Michigan Chemical Company (now Velsicol), St. Louis, Michigan, ceased
production in November, 1974, at the request of the State of Michigan.
Their inventory was exhausted in April, 1975 (McDonald, 1977). All
companies with the potential to produce the hexabrominated biphenyl
consider it to be too toxic to do so.
Two producers have continued to manufacture octabromobiphenyl
and decabromobiphenyl since 1974. They are White Chemical Company, at
Bayonne, N.J., and Fine Organics Division of Hexel Corporation, at
Sayreville, N. J.
The estimated total production of polybrominated biphenyls
in the U.S. for the period 1970 to 1976 is shown in Table 1-1. Avail-
able data indicate that PBBs were not produced on a commercial
basis prior to 1970.
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TABLE 1-1. TOTAL COMMERCIAL DOMESTIC PRODUCTION
OF POLYBROMINATED BIPHENYLS, 1970-1976
(Industry Sources, 1977)
\v ESTIMATED
N^OUNDS PER
PRODUCT xv YEAR
Hexabromo-
biphenyl
Octabromobiphenyl
and
Decabromobiphenyl*
Estimated Total
U.S. Production
of Polybrominated
Biphenyls
1970
20,900
31,000
51,900
1971
185,000
31,000
216,000
1972
2,221,000
32,000
2,253,000
1973
3,889,000
359,000
4,248,000
1974
4,882,000
106,000
4,988,000
1975
0
170,000
170,000
1976
0
805,000
805,000
ESTIMATED
TOTAL
Totals
11,197,900
Totals
1,534,000
Totals
12,731,900
* These figures represent mainly the decabromobiphenyl. Truck load quantities (less than 40,000 pounds) of the
Octabromobiphenyl may have been produced in 1970, 1971, 1972, 1975 and 1976).
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During 1971 and early 1972, a small amount of a developmental
product Firemaster FF-1 was produced by Michigan Chemical: 15,000
pounds in 1971 and 131,000 pounds in 1972. This material was
ground Firemaster BP-6 containing 2% by weight of an anticake agent.
Firemaster FF-1 was prepared by shipping BP-6 to Cincinnati Chemical
Processing Company, Batavia, Ohio, where it was ground and blended
then shipped directly to customers, or returned to Michigan Chemical
Corporation's St. Louis plant.
The process for manufacturing PBBs is a general process that
can be applied to the bromination of a number of organic hydrocarbons. It
consists of a Friedel-Crafts type reaction wherein biphenyl is
reacted with bromine in the presence of chloride .in an organic solvent,
using an aluminum chloride catalyst.
The air emissions from Michigan Chemical's hexabromobiphenyl
operation were controlled by a spot ventilation system with localized
ventilation from various process areas, two absorber vents, and ambient
air in the general process area.
A survey conducted in May, 1974, at Michigan Chemical-.Co.
indicated hexabromobiphenyl concentrations of 3 x 10~6 mg/ 1 at the
spot vent and 2 x 10~^ mg/1 at an absorber vent. This study indicated
the total daily emission of hexabromobiphenyl was approximately 0.45 grams.
This was equivalent to about 0.07 Ib/million pounds. Results
of an ambient air/exposure survey in 1974, at the Michigan Chemical Plant,
indicated atmospheric levels of Firemaster BP-6 in the bagger area
during bagging in the range of 0.01 to 0.03 mg/1 air (Kerst, 1976).
1.1.2 Distribution and Consumption History in the U.S.
In recent years the immense loss of life and property
to fire has led to demands by both governmental and nongovernmental
organizations, for improved fire-resistant materials. Natural fibers have
been relatively easy to treat with flame-retardant materials.
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Flame retardant materials for synthetics have not been as easily
developed. Some brominated organic compounds have been found to be
more effective flame-retardants than chlorinated compounds for appli-
cations in plastic products.
Polybrominated biphenyls have been some of the more promising
flame retardants developed for synthetic materials. These materials
have been able to meet flasie-resistance performance requirements,
and are also economically feasible. Most important, they have little
effect upon the flexibility of the base compounds. For these reasons
extensive interest has been shown in PBBs as flame retardants, especially
hexabromobipheny, octabromobiphenyl, and deeabromobiphenyl. (EPA, 1975).
The only PBB product to reach large scale commercial pro-
duction in the U.S. was hexabromobiphenyl which was marketed as Fire-
master BP-6 by Michigan Chemical Company. However, several other
companies have shown an interest in the use of deeabromobiphenyl and
octabromobiphenyl, ,.as well as hexabromobiphenyl, as flame retardants.
Prior to the halt in production of hexabromobiphenyl in
November, 1974, the chemical had three main commercial uses as a flame
retardant:
(1) In ABS plastics
(2) In coatings and lacquers
(3) In polyurethane foam
Information from Michigan Chemical Company contained in an
earlier report (EPA, 1975) indicates that BP-6's use as a flame retardant
in thermoplastics was confined to those products which do not come into
contact with food or feed and which are not used in fabrics subject to
human exposure. The types of products in which BP-6 was used and the
approximate percentage used in each application are listed in Table 1-2.
No commercial uses of the octabromobiphenyl and deeabromobiphenyl in the
U.S. were reported in the time period 1970-1974. This is probably due
to the fact that the hexabrominated compound was less expensive and
equally effective.
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TABLE 1-2. DOMESTIC USES FOR HEXABROMOBIPHENYL
(EPA, 1975)
Industry
Business machines
and industrial
equipment
Electrical
Fabricated products
Transportation
Approximate Allocation
of Total Firemaster PB-6
Produced (%)
Examples
48
35
12
Miscellaneous
Typewriter, calculator and micro-
film reader housings. Business
machine housings.
Radio and TV parts, thermostats,
shaver and hand tool housings.
Projector housings, movie equip-
ment cases.
Miscellaneous small automotive
parts, i.e., electrical wire
connectors, switch connectors,
speaker grills.
Small parts for electrical appli-
cations, motor housings, components
for industrial equipment.
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1.1.2.1 Former Consumption Sites and Uses
Since the customer lists of Michigan Chemical Co. are
considered confidential and were not disclosed to AAI, the major
former consumption sites (i.e., consumption exceeded 20-30,000 pounds
per year) are discussed for the three use categories and summarized
in Table 1-3.
The chief consumer of PBBs as flame retardants in ABS plastics
was Borg-Warner Corporation, where peak consumption may have been of the
order of two million pounds in 1974 (EPA, 1975). These plastics were
used chiefly for small appliance and automotive applications, and may
have had a PBB content of about 10%. The sites at which PBB was used
include Parkersburg, W. Va., Ottawa, 111. and Oxnard, Ca. However, Borg-
Warner states that they no longer use PBB as a flame retardant
and have no stocks of the material on hand (Arthur, 1977). They are using
other brominated aromatics as substitutes. The flame retardant line
of plastics produced by Borg-Warner represents only a small portion of
their total production of ABS plastics.
Prior to 1975, Standard T Chemicals used Firemaster BP-6
as a flame retardant in cable coatings. They used an estimated 75,000
pounds of the hexabromobiphenyl per year in their Staten Island, New
York plant (EPA, 1975). They no longer use PBBs as flame retardants,
nor do they have any in stock (Waterbury, 1977). Since 1975, they have
used organophosphates such as tricresyl phosphate, triphenyl phosphate,
and cresyl diphenylphosphate as alternative flame retardants. The
selection of any given material is based on availability and price vs.
performance factors. The company is also looking iiito the polybrominated
biphenyl oxides as possible flame retardants. Again, only a small
portion of their total production of coatings are flame retardants.
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TABLE 1-3. MAJOR FORMER CONSUMPTION SITES
COMPANY & SITE
USE
APPROXIMATE
DATE CEASED USE
REASON
Standard T Chemical
Staten Island, N.Y.
Fire retardant
coatings for
industry
1974
Michigan Accident
Borg-Warner
Parkersburg, W. Va.
Ottawa, 111.
Oxnard, Ca.
Fire retardant in
ABS plastics
1974
Michigan Accident
E.A. Burkart Mfg. Co.
(Burkart-Randall Div.
of Textron Mfg. Co.)
St. Louis, Mo.
Corry Foam Products Co.
(Div. of Firestone)
Milan, Te.
Corry, Pa.
Fire retardant in
polyurethane foam for
auto upholstery
Auto manufacturers
advised them to
cease using PBBs
as a F.R. in foam
since the ultimate
disposal (incinera-
tion of automobiles)
was not believed
to occur at a
sufficiently high
temperature to
combust the PBBs,
which would then
accumulate in the
environment
10
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Hexabromobiphenyl was also used as a flame retardant in
polyurethane foam for automobile upholstery. Two of the larger
consumers were E.A. Burkart Manufacturing Company (Burkart-Randall
Division of Textron Manufacturing Company), in St. Louis, Mo., and
Corry Foam Products (Division of Firestone Tire and Rubber Company)
at Milan, La., and Corry, Pa.
Burkart reports that they are no longer using PBB as
a flame retardant in the foam, but would not disclose their sub-
stitute materials as they are considered proprietary (Gilda, 1977).
The equipment which had been used for processing the polyurethane
foam was dismantled after the Michigan accident.
Corry Foam Products reports that they stopped using PBB
as a flame retardant in polyurethane foam in 1972 (Lunderville,
1977). The automobile companies advised them that they did not want
their suppliers to use these materials because the ultimate dis-
posal of scrap automobiles by incineration was not believed to take
place at a sufficiently high temperature to burn the PBBs. This
would lead to the possibility of the compounds accumulating in land
fills, where there would be little opportunity for degradation.
Corry no longer has any stocks of PBBs on hand.
Dow Chemical Company reported the production of experi-
mental quantities of octabromobiphenyl in the early 1970's. This
was tested for use as a flame retardant for polyester fibers by
both Dow and DuPont. Based on toxicity data, the testing was dis-
continued and the process never used commercially (Norris, et al., 1973)
11
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1.1.2.2 General Consumption Process Chemistry for the Main
Commercial Uses
The major PBB consumers provided only limited data concerning
the process chemistry for their flame retardant products because they
consider this information proprietary. For all applications, the
process is basically one of physical blending. The PBBs are not
functional additives, and upon blending with the dry solid or liquid
polymeric material, provide filler-type flame retardant action in
addition to the chemical release of HBr if ignited.
The major user of the hexabromobiphenyl (as Firemaster
BP-6 from Michigan Chemical) was Borg-Warner Corporation. Their
flame-retardant ABS plastics were processed in the same manner as
the regular ABS plastics, which is reported to be a dry mixing and
extrusion process. The resin and flame retardant components are mixed
in a Banbury mixer until the flux point of the ABS resin is reached
and the hexabromobiphenyl flakes are melted. The mixture is extruded,
pelletized and cooled. Although it was indicated in a previous
source (EPA, 1975) that these pellets are water cooled, it is believed
that air cooling is the preferred method.
In the production of flame retardant cable coatings,
Standard T Chemical was the major consumer of hexa-
bromobiphenyl. Again, the process involved blending procedures.
12
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Neither would former consumers of PBBs for flame retarded
polyurethane foam provide details of their fabrication processes,
other than to state that standard blending equipment was used (Builda,
1977, Lunderville, 1977). One company (Burkart Manufacturing Com-
pany) dismantled the equipment used for processing polyurethane
foam and PBB shortly after the Michigan accident. Whether or not
non-flame retarded products were processed in the same equipment
used to produce PBB-containing compounds was not determined.
1.1.2.3 Potential Use Categories for PBBs
This section discusses potential uses for the PBBs based on
a review of the patent and technical literature for the past ten years.
Thirty-four applications of PBBs found in this literature
are summarized in Table 1-4. The majority related to the use of the
PBB as flame retardants in polymeric materials. Other claims included
self-extinguishing properties, improved wearability and machineability:
improved luster or color in the case of thermoplastics; and improved luster,
dyeability and wearability in the case of textiles.
Six applications of PBBs for other than flame retardant
purposes were found, including use in chemical synthesis to prepare
biphenyl esters (Knowles, 1972) or in a modified Wurtz-Fittig synthesis
(Argus Chem. Co., 1968); their use in light sensitive compositions to
act as color activators (Manos, 1970), their use as molecular
weight control agents for polybutadiene (Grenninger, 1969), their use
as wood preservatives (Mischulin, 1974), and their use as voltage
stabilizing agents in electrical insulation (Simplex Wire and Cable Co.
1966, 1967). They are also described as being functional fluids
(Brown, 1966) because they exhibit the properties of heat conductors
and plasticizers and can also function like a dielectric media. Table 1-5
relates the patent assignments to the assignees, who are also listed
in the bibliography.
13
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TABLE 1-4. POTENTIAL USE CATEGORIES FOR POLYBROMINATED BIPHENYLS
APPLICATION
AISS
ACRYLIC ACID
ETIIYLENE COPOLYMER
CELLULOSE TRIACETATE
COLOR ACTIVATOR
CONDUCTORS
ETIIYL ACRYI-ATF,
ETIIYLENE COPOLYMERS
FLAME RESISTANT
FI BEKS
FUNCTIONAL FLUIDS
GLASS FIBER LAMINATE
INSULATORS
MOLDING COMPOUNDS
MONOCROMO- TO TRIBROMO
BIPHENYL BIP11ENYL
Monsanto Chemicals
Ltd. (1966)
TETRABROMOBI-
P11EHYL TO
PENTABROMtiBIPHEN^
1IEXABROMO-
I1IPI1ENYL
I,
Michigan Ciiem.
(1973)
Union Carbide
(1975)
Celancse Corp.
(1975)
General Electric
(1973)
Union Carbide
(1975)
FMC (1972)
FMC (1973)
OCTABROMO-
niPIIEHYL
Michigan Chem.
(1973)
Celanese Corp.
(1975)
DECABROMO-
BIPIIENYL
Celnnese Corp.
(1975)
NOT SPECIFIED IN
ABSTRACT
DuPont
(1970)
Imperial Chemicals
Ltd. (197/1)
General Electric
(1975)
*also Included Ilepta and Nonabroniobiphenyl
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TABLE 1-4. POTENTIAL USE CATEGORIES FOR POLYBROMINATED BIPMENYLS (cont'd)
APPLICATION
MOLECULAR WEIGHT
CONTROL AGENT
NON-SPECIFIED
NYLON <>6
PLASTICS
POLY (ALKYLENE
TEREPIITIIALATE)
POLY (BUTYLENE
TEREPIU'IIALATE)
POLY (ETHER
URETHANE)
POLY (ET1IYLENE
TEREPIITIIALATE)
POLY (PHENYLENE
OXIDE)
POLYBUTADIENE
POLYESTERS
MONOIIKOHO- TO TRIBROMO-
BIPIIF.NYL BIPHENYL
National Distillers
and Chem. Corp. (1969)
Fa. Ugine Kuhlman,
Paris (1970)
Dow Chemical Co.
(1972)
TETRABROMOBI-
PIIENYL TO
PEHTARROMOBIPHEN'i
General Electric
(1968)
HEXABROMO-
UIPHENYL
L
Union Carbide
(1975)
OCTABKOMO-
BIPHF.NYI.
Fa. 1'gine Kulil-
roan, Paris (1970)
* Dow Chemical Co
(1972)
BASF (1973,
1974, 1975)
Allied Chemical
(1975)
Goodyear Tire &
Rubber Co. (1975)
DECAI1ROHO-
BIPHENYL
Fa. Ufiine Kuhl-
man , Parla
C1970)
Dow Chemical Co.
(1972)
Celanese Corp.
(1971)
BASF, (1976)
Celanese Corp.
(1973)
Firestone Tire
& Rubber Co. (197
Celanese Corp.
(1973)
NOT SPECIFIED IN
ABSTRACT
general Tire and
Rubber Co. (1972)
i)
also included llepta and Nonabromobiphenyl
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TABLE 1-4. POTENTIAL USE CATEGORIES FOR POLYBROMIMTED BIPHENYLS (cont'd)
APPLICATION
POLYETHYLENE
POLYETllYLENE-
VINYL ACETATE
COPOLYMER
POLYMERS
POLYOLEFINS
POLYPROPYLENE
POLYSTYRENE
POLYSTYRENE-POLY
(PIIENYLENE ETHER)
MIXTURES
POLYURET11ANES
STYRENE
MONOIJROMO- TO TRT.BROMO
BIPIIKNYL BTPHENYl
Dow Chemical Co.
(1972)
Dow Chemical Co.
(1972)
TETRABROMOBI-
PHENYL TC»
PENTABROMOBIPIIEtf
General Electric
(1972)
HEXABROHO-
UIPIIKNYL
L
Union Carbide
(1974)
Union Carbide
(1975)
Universal Oil
Prod. Co. (1973)
Phillips Petro-
leum Co. (1974)
Chenilsche Fabrlke Ka.lh
C.m.b.H. (1964 and
IQfifil
OCTAI1ROMU-
IIIPI1ENYL
Chemische Fabrlk
Kalk C.m.h.II.
(1QA9)
»Dow Chemical Co.
(1972)
*Dow Chemical Co.
(1972)
DKCARROMO-
I1IPIIKNYL
Cities Service
Co. (1971)
Berk Ltd.
(1971)
Uow Chemical Co.
(1972)
Dow Chemical Co.
(1972)
Monsanto
(1973)
NOT SPEC.IF1KI) IN
ABSTRACT
M 6. T Chemicals
(1975)
Ainer Lean Cyanain i cle
(1972)
Monsanto
(1974)
*also included llepta and Nonabromobii>henyl
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TABLE 1-4. POTENTIAL USE CATEGORIES FOR POLYBROMINATED BIPHENYT.S (cont'd)
APPLICATION
SYNTHESIS '
TEXTILES
VOLTAGE STABILIZERS
WOOD PRESERVATIVE
MONODKOMO- TO TRIBUOMO
UIPIIENY1, BIPHENYL
Simplex Wire & Calile
Co. (I960, 1967)
-TETRABROMOBI-
HHENYL TO
PENTABROMOBIPHEN'
DuPont
(1972)
Argus Chemical
(1968)
Sec. of the Array
U.S. Cov.(1909)
Simplex Wire 6
Cable Co. (1966,
1967)
1IEXAI1ROHO-
BIPIIKNYL
L
Ciba-Cetgy (1975)
OCTABROMO-
I1IPIIENYI.
FMC (197 A, 1974*,
1975)
DECAimOMO-
HIP1IENYL
Wlilte Chemical
(1975)
NOT SPECll-'lKO IN
ABSTRACT
WliLte Chemicals
(197A)
White Chemical
(1974)
*nlso Included llepta and Nonabromobiplienyl
-------
TABLE 1-5. PATENT ASSIGNMENTS BY COMPANY
ALLIED CHEMICAL CO.
AMERICAN CYANAMID CO.
ARGUS CHEMICAL CO.
BASF A.-G.
BERK LTD.
CELANESE CORP.
CHEMISCHE FABRLKE
KALK Gom.boH
CIBA-GEIGY A.-G.
CITIES SERVICE CO.
DOW CHEMICAL CO.
E,I. DU PONT
FA. UGINE KUHLMAN,
PARIS
FIRESTONE RUBBER AND
TIRE CO.
FMC
GENERAL ELECTRIC CO.
GENERAL TIRE AND
RUBBER CO.
GOODYEAR TIRE AND
RUBBER CO.
IMPERIAL CHEMICALS
LTD.
1975
1972
1968
1973
1974
1975
1976
1973
1974
1975
1962
1964
1966
1971
1972
1970
1972
1972
1973
Koch, P.J. et al.
Murray, R.
Wurmb, R. et al.
Seydl, W.
Horm, Po and W. Seydl
Schlecking, K. et al.
J. Appl. Polym. Sci. 19(1).
U.S. Patent 3,699,077.
Patent 1,128,896.
Brit.
Ger.
Ger.
Ger.
Ger.
1971 Abbott, C.J.
Perard, R.
Rossart, N.
Offen. 2,226,931.
Offen. 2,307,583.
Offen. 2,416,844.
Offen. 2.438,102.
Ger. Offen. 2,110,219.
Brit. Patent 1,340,013.
Ger. Offen. 2,335,009.
Canada Patent 966,259.
Hahn, H. Ger. Offen. 1,131,006.
Lampe, W. Ger. Offen. 1,169,119.
Jenkner, H. andH. Muller Ger. Offen. 1,226,780.
Jenkner H. U.S.Patent 3,285,965.
Mayer, F. et al. Ger. Offen. 2,428,390.
Green, J, and J. Vernsel U.S. Patent 3,730,942.
Mills, J. et al. Ger. Offen. 2,150,601.
Manos. P.
Knowles, R.
1970 Nagy, G.
U.S. Patent 3,390,995.
U.S. Patent 3,636,082.
Gen. Offen. 1,950,607.
1975 Lawson, D. and D. Lahr U.S. Patent 3,867,327.
Wright, C. and
H. Beachatn
Beacham, H.
1974 Kwopka, W.
1974*
1975 Greshan, J.
1968 Gowan, A.C.
1972 Hoof, W.
1973 Nicodemus, P. and
H. Wilson
1975 Copper, G.and V.Abolins
1972 Fabris, H. et al.
1973 Callander, D.
1974 Tyler, G. et al.
Ger. Offen. 2,105,188.
Ger. Offen.
Ger. Offen.
Fr. Demande
Ger. Offen.
Fr. Demande
Ger. Offen.
U.S. Patent
Ger. Offen.
2,246,657.
2,402,803.
2,215,491.
2,443,957.
1,512,082.
2,037,510.
3,772,455.
2.446,452.
Ger. Offen. 2,134,113.
U.S. Patent 3,909.489.
U.S. Patent 3.839,140.
18
-------
TABLE 1-5. PATENT ASSIGNMENTS BY COMPANY (continued)
M & T 1975
MICHIGAN CHEMICAL CO. 1973
MONSANTO CHEMICALS
LTD.
NATIONAL DISTILLERS
AND CHEMICAL CORP.
1966
1973
1974
1969
PHILLIPS PETROLEUM CO. 1974
SEC. OF THE ARMY,
U.S. GOV. 1969
SIMPLEX WIRE AND
CABLE CO.
1966
1967
Touval, I.
Lindemann, R. and
J. Anger
U.S. Patent 3,912,792.
Ger. Offen. 2.262,779.
Brown, J.P0 Brit. Patent 1,029,874.
Parts, L. and J. Miller U.S. Patent 3,766,157.
Parts, L. and J. Miller U.S. Patent 3,825,520.
Grenninger, L. and
L. Meeks U.S. Patent 3,448,093.
Underwood, J. et al. U.S. Patent 3,850,882.
Hoess, E.
Gross, R.E.
U.S. Patent 3,431,221.
Brit. Patent 1,021,681.
U.S. Patent 3,350,312.
UNION CARBIDE CANADA,
LTD. 1974
1975
1975*
UNIVERSAL OIL
PRODUCTS, CO.
Goeckel, B. and H.Larsen Ger. Offen. 2,404,537.
Goeckel, G. and H.Larsen Ger. Offen. 2,507,289.
Goeckel, G. and H.Larsen U.S. Patent 3,927,145.
1973 Cyba, H.
WHITE CHEMICAL CO. 1974
1975
Mischulin, V.
Mischulin, V.
U.S. Patent 3,723,383.
Ger. Offen. 2,352,923.
U.S. Patent 3,877,974.
19
-------
Five of these patents are discussed in an earlier report
(EPA, 1975), to which the reader is referred for details as to the
proposed process technology. These include the use of PBBs and
phosphonium bromides as flame retardants for olefin polymers (Murray,
1972), the use of hexabromobiphenyl with other flame retardant
components with a variety of base plastic materials (Cyba, 1973),
PBBs as part of a mixture yielding non-drip, self-extinguishing poly-
ethylene (Green, 1971), the use of a combination of tetrabromobiphenyl,
hexabromobiphenyl and octabromobiphenyl in a flame and moisture
resistant material for impregnating fibrous insulating materials for wire
and cable (Nicodemus, 1973), and the use of octabromobiphenyl as a flame
and smoke retardant in styrene polymers (Parts, 1973). All of the com-
panies to whom the above patents were assigned were contacted, and none
indicated that they were using the patent or planned to be using it
in the near future (EPA, 1975). Additional contacts with potential
users verified that no company with the capability of utilizing the PBBs
in any of their .products contemplated doing so.*
1.1.3 Disposal and Ultimate Fate
PBBs were used chiefly in the formulation of flame retardant
plastics. As such the disposal and ultimate fate of PBB would be the
same as the plastic component. Information concerning the probable
fate of PBB in the environment was reported earlier (EPA, 1975) as
follows:
"Although no data on soil migration of BP-6 are available, a
Michigan Chemical spokesman believes that migration is minimal.
This opinion is based on two factors: (a) BP-6 is known to be
tightly bound into the plastic into which it is incorporated; and
(b) a Monsanto study on polychlorinated biphenyl migration in soil
indicates that such compounds, especially the highly chlorinated
biphenyls, exhibit an extremely small migration tendency. Since
BP-6 should exhibit properties similar to the higher poly-
chlorinated biphenyls, BP-6 does not seem to be easily leached
from the soil."
*Private industrial sources.
20
-------
Norris et al. (1973), conducted a study on leaching of
decabromodiphenyl oxide (DBDO) from pellets of acrylonitrile-butadiene-
styrene (ABS) terpolymer containing DBDO. An analysis of aliquots showed
that the extraction of DBDO was below limits of detection for bromine
(0.5 ppm) in many of the samples. The lack of increase of bromine
concentrations with time and the erratic values of bromine determined
are best explained by assuming that extraction of DBPO was previously
due to erosion of surface particles. Evidently, migration of DBPO within
the plastic was not significant.
A static leaching experiment reported by the same authors
in the same article showed no detectable amounts of DBPO in the water
(detection limit - 0.075 ppm). Although this study was not done with PBBs,
similar results for PBB can be postulated based on the similarity in pro-
perties of the two chemicals.
The ultimate fate of wastes .resulting from PBB manu-
facture is reported by Michigan Chemical to be in a landfill operation.
A report by Hesse (1977) stated that analyses of water and
sediment samples obtained in the vicinity of the Gratiot County landfill
on March 1, 1977 showed PBB concentrations of 0.1 to 0.2 ppb in the
water samples and between 0.35 and 1.2 ppm in sediment samples from
drainage ditches and a catch basin. The Gratiot County landfill was the
disposal site used by Michigan Chemical.
A study by Jacobs and Filanow (1976a) indicated that PBBs were
absorbed on soils and that:
(L) absorbtion increased with increasing organic carbon
content of soil.
(2) less than 0.6% of the PBB was lost from the soils using
leachate quantities 20 times the average Michigan rainfall.
They concluded that PBB present in farm soils should not leach below the
depth of incorporation.
It was also demonstrated that orchard grass and carrots grown
in PBB contaminated soil "showed no or only very minor uptake of PBB."
21
-------
These studies corroborate the conclusions reached in the
EPA (1975) report quoted above, that "PB-6 does not seem to be
easily leached from the soil."
The incineration of plastics containing PBB has been
investigated by Benbow and Cullis, (1975). it was found that in-
cineration of plastics containing PBB resulted in the complete conversion
of PBB into HBr, C02 and 1^0. However, if the plastic material was
heated without combustion, then PBB was volatilized without change.
Studies on the ultimate fate of PBB discharged into
streams showed that there was a tendency for fish to concentrate the
PBB in the fat tissues (Hesse, 1974).
As a result of the accidental contamination of feed
that occurred in Michigan, a number of studies showed PBB concen-
tration in liver and fat tissues (EPA, 1975). Milk from affected cows
was found to be contaminated with PBB residues as high as 100 ppm.
1.1.4 Market Factors
The market factors affecting the consumption of PBBs
were limited to competitive cost-performance characteristics
of PBB compared to other flame retardants. With increasing
governmental regulations with respect to improving flame retardant
properties of plastic and textile materials, the market for such
compounds appeared to be growing rapidly.
The subject of toxicity and potential hazard to health
and the environment has resulted in an evaluation of chemicals with
good flame retardant properties. Risk-benefit studies of these
compounds have npt been fully documented. Until they are, the general
market for flame retardant chemicals must consider the health and
environmental hazard in the manufacture, sale, and distribution of this
class of chemicals.
Shipping practices for hexabromobiphenyl included shipment
by motor carrier or railroad.
22
-------
The materials were shipped in fiber drums and 5-ply construction
bags. (Kerst, 1976).
Spokesmen for current manufacturers of octa-and decabromobi-
phenyl generally confirmed the shipping practices of Michigan Chemical.
They reported that their material was shipped from their plant to the
docks only in motorcarrier for export via ocean freighter.
When Michigan Chemical Co. produced PBB, they packaged the
material in distinctive colored bags. Bags of the same type, but
different color were used for magnesium oxide, an animal feed supplement.
Despite the fact that the PBB bags were correctly marked, a ware-
houseman accidentally mixed some pallets containing bags of PBB in the
storage area for magnesium oxide. This error resulted in the shipment
of some PBB to the Michigan Farm Bureau, who did not read the bag labels,
compounding the initial error by mixing the PBB into the animal feed.
Stockpiling of PBB by the manufacturer was done only to the
extent necessary to maintain supplies for normal distribution demands.
The consumers also stockpiled PBB, but only to the extent
that was normal for their operations. The historical supply-demand
position in the United States was in balance. Supply was able to
keep up with demand.
There is currently no U.S. domestic sale of PBBs. There
would appear to be a growing European demand for decabromobiphenyl as
evidenced by increasing exports of this chemical during the past
several years (see Section IV).
23
-------
1.2 SUMMARY OF MANUFACTURING PROCESSES AND END PRODUCTS
Manufacturing processes are considered proprietary by the
several companies who make, or have made, polybrominated biphenyls.
The patent literature contains a number of references for the processes
of the bromination of biphenyls. These patents generally describe
the chemical reaction process and refer briefly to recovery, puri-
fication and by-products. In most cases, the biphenyl is reacted
with bromine and chlorine in a solvent with an aluminum chloride
catalyst. These patents,, summarized in the following section,
are described in an earlier report (EPA, 1975).
1.2.1 Patented Manufacturing Processes
The Dow Chemical Company was issued a patent in 1974 con-
cerning, among other reactions, bromination of biphenyl with bromine
chloride under pressure to produce a product containing five bromine
atoms on each aromatic ring (Moore et al. 1974). This process consists
essentially of brominating biphenyl with bromine chloride (BrCl) in the
presence of iron or a Friedel-Crafts catalyst in a closed vessel at or
near autogenous pressure to obtain rapid polybromination of the aro-
matic nucleus. The reaction may suitably be conducted at about room
temperature, and is completed in a few hours, with yields in excess of
80% generally being obtained.
Bromine chloride is prepared by mixing equal molar amounts
of bromine and chlorine in a closed container; the bromine chloride
thus formed is withdrawn from the liquid phase in the vessel.
Decabromobiphenyl,. and lower polybrominated biphenyls
are prepared by adding a catalyst (aluminum chloride) and
biphenyl to a batch reactor, and then slowly adding bromine chloride
in 0 to 20% stoichiometric excess. For example, 10 moles of
bromine chloride may be reacted with each mole of biphenyl.
As the bromine chloride reacts with biphenyl, the hydrogen
chloride formed as by-product is retained in the reactor under essen-
tially autogenous pressure. The pressure may range from 10 to 200 psig
during the course of the reaction. The reaction temperature is not
24
-------
critical; the temperature may range from 10 to 150°C. A solvent,
such as methylene chloride, may be used in the reaction, although good
conversions and yields are obtained by using excess bromine
chloride as the solvent. Best results are obtained when the reactor
is operated under essentially anhydrous conditions; water apparently
deactivates the catalyst. Essentially complete bromination is generally
obtained within a few hours. After the reaction, the solid products
are separated from the methylene chloride solvent. The advantages
claimed for this process include high product yields, low yields of
chlorinated compounds, short reaction periods, and efficient
utilization of bromine.
Chemische Fabrik Kalk G.m.b.H., Cologne-Kalk, Germany, obtained
both a U.S. and German patent in 1966 for a process of bromination of aro-
matic compounds, especially diphenyl, diphenyl ether, and mixtures thereof
(Jenkner, 1966). The bromination process is carried out at 20 to 65°, using
1.01 to 1.2 g-atoms of bromine chlorine which, at most, is equimolar with
respect to the bromine. The product contains at least 4 g-atoms of bromine
per mole of aromatic compound used as a raw material. Following completion
of the bromination reaction, a quantity of an alkylene (e.g., ethylene
or propylene) is added to the reaction mixture to react with the excess
bromine with the formation of the corresponding alkylene bromide (dibromo-
ethane). A modification of the process involves the use of alkylene
bromide as a solvent.
An example of the application of this process for preparation
of brominated diphenyl is described in this patent. Diphenyl (308
parts by weight) was dissolved in 800 parts of ethylene bromide and 4
parts of iron powder were added. Then, 1,430 parts of bromine
and 632 parts of chlorine were introduced into the mixture with vigorous
stirring over a period of about 2 hr. During the addition of bromine
and chlorine, the temperature of the reaction mixture ranged from 20 to
60°C. After the bromination had been completed, the excess bromine
contained in the reaction mixture was eliminated by adding ethylene to
form ethylene bromide. The pasty reaction mixture was filtered, and the
ethylene dibromide obtained as filtrate was suitable for reuse as sol-
vent. The filter cake was washed with ethanol and dried. The dried
25
-------
solid product contained 1,740 parts of octabromodiphenyl containing
80.9% of bromine and 1.5% of chlorine. This product yield was
93.5% of the theoretical yield.
An improved method for preparing polybrominated biphenyls
was described in a patent issued to Ethyl Corporation (Mitchell, 1973).
This process consists of reacting an aromatic compound with bromine
in the presence of a halogenation catalyst (aluminum chloride or
aluminum bromide) and a solvent (methylene bromide) at a temperature
sufficient to sustain a rapid reaction rate. Reaction temperatures
are below 100°C, and reaction time is from 2 to 10 hours. By-product
hydrogen bromide is produced.
When the desired degree of bromination is achieved, the
reaction is stopped by quenching with water. According to the patent,
the reaction mass is successively washed with acid, alkali,and finally
water. The organic layer is then dried by adding sodium sulfate, and the
solvent is stripped to recover a crude product. This product can be
recrystallized from solvent or washed with solvent followed by solvent
stripping in an evaporator. The hydrogen bromide gas is removed
from vent gases by scrubbTng with sodium hydroxide. Examples of
quantities of reactants,operating conditions,and results claimed are
summarized in Table 1-6.
From a perusal of permit applications made to the State
of New Jersey (1973, 1975, 1976(a), 1976 (b), 1977) it would appear that
the process described is generally being followed by the companies
who currently manufacture the polybrominated biphenyls. The solvents
used differ from the one noted in the patent, and chlorine is intro-
duced to aid the reaction. Separation of the product is by
centrifugation. There is no analytic data available to indicate whether
or not the introduction of chlorine results in the formation of
PCBs as a by-product.
The solvent extract is stripped to recover the solvent,
or may be recycled to the next batch. The centrifuged product is
dried, and pulverized. • An alternative is to dry the product, then
melt and flake the PBB on a chilled roll.
26
-------
TABLE 1-6. BROMINATION OF BIPHENYL
Example
Ho.
1
2
3
A
5
6
7
(Moore et
Rcactants (Parts by Weight)
Br2
Er-^
by moles of (C^ll,^.
b_/ Average broblnc nirnber detertalned by VPC; certain peaks assumed to be hopta-, octa-, non-i-, and decabrocioblphenyl based on retcr.ttcn
time. Area percent used for calculations.
-------
1.2.2 By-Products and End Products
Unreacted bromine may be recovered from the reaction vent
gases by scrubbing with the solvent. By-product hydrogen bromide
is recovered by scrubbing with water or sodium hydroxide. Bromine may
be recovered by treating the sodium bromide solution with chlorine and
stripping with steam.
Lower polybrominated biphenyls (hexabromo- and lower) may be
carried out from the reactor with the vent gases. If they are not
absorbed in the bromine solvent scrubber, they may be carried over
to the hydrogen bromide scrubber where they could contaminate the
recovered sodium bromide solution and regenerated bromine.
1.2.3 Imports and Exports
There are currently no imports of PBB into the U.S. in
commercial quantities. Exports of PBB from the U.S. to Europe,
consisting chiefly of the decabromobiphenyl, totalled 805,000 pounds
in 1976.
28
-------
SECTION II. CURRENT MATERIAL BALANCE
2.1 NATURAL SOURCES
There are no data that show any source of any polybrominated
biphenyl occurring in the environment naturally.
2.2 MANUFACTURING
There are only two polybrominated biphenyls currently being
produced commercially in the U.S. Octabromobiphenyl production in
1976 was reported to be 30,000 Ibs. Decabromobiphenyl production
in 1976 was reported to be 775,000 Ibs.
Air losses as particulate matter at the manufacturing
sites, calculated per million pounds produced, amounted to a probable
maximum of 900 Ibs. in 1976.
There are no data available on liquid losses at the two
plants, that produced PBBs in the U.S. in 1976. Calculations can
be made using batch composition data provided in the Permit
Applications to the New Jersey State Department of Environmental
Protection (1973, 1976), combined with the reported solubility of PBBs
29
-------
in water of 20 to 30 ppb. The raw material data contained in the N.J.
Permit application shows that 0.23 Ibs. of process water is used per
pound of product. Making the assumption that this number is valid
for all current PBB production methods, then about 185 thousand pounds
of water were wasted in 1976.. At a 20 ppb solubility, the amount of
of PBB lost in liquid wastes in 1976 can be calculated to be 0.0037 Ibs.
Accidental production of PBBs in other commercial chemical
processes has not been documented. Based on discussions with producers
of other chemicals which are intermediates in bromination processes,
we have concluded that it would be a small amount, on the order of 500
pounds per year (see Section 5.5 ).
2.3 IMPORTERS
According to communications from the U.S. Embassies in London and
in Germany, there is no exportation of any polybrominated biphenyl
to the United States (Cox, 1977, Dept. of State, 1977). A spokesman for
Solchem Corporation, an Israeli bromine producer, stated they do not
manufacture any polybrominated biphenyl (Zafran, 1977).
From all available information, there are no other countries
in which there are manufacturers of PBB (see Table 4-1).
It may be concluded that PBB is not imported into the U.S. ,
except, perhaps, in finished products.
2.4 CONSUMPTION AND USERS
All PBBs currently produced in the U.S. are exported.
This has been verified by spokesmen for the two companies which produced
commercial quantities of octa- and decabromobiphenyl in the U.S.
2.5 EXPORTERS
According fo spokesmen for the two companies manufacturing
octa- and decabromobiphenyl in the U.S., the total amount produced
was exported. In 1976 this amounted to approximately:
octabromobiphenyl 30,000 Ibs.
decabromobiphenyl 775,000 Ibs.
Total PBB 805,000 Ibs.
30
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2.6 FINAL DISPOSAL AND ENVIRONMENTAL FATE
At present, none of the octa- and decabromobiphenyl
produced in the U.S. have been consumed in the U.S. Final
disposal of these materials will be made in Europe. It is possible
that PBB-containing plastics are used by foreign producers to manu-
facture various finished products, such as television sets, for export
to the U.S. These items would then have their final disposal in the
U.S. There is presently no information regarding this matter.
Table 1-1 shows that during the period 1970-1974 approx-
imately 11.8 million pounds of a commercial hexabrominated biphenyl
were produced and sold in the United States. Substantially all of
this quantity was used in the production of flame retardant plastic
products. Based on an estimated 5 to 10 year life of the plastic
products, most of the PBB produced.in the United States is presently
contained in useful products. Within the next five years, these
PBB-containing products, such as TV cabinets and business machine
housings, will be disposed of through landfills or incineration, and
enter the environment.
Based on a PBB content of 10% as ABS resins, it can be esti-
mated that approximately 118 million pounds of plastic products were
made flame retardant with PBB. During the period when PBBs were
used as a flame retardant (1971-1975) the total production of ABS
resins is estimated to be 2.4 billion pounds. About 5% of this
estimated production could have been formulated with hexabromobiphenyl
(Firemaster PB-6).
31
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2.7 AREA MASS BALANCE
Both companies who manufactured PBB in the U.S. in 1976
are located in New Jersey. Environmental losses of PBB due to
manufacturing will be limited to this state at present.
There is no information available to determine if there is any
accidental PBB contamination of other brominated products produced by
these two companies.
Figure 2-1 shows an estimated input/output summary for current
(1976) PBB production, as the decabromobiphenyl. Calculations
were based on the stoichiometric equation:
C12 H1Q + 10Br2 > C12 Br1Q + 10 HBr
No data on solid losses at the current production sites are available.
Thus, the number given is an estimate based on disposal of hexabromo-
biphenyl at the Michigan Chemical Co. site (Kerst, 1976). It should
be noted, however, that there is no evidence that indicates this loss is
paralleled in processes used by the current producers of octa- and
decabromobiphenyl.
32
-------
Recovery of HBr
725,053 Ibs.
137,850 Its.
Biphenyl
1,432,203 Ibs.-
Bromine
1
PBB
MANUFACTURE
Losses to atmosphere
900 Ibs.
Losses to Sewer .0037 Ibs,
(liquid)
Losses as Solid Waste to
Landfill 40.,250 Ibs.*
Total
Estimated
Losses
41,150 Ibs
\/
PBB AS DECABROMO-
BIPHENYL
805,000 pounds
Export
See text for estimate description. Probably includes waste catalyst,
in addition to PBBs of varying degrees of bromination (exact composition
not known).
Figure 2-1. Estimated Input/Output, U.S. Manufacture
of PBB as Decabromobiphenyl Equivalent for 1976
33
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SECTION III. MANUFACTURING PROCESSES STUDY
3.1 PURPOSEFUL MANUFACTURING
Octabromobiphenyl and decabromobiphenyl are being pro-
duced in the U.S. for export. An estimated 30,000 pounds of octabromo-
biphenyl and 775,000 pounds of decabromobiphenyl were produced in 1976.
There are no current manufacturers of the hexabromobiphenyl.
3.1.1 Manufacturing Sites
The earlier survey (EPA, 1975) cited two companies, Michigan
Chemical Co. and White Chemical Corporation, as being the only domestic
producers of polybrominated biphenyls during the past decade. However,
a third company, Fine Organics Division of Hexel Corp. has produced
commercial quantities of the decabromobiphenyl since 1973. In view
of the current investigations concerning the polybrominated biphenyls
this company has suspended all production of this chemical.*
Table 3-1 summarizes current commercial domestic production
levels and estimated total capacity. Capacity estimates have been
derived from data supplied by the New Jersey Department of Environ-
*Personal communication with private industry sources.
34
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TABLE 3-1. COMMERCIAL DOMESTIC PRODUCTION AND ESTIMATED PRODUCTION
CAPABILITIES FOR POLYBROMINATED BIPHENYLS. 1976
(Industry Sources, 1977, New Jersey Dept.
of Environmental Protection, 1977)
COMPOUND. LBS/YR
Hexab romob ipheny1
Octab romob ipheny1
Decabromobiphenyl
Estimated Capacity
20-30,000
775,000
5,725,000
-------
mental Protection (1977). The equipment can be used for other
bromination processes, as demand warrants. It should be noted
that all PBBs produced by these companies are for export, principally
to Europe. None are sold domestically, and no hexabromobiphenyls
are currently being produced in the U.S.
In addition to the current commercial producers, there
are four chemical companies who manufacture the lesser brominated bi-
phenyls, chiefly the mono- and dibromo-compounds, e.g. 4-4'-dibromo-
biphenyl. These are produced in small batches varying from 100 gm to
one kg, on a custom order basis for laboratory use. Table 3-2 lists
the suppliers of the lower brominated biphenyls. It should be noted that
Eastern Chemical (Globus, 1977) states they do not produce 4-bromoblphenyl,
but maintain a "small" inventory of this and other unspecified PBBs.
They did not indicate the source of their supply.
Both Ethyl Corporation (Baton Rouge, La.) and Fairfield
Chemical Company (Blythewood, S.C.) were previously reported to be
small-volume producers of brominated biphenyls (EPA, 1975). Ethyl
Corporation currently reported that to the best of their knowledge, they
have not produced any quantities of any brominated biphenyls within the
past five to six years (Buchholz, 1977). Fairfield Chemical Company
stated that they had at one time acted as a wholesaler for brominated
biphenyls manufactured in England by Specialty Organics. These had
consisted chiefly of 2-bromobiphenyl and 4-bromobiphenyl, handled
in approximately 100 gm lots. However, they do not have any
brominated biphenyls on inventory at the present time (Allen, 1977).
Chemical Samples Company (Columbus, Ohio) reported that they
had produced 4-4'-dibromobiphenyl several years ago, but no longer
produce it. No more than a few kilograms were produced and sold.
Production ceased because it was uneconomical (Greelee, 1977).
3.1.2 Manufacturing Processes by Site
Polybrominated biphenyls may be defined by the following
general chemical formula:
36
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TABLE 3-2. DOMESTIC PRODUCERS OR SUPPLIERS OF LABORATORY QUANTITIES
OF BROMINATED BIPHENYLS, 1976
(Industry Sources, 1977*)
COMPANY
COMPOUNDS
APPROXIMATE
QUANTITIES PRODUCED
Biochemical Laboratories, Inc.
Hawthorne, CA.
All degrees of
bromination on
request
100 gm batches
Chemical Samples Co.**
Columbus, OH.
4-4'-dib romob ipheny1
1 kg batches
Columbia Organic Chemical Co.
Columbia, S.C.
mono- and
d ib romob ipheny1s
1 kg batches
Eastern Chemical
Hauppage, N.Y.
Inventories of
various degrees of
bromination
Research Organic/Inorganic
Chemical Corp.
Belleville, N.J.
4-4'-dibromobipheny1, 1 kg batches
other degrees of bromination
K & K Laboratories
Plainview, N.Y.
2-b romob ipheny1
3-b romob ipheny1
4-bromobiphenyl
1 gm to 1 kg
batches
*Industry Sources: Berg, 1977; Gergel, 1977 ; Greenlee, 1977;Globus, 1977; Brill, 1977;
Weiss 1977.
**No production since 1975.
37
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where the subscripts (n & m) represent the bromine content of the
compound. Bromination of biphenyls occurs in stages.
Table 3-3 gives physical data for biphenyl, hexabromobiphenyl,
octabromobiphenyl and decabromobiphenyl. These data show that the
higher the degree of bromination, the lower the vapor pressure, and the
higher the melting point and the "boiling" point.
Both White Chemical Corporation (Bayonne, N.J.) and Hexel
Corporation, Fine Organics Division (Sayreville, N.J.) manufacture poly-
brominated biphenyls using essentially the same process. Biphenyl is
reacted with bromine in the presence of chlorine, in an organic solvent
such as tetrachloroethane or ethylene dichloride, using aluminum
chloride as a catalyst. In this Friedel-Crafts type reaction, a mea-
sured quantity of solvent is precharged into the bromine absorber hold
tank. A measured quantity of water is precharged to the hydrogen
bromide solution hold tank. Recirculation is started in both loops.
Solvent, chlorine,and biphenyl are blown into the reactor, the catalyst
is added, and bromine is pumped in or fed by gravity from a scale tank.
The reaction is initiated by heating the batch to 60°C, at approxi-
mately atmospheric pressure. Excess bromine is distilled off the product,
which has a high melting point (see Table 3-3), and recovered. The
bromine is recovered from the solvent and returned for use in the
reaction. Hydrogen bromide gas emitted from the reactor is cooled in a
heat exchanger and then absorbed by water in the HBr absorber towers.
The absorbers and recirculation tanks are vested through an
absorber which exhausts into a packed salt water scrubber.
After the desired degree of bromination has been attained,
the reaction mass is quenched with water. This releases additional
quantities of hydrogen bromide, to the vent scrubbers. The aqueous
layer, containing the catalyst, is separated and sent to waste disposal.
The PBBs suspended in the solvent are removed by centrifugation,
solvent washed, tray dried, then ground to a powder. White sent the
centrifuge cake to Fluidized Processing for drying and grinding
(EPA, Region II, 1977).
The process is carried out in glass-lined steel reactors.
Table 3-4 is a summary of the manufacturing process.
38
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TABLE 3"3. PHYSICAL DATA FOR BIPHENYL AND BROMINATED BIPHENYLS
(Norris et al., 1973; EPA, 1975)
Melting Point
Boiling Point
Biphenyl
70°C
255.6°C
Hexa-*
Bromo-
Biphenyl
72°C
Octa-**
Bromo-
Biphenyl
Deca-*
Bromo-
Biphenyl
200-250°C 380-386°C
Vapor Pressure (mmHg)
90°C
140°C
220°C
.000076
0.0076 mm
0.76 mm
Volatility 70 Wt Loss
<5
<25
<50
250°C
310°C
350°C
341°C
363
388
Solubility g/lOOg
Solvent
Acetone
Benzene
Solubility in H20, ppb
6
75
11
1.8
8.1
20-30
*EPA, 1975
**Norris et al., 1973
39
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TABLE 3-4. SUMMARY OF THE MANUFACTURING PROCESS FOR PBBs
Raw Materials
•P-
o
Bromine
Aluminum Chloride
Tetrachloroethane
or Ethylene
Dichloride
Biphenyl
Chlorine
Intermediates
none
By-
products
HBr
Product Grade
or Type
Commercial
Capital
Value
<$500,000
Process
Friedel-
Crafts
type
reaction
Distribution
Export
-------
3.1.3 Transportation and Handling
The polybrominated biphenyls are shipped and handled as dry
powders. None of the chemicals in this class are listed in the Department
of Transport List of Hazardous Materials, and no special handling
methods have been developed for transport, storage or disposal of spills.
The compounds are packed in 50 pound bags or 100 pound fiber drums for
shipment. The major exporter of polybrominated biphenyls reports that
the material is shipped to Europe via water carrier.
3.1.4 Current Environmental Management Practices
This section discusses the available data concerning losses
to the environment and pollution control practices for the two current
(as of Dec. 1976) manufacturing sites, White Chemical Company (Bayonne,
N.J.) and Fine Organic Division of Hexel Corporation (Sayreville, N.J.).
A study on the environmental management at the former PBB manufacturing
site at Michigan Chemical Co. (St. Louis, Michigan) which is of historical
interest, was discussed in Section 1.1.
3.1.4.1 Losses or Disposal via Air, Water and Solids
Losses of PBBs to the environment at manufacturing sites
occur through:
(1) Emission to the air from the vents of the
hydrogen bromide recovery system
(2) Losses in waste waters resulting from
the quenching and washing of the PBBs as
they are recovered from the reaction mass
(3) Solid losses to landfills resulting from
drying, handling of the product, shipping
and transportation.
Air emissions have been calculated by one manufacturer for the
following charge (New Jersey State Dept. of Environmental Protection, 1973)
Raw Material Quantity, Ibs/batch
Bromine 3700
Aluminum Chloride 50
Biphenyl 460
Chlorine 1060
Ethylene Dichloride 4000
Total 9270
41
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The calculated air emissions from this operation based on three
8-hour batches per day, are shown in Table 3-5. The data represent emissions
resulting from the use of control apparatus as discussed in Section 3.1.4.3.
TABLE 3-5. TYPICAL AIR EMISSIONS DURING PBB MANUFACTURE
(New Jersey State Dept. of Environmental Protection, 1973)
Air Contaminant Quantity, Ib./hr.
Hydrogen Chloride 0.017
Bromine 0.009
Ethylene Bichloride 0.339
Total 0.355
A second manufacturer reported similar air emissions, i.e., total
quantity of contaminants less than 0.5 lbs./hr., for a comparable process
(New Jersey State Dept. of Environmental Protection, 1976).
The two sites for which air emissions data are reported are both
concerned only with the production of the higher brominated biphenyls, i.e.
octabromobiphenyl and decabromobiphenyl. The probability of emitting the
higher PBBs from hydrogen bromide recovery system vents should be extremely
low. For example, the vapor pressure of the hexabromobiphenyl at 90°C has
been reported to be 7.6 x 10-5 mm Hg (EPA, 1975). On the basis of partial
pressure, this would be equal to 100 ppb if air were passed over the pure
chemical. The vapor pressure of the octa- and decabromobiphenyl is substan-
tially lower, hence the air emission of these chemicals would be proportion-
ally less.
Losses of PBBs in waste waters can occur by solution or as a
suspension from washing of the product, or washing equipment and floors.
During the bromination process, water is used to quench the
reaction mass once the desired degree of bromination is achieved. This
aqueous layer, containing the catalyst and parts per billion of the PBBs,
is separated and sent to the chemical sewer. Since the solubility of the
higher PBBs in water is very low, on the order of 10 to 20 ppb, the prob-
ability of entry of PBBs into the environment from this source is very
low , except for particulate suspension.
42
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Both manufacturers have reported the use of centrifugation
equipment for removal of solids from the reaction products. Losses in the
form of a suspension of PBBs.in plant wash water would be dependent on
general plant housekeeping and the efficiency of settling equipment prior
to out flow into the local waste water system.
Solids emitted from drying, grinding and packaging equipment
in the form of dusts, can be recovered using dust control equipment,
to effect substantially complete solids removal (99+ percent). However,
no data on solids losses has been reported. Any solids that might result
from manufacturing operations can be disposed of in sanitary land-
fills.
3.1.4.2 Reclamation
In the manufacture of polybrominated biphenyls, the excess
bromine, the reaction solvent, and by-product HBr are recovered.
The vaporized solvent, which may be ethylene dichloride or
tetrachloroethane, and the unreacted bromine are recovered by a combination
of condensation and absorbtion. These materials are recycled to the next
batch.
The solvent in the reaction mass is separated from the polybromo-
nated biphenyl by centrifugation or filtration. It may be recycled to the
next batch, or it may be recovered in a pure form by distillation.
Hydrogen bromide, a by-product of the bromine-biphenyl reaction,
is recovered by scrubbing with water. The process is described in
Section 3.1.4.3 below.
3.1.4.3 Pollution Control Practices and Technologies
Typical pollution control practices for the recovery of the
hydrogen bromide (HBr) generated during the reaction, excess bromine
(Br«) and solvent are shown in Figure 3-1. These materials, emitted
during the reaction,are cooled in a condenser or heat exchanger, the
solvent and Br« removed in the Br9 scrubber and sent to the Br9-solvent
solution hold tank for reuse. The HBr gas is absorbed using sodium
43
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NaOH
H20
REACTOR
CHARGE
REACTOR
CONDENSER
-> PRODUCT
SOLVENT
AND Br2
SCRUBBER
HBr
ABSORBER
TOWER
BROMINE
SOLVENT
STORAGE
HBr
VENT
ABSORBER
NaBr - H20
SOLUTION HOLD
TANK
INDUSTRIAL
SEWER
TO BROMINE
REGENERATION
Figure 3-1. Flow Diagram for Typical Recovery of Hydrogen Bromide, Bromine and Solvent
-------
hydroxide solution in an absorbtion tower. These typically consist of
glass columns packed with ceramic saddles; the recovered HBr (as sodium
bromide) is sent to a bromine regeneration unit.
Absorbers and recirculation tanks are vented through an
absorber which exhausts into a salt water scrubber. When bromination
is completed and quench water added, the gases emitted, chiefly HBr, are
absorbed as above. All outlet water goes to an industrial sewer.
Pollution control technologies are also applied to the grinding
and collection of the polybrominated biphenyl products. Typically, the
apparatus is a bag type dust collector with exhaust fan that draws product
laden air through filter bags. Since the air contaminant is a saleable
product it is further processed and recovered.
3.2 CHEMICALS PRODUCED WITH PBB AS AN ACCIDENTAL IMPURITY BY-PRODUCT
Other chemicals produced with the polybrominated
biphenyls as accidental impurities can occur either in the final
product or in the waste stream from the manufacture of PBBs.
3.2.1 Accidental Impurities in the PBB Product
The major source of impurity that occurs in PBBs results from
the spread in the degree of bromination. Most of the commercially avail-
able polybrominated biphenyls, and those which have been tested extensively,
are mixtures of various brominated biphenyls and generally contain
amounts of hexa-, hepta-, and octabrominated biphenyl. For example, the
composition of Firemaster BP-6, marketed as a hexabrominated biphenyl was
given as follows:
Hexabromobiphenyl 63%
Heptabromobiphenyl 14%
Pentabromobiphenyl 10%
Tetrabromobiphenyl 2%
Other bromobiphenyls 11%
More than one-quarter, and possibly one-third, of the product consisted
of lower brominated biphenyls which are more volatile. It is the
lower brominated materials that are most likely to occur as a PBB impurity
45
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due to incomplete bromination reaction.
The major current domestic producer of PBBs,
who exported about 750,000 pounds of decabromobiphenyl in 1976, reports
that their material is more than 98 percent pure, the remaining
2 percent being nonabromobiphenyl*. It is manufactured by a proprietary
process in a chlorinated solvent which completely brominates the biphenyl
and results in no brominated by-products.
Other accidental impurities which can be produced with the
PBBs result from impurities in the biphenyl feed material. Two
major manufacturers were contacted concerning the possibilities of impurities
in the biphenyl grade used for bromination. One reported* their
biphenyl contained less than 5 ppm total impurities; no analysis was available.
The other manufacturer reported* that there were typically less than 0.5%
impurities in their bromination grade biphenyl. These had been identified
as:
Toluene
Naphthalene
Methylene biphenyl (fluorene)
Various methyl biphenyls
No data were available detailing whether these chemicals would undergo
bromination under the conditions of the biphenyl bromination reaction.
* Private industry source.
46
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3.2.2 Accidential By-Product Impurities in. Waste Streams from PBB
Manufacture
There are no data available on actual impurity by-products
in the waste stream formed along with the manufacture of PBBs. it is
known that HBr formed as a reaction by-product is reclaimed. Other
accidental impurities which could be produced with the PBBs and appear
in the waste stream could be the result of impurities in the biphenyl.
Any contaminants which might result from biphenyl impurities would
probably be concentrated in the tar stream. The solvent in which the
reaction is carried out is reused and may eventually concentrate
any brominated impurities. A waste stream pollution problem can occur
if the tar stream is disposed of in landfill instead of by
proper incineration.
47
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SECTION IV. CONSUMPTION PATTERNS
There are currently no domestic commercial consumers of
any polybrominated biphenyls. All consumer industries have found
alternative flame retardant additives to replace the hexabromo-
biphenyl is their plastics formulations.
4.1 IMPORTERS
In discussions with American and European producers,
former producers, and former consumers of the PBBs, AAI has been
unable to uncover any indications of imports of any polybrominated
biphenyls within the past year. Since all industry reports confirm
that there are no domestic consumers of PBBs, it seems unlikely
that an import market exists.
F.W. Berk Co., England, reported that they formerly
produced the decabromobiphenyl, Flamex B-10. They no longer produce
it or any other PBBs. They do not believe there are any other current
PBB producers in Britain (Cox, 1977).
48
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AAI received unconfirmed reports from several industry
sources, here and abroad, that an Israeli company was producing PBBs
in Holland. This company has been identified as the Solchem Dead Sea
Bromine Group of Solchem, Inc., with two bromine plants in Holland.
Solchem reported that they have not made, and do not plan to make,
any of the polybrominated biphenyls. However, they say they may
produce polybrominated biphenyl oxides in the future (Zafran, 1977) .
v According to industrial sources, Kalk A.B., Cologne-Kalk,
Germany, is reported to be producing both the hexabromobiphenyl and the
octabromobiphenyl. It has been confirmed that they are not exporting
PBBs to the U.S. (Department of State, 1977).
The information on potential sources of imports of PBBs in-
to the U.S. is summarized in Table 4-1.
4.2 EXPORTERS
Decabromobiphenyl, and small quantities of octabromobiphenyl
(no more than 20-30,000 pounds) are exported to Europe by Fine Organics
Division of Hexel Corporation, and White Chemical Company. The total
amount of PBB exported in 1976 was approximately 805,000 pounds.
4.3 TRANSPORTATION AND HANDLING
The major exporter of polybrominated biphenyl reports that
the material is shipped to Europe via water carrier. It is transported
in 100 pound, polyethylene lined, fiber drums.
49
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TABLE 4-1. POTENTIAL SOURCES OF PBB IMPORTS TO THE U.S.
COMPANY & SITE
PBB
PRODUCTION STATUS
EXPORTS TO U.S.
COMMENTS
F.W. Berk Co.
England
None
none
confirmed
Kalk A.G.
Cologne-Kalk
Germany
hexabromobiphenyl
octabromobiphenyl
none
confirmed
Solchem Dead Sea
Bromine Group
The Hague, Holland
(U.S. Office:
415 Madison Ave.,
New York, N.Y.)
none
none
confirmed
50
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SECTION V. SUMMARY OF CHEMICAL LOSSES
5.1 AIR EMISSION FROM MANUFACTURING PLANTS. PROCESSING PLANTS
AND OTHER USERS
The vapor pressure of polybrominated biphenyls is very low.
Exposure of this class of materials at room temperature to the atrios-
phere results in vaporization in quantities too small to be measured
by current analytical techniques (see Table 3-3).
The processes currently in use for the manufacture of octa-
and decabrominated biphenyls show that off-gases from the reactor pass
through a series of scrubbers and condensers. This reduced the concen-
tration of the volatile materials (bromine, hydrogen chloride, hydrogen
bromide and solvent) from 0.5 Ibs./hr. equivalent to less than 0.00033 Ibs,
per pound of product. No mention was made that these residual gases
contained any measurable concentration of PBBs.
51
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According to a spokesman for a former manufacturer of
PBBs (Kerst, 1977), evidence was found that the lower
brominated biphenyls in particular are carried over with the by-
product HBr and remain as impurities in the recovered HBr solution.
Information on the concentration is not available,but it is believed
to be on the order of ppm. or ppb.
Usually, the recovered HBr is converted to bromine. Any
PBB present as a contaminant in the HBr feed has been found in the
recovered bromine.
The octa- and decabrominated biphenyls are insoluble in the
solvent used during bromination and will be present in the reaction
product as a slurry. The PBBs are recovered from this slurry by
centrifugation. One of the New Jersey permit applications, (New
Jersey State Department of Environmental Protection, 1977) reports
that some particulate PBB is lost to the atmosphere during this step.
The quantity noted in the permit is less than 0.0005 Ibs. per pound
of product.
Following recovery by centrifugation, the octa- or deca-
bromobiphenyl is dried and then ground to a fine powder using pulver-
izing equipment. Dust from this operation is removed in a bag type filter,
Data supplied for a permit application to construct pollution control
equipment in New Jersey showed that the vent air stream from the air
filter on the grinder could contain 0.000625 Ibs. of PBB per pound
of product (New Jersey State Department of Environmental Protection,
1975).
Summarizing this information, calculations show that the
maximum emission of PBBs to the atmosphere during 'manufacture
by the U.S. producers does not exceed 1,125 pounds of PBBs as
particulate matter, per 1,000,000 pounds of PBBs manufactured.
Air emissions from processing plants would be in the form
of particulate matter emission occurring during the blending of PBBs
with resin prior to extrusion or other polymer converting operations.
No data are available on the potential emission from these sources.
52
-------
No data are available on probable air emissions from plants
that produced hexabromobiphenyl. This chemical has a higher vapor
pressure than either the octa- or decabromobiphenyl. At 90°C it
is less than 1 x 10 mm Hg, equivalent to a partial pressure of
_Q
less than 1.3 x 10 . At room temperature, the partial pressure
would be substantially less. Emission of this material as a vapor
contaminant in vapor streams leaving scrubbers or equivalent equipment,
can be calculated to be less than 1 ppb at ambient temperature.
Emissions of hexabromobiphenyl as particulate matter may be
assumed to have been of the same order of magnitude as that reported
by present manufacturers of octa- and decabromobiphenyls. However,
no data are available concerning particulate matter emissions of
hexabromobiphenyl.
5.2 SOLID WASTE DISPOSITION OF POLYBROMINATED BIPHENYLS
In an EPA (1975) report, the fate of Firemaster BP-6 in the
environment was discussed. It was stated that,
"Based on Michigan Chemical Company's knowledge of the
end-use products into which the BP-6 was incorporated
the major portion of these products (which have a use-
ful life of 5 to 10 years) end tip in a junk pile or
buried in a sanitary land fill."
According to this report, the ultimate disposition of PBB
upon burial is uncertain. It was believed by Michigan Chemical that.
the hexabromobiphenyl eventually underwent oxidative/biological de-
gradation, forming C0», water, and bromide ion. Degradation proceeds
more rapidly when a chemical change in the PBB molecule occurs.
53
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The quantity of BP-6 incorporated into plastic products
during the period 1970-1974 is given in Table 1-1 as 11,800,000 Ibs.
During the next 5 to 10 years (the useful life of plastic products)
it can be expected that this amount of BP-6 will be disposed in landfills
or by incineration. The probability of leaching PBB from discarded
plastic products was discussed in section 1.1.3. It was concluded
that leaching of PBB from discarded plastics materials was non-detectable.
Leaching could occur if the plastic was eroded, exposing the PBB particle
to the action of water.
Other studies noted in paragraph 1.1.3 reported that leaching
of solid PBB, not mixed or coated with polymer, could be found in
leaching waters to the extent of 0.1 to 0.2 ppb and in sediment
samples where concentrations as high as 1.2 ppm were found. These
studies were made on landfills used for disposal of manufacturing
wastes.
Leachate from landfills in which BP-6 flame retardant
formulated plastics products were disposed would have markedly lower
amounts of PBB and in most cases would probably be non-detectable.
Solid waste material containing PBBs may be obtained from
current manufacturing practice as the residue from the recovery of
the solvent used in the reaction.
The only information on the amount of solid waste resulting
at a manufacturing site is that reported by Michigan Chemical Co.
for their former hexabromobiphenyl production operation (Kerst, 1976).
This was stated to be 0.05 Ibs/lb hexabromobiphenyl produced.
-------
No other information is available concerning the quantity of PBB
contained in solid waste.
It has been reported that any solid or semi-solid wastes from
the production of octa- and decabromobiphenyl are put into drums and
removed by a solid-waste disposal firm. Ultimate disposal methods
are not known, but it is believed that the drums are buried in a
chemical waste disposal pit. Michigan Chemical sent their solid wastes
both to landfills and to a chemical disposal service. There are no
reports that deep well disposal or off-shore disposal methods are
used for solid wastes from PBB manufacturing processes.
5.3 LIQUID EFFLUENT EMISSIONS
The polybrominated biphenyls are solid at ambient temperatures.
To some extent, PBBs are soluble in various solvents. Liquid losses
can occur if these solutions are sewered; however, according to current
PBB producers * all solvent streams are collected and the
solvents recovered. Disposal residues from the recovery systems
have been discussed in Section 5.2 above.
By-products, or lower brominated biphenyls that may be present
in the recovered solvent stream, are recycled to the process. They
can also be present in the residue from the distillation recovery of
the solvents. These by-products are considered waste materials and
will, most probably.be sent to a chemical disposal area. The producing
companies did not discuss this portion of their process.
A study of waste water samples at Dow Chemical's
plant in Midland, Michigan (June 1976) by Mr. Tom Wilcox of the
Michigan Department of Natural Resources showed the presence of PBBs in
various waste locations in concentrations ranging from less than 0.1 ppb
to less than 10 ppb. The source of the PBBs was attributed to their
formation as a result of diphenyl impurities present in diphenyl oxide
used to produce decabromodiphenyloxide (DBDPO).
Mr. Wilcox was also contacted concerning the actual levels
of PBB reported. The use of the expression "less than" represented
the limit of sensitivity of the test method. He reported that no PBB
was detectable in the effluents checked at the Dow plant.
55
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5.4 GENERAL ENVIRONMENTAL POLLUTION BY POLYBROMINATED BIPHENYLS
General environmental pollution by PBBs during production
is most likely to occur as a result of particulate matter in vented
gas streams or liquid effluents flowing into natural water bodies.
Exhaust gases leave production areas as vented material
from by-product HBr scrubbers, or from the ventilation of grinding
and packaging operations.
Any environmental pollution occurring during these
operations is limited to dusting and resultant fall-out,
in the area immediately surrounding the point of use or fallout
in the area immediately surrounding the manufacturing building if
a building or room exhaust ventilation system is used.
The material is generally packaged in 50 pound bags. Unless
rupture occurs as the result of an accident, there is no general
environmental pollution by the chemical during normal transport
and storage.
The major application of PBBs is in the formulation of
flame retardant plastic materials. In this area, PBBs are blended
with resins in high intensity solids mixers such as Banbury mixers
or extruders.
General environmental pollution resulting from this operation
occurs when material is fed to the solids mixer or from the
volatilization of organic components during the high intensity
mixing step.
The principal formulator of PBB containing resins has confirmed
these routes of general environmental pollution (Gilligan, 1976).
Air emissions were never analyzed as the company believed that the
temperatures needed to volatilize PBBs were not reached in the high
intensity mixer.
This former consumer company also noted that solid losses could
occur from spillage. This was normally swept or vacuumed
and the collected dirt hauled to disposal area.
The final cleanup of the floors was by hosing. A sample
of the effluent from the primary and secondary waste treatment at this
plant taken in May 1976 indicated a PBB concentration of 0.5 ppb.
56
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Degradation of PBB containing plastics can occur in
landfill disposal areas and can result in environmental exposure
to PBB. This is a slow process which, in the opinion of producers and
former producers, eventually results in oxidative-biologic degradation
forming CO., H-0 and bromide ion. (EPA, 1975).
In studies of environmental pollution by octabromobiphenyl
(OBBP) contained in end-use products, samples of polypropylene
containing 5% OBBP were burned (Morris, et al., 1973). Analysis of
the combustion gases showed that all of the bromine in the consumed
samples was converted to HBr. Photolic studies showed that the OBBP
degraded when exposed to UV radiation. Under the same conditions,
chlorinated biphenyls did not degrade.
In another study on the incineration of plastic containing
polybrominated biphenyls as a flame retardant, it was demonstrated
that heating the plastic without combustion resulted in the expected
release of non-degraded PBB. However, when combustion occurred, the
PBBs were degraded to C0_, H.O and HBr (Benbow and Cullis, 1975).
Environmental pollution can occur as a result of accidental
mishandling of the chemical, as in 1973, when Michigan Chemical Co.
accidentally shipped their Firemaster BP-6 (hexabromobiphenyl) instead
of magnesium oxide, to the Michigan Farm Bureau. The accident occurred
as a result of a shortage of paper bags, which caused Michigan Chemical
to package the two products in the same color bag. The bags were
properly marked to show their chemical content. During transfer
to and from warehouse areas, a fork lift operator failed to notice
what he was moving, and as a result, both materials were stored in the
same area. Thus, when the Michigan Farm Bureau ordered magnesium oxide,
the order was filled from this mixed bag area (EPA 1975, Chemical and
Engineering News, 1975).
The result of this accident was the contamination of cattle
feed, and the subsequent death, or destruction of 11,000 cattle, 2,000
hogs, 1.5 million chickens, and 4.5 million eggs. In addition, 683 million
tons of contaminated feed were buried (Chemical and Engineering News, 1975).
57
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5.5 POTENTIAL FOR INADVERTANT PRODUCTION OF PBBs IN OTHER
INDUSTRIAL PROCESSES AS A BY-PRODUCT
The accidental production of brominated biphenyls during
the production of other brominated chemicals can occur if;
(a) Biphenyl is present as an impurity in the raw
material being brominated.
(b) Biphenyl is formed as a degradation product of
a complex phenyl compound.
(c) Brominated biphenyls are carried out with
the by-product HBr and recovered bromine released
during the production of PBB.
A previous report on the pollution potential of PBBs
(EPA, 1975) discussed possible sources of their inadvertant production
in connection with various water waste outfalls at the Michigan Chemical
Co. plant. The potential sources given included:
(1) Recovery and reuse of PBB contaminated bromine from
by-product hydrogen bromide released during the
production of PBBs.
(2) The coupling of polybromobenzene molecules
during the manufacture of hexabromobenzene
(3) The bromination of biphenyl that might be
present in bisphenol A used in the manufacture
of tetrabromobisphenol A.
In addition to these potential sources, there is the potential
for the presence of biphenyl in diphenyl oxide used as the raw
material to manufacture decabromodiphenyl oxide.
The subject of biphenyl as an impurity in the production
of aromatic chemicals that can be brominated subsequently such as
diphenyl oxide, was reviewed with manufacturers of biphenyl.
Biphenyl is manufactured by dehydrogenation of benzene or the
hydrodealkylation of toluene. Both reactions occur at elevated
temperatures and pressures and in the presence of specific catalysts.
The hydrodealkylation of toluene is one of several processes
used commercially for the synthesis of benzene. Biphenyl and
substituted biphenyls are recovered as by-products of this process.
It is conceivable that benzene made by this process contains biphenyl
58
-------
as an impurity on the order of fractions of a percent ( Lowenheim and
Moran, 1975). If biphenyl-contaminated benzene is used to produce
brominated benzenes or to synthesize other aromatic chemicals that
are subsequently brominated (as bisphenol A), it is possible that PBBs
can be formed as an impurity on the order of ppm.
Bisphenol A is manufactured by the low temperature reaction
of phenol and acetone. This material is used in the manufacture of
epoxy resins and polycarbonate resins. Neither of these processes
involve bromination.
Small amounts of bisphenol A are brominated to form tetra-
bromobisphenol A* used as a flame retardant in rubber and certain
plastic materials.
The subject of breaking the isopropyl linkage between
phenyl groups in bisphenol A under bromination conditions and the
linking of the resultant phenyl groups to form a biphenyl type
linkage was discussed with companies who manufacture bisphenol A.
It was concluded that this would be a difficult if not impossible
reaction.
It may be hypothesized that if bisphenol A, manufactured
via phenol made from biphenyl contaminated benzene, is brominated to
form tetrabromobisphenol A, then the biphenyl contaminant could also
be brominated to form PBBs.
Two manufacturers of diphenyloxide (DPO) supplied analytical
data. One company reported that the raw material used
to produce DPO was USP grade phenol and their product contained
no biphenyl as determined by GLC and mass spectrograph analysis.
A typical specification of impurities for this company's DPO
manufactured from USP grade phenol, 'is as follows:
Dibenzofuran less than 40 ppm.
Phenol 40 ppm.
Methyl naphthalene less than 5 ppm.
Naphthalene " " 5 ppm.
Phenylphenol " " 5 ppm.
*Manufactures include Great Lakes Chemical Co.,
White Chemical Corp. and Solchem Inc.
59
-------
The second company reported that their regular production
grade of DPO used for bromination contained less than 200 ptnm
biphenyl. This was determined using special GLC techniques, since
DPO would normally mask the presence of biphenyl. The commercial
grade of DPO was reported to contain up to 2,000 ppm of biphenyl.
5.6 POTENTIAL FOR INADVERTANT PRODUCTION OF PBBs IN THE
ENVIRONMENT
There is no information on this subject. However, based on
the process conditions for bromination, the simultaneous presence
of bromine, with biphenyl, under conditions that would form a
polybrominated biphenyl, is not believed to be possible. This view
is particularly reinforced by the fact that neither elemental bromine
nor biphenyl are normally found in the natural environment.
60
-------
SECTION VI. FUTURE PROJECTIONS
The current market for PBBs is Europe, where there is
continued acceptance of the use of these materials as flame retardants,
based on their cost-effectiveness. However, the major U.S.
exporter has suspended production of decabromobiphenyl. Further
production for export is uncertain, pending the outcome of current
investigations concerning PBBs. There is no U.S. market.
61
-------
SECTION VII. USE ALTERNATIVE ANALYSIS '
This section reviews alternative chemicals and processes which
could replace polybrominated biphenyls as flame retardant additives
to resins and other polymeric materials.
Interest in flame retardant additives has grown in recent
years as a result of greater governmental emphasis on safety
in all areas of human activity. Prior to this, major interest in
flame retardants in plastics was in electrical applications of plastics,
sponsored chiefly by insurance companies and Underwriters Laboratories.
Fifteen years ago, the major flame retardants included:
• Antimony Oxide
• Chlorinated hydrocarbon waxes (C^g to C-JQ)
• Alkyl and Aryl Phosphates
• Chloroalkyl Phosphates
Brominated compounds were just being introduced.
62
-------
In the intervening years, new plastics have been developed
with accompanying new applications. These changes have created new
requirements that could not be met completely by the few flame retardants
available in 1962. Many new flame retardant chemicals have been
marketed. Chlorinated and brominated aromatics have been in the fore-
front of this development.
As the emphasis on health safety has grown, toxicological
studies have shown that some of the flame retardant products used in
plastic and polymeric materials were potentially hazardous to health.
7.1 ALTERNATIVE CHEMICALS AS REPLACEMENTS TO PBBs IN EXISTING
PROCESSES AND PRODUCTS
U.S. commercial sales of PBB-containing products, chiefly the
hexabromobiphenyls, began about 1970 and rose rapidly till 1974. Pro-
duction in the U.S. ceased in Nov., 1974 as a result of the accidental
contamination of cattle feed in Michigan.
PBBs and alternative flame retardant chemicals are processed
by blending them with plasticizers, other additives and the resin
in standard equipment, following which the blend is extruded in the
form of pellets. No basic design changes are required unless the
alternative flame retardant chemical selected is a liquid, in this
case small design changes in the feed and materials handling equipment
will be required. Capital cost for such changes in most cases should
not exceed the low tens of thousands of dollars.
63
-------
Use of alternative flame retardant chemicals does not
alter the general character of losses from the resin blending and
pelletizing processes which result from handling spills and dust.
7.2 ALTERNATIVE PROCESSES AND PRODUCTS WHICH COULD BE USED
AS A REPLACEMENT .FOR PBB
Many of the alternative flame retardant chemicals are halogenated
aromatics. The processes for the manufacture of a number of these
products are similar in many respects to those described for the
bromination of biphenyl in Section 3.1.2. Thus, most of the equipment
used to make PBBs can be used interchangeably for making many of the
alternative chemicals.
Batch processes using corrosion resistant reactors and acid
scrubbers are also used to manufacture most of the non-halogenated
flame retardant chemicals. The capital required to modify a PBB
plant for such uses is not excessive.
Many of the companies who produce the various flame retardant
chemicals do so because these products are compatible with their
marketing and product lines. The manufacture of these materials, at
least for the larger companies, has probably been developed to serve as
an outlet for other products (e.g. Dow produces bromine, biphenyl,
diphenyl oxide, bisphenol A; FMC produces phosphoric acid; Great Lakes
Chemical produces bromine) or because they are "specialists" in certain
types of specialty organic syntheses (e.g. White Chemical Company and
Fine Organics).
-------
The change to producing chemicals that do not fall
within the marketing or manufacturing area of a given company could
represent a greater economic hardship than the capital investment
to modify a given batch process.
7.3 . ALTERNATIVE PRODUCTS
A large number of chemicals, both organic and inorganic,
can provide flame retardant characteristics to all of the plastic
and resin materials in commercial use. A probable reason for the
development of the PBBs earlier than the decabromobiphenyl oxide is
the cost of the raw material: 18c/lb. for biphenyl vs. 60c/lb. for
biphenyl oxide (ether). There are over 50 organic-based and more
than a dozen inorganic-based flame retardants available today.
These chemicals, and their applications, are shown in Table 7V1.
Alternative products compete on the basis of compatibility
with the plastic, effect on physical properties, price and cost-
effectiveness.
An example of relative cost effectiveness is the statement that
1.4 parts of tetrabromobisphenol A (TBB-A) are required to replace 1
part of decabromobiphenyl oxide (Plastics World, 1976). On a cost-
effectiveness basis, the cost to achieve equal flame retardancy is $1.22
for the TBB-A vs. $1.87 for the decabromobiphenyl oxide, per pound
substituted.
Examples of the cost of some flame retardants are given
in Table 7-2.
65
-------
TABLE 7-1. ALTERNATIVE FLAME RETARDANT CHEMICALS AND THEIR APPLICATIONS
(Modern Plastics Encyclopedia, 1975)
\, APPLICATION
ADDITIVE SV
^\
UdHhra*, orjanie
Phosphate esters
AUcyl diaryl phosphate
Cresyl diphenyl phosphate
Dtethyl-3-acetyI-4-hjrdroxy-
benzyl phoaphonate
Hexabromobeozene
HexabramocycJododecana
Octabromodipheayl
Decabramodiphenyl oxide
Tria (bromochloroisopropyl)
phosphate
Octyl diphenyl phosphate
Tetrabromoethane
Trialkyl boron ester
Tricresyl phosphate
Tributyt phosphate
Tributoxyethyl phosphate
Halogenated hydrocarbons
Thortyl phosphate
Triphenyl phosphate
Trixylenyl phosphate
Tri-iaopropylphenyl-
phoaphate
Phenyl-isopropyl-
phenylphosphata
SM
X
X
X
X
X
X
X
X
X
X
X
X
5
X
X
X
X
X
X
X
X
X
X
ellulosa acetate
X
X
X
X
X
X
X
X
X
X
ellulosa acetate butytata
X
X
X
X
X
X
X
ellulosa nitrate
X
X
X
X
X
X
X
X
X
I
X
X
X
X
X
X
X
X
X
X
!
I
•t
X
X
X
X
X
X
X
X
X
J
3
1
X
X
X
X
X
X
X
X
olycarbonatas
X
X
X
•
5
i.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
}
J
£
X
X
X
X
X
X
X
X
X
X
X
X
X
X
g
a
*
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
'olyvmyl acetata
X
X
X
X
X
X
X
X
X
X
X
X
X
olyvinyl chloride
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
i
I
2
1
5
X
X
X
X
X
X
X
X
X
X
X
X
X
a
2
i
o
X
X
X
X
X
X
X
X
ntumoscent paints
X
X
X
X
X
(on-intumoscent paints
X
B
B
X
X
X
X
i
(V1
X
X
X
X
X
D
5
u
X
X
X
X
D
3
X
X
X
X
X
X
=
i
X
X
X
i
[
1
5
X
i
3
X
X
X
X
X
X
X
X
X
X
1
X
X
textile coatings
X
X
X
X
X
i
X
X
Trade names
EacoflexCDP
Antoxol
PUaarac
Kronitex
teddrua
EacoflexCDP
Saatidzerl40
Diaflamoll DPK
Phoaflex 112
PliabracCDP
Kronitex COP
Busorfa34
Great Lakes BZ-87
Fireouster HUB
Great Lakes CD-73
Great Lakes BP-79
FR-300-BA
Great Lakes DE-83
Great Lakes TP-43
Santicizer 141
Diaflamoll DPO
TBE
Flameout5600-Bl
EacoflexTCP
Lindol, Phoaflex 179A, C 4 EG
TCP powder
Kronitex TCP
Phoaflex 4
Kronitex TBP
EscoflexTBEP
Phoaflex T-BEP
KP-140
Flami thane MJC4T
Chlorez
Chlorpareffines Hoechat
Citex BC-26
DirfamoII TOF
Kronitex TOP
Escoflex TPP
DisflamollTP
PhosflexTPP
Kronitex TXP
Kronitex 100
PlUbrac 519, 521 4524
66
-------
\xAPPLICATION
ADDITIVES \.
MdKrm. organic (Cont'd)
Halogenated organic
polyphoephonate
Halogenated organic
phoephate
Halogenated organic
Tris (betachlorethyl)
phosphate
Trichloropropyl phosphate
Tris (dichloropropyl)
phosphate
Monochloro propyl
phosphate
Triaryl phosphate (synthetic)
Phosphonate esters
Phosphonated chlor epoxy
Phosphonitrogen polymer
Chlorinated polyphosphate
Chlorinated mixed phosphate
Nitrogenous polymer
Nitrogen-phosphorous
polymer
Ethylene bis tris
(2-cyanoethyl)
phosphonium bromide
Phosphonium bromide
Tris (2,3-dibromopropyl)
phoephate
Borophosphate, organic
Methyl pentachlorostearate
Pentabromochloro-
cyclohexane
Pentabromoethylbenzene
Pentabramotoulene
Chlorinated paraffin
m
X
X
X
X
X
X
_o
I
X
X
X
X
X
X
X
X
X
X
X
X
X
Cellulose acetate
X
X
X
X
X
X
X
X
X
xxx
Cellulose acetate butyrate
X
X
X
X
X
X
X
X
X
Cellulose nilrale
X
X
X
X
X
X
X
XXX
VI
'x
o
CL
UJ
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Ethyl cellulose
X
X
X
X
X
X
X
[ xxx
Phenoiics
X
X
X
X
X
X
X
X
X
X
xxx
Polycarbonates
X
X
X
Polyesters
X
X
X
X
X
X
X
X
X
X
xxx |
wt
E
Ol
o
1
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Polystyrene
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Pclyvinyl acetate
X
X
X
X
X
X
X
| xxx
Pclyvinyl chlartde
X
X
X
X
X
X
X
X
X
X
xxx
Urethane foam, flexible
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
1 xxx
•g
1
o>
c
f]
a
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Intuiivescent paints
X
X
X
X
X
X
X
XXX
N-nn-intumescent paints
X
X
X
X
X
X
X
X
X
6
M
a
X
xxx 1
latex foam
| xxx
a.
o
01
Z
X
xxx
»
z
X
X
xxx
Paper coatings
X
X
X
X
X
X
X
X
X
Potting compounds
X
xxx
S]
a
ct
X
X
X
X
X
X
xxx
u
n
if
X
X
X
X
Textile coatings
X
X
X
X
X
X
X
X
X
xxx
VI
3
X
xxx
Trade names
Phougard C-22-R
PC-46
Phoxgard 2XC-20
Dechlxrane 304 & 604G
Chlorex
Douse 499
TCEP
Fyrol CEF
Great Lukes TP-37C
Disflamoll TCA
TCPP
Firemaster T33P
Fyrol FR-2
Great Lakes TP-49C
Daltogard F
DisBamoll 200 & 400
Kronitex 100
PIiabrac5t9,521&624
Escoflex
Isofirex
Castall 202 ER & 203FR
Rez471R
Sungard 134B
Fyrol99
Phoeflcx 200, 300, 400 & 500
Esconei2,3,4&SF
Sungard 131
Sungard 959
CyagardRF-1
Cyagard RF-473
Firemastcr T23P & LV-T23P
DBP-TP
Great Lakes TP-69
Fyrol 32B & HB-32
FR-2406
FR-2406-HP
FR-2406- HPX
Waroonyl D
MPS-500
FR-6S1-A
Great Lakes EB-80
Great Lakes TL-82
Chlorowax liquids
Chlorowax solids
CPKl-33
FLXl-12
ChJorcz .sotidfl & Paroi) liquids
67
-------
^^APPLICATION
ADDITIVES ^\ «
^V^ CO
Additim. organic. (Cont'd)
Chlorinated paraffiin (Cont'd)
Emulsions and
dispersions of
chlorinated paraffins
Chlorinated
hycrocarbon
Modified carbamide
Brominated organic
Brominated organic salt
Emulsifiable brominated organic
Emulsion of brominated organic
Chlorinated organic
Chlorinated anhydride
Chlorinated phosphate
Dibutyl chlorendate
Dimethyl chloreodate
Bromof orm adduct ol tri-alkyl
phosphate
1.4,5.6.7,7 hexachloro-N, N'
bis (thiocarbamoyl>-5-
norborene-2,3 dicarboxamide
Ethylene vinyl chloride
latex
Aromatic bromide
Decabromobiphenyl
TetrabromosaJicylanilide
Additives, inorganic
Aluminum oxide tri-hydratcd
Ammonium bromide
Ammonium fiuoborate
Ammonium sulfamate
X
X
X
X
X
X
X
X
X
X
X
u
K-
u
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Cellulose acetate
X
X
X
X
X
X
X
X
X
X
X
X
X
Cellulose acetate butyrate
X
X
X
X
X
XXX
X
X
eu
'5
o
3
c:
7:
n
u
z
X
X
X
X
X
X
X
X
X
X
X
X
X
X
£
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
I
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
4>
a.
rj
X
X
X
X
X
X
X
X
X
X
X
X
X
X
in
ej
X
X
X
X
X
X
X
c
13
o
u
-------
ADDITIVES >v
^v
Mditi«ei,lnor|tnic(Cont'd)
Antimony oxide
Antimony oxide
dispersions
Barium inelaborate
Bore- phosphate,
inhibited
Phosphorus-nitrogen polymer
Zinc berate
Zinc borate dispersions
Ammonium sulf amate
Complex inorganic phosphate
Boric acid type
Phosphonitrilic chloride
Tin chemical
Organic-inorganic additive
Ammonium orthophosphate
Ammonium polyphosphate
Reactive typei
Bromine containing prepolymer
Bromine and phosphorus
containing high
molecular weight polyol
Chlorine containing polyol
0,0-diethyll-N,N-bis
(2-hydroxyethyl)
aminomethylphoaphonate
Di (polyoxyethylene)
hydromethyl phoaphonate
Dibromobutenediol
Dibromobutenediol
diacetate
Dibromophenol
Tnbromophenol
N
1
X
X
X
X
X
X
X
8
X
X
X
X
Cellulose acetate
X
X
X
X
X
41
•s
1
3
"
X
X
X
;ellulose nitrate
X
X
X
X
8
I
X
X
X
X
X
X
X
X
X
X
X
X
X
X
5!
o
3
1
£
X
X
X
'henoiics
X
X
X
X
X
X
X
X
'olycarbonates
X
M
"o
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
'olyotefins
X
X
X
X
X
X
X
X
X
X
'olystyrene
X
X
X
X
X
X
'olyvinyl acetate
X
X
X
X
X
X
•S
3
s.
u
f
o
X
X
X
XXXXXX
X
X
X
X
X
X
X
o
01
1
1
•~
X
X
X
X
X
X
X
X
X
X
X
X
X
X
s
C4
.g
%
1
^
^
X
X
X
X
X
X
X
X
X
X
XXX
X
X
X
X
nlumescent paints
—
X
X
X
X
X
X
X
X
X
X
X
ion-inlumescent paints
^
X
X
X
X
X
X
X
X
X
i
X
01
•R
~*
X
X
X
X
X
atex loam
X
X
X
X
X
X
X
(eoprene
X
X
X
X
X
X
X
X
X
Vt
4j
5
*
X
X
X
X
X
X
X
X
'aper coalings
^
X
X
X
X
X
X
X
X
X
X
X
04
cz
i
X
X
i
*•
X
X
X
X
X
X
X
X
X
u
i
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s,
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X
X
X
XXX
X
X
X
X
X
X
X
X
X
X
X
X
X
M
m
J
Trade names
H&L
KR & White Star grades
Regular, Red & White
Star grades; Oncor 23 A,
75RA&75RAZ
Thermoguard FR, S, 3-711, S-790,
S-801 & 842
Rez-O-Sperse A4
Dechlorane A-0
Autiox White Star
Autiox Blue Star
Harwick SD-200 aeries
Ampacetlll28
Buaanll-Ml
Antoxol M
Gaftex RC & RCW
PyrotardB
ZB-112.325&237
FirebrakeZB
-
Amgard AS
Gaftex 281 & RCY-2
Sungard351A
-
Thermoguard FR-2120
Arsonax 1238 & 1230
Phoa-Chek A. 31 259 DAP &
MAP
Fire Retardant A & C
Phoa-Chek P/30
Brominex 9113 & 9117
Brominex 160P
Brominex 161P
Brominex 163P
Brominex 7 IIP
Thennolin RF-230
Thermolin RF-420 II
Thermolin X-450 U
FyrolS
Fyrol HMP
-
-
Great Lakes PH-63
DBPH
Great Lakes PH-73
KR-100-BA
69
-------
\APPLICATIQN
ADDITIVES ^\
\3
HweUwTypMfConfd) •
THbraawpiwaai (Gaframopbth*Jieaah7drU*
Alkonto iddacu ofTBPA
Ethytant *T*r**fT Adduce of
TBBPA
'friMfhlamhiral'iannl A
Attaxid«»dductofTCBA -
PnnrkM oiid* (dduct of TCBA
Bromatrichlara awtfaaiw
VlBjrlbromid*
^^il«M^i»«tif» B^jffj mi A&bydnd*
poJyota
Tfq^frfaMptrtlnlfc tphy^r'^
TvcrmkU (hydroxyButhyU
p|^5HpK*itiM|wi rMfpitfa
Triph«nyliA<»piuea
•90x7 (nd«
Ibzadiloncycio pMilMiiMM
X
S
1
X
Cellulose acetata
X
i
£
1
j[j
*«
u
X
Cellulou nlUale
X
5
i
U4
X
X
X
X
X
X
X
X
X
^
1
Z
X
8
j=
&
Polycarbonate*
X
X
X
Polyester*
X
X
X
X
X
X
X
X
Polyolefim
X
Polystyrene
m
m
S
^
a.
X
X
Polyvinyl cliloridi
X
X
Utelliana loini, fletltill
X
X
X
X
X
X
X
X
Urathana loam, rigid
X
X
X
X
X
X
X
X
X
X
Intumetcant paint*
X
X
X
X
Nan-liituinaicani paints
X
X
X
Ltlax film
lalax loam
X
I
O
€'
o
I
f
3
1
«t
^n
i
HETAodAAahydnd.
TCEP
VbeoJ 82 A V-C Bll
FRP-8
TMntlul A T««r»th«l fin*
THPCARoni
-
CM
PCI
Reprinted from the 1974-75 issue of Modern Plastics Encyclopedia.
Copyright 1975 by McGraw-Hill, Inc., 1221 Ave. of Americas, New York,
N.Y. 10020. All rights reserved.
70
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Table 7-2 COST OF ALTERNATE FLAME RETARDANTS
(Plastics World, 1976)
Decabrotnobiphenyl oxide $1.82/lb.
Tetrabromobisphenol A 0.87/lb.
Firemaster 680 1.50/lb.
Isopropylphenyldiphenylphosphate 0.70/lb.
Antimony Trioxide 3.30/lb.
Information for a full comparative analysis of all the poiats
used to judge economic feasibility for the large number of potential
alternative materials used in formulating the major flame-retarded plastics
materials is not available.
7.4 ALTERNATIVE FINAL USE PRODUCTS
The final products containing flame retardant chemicals are
resins that are used to produce many consumer and industrial products.
The selection of a given resin is based on a combination of price and
performance (physical and chemical properties).
Thus, ABS resins have high impact strength, higher tensile
strengths, and higher costs when compared to a high impact polystyrene
Hence the markets for ABS resin generally are not the same as those for
polystyrene.
Flame retardant plastics are selected on the basis of their
ability to perform. Plastics, in general, are alternatives to older
construction materials such as metal and wood. In this sense, flame
retardant plastics, as end products, are, themselves, the alternative to
materials formerly in use.
7.5 TRANSPORTATION AND HANDLING
Flame retardant chemicals, by their nature, are non-flammable
They are usually high boiling liquids or solids. As a class, they are non-
hazardous. The materials are shipped in multi-wall paper bags, fiber or non-
returnable metal drums. Normal care must be exercised in handling these
materials to ensure that rupture or puncture of the containers does not occur.
71
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Flame retardant containing resins are shipped as a finished
product suitable for extrusion or molding, or as a concentrate to
be blended with uncompounded resin prior to extrusion or molding.
These formulated products also present no fire or vapor pressure
hazard and there are no governmental regulations concerning the
handling or transportation (normally by truck or rail) of the formu-
lated resins. There are no restrictions on air or boat transport.
These materials, when packaged in standard containers, may be
stored in normal storage or warehouse facilities. No unusual precautions
are required. With regard to the handling of spills, if container
breakage occurs, normal cleanup practice as for any spilled
solid should be followed. Waste materials should be disposed of in a
normal manner (to land fill).
7.6 CURRENT ENVIRONMENTAL PRACTICES
The alternative flame retardant chemicals with physical
properties similar to those of the PBBs (solid, fine powder, high
boiling, non-corrosive) are handled in the same manner as the PBBs.
Losses will be those expected from handling powder materials.
Suitable filters are used on ventilating systems associated with grinding,
loading and mixing operations. Materials reclaimed from the filters can be
reused as they are not contaminated with dust or other impurities.
Otherwise, together with floor sweepings, they will be drummed
and sent to approved landfills.
Small users of these materials would combine the flame
retardant wastes with general plant wastes.
For reuse in the process, the user (i.e., the resin compounder)
seldom reclaims any solids recovered from pollution control devices.
Losses of the compounded flame retardant resin resulting from scrap
are seldom recovered and are usually combined with other plant wastes for
general solids disposal.
72
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Because of the high boiling point of most of the chemicals
used as flame retardant additives, plastic extrusion temperatures
rarely reach the point at which the additive is vaporized. In the
event that such a temperature is reached, suitable ventilating
equipment can be used. In most plants the exhaust air is emitted
through stacks without further control.
The available data are insufficient to assess quantitatively
the potential environmental contamination from these sources.
73
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REFERENCES
Abbott, C.J. (1971), Ger. Offen, 2,110,219, September 30.
Allen, H. (1977), Fairfield Chemical Co., Personal Communication, April 20.
Argus Chemical Co. (1968), Brit. Patent 1,128,896, October 2.
Arthur, R. (1977), Borg-Warner Corp., Personal Communication, March 24,
Beacham, H. (1973), Ger. Offen. 2,246,657, March 29.
Benbow, A.W. and C.F. Cullis (1975), "The Formation of Toxic Products
During the Combustion of Halogen-Containing Polymers," Eur. Polym.
J., 11,723-7.
Berg, P. (1977), Biochemical Laboratories, Inc., Personal Communication, March 25.
Brill, G. (1977), Research Organic/Inorganic Chemical Corp., Personal
Communication, March 25.
Brown, J.P. (1966), Brit, Patent 1,029,874, May 18.
Buchholz, B. (1977), Fairfield Chemical Co., Personal Communication, April 20.
Callander D. (1975), U.S. Patent 3,909,489, September 30.
Celanese Corp. (1973), Brit. Patent 1,340,013, December 5.
Chem. Eng. News (1975), "Feed Contaminant in Farmers' Blood," 53(8),7.
Copper, G. and V. Abolins (1975), Ger. Offen. 2,446,452, April 10.
Cox (1977), F.W. Berk, Co., Personal Communication through Mr. Douglas
Hartley, U.S. Embassy, London, March 29.
Cyba, H. (1973), U.S. Patent 3,723,383, March 27.
Department of State (1977), American Consulate, Dusseldorf, Telegram, May 9.
Environmental Protection Agency (1975), "Survey of Industrial Processing
Data: Task II. Pollution Potential of Polybrominated Biphenyls."
EPA 560/3-75-004.
EPA Region II (1977), Personal Communication Through Mr. Kopp.
Fabris, H. , E. Maney, and H. Velzmann (1972), Ger. Offen. 2,134,113, January 13.
Filonow, Alexander B., Lee W. Jacobs and Max M. Mortlund (1976b)
"Fate of Polybrominated Biphenyls (PBBs) in Soils, Persistence
and Plant Uptake", J. Agric. Food-Chem. Vol. 24, No.6, 1198-1201.
FMC Corp. (1974), Fr. Demande 2,215,491, August 23.
Gilda, A. (1977), Burkart Manufacturing Corp., Personal Communication, March 24.
Gergel, M. (1977), Columbia Organic Chemical Co., Personal Communication, March 25.
74
-------
Gillian, J.R. (1976), Letter to Mr. Dale Bryson, Acting Director,
Enforcement Division, EPA Region V, Chicago, 111., July 1.
Globus, A. (1977), Eastern Chemical Co., Personal Communication, March 15.
Goeckel, B. and H. Larsen (1974), Ger. Offen. 2,404,537, August 29.
Goeckel, B. and H. Larsen (1974*), Ger. Offen, 2,507,289, September 11.
Goeckel, B. and H. Larsen (1975), U.S. Patent 3,927,145, December 16.
Gowan, A. (1968), Fr. Demande 1,512,082, February 2.
Green, J. and J. Versnel (1971), U.S. Patent 3,370,947, October 8.
Greenlee, K. (1977), Chemical Samples Co., Personal Communication,
March 25.
Grenninger, L. and L. Meeks (1969), U.S. Patent 3,448,093, June 3.
Greshan, J. (1975), Ger. Offen. 2,443,957, March 20.
Gross, R. and G. Hunt (1967), U.S. Patent 3,350,312, October 31.
Hahn, H. (1962), Ger. Offen. 1,131,006, June 7.
Hecht, A. (1977), "PBBs: One State's Tragedy," FDA Consumer, 11(1),
22-7.
Hesse, J.L. (1974), "Water Pollution Aspects of Polybrominated Biphenyl
Production: Results of Initial Surveys in the Pine River in the
Vicinity of St. Louis, Michigan." Presentation to the Govenor's
Great Lakes Regional Interdisciplinary Pesticide Council, October 17.
Hesse, J.L. (1977), Michigan Dept. of Natural Resources, Review
of Gratiot County Landfill Leaching.
Hoof, W. (1972), Ger. Offen, 2.037,510, February 3.
Hoess, E. (1969), U.S. Patent 3,431,221, March 4.
Horm, P. and W. Seydl (1975), Ger. Offen. 2,416,844, October 23.
Jacobs, Lee W. Sheng-Fu Chou and James Mitiedje (1976), "Fate of
Polybrominated Biphenyls (PBBs) in Soils, Persistence and
Plant Uptake," J. Agric. Food Chem. Vol. 26, No.6, 1198-1201.
Jacobs, Lee W. and Alexander B. Filonow, (1976a) J. Agric.
Food Chem. 24 (6) 1198-1204.
Jenker, H. (1966), Ger. Offen. 1,226,780, October 13.
Jenker, H. (1966), U.S. Patent 3,285,965, November 16.
Kerst, A.F. (1976), Michigan Chemical Co., Letter to Mr. Dale Bryson,
Acting Director, Enforcement Division, EPA Region V, Chicago,
111., November 11.
Kerst, A.F. (1977), Michigan Chemical Co., Personal Communication, May 25.
75
-------
Kmopka, W. (1974), Ger. Offen. 2,402,803, August 1.
Knowles, R. (1972), U.S. Patent 3,636,082, January 18.
Koch, P.J., E.M. Pearce, J.A. Lapham, and S.W. Shalaby (1975), "Flame-
Retardant Poly(Ethylene Terephthalate)," J. Appl. Polym. Sci.,
li(l), 227-34.
Lampe, W. (1964), Ger. Offen. 1,169,119, April 30.
Lawson, D. and D. Lahr (1975), U.S. Patent 3,867,327, February 19.
Lindemann, R. and J. Anger (1973), Ger. Offen. 2,262,779, July 12.
Lowenheim, F.A. and M.K. Moran, editors (1975), Faith, Keys, and Clarke's
Industrial Chemicals. 4th Edition, Wiley-Interscience, Inc., New York.
Lunderville, J. (1977), Corry Foam Products, Inc., Personal Communication,
March 24.
McDonald, J.O. (1977), Enforcement Division, Environmental Protection
Agency, "PBB Summary," March 28.
Manos, P. (1970), U.S. Patent 3,390,995.
Mayer, F., J. Kern, and H. Nachbur (1975), Ger. Offen. 2,428,390,
January 23.
Mills, J., R. Furlow, W. Weaver, and J. Gunsher (1972), Ger. Offen.
2,110,601, April 20.
Mischulin, V. (1974), Ger. Offen. 2,352,923, May 2.
Mischulin, V. (1975), U.S. Patent 3,877,974, April 15.
Mitchell, L.C. (1973), U.S. Patent 3,763,248, assigned to Ethyl Corporation,
October 2.
Modern Plastics Encyclopedia (1975) McGraw-Hill, New York, New York.
Moore, D.E., J. F. Mills, and J.A. Schneider (1974), U.S. Patent 3,845,146,
assigned to Dow Chemical Co., October 29.
Murray, R. (1972), U.S. Patent 3,699,077, October 17.
New Jersey State Department of Environmental Protection (1973), Application
for Permit to Install or Alter Control Apparatus, Permit No. P-13213,
Filed October 12.
76
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New Jersey State Department of Environmental Protection (1975), Application
for Permit to Install or Alter Control Apparatus, Permit No. P-21352,
Filed October 28.
New Jersey State Department of Environmental Protection (1976), Application
for Permit to Install or Alter Control Apparatus, Permit No. P-30082,
Filed June 11.
New Jersey State Department of Environmental Protection (1976), Application
for Permit to Install or Later Control Apparatus, Permit No. P-30186,
Filed September 22.
New Jersey State Department of Environmental Protection.(1976), Application
for Permit to Install or Alter Control Apparatus, Permit No. P-30812,
Filed February 3.
Nagy, G. (1970) Ger. Offen. 1,950,607, August 6.
Nicodemus, P. and H. Wilson (1973), U.S. Patent 3,772,455, November 13.
Norris, J.M., J.W. Ehrmantraut, C.L. Gibbons, R.J. Kociba, B.A. Schwetz,
J.Q. Rose, C.G. Humiston, G.L. Jewett, W.B. Crummett, P.J. Gehring,
J.B. Tirsell, and J.S. Brosier (1973), "lexicological and Environmental
Factors Involved in the Selection of Decabromodiphenyl Oxide as a Fire
Retardant Chemical," Appl. Polym. Sci. Symp., No. 22, 195-219.
Norstrom, K. Anderson and C. Happe (1976), "Major Components of Some Bromi-
nated Aromatics used as Flame Retardants" Chemosphere, No.4, 255-261.
O'Keefe, Patrick W. (1977) "Analysis of Environmental Samples for Trace
Components from Polybrominated Biphenyl Fire Retardants". Preliminary
Report.
Parts, L. and J. Miller (1973), U.S. Patent 3,766,157, October 16.
Parts, L. and J. Miller (1974), U.S. Patent 3,825,520.
Perard, R. (1974), Ger. Offen. 2,335,009, January 31.
Plastics World (1976), July 19, 48.
Rossart, N. (1975), Canada Patent 966,259, April 22.
Schlecking, K., R. Wurmb, H. Perzer, and W. Seydl (1976), Ger. Offen.
2,438,402, February 19.
Seydl, W. (1974), Ger. Offen. 2,307,583, July 25.
77
-------
Simplex Wire and Cable Co. (1966), Brit. Patent 1,021,681, March 9.
Stoddard, J.W., O.A. Pickett, C.J. Cicero, and J.H. Saunders (1975),
"Flame-Retarded Nylon Carpets," Tex. Res. J., 45_(6), 474-83.
Touval, I. (1975), U.S. Patent 3,912,792, October 14.
Tyler, G., A. Mahajer, and F. Bell (1974), U.S. Patent 3,839,140, October 1.
Underwood, J., J. Reed, and J. Dix (1974), U.S. Patent 3,850,882, November 26.
U.S. Department of the Army, (1971) Corps of Engineers, Application for
Permit to Discharge in Navigable Waters, Application M1-070-OX5-2-710319,
Filed by Michigan Chemical Co., June 17.
Waterbury, R. (1977), Standard T Chemical Co., Personal Communication,
March 18.
Weiss, J. (1977), K and K Laboratories, Personal Communication, April 19.
Wright, C. and Beachman H. (1972), Ger. Offen. 2,105,188, June 22.
Wurmb, R. and H. Pohlemann (1973), Ger. Offen. 2,226,931, December 13.
Zafran, H. (1977) Solchem Dead Sea Bromine Works, Personal Communication,
April 27.
78
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TECHNICAL REPORT
(Please read Instructions on the reverse
DATA
before completing)
1. REPORT NO.
EPA-560/6-77-017
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Market Input/Output Studies
Task IV
Polybrominated Biphenyls
5. REPORT DATE
August 1977
6. PERFORMING ORGANIZATION COOE
7. AUTHOR(S)
M. Lynne Neufeld, Marcus Sittenfield (Marcus
Sittenfield & Associates^ Kathryn F. Wolk
8. PERFORMING ORGANIZATION REPORT NO.
AAI 2378/2379-104-TR-3
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
AUERBACH Associates, Inc.
121 North Broad Street
Philadelphia, Pa. 19107
(AAI)
11. CONTRACT/GRANT NO.
EPA 68-01-1996
12. SPONSORING AGENCY NAME AND ADDRESS
i
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, B.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Technical Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The recent Michigan incident, in which livestock feed was contaminated by
polybrominated biphenyls (PBBs), prompted this investigation. This report
reviews the technical and commercial history of PBBs and also gives a general
overview of the production, consumption and ultimate fate of these compounds.
A detailed discussion of the manufacturing process and consumption patterns
identifies possible points of entry of PBBs into the environment. A summary
of air emissions, and the technology involved is discussed; and the ultimate
disposal of liquid and solid waste material was investigated. Finally, a
cost/performance analysis of alternative flame retardant is presented.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Polybrominated Biphenyls
Hexabromobiphenyl
Octabromobiphenyl
Chemical Marketing Information
Decabromobiphenyl
Pollution
Environmental fate
Flame Retardants
18. DISTRIBUTION STATEMENT
Document is available to the public throuj;
the National Technical Information Servic<£
Springfield. Virginia 2215L .
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
85
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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