PB-243 690
SURVEY OF INDUSTRIAL PROCESSING DATA
TASK II - POLLUTION POTENTIAL OF POLYBROMINATED BIPHENYLS
MIDWEST RESEARCH INSTITUTE
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
JUNE 1975
DISTRIBUTED BY:
National Technical Information Service
U. S. DEPARTMENT OF COMMERCE
-------
-------
EPA - 560/3-75-004
SURVEY OF INDUSTRIAL PROCESSING DATA
Task II -Pollution Potential of Polybroailnated Biphenyls
JUNE 1975
FINAL REPORT
ENVIRONMENTAL PROTECTION AGENCY-
OFFICE OF TOXIC SUBSTANCES,
4TH AND M STREETS, S.W.
WASHINGTON, D.C. 20460
-------
M.IOCRAPHIC DATA
•2.
EClQfc
Title aifl Subtitle
Surve of Industrial IVocessing Data
Task J.JL - Pollution Potential of Polybromlnated Biphenyls
7. Author(s) Charles E. Mumma
...... Dennis D. Wallace
Performing Organization Name and Address
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
5. Report Date
June 1975
6.
8. Pcrforminr, Ornnnisntiou s\ir-',,
No.
.-J
10. Project/TadfC/Work Unit No.
Task II
68-C1-2105
12. Sponsoring Organization Name and Address
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
13. Typ* of Report
Final to Juna IS?:-
lC-7;'
14.
IS. Supplementary Notes
16. Abstracts
This' study was made to help the EPA evaluate the potential fcr en^jroTr^:.-:-!:^!
contamination by brominated biphenyls. The information collection and eva-luaticr,
activities were designed to identify sources of brominated biphanyls and the
environmental and health effects of these substances. The scope of the ctuciy
included identification and evaluation of production sites and volumes, manufactur-
ing processes and waste disposal practices, commercial uses and substitutes for
products and environmental and health aspects.
17. Key Words and Document Analysis. 17o. Descriptors
Chemistry Engineering
Chemical Manufacturing
Chemicals, Manufacturing, Storage, and Transportation
Hydrocarbons
Industrial Processes aind Processing
Organic Chemistry
17b. Identifiers/Open-Ended Terms
Polybrominated Biphenyls
i7c. COSATI Field/Group chemistry/Organic Chemistry
|2). No. of I
18. Availability Statement
19. Security Cl»i» (Thi«
Report)
UNf I ASSIFIED
20. Security Clans (I ht»
"ORM NTis-39 (REV. io-7ai hNlXjRSKI) MY ANSI AND UNESCO.
THIS FORM MAY UK KKf'KOlMJCKU
3C 1?*S-'-V«
-------
EPA - 560/3^75-004
SIJRVEY OF iNDUSTRIAL PROCESSING DATA
Task II - Pollution Potential of Pblybromihatea Biphenyls
by
Charles E. Murama
D. Wallace
'425 Volk^r
RahsaS 'City, Missouri 64110
'EPA Contract No* #8^61-2105
^r* TJhbtnas $•< Kopp
-For
A'GENGY
r6f TOlEtC ^t&ST
4&I& ft STRE'Ef-Sr, 'S vW'i
-------
PREFACE
This report presents the results of Task II of a project entitled
"Survey of Industrial Processing Data." This study, "Pollution Potential of
Polybrominated Biphenyls," was performed by Midwest Research Institute (MRI)
under Contract No. 68-01-2105 for the Office of Toxic Substances of the
U.S. Environmental Protection Agency. The MRI Project No. was 3822-C.
This study was conducted from 1 December 1974 to 6 June 1975 under
the supervision of Dr. E. W. Lawless, Head, Technology Assessment Section.
Mr. C. E, Muraraa, Senior Chemical Engineer, served as project leader. Other
MRI personnel who contributed significantly to this study include Mr. D.
Wallace, Junior Analyst, and Mr. D. Punzak, Junior Chemical Engineer.
The final report for this study was prepared by Mr. Murama and
Mr Wallace with assistance from Dr. Lawless.
Approved for:
MIDWEST RESEARCH INSTITUTE
rector
Physical Sciences Division
10 July 1975
-------
TABLE OP CONTENTS
Page
I. Introduction 1
II. Summary 3
III. Conclusions 8
IV. Discussion of Methodology , 9
A. Selection of Toxic Substances 9
B. Identification of Production Sites and Volumes 9
C. Manufacturing Processes 10
D. Waste Disposal Practices 10
E. Commercial Uses and Substitutes for PBB Products .... 10
F. Environmental and Health Aspects of PBB's 10
V. Production Sites and Volumes ............ 11
A. Commercial Producers 11
B. Suppliers of Laboratory Quantities 11
VI. Manufacturing Methods, By-Products, and Contamination Risks. . 14
A. Introduction 14
B. Manufacturing Methods Discussed in Patent Literature . . 14
C. Description of the Michigan Animal Feed Contamination
Incident 16
D. Water Pollution Aspects of Polybrominated Biphenyl
Production 20
VII. Waste Disposal Practices in Manufacturing Operations 22
A. Introduction 22
B. Discussion of Waste Disposal Practices at Michigan
Chemical Corporation Plant 23
VIII. Commercial Uses for PBB's and Related Compounds 32
A. Introduction 32
B. Existing Uses 32
C. Potential Uses 35
D. Brominated Substitutes for PBB's 38
Preceding page blank
-------
TABLE OF .CONTENTS (Concluded)
IX. Health and Environmental Aspects. 40
A. Introduction. ....... , 40
B. Health Aspects. . 40
C. Environmental Aspects 43
References. . . 46
LIST OF FIGURES
No. Title Page
1 Waste Discharge Flowsheet for Outfall 002—Michigan
Chemical Corporation. .......... ... . 25
2 Waste Pischarge Flowsheet for .Outfall 014—Michigan
Chemical Corporation. .................. 27
3 Waste •Discharge Flowsheet for Outfall 013—Michigan
Chemical Corporation.. 28
4 Waste •Pischarge Flowsheet for Outfalls 005 and 006—Michigan
Chemical Corporation. ............ 30
LIST OF TABLES
No. Title Page
I Domestic Pro,duc,tipn Data for Brpminated Biphenyls 12
II ppjmestic Suppliers pf Laboratory Quantities of Brominated
Biphenyls'] 13
f If Brpjninafion pf Bighenyl 17
IV Was^te Discharge :Pa|:a for MichiRan .Chemical Corporation
Manufacturing .Facility at St". Loui.s, .Michigan 24
Y Current Domesitijc Us^es for Ffremaster BP-,6 > 33
vi
-------
-y-
I. INTRODUCTION
Polybrominated biphenyls (PBB's) are a class of chemicals first
produced in the U.S. in commercial quantities in 1970, about 40 years after
introduction of their chlorinated analogues, the PCB's. The PBB's have been
produced domestically on a limited scale for use as flame-retardant additives
in commercial plastic products. Some of these products have toxic properties
and are, therefore, sold only for applications in which the end-use product
is not exposed to any food materials or contained in any fabrics subject to
human exposure.
The PBB's which have been produced domestically include Firemaster
BP-6, octabromobiphenyl and decabromobiphenyl. The structure and chemical
composition of these products are as followst
Firemaster BP-6
General structure
n + m — 6
Composit ioni BP-6 is a mixture of brominated biphenyls (i.e.,
tetra-, penta-, hexa-, hepta-, and others) with an average hexabromobiphenyl
content of about 637.. Several structural isomers of each of these brominated
biphenyls are possible and probably present in BP-6.
Octabromobiphenyl
General structure
Rv
n + m = 8
De cabromob ipheny1
General structure
Br Br Br Br
Bromine content, 82%
minimum
-------
During the spring of 1973 a, quantity of a polybrorainated biphenyl,
produced for use as a fire-retardant chemical, was mistaken for a feed-
supplement (magneslura oxide), and inadvertently added to dairy cattle feed
in Michigan. Grpssr.contamination of other animal feeds subsequently occurred
in feed mi^ls and this accidental contamination caused much public concern
about PBB1 s,. By June 1974, the accidental contamination of cattle had spread
to 20 dairy herds in Michigan, and the EDA was testing cheese, butter and
condensed milk for- brominated biphenyl residues.—' In 1974, dairy cows and
milk were sampled in Michigan and eight other states for yiolative PBB res-
idues by the USDA and the FDA.I/ In February 1975, it was reported that
large numbers of Michigan farm animals and food products contaminated with
PBB had been destroyed and buried.!/ As a result of this incident. Farm
Bureau Services, Michigan Chemical Corporation, and their insurers spent
or committed $11.5 million to pay damage claims,!/ and litigation was un-
derway in ^ebruary 1975 to the extent of about $275 million.
Because of this recent incident of PBB contamination and concern
about the potential environmental and health hazards of these substances,
the Office of Tpxic Substances, EPA, directed MRI to undertake this study
on 1 December 1974. Much of the. effort was designed to identify possible
sources and effects of brpminated biphenyl compounds in the environment.
The scope of work fpr this task included the following major ac-
tivities:
1. Identification of production sites and estimation of produc-
tion volumes.
2. Characterization pf manufacturing processes, by-products,
contamination,, and risks,,
3,. Characterization qf waste disposal practices used in manufac-
turing operations.
'-• — --..." «\*J, V ** »v l> "' •• ',• V*-*--'*" »
^. ^Ascriptions of uses, and substitutes for brominated biphenyl
products.
\" '• ~v. *.*» fir \ T»* ~
5. D(e script ions $f environmfntal and health aspects,
fhe following sections, of this repprt discuss methodology and the
FeJ»|ts; o.bta.itje^ in, eacfe mgjqr ^ctiyity.
-------
II. SUMMARY
A class of chemicals, known as polybrominated biphenyls (PBB's),
has been produced domestically on a limited scale for use as flame-retardant
additives in plastic products. Until recently, the commercial PBB's were
Firemaster BP-6 (a mixture of brominated biphenyls with various structural
isomers of hexabromobiphenyl as the principal constituents), octabromobi-
phenyl and decabromobiphenyl. The bromine content of these products ranges
from about 63% for BP-6 to about 82% for decabromobiphenyl. The structure
of BP-6, the principal PBB product in the U.S., is as followsi
n + m
In addition to the three commercial PBB products, laboratory (kilo-
gram) quantities of monobromobiphenyl and dibromobiphenyl are also sold by
domestic suppliers.
Firemaster BP-6 was involved in an animal-feed contamination inci-
dent in Michigan in 1973, when it was mistaken for a feed-supplement (mag-
nesium oxide) and inadvertently added to dairy cattle feed. This incident
caused an agricultural calamity in the state, and stimulated research studies
of the potential environmental and health hazards of PBB's.
The present study, conducted during the period of 1 December 1974
to 6 June 1975, was made to help the EPA evaluate the potential for environ-
mental contamination by brominated biphenyls.
The information collection and evaluation activities were designed
to identify sources of brominated biphenyls and the environmental and health
effects of these substances.
The scope of the study included identification and evaluation of
production sites and volumes, manufacturing processes and waste disposal
practices, commercial uses and substitutes for products and environmental
and health aspects.
Sources of information for the project team included several stand-
ard reference publications, technical literature for the chemical process
Industry and telephone and letter inquiries to producers, consumers, and
government agencies.
-------
the major findings in this study are briefly described in the fol-
lowing subsections.
1. Chemical product ion vo lumes , sites . and manufacturers t During
the last decade, only two domestic chemical companies produced brominated bi-
phenyl compounds oh a commercial basis. Commercial production started in 1970
and was discontinued in 1974, apparently because of one contamination incident
and the ridk of other environmental or health hazards, these companies, their
production sites, and the compounds of interest they formerly produced, aret
* Michigan Chemical Corporation (a subsidiary of Northwest in-
dustries) at St. Louis, Michigan, produced Firemaster BP-6, a
mixture of polybrominated biphenyls consisting principally of
hexabrombblphenyl. A company spokesman has reported that this
plant was shut down in November 1974, and that inventory stocks
of BP-6 were still being sold In April 1975.*/
* White Chemical Corporation at Bayonne, New Jersey, produced
octabromobiphenyl and decabromobiphenyl. According to a com-
pany spokesman, this production was discontinued In 1973 .A/
Michigan Chemical produced a total of about 5,088,435 kg Of Fire-
master BP-6, during the period of 1970 to 1975, A/ and White Chemical Corpora-
tion produced about 45,350 kg of octabfomobiphenyl plus decabromobiphenyl
from 1970 to
there ate about nine domestic chemical suppliers of brominated bi-
phenyls who have either custom-produced or imported small quantities of these
chemicals sometime during the last 10 years. The annual sales volume for any
one supplier is reported to be a maximum Of about 2 kg/year, the principal
products life monobromobiphenyl and dibromobiphehyl.
NO evidence Was found that significant quantities of brominated
blpheriyls ire imported into the uYSij imports apparently amount to kilogram
quantities at most.
2, rtanufactutihg processes that produce brominated biphenyls t In-
formation on production methods was not available from domestic producers
because the companies coiisi'der such operations to be proprietary. A survey
of patent literature provided some detailed data on manufacturing processes.
The U.S. patents 6f interest to this study describe preparation methods which
involve reaction of blphehyl with bromine (Br^) or bromine chloride (BrCl)
in the presence of a catalyst* the major by-products are hydrogen bromide
and/or hydrogen chloride.
PBB's may also be unintentionally produced in the manufacture of
othar br-oMri'&'t'Sfd carbon compounds, as discussed in the next subsection of
this summary* but definitive data ate
-------
3. Waste disposal In manufacturing PBB's* In May 1975, the Per-
mit Branch of EPA provided MRI with copies of all permit application data
for waste disposal by the Michigan Chemical Corporation at their St. Louis,
Michigan, plant.£/ MRI has evaluated these data, as well as information re-
ported for a water pollution study of the same facility conducted by the
Michigan Bureau of Water Management. Results of this evaluation show that
measurable quantities of PBB's (0.1 to 104 pg/liter) are contained in the
waste outfalls from manufacturing facilities which are not associated with
the direct production of PBB's and from one facility associated with PBB
manufacture. A preliminary assessment by MRI indicates that some probable
sources of PBB generation in these manufacturing operations ares
* The recovery and reuse of bromine from by-product hydrogen
bromide (HBr) that is contaminated with PBB's.
D * The coupling of molecules of polybromobenzenes in the produc-
tion of hexabromobenzene.
* The bromination of biphenyl present as an impurity in biphenol
A feed materials.
* Losses to waste of some PBB's directly produced in the manu-
facture of Firemaster BP-6,
Results of the water pollution study showed that measurable con-
centrations of PBB's were present in river water samples and in fish samples
taken 12.9 km downstream from the plant (i.e., 0.01 to 3.2 jig/liter for
river water and 0.09 to 1.33 ppm in fish).
4, Commercial uses and substitutes for PBB's; Recent uses for
Firemaster BP-6, the principal PBB compound produced domestically, are shown
in the tabulation on the following page.
MRI Identified two major domestic consumers of BP-6i Borg-Warner
Corporation and Standard T Chemical Company. For all applications, BP-6 is
thoroughly blended Into various plastic resins at temperatures above the
melting point of the PBB mixture. These impregnated resins are subsequently
used to fabricate various plastic products. In all cases, the BP-6 serves
solely as a fire retardant. The plastic manufacturers report that there are
no by-products or waste streams associated with their processes for blending
BP-6 into ABS (acrylonitrile-butadiene-styrene) resins.
One of the major consumers, Borg-Warner Corporation, recently re-
ported—' that it is now in the process of completely phasing out its use of
Firemaster BP-6 and will soon start using substitute products.
-------
,CUftJUEHf..<:B(3HECTlG. USES TOR. FiREMAJSTER BE-6~
JhdustjrV
Business machines
and industrial
equipment
Electrical
Fabricated products
transpd rtation
Approximate
Allocation of
total
Hreraaster BP-6
... Produced..(%)....
48
35
12
MlsceiianedUs
Examples
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.
Hisceiiaheous small automotive
parts' i*e*, electrical Wire con-
nectors, switch connectors, speaker
s.
Small parts fbr electrical appli-
cations, motor housings, components
for industrial equipmant^
-------
A potential product of interest is a flame and moisture resistant
material that contains PBB's, rubber, alumina, halogenated phthaiic anhydride,
and antimony trioxide, and can be used to impregnate fibrous-insulating mate-
rials (e.g., for cables or wires used in dishwashers and clothes dryers).£/
The company granted this patent has indicated that no wire or cable insula-
tion is being produced by this method. Another potential use is disclosed in
a patent covering the production of smoke retardant styrene polymers with
octabromobiphenyl.!/ The company owning this patent has indicated that none
of its AfiS products has reached the commercial stage.lH/ Polyurea shrink-
resistant coatings for wool can be made flame resistant by addition of large
quantities of hexabroraobiphenyl.il/
One former PBB producer has suggested that decabromobiphenyl can
be used as a flame retardant for polyethylene, polypropylene, polycarbonates,
polyester fibers, polyester resin, and polyamide fibers.ll/ The same producer
has indicated that hexabromobiphenyl can be used as a flame retardant for
polyurethane foams and synthetic lattices.
Two of the most promising potential substitutes for PBB products
are decabromobiphenyl oxide (DBBO) and a halogenated aliphatic compound.
Both of these compounds currently sell at a significantly higher price than.
Firemaster BP-6. Both substitutes appear to be significantly less toxic than
PBB's.
5. Environmental and health aspects of PBB's; Studies of biologi-
cal effects of PBB's have been directed to three basic areas. First, acute
toxicity has been investigated in several different animals. Second, studies
have been made on the effects on animal reproduction. The third type of study
has dealt with retention and paths for excretion of PBB's in various animals.
The results to date indicate that PBB's have a low acute toxicity. PBB's
have shown adverse effects on animal reproduction and a tendency to accumu-
late in fatty tissues. Adverse effects on organs (especially the liver) have
also been attributed to these compounds*
-------
III.. CONCLUSIONS
The following- conclusions, drawn on the basis, of findings in this
study, are arranged' in, the same general order as the sections of the study.
l.f In November, 1974, the only domestic commercial manufacturer
of PBB't stopped; production of these compounds.il/ At present (May 1975) no
U.,S. company produces, these chemicals commercially, and; it. appears to be un-
likely that: domestic production will be resumed in the near future.
2,, Data recently developed in a water pollution study by the
Michigan Bur.eau. o,f Wa.ter Management (for a plant which manufactures PBB's)
indicate* that some, unidentified chemical; production processes not related
to direct production, of PBBi's. can generate measurable quantities of PBB's
in liquid wa/pte streams,. The- exact. cause: of this. PBB generation is unknown,
but toot* pot,entta.t PBB sources, have been identified by MRI (Section V,
P. 22),.,
3., The potential: f:OT; water, pollution by PBB's appears, to be re-
lated p.rima:r,ily t,o, Rrodu.ct.ion and* formulation: process.es rather than to usage
and disposal* of plastic products: containing these compounds.—'
4., Domes tie, manufacturing, sites at which PBB's are used as. raw
material:' f.oi? plastic forraulaitions and; manufacture of various thermoplastic
products *rei potential- so.urc.es of waste materials containing PBB's. Ap-
parent ly> none, off the«e »ttes; has. been monitored for PBB's to date to deter-
mine any poss.ible. environmental pollution.—'
5., Thft p:r;incipa>l: use. of PBB;.'s: in, the U..S. has been as a fire-
r«ta;rdan.t, adjd-ifeiye, in, thermoplastic; products.M/ In these applications, the
product.* do: not: come; into, contact with human food or clothing. There are no
a£pA;ieafei\oi'M»j fo,^- PJlBj'*; ^Sje^tiip^VI,, p:.. 32;).
6.>., The,; p.p.ese.nft use.i of" P-BB;,''s,; solely from inventory supplies,, is
b.ectng. pha:sedj oust. b>y/ the. li^r.gest. dpmesttc consumer in favor of the use of sub-
sti;tufe.e,, ftref-r.etardant produ.cts. which: are. I'ess: toxic>^' The generally higher
product, prices fo^- these, substitutes; are a deterrent to this transition.
7., Re.SiU.l't.s: o4; b-ijo.logicft.1 st.u.d-ies; t;O: date indicate that PBB''s have
a- low? acute tQXic.iiity,} (e^.g;.,,, s.tudi.e.s. of aAM.te> oca!, toxicity show an acute
tPjjQ, Q,f about 21... 5 g/kg-X^ e.an, bioaccumulate. in; fatty, tissues, and can cause
advecte , e€f3Wl*A o.nt «a-Jl(Mfe4 o«gjan,%c e,s|?eci»ijl^ thfr liver (Sect ion. VII, P. 40).
-------
IV. DISCUSSION OF METHODOLOGY
A study was made to develop information on the potential hazards
to man and the environment associated with the production and use of the
class of chemicals known as brominated biphenyls. A discussion of the major
steps in the study follows.
A. Selection of Toxic Substances
The EPA task officer specified the class of chemicals known as
brominated biphenyls as the subject for investigation. Polybrominated bi-
phenyls (PBB's) are the only brominated biphenyls produced and used com-
mercially to any significant extent, and the investigation was concentrated
on them.
B. Identification of Production Sites and Volumes
1. Production sites; The domestic production sites for brominated
biphenyls were identified using several standard reference publications, in-
cluding the following:
* Ghent Sources - USA, Directories Publishing Company, Inc.,
Flemlngton, New Jersey (1975).
* "Directory of Chemical Producers," Stanford Research Institute,
Menlo Park, California, 1974 and 1975 editions.
* Chemical Week. 1973 Buyer's Guide Issue, McGraw Hill Publishing
Company (1973).
In some cases, letter and telephone inquiries were made to confirm
information derived from these reference publications.
2. Production capacity, production volumes, and imports; The
available information of this type In the published literature was very meager.
Most of these data were obtained by letter and telephone inquiries to specific
chemical producers or distributors, trade organizations, and the U.S. Customs
Bureau (Washington, D.C.).
-------
C. Manufacturing Processes
Most of the information on domestic production technology for bromi-
nated biphenyls. was obtained by a survey of the U.S.. patent literature. A
limited amount of data were obtained by telephone and written inquiries to
chemical producers. A search of the chemical abstracts was made covering the
period 1963 to 1974j; very little' useful information was found concerning com-
mercial production methods for brominated biphenyls.
&• Waste Disposal Practices
The; principal source of data on this subject was a copy of the waste
discharge, permit application submitted by Michigan Chemical Corporation to
the Michigan Water Resources Commission. Michigan Chemical Corporation was
selected as, the source because this corporation was the sole U.S. producer
of PBB's from 1973, until November 1974j at this, latter date their PBB plant
was shutdown indefinitely, and at present (May 1975) no domestic plant pro-
duces PBB's on a corarnercial basis..
Data furnished in this permit were used as the basis for a descrip-
tion and evaluation of waste disposal practices utilized in manufacturing
operations.
E. Commercial! Uses and Substitutes for; PBB Products
InfonMtion concerning t^e exist ing and potential commercial uses
for brominated biphenyl products) and substitute products was acquired largely
by telephone cpjit^ct%wlt^
F-> Environmental and Health Aspects of PBB's
Data on physl^a:! and chemical properties, the environmental fate
q,f products, and; to^icityj Aspect s. were obtained from personal communications
with producers and cpnj8,ujjie£gr end; • fcr.oro. pjubl^s^ed and unpublished technical
literature.
10
-------
V. PRODUCTION SITES AND VOLUMES
This section provides a brief synopsis of plant locations and pro-
duction volumes for broroinated biphenyl compounds. A list of individual plant
sites and production volumes, together with annual gross production for the
last 10 years, is presented.
A. Commercial Producers
During the last decade, only two domestic chemical companies pro-
duced brominated biphenyl compounds in commercial quantities. (Commercial
production in the U.S. was started in 1970.) these companies and their PPB
products ares
* Michigan Chemical Corporation (a subsidiary of Northwest In-
dustries) at St. Louis, Michigan. Firemaster BP-6 is the only
biphenyl derivative produced by this corporation. The major
constituent in BP-6 is hexabromobiphenyl.
* White Chemical Corporation at Bayonne, New Jersey. Octabromo-
biphenyl and decabromobiphenyl have been produced by this
corporation.
In May 1975, brominated biphenyls were not being produced on a commercial
basis by any domestic manufacturers.
Production data for commercial PBB producers are shown in Table I.
These data show that during the period of 1970 to 1975, Michigan Chemical
produced a total of about 5,088,435 kg of Firemaster BP-6 and White Chemical
Corporation produced about 45,350 kg of octabromobiphenyl plus decabromobi-
phenyl. The estimated total production of PBB's during this period is
5,133,785 kg (or 5,660 short tons). The available data indicate that PBB's
were not produced domestically on a commercial basis prior to 1970. PBB's
were not commercially produced in the U.S. from 1 January to June 1975 and
it appears unlikely that any U.S. company will produce these chemicals dur-
ing the period of 1975 to 1978 (MRI projection, based on private communica-
tions with former producers of PBB's).4^57
B. Suppliers of Laboratory Quantities
MRI identified nine domestic chemical suppliers who supply bromi-
nated biphenyls, and who have either produced or have imported laboratory
quantities at certain periods during the last decade. Private communications
with some of these suppliers indicate that the maximum production or importa-
tion of brominated biphenyls for each organization has been about 2 kg/year,
"11
-------
TABLE I
DOMESTIC PRODUCTION DATA FOR BROMINATED BIPHENYLS-
Chemical Products.
•»->t.V'-'*rCy-/AO-«t.y>
Producer and; Location.
Year
(a; subsidiary, of Northwest:
Induftriea), St. Louis,, Michigan 1971
" " ' *"'" ' "" ' "" ' 197-2
White Chemical Corporation
and l>ecabroiapbiphe.nyl Baypnne,, New. Jersey
1974
1975
19j65-1970
19b70rl973
1974
1975
1976-1978
Production,,
Quantity
(kg>
None
9>Q70
90,703
1,043,084
1,768;, 707.
2,176,871
None
None
None
45,350
None
None
None
Comments
MRI projection^
MRI projection
projection
MRI projection
Estimated total U.S. production 1965-1975
5,133,785
-------
and that the products are prepared only on a custom synthesis basis* **•"
Thus, the total PBB quantity involved for these suppliers is considered to
be negligible compared to the volume of domestic commercial producers. A
list of these suppliers is shown in Table II.
TABLE II
DOMESTIC SUPPLIERS OF LABORATORY QUANTITIES
OF BROMINATED BIPHENYLSa.
Company
Fine Organics
Biochemical Laboratories, Inc.
Eastern Chemical
Chemical Samples Company
Columbia Organic Chemical Company
K&K Laboratories
Fairfield Chemical Company
Ethyl Corporation
Research Organic/Inorganic
Chemical Corporation
Location
Lodi, New Jersey
Hawthorne, California
Hauppage, New York
Columbus, Ohio
Columbia, South Carolina
Plainview, New York
Blythewood, South Carolina
Baton Rouge, Louisiana
Belleville, New Jersey
Companies which had a capability to produce kilogram quantities of
brominated biphenyls during the last decade. Some of these companies
apparently never produced these chemicals.
The available data indicate that there are no significant imports
of brominated biphenyl compounds!!' (i.e., the total imports apparently amount
to only kilogram quantities).
13
-------
VI. MANUFACTURING METHODS. BY-PRODUCTS. AND CONTAMINATION RISKS
A. Introduction
The following discussion covers the basic process technology for
commercial production of polybrominated biphenyls (PBB's), including poten-
tial sources of environmental contamination by PBB's. The first subsection
discusses, In a general manner, the operating parameters that affect the
production of these chemicals as by-products or wastes. The principal source
of information on production technology was the U.S. patent literature. The
second and third subsections describe the recent Michigan animal feed con-
tamination incident and a study by the Michigan Bureau of Wat^r Management
of water pollution in the area of the Michigan Chemical Corporation plant at
St. Louis, Michigan.
Until recently (see Section III), two domestic chemical companies,
Michigan Chemical Corporation and White Chemical Corporation, produced com-
mercial quantities of PBB's. No evidence was found of any current (1975)
produce ion of PBB's in the U.S. Spokesmen for these two companies have re-
ported that the actual production processes used are proprietary; therefore,
only general information was obtained from these sources concerning process
technology. Michigan Chemical Corporation has indicated that there are no
patents covering manufacture of their only PBB product, Firemaster BP-6.
Information provided by a private communication!!/ indicates that the by-
product hydrogen bromide (HBr) formed during production of Firemaster BP-6
is contaminated with PBB's, and that much of this HBr is processed to recover
bromine for use as a raw material in the same plant.
A description of production processes identified in the patent lit-
erature it given in the following subsection*
B. Manufacturing Methods Discussed in Patent.Literature
The Dow Chemical Company was issued a patent in 1974 concerning,
among other reactions, bromination of biphenyl with bromine chloride under
pressure to produce a product Containing five or six bromine atoms on each
ardmatic ring..187 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 hear autogenous pressure to obtain rapid
polybromination of the ardmatic nucleus. The reaction may suitably be con-
ducted at about room temperature, and is completed in a few hours, with
yields in excess of 807. generally being obtained.
-------
Bromine chloride is prepared by missing equal salar amounts of bromine
and chlorine in & closed contain®?; Che broain© chloride fclhus f©m®d is, with°
drawn from the liquid phase in Che vessoL
Decabromobiphenylp in addition Co 3 lower polybrominated product;,
is prepared by adding a catalyse (aluminum chloride) and biphenyl to a batch
reactorp and then slowly adding bromine chloride in 0 to 20% stoichioiaetric
esscessc, For esamplefl 10 to 12 moles of bromine chloride may be s-oacesd with
each mole of biphenyU
As the bromine chloride reacts with biphenylp the hydrogen chlor-
ide formed as by-product is retained in the reactor under essentially auto-
genous pressure<> The pressure may range from 10 to 200 psig during the course
of the reactions The reaction temperature is not critical; the temperature
may range from 10 to 150°C0 A solvent,, such as methylene chloride,, may be
used gin the reaction^ although good conversions and yields are obtained by
using excess bromine chloride as the solvento Best results are obtained when
the reactor is operated under essentially anhydrous conditions! water ap-
parently deactivates the catalyst^ Essentially complete broraination is gene-
rally obtained within a few hourSo After the reaction^ the solid products are
separated from the methylene chloride solvents The advantages claimed for this
process include high product yields^ low yields of chlorinated compounds0 short
reaction periods,, and efficient utilization of bromine<,
A patent issued to the Ethyl Corporation in 1973 concerns an improved
method for producing polybrominated aromaticSoil/ This process involves react-
ing an aromatic compound with bromine in the presence of a halogenated catalyst
and solvent quantities of methylene bromide at a temperature sufficient to
sustain a rapid reaction srat®0 The invention is applicable to a large variety
of aromatic compounds5 however^ biphenyl is the most preferred compound,,
The preferred amounts of bromine utilized in this process are from .
7 to about 9 moles of bromine per mole of biphenylo The reaction of bromine
with biphenyl is usually conducted in the liquid phase,, and is initially exo-
ChermiCo A preferred reaction temperature range is from room temperature to
100°Co The amount of catalyst required depends on the desired degree of bromi-
nation<, The catalyst (aluminum chloride or aluminum bromide) is generally sup=
plied to the reaction mixture in amounts of from 0000i to 0<>007 mole/mole of
bromineo The use of solvent quantities of methylene bromide allows the reac-
tion to proceed to the point of producing highly brominated biphenylp without
the product becoming a solid or agglomerating and preventing further bromine-
tion<> Generally,, sufficient solvent is required to maintain the reactants
and brominated products in an adequate homogeneous reaction mixture0 The pre-
ferred ratio of solvent to aromatic compound is about 10 or ISsl (moles per
ssole)0 Although reaction time is not critical; the preferred reaction time
is fro® about 2 to 10 hr0 Hydrogen bromide is famed as a by°producto
-------
The product consists of polybrominated biphenyl In tho solvent with
b^Qsain® and': smalt, amo.unts of catalyst and. partially 1 • v> <'inated bi=
. fch®; desired? degree of broraination is obtained^ the ..saction is
stopped' by. cooling; and- successively washing the reaction mixture *-lth acid;,
t-hen a..l'ka-1-iip, and; flnal-ly. water .•«,. The organic portion of these washings is dried
b> adding.; sod'iura, su.Lfate.o. The drying agent is removed by filtration and the
solvent 10' stripped to r@cov.er a crude product 0 This product can be recrystal-
1'ised' from sol'v.ent 05 washed with solvent; followed by solvent stripping in
an-. e.v«j>o.-Bafco-?i>j depending upon the product purity required,, Gas evolved during
the. reaction. can. be scrubbed: with a caustic soda solution to remove noxious
chemicals., before being, vented to the atmosphere,, Example quantities of sreaefc-
ants,,, operating conditions;, and results claimed for this patented process as:®
sunsaarized in Tab.le
Cheraische Fa.br.lk. Kalb, G0m0b0H0!). Cologne-Kalkj, Germanys obtained a
UcSo, patent, in. 1966 for, a- process, of bromination of aromatic compound s0 es°
peclally di$>henyl.[,. diphenyl ether.B and mixtures thereof 0J2/ The bromination
pro.ces.s is;!carried; out at 20 to 650C9, using loOl to 102 g=atoms of bromine
per grara=atpra of hydrogen which, is being substituted, and a quantity of
chlorine whrichp; at mostp. is equiinolar with re.sp.ect to the bromine,, The prod-
uct^;, contain a.t: least 4 atoms, of bromine per mole of aromatic compound used
as, a raw ma,te^ial'0. Eo.ll'owing. comp.l;etion: of the. bromination react ion p a quan-
tit.y. of; an> alkylsne; C-Co-g^o. ethylene or- propyl'ene). is added to the reaction
mixture to bind-: the. free-. br.Qmine with the formation of the corresponding
a:lky.l:ene, di;bromide0, A. mo.di-fiicsfcion of the process involves the use of alky=
l;en®; bs-omidb a$. e- solvent „,
e: of the. application- of this process for preparation of
lenyl5 i'S; des;crlb.e.d} in: this patentOx Diphenyl (308 parts by weight)
£ in-. 800? p,a,rt;s of e_thylene bromide and 4 parts of iron powder are
addtsd these6.o>.. Th«wDj 1:0.430) parts of bromine and 632 parts of chlorine were
introduced' int.o- the' mixture- wi-th; vigorous stirring over a period of ©bout 2
Kr.,0. During, She; ad/dit.i'on.: of bromine and- chl'orinep the temperature of the reac°
tipn. mixture ranged; f x-pra; 20? to 60°'Ce, After &h.e bromination had been completedp
the, e.KC,es;S; dromtne.- epnteined? in the. reaction mixture was bound by ad4ing
ethylene: to fptrni-, e^h^l-ene: dibromideo The; pasty reaction mixture was filteredp
and the; e£hy(lene, dibsr.pmtde- obtained^ as filtrate was suitable for reuse as sol°
The fi,lite.E- eake wa;S,-wa.sh;ed; with, ethanpl; and dried0 The dried solid
contained] I.fc7.4,0: Ba^tS; o;f pctabroraodiphenyl containing 80,9% of bro-
mine. and; to,5%, pf Qhtarinia?., This^ p,rp.dii.ct. yield was 9305% of theoretica.lo
BiBiS.cgiigfttQq. o.g the M(t'ch>i;ga-CT; An&vail; Ifeed Contamination Incident
The. refii^n*, a£C;£4J)[. c.o.nfeamina£i;pn. of ariiiJna-1 feed; and livestock
thro.ugho;u&. Kit.Ghl:g>aR-, w.iith- pQ.l-ybroraIna£ed biphenyl fire retardant stimulated
' o£' re.aas,-!?eh: &£.u,d;i'e,s;^ including an eva-luaEion; of the poteiatiel for
0iEo4u?e.'6ifp,n; af FBB:.8;?.— »ss.' ^e.i;l 'w scudies. of fctoe
1*
-------
TABLE III
19/
BROMIHATION OF BIPHEMYL—
Reactants (Parts
Example
Ho.
1
2
3
4
5
6
7
(Wi
17.8
17.8
17.8
17.8
17.6
17,8
17.8
Br2
122
122
157
161
169
184
175
197
187
200
200
250
267.5
250
by Weight)
Catalyst
0.88 AlBr3
0.99 AlBr3
1.12 A1C13
0.60 A1C13
0.38 AlCLj
1.93 A1C13
0.99 A1C13
Conditions
Br2
Equiv-
alent*/
9.2
9.2
8.5
8.75
9.2
10.0
9.5
Time
(hr)
7.2
4.3
2.5
3.0
2.75
4.0
2.1
Temp.
25-85
25-98.5
25-95
25-95
25-95
25-95
25-95
Weight
(parts)
97.7
98.2
85.3
95.0
96.5
95.5
100.0
Products
Avg.
Br2
Number^/
8.69
8.75
8.4
8.41
8.53
8.85
8.9
Weight
Percent
Br
81.0
80.3
80.0
79.4
79.6
81.6
82.2
Percent Yield
Based on Avg.
Br Number
'Quantitative
Quantitative
90.4
Quantitative
Quantitative
97.4
Quantitative
&/ Br2 equivalents are number of Br atoms available for reaction with biphenyl from Br2 charged; calculated by dividing moles of Br2
by moles of (C6H5)2.
b/ Average bromine number determined by VPC; certain peaks assumed to be hepta-, octa-, nona-, and decabromobiphenyl based on retention
tiiee. Area percent used for calculations.
-------
and biological properties of this class of chemicals. Because of the public
concern resulting front this contamination, a detailed description of the
Michigan animal feed contamination incident is included here.
Some Michigan farm crops (e.g., corn silage) commonly used in the
feed rations for dairy cattle have relatively low contents of magnesiurn--a
desirable element in the feed. Therefore, it is a common practice in Michigan
feed mills to supplement dairy cattle feed concentrates with purchased mag-
nesium oxide powder.
The Michigan Chemical Corporation of St. Louis, Michigan, is one
supplier of magnesium oxide feed supplement to cattle feed mills throughout
Michigan and in some other states. This corporation also manufactures a num-
ber of other chemicals, including Firemaster BP-6, a fire retardant product
containing a mixture of PBB's. Firemaster BP-6 is a powdery product similar
in appearance to magnesium oxide powder.i'
For a number of years, magnesium oxide and Firemaster BP-6 were
bagged by Michigan Chemical in labeled paper bags with distinctive colors.
During the spring of 1973, however, a paper shortage developed and the bag
supplier could* no longer deliver both types; Michigan Chemical then began
using the same type of colored bag for packaging its Firemaster BP-6 and
magnesium oxide. Both materials were still being manufactured, bagged, and
labeled correctly. Then during transfer of some of the filled bags to a com-
pany warehouse, a fork lift operator apparently failed to identify correctly
his cargo, and bags of both types of products, were accidentally stacked to-
gether in a storage area. When the Michigan Farm Bureau subsequently ordered
magnesium oxide from Michigan Chemical, the shipment was made from the stacks
of mixed products. After delivery to the Farm Bureau, the material was either
used ia local feed- mills or shipped out to satellite mills for incorporation
into cattle feed. This cattle feed' was widely distributed and used by Michigan
farmers. Subsequently, cross-contamination of other animal feeds with Fire-
master BP-6 occurred in these mills and thus the contamination was spread to
11' /
other farm animals.£i'
Information on one Michigan dairy herdl±' indicates that the con-
taminated feed; supplement was incorporated into a pelleted feed product at
the rate of 4 kg/M$. Thus> the maximum concentration of BP-6, which could
have been present in the contaminated feed, was, probably about 400 ppm.
This incident of accidental contamination of animal feeds resulted
in several' adverse environmental and health effects; some of these effects
have not yet; been: fuMy identified and assessed.
-------
A recent technical article reports on s syndrome of acute to chronic
toxicosis associated with feed contamination in one Michigan dairy herdoU/
Clinical signs of PBB contamination in the cows included an initial fflasHssd
decrease in milk production and feed consumption,, followed by development of
abscesses and heroatomasc Liver lesions were one of the most commonly reported
pathological changes,, and the results indicated that PBB in the diet of cows
can adversely effect their reproductive organs,, Concentrations of PBB°s in
tissues from two cows that had consumed contaminated feed ranged from 84 ppm
in kidney fee to 310 ppm in liver fats the concentration in milk fat ranged
from 43 to 56 ppra0J2/
Although cattle began getting sick in October 19730 PBB was not
identified as the cause until April 1974.— Not all of the contaminated ani-
mals died or even got sickp but all suspect animals and their products were
quarantined by state officials and could not be sold. In Hay 19740 more than
30 Michigan dairy herds were quarantined by the State Department of Agricul-
ture/ and the owners were unable to sell milk or meat or to dispose of dead
animals from their farms. By July 1974,, 92 food producing premises .in Michigan
were under quarantine; 44 of these involved cattle and the remainder involved
poultry and swine. Starting in 1974P the FDA tested cheese^ butter and con-
densed milk for brominated biphenyl residues,.—' \
In June 1974,, dairy cows and milk were being sampled in Ohiop
Wisconsin, Georgiap Missouri,, Indianaj> Illinois,, Iowa,, Kentucky^ and Michigan
for violative PBB residues by the USDA and the FDA, The Agriculture Depart-
ment found PBB residues as high as 100 ppm in cattle; the FDA sampled and
tested milk using a guideline of 1 ppm of PBB<*i' Michigan Chemical Corpora-
tion reportedly has recalled all lots of magnesium oxide manufactured since
March 1973 from eight states because of the risk that the shipments contained
PBB, Also,, the Farm Bureau service in Battle Creekp Michigan,, is reported to
have recalled its "24% Hi Moisture Corn and Silage Balancer Noo 402" manu.£ac°
tured sine® March 19730 because the fire retaedant was u@@d as additive in-
stead of feed supplement,—'
In February 19750 a news article reported that many farm animals
and food products contaminated with PBB had been destroyed and buried. The
casualty list included 11P000 cattle^ 2D000 hogsp 105 million chiskasisD 4,6
million eggs and small amounts of dried milkp cheese,, and butterj also 683
MT of contaminated feed were buriedo!/
PBB has also found its way into the blood of farmers who were ex=
posed to the contaminated animal feed. It has been reported that many of the
blood samples taken in June 1974 from 211 people who had contact with the
contaminated feed contained PBB.— More derailed tests, involving blood sam-
ples,, physical examinee ionsp and medical histories were underway in February
1975 on another 300 people. Half were exposed to the feed$ £h® ofcheir half were
controls who had no known contact with PBB. No evidence was found
has caused sickness in any humans,,
19
-------
(A number of related research investigations and -studies have been
conducted in the wake of this Michigan incident. For example, two technical
papers on /PBB's are scheduled to be presented in June 1975 at a conference
in Columbia, Missouri. 123 Also, a technical .paper, "The Distribution and
Clearance -of Polybrominated Biphenyls by Cows," is scheduled for presenta-
tion at a meeting of the American Dairy Science Association in Manhattan,
Kansas,, in June 1975.1ft/ The U.S. Food and Drug Administration was recently
reported to be contracting with the Michigan State Department of Health,
Bureau of Community Health in regard to an epidemiclogic study of health
effects associated with the consumption of milk, meat and other food con-
' 2S/
taminated with polybrominated biphenyl.—'
D. Water Pollution Aspects of Polybrominated Biphenyl Production
The incident of accidental contamination of animal feed in Michigan
stimulated an independent evaluation of the potential for water pollution from
production of PBB by the Michigan Bureau of Water Management of the Department
of Natural Resources. This Bureau has reported recently on a study of the water
pollution aspects of PBB production,!^/ This study covers an initial evalua-
tion of contamination of the Fine River downstream from the Michigan Chemical
Corporation plant at St. Louis, Michigan, where the entire U.S. production
of PBB's is centered. This plant is situated near the bank of the river and
waste effluent is discharged through several outfalls directly into the river.
The PBB concentrations measured by the Bureau in various outfalls are presented
In Section V (.p. 22). . A discussion of the major findings of this water pollu-
tion study iis given in the following .subsections.
1, Receiving water concentrat ionst Water samples were taken from
the Pine River at .points downstream from the Michigan Chemical Corporation
St. Louis pliant. The reported PBB concentrations ranged from 3,2 pg/liter at
the Impoundment 69 m downstream from the plant to 0.01 ug/liter about 12.8
km downstream. Concentrations of samples taken 19.3 and 32.2 km downstream
were below 'the sensitivity level of 0.01 ug/liter.
2.. Fish 11 ssue .analysesi Fish samples collected by gill netting
and angling 'from-the Pine River were analyzed for PBB's by either the U.S.
Food and Drug Administration Laboratory in Washington, D.C., or the Michigan
Department of Agriculture Laboratory in East Lansing, Michigan. Elevated PBB
levels were reportedly found in Pine River fish ranging up to a maximum of
1.33 ppm in .carp (whole fillets; wet weight) captured in the reservoir im-
mediately below the Michigan Chemical plant. Carp captured 4.8 km downstream
showed a concentration of 1026 ppm, .and measurable concentrations (0.09 ppm)
were determined in carp sampled 12.9 km downstream. The reported concentra-
tions of PBB's in bullheads were low at all stations. The study report states
that the I-'&eh •eOTst-asatestioti appears to be limited to tlie Pine River.
20
-------
3. Discussion of results of water pollution study: Michigan.
Chemical Corporation officials are reported to have indicated that residues
detected in fish during the Bureau surveys do not accurately reflect current
operations, but rather are a result of losses that occurred prior to improve^
raents made in 1972 in the plant waste disposal systems. To test this hypothe-
sis, the Bureau staff initiated a study of PBB uptake in caged fish held in
the area of plant discharges and at stations upstream and downstream from the
plant. Measurable PBB uptake in newly Introduced fish would imply that plant
discharge rates of PBB's were still contributing to the problems In a recent
telephone communication,!^/ a Bureau representative stated that the results
of these caged fish tests indicate that recent (1974) Michigan Chemical Cor-
poration plant discharges have contributed significantly to the problem of
PBB contamination in the environment.
The Bureau report indicates that PBB bioconcentration factors com-
puted by comparing levels in fish to Pine River water concentrations are ap-
proximately 20,000 to 30,000. The fact that this compares closeIv to reported
concentration factors for polychlorinated biphenyls (PCB's),12jt2£,' suggests
that fish in the Pine River in 1974 were probably in equilibrium with the
existing level of stream contamination.
The significance of reported PBB concentrations in Pine River fish
is unknown. No studies have been reported on possible adverse effects on these
local fish populations. According to the Bureau report, the U.S. Food and Drug
Administration had no established tolerance level for PBB's in fish tissue
for human consumption in October 1974; the FDA guideline for PBB's in meat
and chickens at this time was 1.0 ppra on a fat basis. If this guideline were
applied to fish, the carp tested in the St. Louis, Michigan, area of the Pine
River near the discharge from the Michigan Chemical Corporation plant and
at least 4.8 km downstream would exceed this value.
A spokesman for the Michigan Bureau of Water Management has reported
that the potential for water pollution by PBB's appears to be primarily re-
lated to production and formulation processes rather than through usage and
disposal of plastic products containing these compounds.^/ He also indicated
that domestic manufacturing sites where PBB's are used as raw material for
plastic formulations and manufacture of various thermoplastic products are
potential sources of waste materials containing PBB's. Apparently, no moni-
toring of these plastic formulation and finishing plants has been conducted
to date to investigate possible environmental pollution by PBB's.
-------
VII. WASTE DISPOSAL PRACTICES IN MANUFACTURING OPERATIONS
A. Introduction
The PBB producers declined to provide MRI with specific informa-
tion concerning waste disposal practices, since the production processes are
proprietary.
The White Chemical Corporation at Bayonne, New Jersey, is reported
to have produced BBB's from 1970 to 1973; this corporation then permanently
shut down ifcs PBB manufacturing facility because of the Michigan incident and .
the risks of environmental contamination created by the operations.^?/ During
this operating period, White Chemical accounted for only about 4% of the total
domestic production of PBB's, For this reason, the waste disposal practices
for this company were not investigated by MRI. A spokesman for the Michigan
Chemical Corporation at St. Louis, Michigan, has reported that his company
produced PBB's from 1970 to 20 November 1974; the manufacturing facility for
these chemicals was shut down for an indefinite period on the latter date.il'
At the time of this shutdown, company officials were planning on future dis-
posal of wastes from PBB operations by deep-well injection. In May 1975, a
Michigan Chemical official indicated that the corporation planned to utilize
the former PB2 prpciuctipn facility for other products and would not resume
production p£
The Michigan Chemical Cprppration facility at St. Louis* Michigan,
has. been in operation since 1935; the plant had about 400 employees in 1970.
The major raw material is b'rine pumped from wells which are 914 to 1,219 m
deep. Salt (IJaCl) and bromine are extracted from this brine; other impor-
tant products which have be en manufactured at this site includes
* Brpminjted phajtma ceutical and industrial compounds including
anhydrcrus hydrogen £fPjM4? and hydrpbroraic acid.
•*• .Pharmaceutical (and industrial intermediates.
* Magngsjium .compojuaj.ds ^HgQ^^^2t ^^3^'
* ^r-i!Cul\tiu;jpajl ^^. .^hemieals; :^r;ajin(,. fruit,, and soil fumigants).
* Rare : ea;r;tj> compounds and metals,, and development compounds.
*
rpiirema.a|fer Pf ?4 :.(:a "I^JMKS1 9l :PoAyt!.!?ominate,d biphenyls, with an
.awer.age of (> .atojnis... :p>f trpmine per mole of blphenyl).
3 ^ditrpmppropyl) phosphate.
-------
T33PP tris(l03=dichlL©gepgojp>yi)
Finssaaster PHT40 tetrabromophthalic &nhydride0
The Michigan Hater Resources Commission has issued a number of 're=
ports on wastewater surveys (conducted in 1967„ 19700 and 1973) covering the
Michigan Chemical Corporation facility (St0 Louis0 Michigan) discharges to
the nearby. Fine &iver0 The purpose of these surveys was to dstisssaira® £h©
quality and quantity of wastewmter being discharged by this .plant to th@
Biv<2r0 The reported data do not include. PPB comesistration i@vsl.8o
B. Discussion of Haste Disposal Practices at Michigan Chemical Coggogation
Plant
In May 19750 the Permit Branch of EPA (Chicago0 Illinois,) office)
provided MRI with copies of all permit applications data for wast® discharge
by the Michigan Chemical Corporation at St0 Louis0 MichigancJL' These data
have been used by MRI as the basis for a description and evaluation of the
waste disposal practices utilized by this corporation,. Data of special in°
terest to this project,, for four outfalls (discharge streams) selected from
25 outfalls listed in this permit information^ are presented in Table XVo
This table also includes related outfall sampling and chemical analyses data
obtained from a report by the Michigan Bureau of E?ater Management0M/ Waste
discharge flowsheets for each outfall are referenced in the table,,
As shown in Table IVD four Michigan Chemical Corporation production
units had measurable concentrations of PBB in their liquid waste outfalls in
19740 The PBB concentration in these outfalls during sampling periods in 1974s
ranged from 00l°. jjg/liter for Outfalls NoSo 005=006 to 104 (ig/liter for Out=
fall Noo 002o All outfalls discharge into the Pine River0 A brief discussion
of each plant outfall of interest is given in the following subsections
10 Outfall 002s The manufacturing unit which has this outfall
produces tetrabromophthalic anhydride (the principal product)0 hexabromo-
benzenep bromoacetic acid,, and tetrabromobisphenol Aa
As shown in Figure 19 Outfall 002 serves noncontact cooling water
and product wash waters and final filtrate for the manufacturing operations,,
The waste stream is composed of wash liquor and filtrate from washing of
product filter cake and cooling water from process reactors0 £?aste°abatement
equipment includes a solids separator to clarify wash water,, and practices
include dilution';,' segregation and storage of waste acid for by-product sale
or disposals A • 'fume scrubber is operated using circu tat ing '.aci«3 to avoid
water washing and the attendant problems,, the outfall dischegg® ffafra is
about 427p700 liters/days 'the average pH is 1*2<>
23
-------
TABLE IV
: BCA ft*.MICHIGAN CHEMICAL CORPORATION: MANUFACTURING FACILITY AT ST. LOUIS. MICHIGAN
Wast*,-
outfa.li-
.
005^'
OOiSJ
IcelSf (Sia Mo.-., 281fr)-npt: otherwise; clasr
sifted;
FrodoctlonAof; brovlnated^organlc. com-
pounds^ Including tetrabroaophthallc.
aolwdtld*. hexabroopbemene. broao-
, tetrabroisobis phenol; *•.
Product Ion, of 'H«c.bro»obtphenTl.
Discharge of cooling water , water, uied -
in.- area- clean-up.
Manufacture of Industrial chemicals.
Cooling,water used In.r.frlgeratlon plant.
Rafrlger.t.4 calclua.chloride.print clr-
culated to processes for coolant.
Hut.. Ab.ta.ot. BqulceiBnt
and/or- Practice**.'-'
S»lU*iiMp.Tator-. to ciartfyftMMhr
Reference.Waste.
Discharge Flowsheets
Ho. FU. Ho.
K-
c l*rlf lection ,. and.' «torag. of 'waste •
.cldrfor-byrproduct- >al* or,dis-
poul. F\a»e.acrubber uslng^clrcur
L*Cln*]^.cldr,to> avoid, water washing,.
apd? .ttendant • pr.obleiu.
l•; hydrogen ibroalde and;
hydrobroatnated^interaedlates.
Production; o f; anhydrous, hvdro«enf brosUdei>
(SIC;No,. 281-3')-.; hydrob'rosrix ac id:-solutions*
and?tlnc: broBldes(SlC,Ho^ 2819');.and^trlr
s».thT-lene. chlorobroatde-..alky 1-broa>ides.'
and^bromptrlchloromethane,(SIC.Ho; - 2818)•.
Mcuutacture-of elesiental' bromine- and^
orga&ic,derlvatlye». Trls. 2.3-dtbroac-
pronyl'phosphate.
Manufacture.of .• elemental:- bromine. (SIC: No.
2819-).'. methyl: bromide^. ethyl-.bromide.,
hrorainated.flane-retardants, and^other,
organic• intermediates:.(SIC; No. 2818):
Manufacture' of-. Industrial organic-chest-
ot. waste; acldc tort re.-use
l»i other, operations., collect ton-.- of
«Mt«s/ for. contract incineration.
o-and'collection of cer-.
tala.wastes. surface condensers,
specialspvsaps;,, recovery, and'.recycle,,
cootracti Incineration, traps, in .out-
let . use. of < spent brine- In other.
processes.
27'
28;
30
Segregation of waste acid, use of
surface condensers to recycle-mate-
rtals, use of recovered, by-product,
use of •: chealca Is - producing;, alnlnuai
waste products. Traps•to-prevent
spills from reaching drains,and to.
•kla> off any: accidental losses which
do reach drain.
Hell water used to cool refrigeration 30
compressor colls Is reclrculated
tbroogh systesi. Bleed off to river
to Balntaln teaper.ture . No contact
with process aaterlaIs.
Outfall
Discharge.
fete 10°
Uteri/da y*-
0.4777-
(0.113: gpd).
1.6578-,
<0.43a.gpd)
1.6351
(0;432 gpd)
0^3066
(0;081
0;54JO
(0.1*4 gpd)
Pot fall. Sampling, and. Cra luailoo-'
PBB', Osleulated. rBB'.Dls-
Conceo- charge-.Kate. Based
SapUnt;- tr.tlon. on Sample. Data.
n«/i Cr«»s Qf.ftB's/DaT
104-
9/4-5/74*
9/4-5/74-
36:
J9-.7-
9/4-5/74'
10.
16.4
. £/
6/6/74
8/20/74
8/23/74
4/5/74.
9/12/74
9/13/74
3.8:
2.3. 3.6
0.1:
6.6.
5.5
3.1
2.07
1.61
0.05
3.60
3.00
1.69
a/ Based on data contained- In waste discharge penat application filed with U.S. Any^Corpe. of Engineer. (Aacilleatloo Bb. M1-OTO-OX5-2-710319)-at Detroit, Michigan, on
' 17 June W71. Oader the heading "Manufacturing Activity or Process;" the principal Manufactured products .r. underlined.
b/ Based on data fro*:* paper, 'Mater Pollution Aspects of Polybromlnated Blphenyl Production: Results of Initial Sorveys in the Pine Rlv.r In Vicinity of St. tool*.
Michigan," presented to the Governors Great Lakes Regional Interdisciplinary Pesticide Council on 17 October 1974 by John L. Basse, Aquatic Biologist. Hater Q-sllty
Appraisal Section, Michigan Bureau of Water Managnent, Department of Natural Resources.
c/ Outfalls Hos. 005 and 006 have been combined as ooe outfall by Michigan Chemical Corporation; at the tlav of outfall sampling and evaluation the OOS •anafaccurlng facility
was not In operation.
-------
Filtrate
O.lOOMgpd
.Cooling Water
(Well or River
Water)
Product
Cake
Product
Slurry
City Water
0.013Mgpd
Washes
Product
Slurry
in H2O
Recovery
Drying
Packaging
Final
Filtrate
(Adapted from a drawing provided by
Michigan Chemical Corporation)
Mgpd ss Million gallons per day
Outfall 002
0.1)3 Mgpd
To River
Figure 1 - Waste Discharge Flowsheet for Outfall 002--Michigan
Chemical Corporation
25
-------
A sample of this outfall had a PBB concentration of 104 p,g/liter
(I U£/liter is equivalent to 1 part per billion (ppb)), the highest found in
any of the four selected outfalls. This sampling and analysis study was con-
ducted by the Michigan Bureau of Water Management in 1974. No information
was found which explains the presence of PBB's in this outfall. An analysis
by MRI shows that one potential source is PBB contamination of bromine raw
material reclaimed from by-product HBr contaminated with PBB. Also, the coup-
ling of molecules of partially brominated benzenes during the production of
G^Brg may be a source of PBB's. The possible presence of some biphenyl as
an impurity in the chemical bisphenol A, used as raw material in the prepara-
tion of tetrabromobisphenol A, may be another source of PBB generation. Pos-
sible side reactions during the preparation of tetrabromobisphenol A and/or
tetrabromophthalic anhydride appear to be less probable sources of PBB's in
these manufacturing operations.
As shown in Table IV, -the calculated dally PBB discharge rate for
Outfall 002 (assuming that sampling data applies on a daily basis) is 44.5
g/day.
A planned improvement in the waste control system involves a col-
lection dump 'for washes and transfer of the waste to a centralized sulfuric
acid treatment 'System which will neutralize wastes. A company spokesman
indicated in May 1975 that construction of this system was nearing comple-
ttonJfi/
2. Outfall .0,144 This outfall services a multiple product area in
which the principal products are anhydrous hydrogen bromide, trimethylene
chlorobromide, and hydrobromic acid. Other products are listed in Table IV.
The liquid waste effluent contains city water used in this opera-
tion as shown in Figure 2, along with 'segregated cooling water, water from
vent 'scrubbers, -and product washes. Segregated cooling water from the 013
area '(see .Figure 3) is discharged to this outfall drain at some distance
from the -process 'area. .Several yard .drains also enter this sewer as it
crosses the plant. Tank cars and trucks are washed near these drains. The
.outfall discharge rate *s 1,657,830 liters/day ari'd the average pH is 7.5.
The .reported waste-abatement .practices include recovery of by-
product acid and traps ..oh the -wash water to assure that no product is lost
with the wafer. .Plans call fb:r collecting the washes for diversion to a brine
disposal system (deep-well injection).(Organic residues and wastes are segre-
gated 'and sorted for •pick-up toy a waste contractor.
Analysis o'f a sample of this outfall, taken in September 1974
•(Ta'b'le IV), showed $'6 ^/liter «>f PBB['s. On .a dally outfall basis, this con-
centration would result in a -total discharge of 59.7 g of PBB's.
126
-------
Vent Inerti
City H2O
O.ISOMgpd
Recirc.
Absorber
By-Product
Acid
Cooling H2O
0.120Mgpd
Washes
Neutralizer 0.002M god
Wash '
IT
H2O
Condenser
H2O
Product
(Adapted from a drawing provided by Michigan
Chemical Corporation)
Mgpd = Million gallons per day
Vent
Scrubber
Scrubber H2O
0.058 Mgpd
-O.ISOMgpd
Segregated
Cooling H2O
(160- ISOgpm)
Recirculated
from 013 Area
0.258 Mgpd
Yard Drains
Car Wash
Outfall 014
0.438 Mgpd
To River
Figure 2 - Waste Discharge Flowsheet for Outfall 014--Michigan
Chemical Corporation ')
-------
Condenser
Water Inlet
0.432 Mgpd
25%: City H
75% Rive* W2O
Feed: Brine.
& Steam
0.259;Mgpd:
(Adapted from &
provided by Michigan
ehemlca-I C6r:p6ra£i6n$
M'gp&e»ft(r£l'i:6n: gallon* per day.
Segregated Cooling
HjO (City H2O)
for Reuse or to
Outfall 014
0.258Mgpd
Methyl
Bromide
Area
(G)
Bromi noted
Products
Area
rne
Area
I
Brine to
Further
Proeessing-
Outfoll 013
0.432 Mgpd
to River
Process Wastes,
Equip. Wash
Water 0.014Mgpd
Condenser
H2O for
Reuse
Condenser &
Scrubber H2O
Washes
0.418Mgpd
Occasional
Equipment
Washing
Yard
Drain
Piowsfiefet foe Otttfa*! 013^ -Michigan
Gorpottftion
-------
Potential sources of PBB's In this outfall include contaminated
by-product HBr used in the absorber and feed material for the reactor (Figure
2).
3. Outfall 013: A multiple-product area producing bromine, brorai-
nated products and methyl bromide is serviced by this outfall, as shown in
Figure 3. The principal products are elemental bromine and tris(2,3-dibromo-
propyl) phosphate. Cooling water (city water) from the bromine plant condens-
ers is collected for reuse in other areas and discharged to Outfall 014.
The brominated products area (B) uses a mixture of city water and
river water for various purposes. Noncontact and contact cooling water, and
off-gas scrubber water containing HC1 from process vent gases and process
washes, are all discharged together. Corporation plans call for installation
of an HC1 recovery absorber to control acidity.
Area (C) discharges segregated cooling water (reused city water)
to Outfall 014. Small quantities of equipment wash water and condensate are
discharged to Outfall 013 along with about 1,136 liters/day of sulfuric acid
wastes. Michigan Chemical plans to treat these acid wastes in a central acid
treatment plant.
The waste abatement practices described in the discharge permit
applications.' include segregation and collection of certain wastes, use of
traps in the waste outlet, contract incineration of certain wastes, and use
of spent brine in other processes.
The Outfall 013 discharge rate is 1,635,120 liters/day; the average pH
is 3.8. Analysis of a sample of this outfall, taken in September 1974, showed
a PBB concentration of 10 ug/liter (Table IV); this concentration corresponds
to a daily discharge of 16.4 g of PBB in this outfall. A possible source of
the PBB's in this outfall is the yard drain equipment wash water from opera-
tions involving bromination of various compounds.
4. Outfalls 005 and 006: As indicated in Table IV, these two out-
falls have been combined by Michigan Chemical Corporation into one discharge
stream. The 005 manufacturing facility produces industrial organic chemicals;
the principal product is hexabromobiphenyl. The waste-abatement methods in-
clude segregation of waste acid and recovery of by-product HBr (containing
PBB's as a contaminant^/) and use of surface condensers to recycle materi-
als. Traps are used to prevent spills from reaching drains. Outfall 005 is
reported to consist of segregated cooling water and steam condensate (see
Figure 4). The specified discharge rate for the 005 outfall is 306,585 liters/
day; the average pH of this discharge stream is 7.7. This facility was re-
ported to have been shut down during the period (6 June to 13 September
1974) that outfalls were being sampled and monitored.^/
29
-------
Vent lnert<
Demineraiized
H2O as Req.
Recovered Acid
to Process
City H2O
0,081 Mgpd
Product
0.144 Mgpd
. ..... or
Refrigeration
Plant Heot
'Exchangers
i(;Nbn-Gon'tact.) j
0.144 Mgpd
Cooling HjO
Bleed-Off
(Adapted from a drawing ;provided by
'Michigan Chemical
-------
The 006 facility involves primarily a refrigeration plant and the
circulation of refrigerated calcium chloride brine (as a coolant) to various
plant processes. Waste-abatement practices include the prevention of direct
contact of the cooling water with process materials and reclrculation of
cooling waters.
Outfall 006 consists of well water recirculated over the refrigera-
tion plant heat exchanger (see Figure 4). No treatment or process wastes are
added to this water; at the time of the discharge permit application, Michigan
Chemical had no plans for controls on this outfall. The specified discharge
rate for this outfall is 545,040 liters/day and the average pH of this dis-
charge is 7.8.
Chemical analysis of Outfall 006 samples taken between 6 June and
13 September 1974, by the Michigan Bureau of Water Management shows PBB con-
centrations ranging from 0.1 to 6.6 p,g/liter. This range of concentrations
is equivalent to a discharge of PBB's ranging from 0.05 to 3.6 g/day.
31
-------
VIII. COMMERCIAL USES FOR PBB'S AND RELATED COMPOUNDS
A. Introduction
In recent years the immense loss of both lives and property to fires
has led to demand by both governmental and nongovernmental organizations for
Improved fire-resistant raaterials.il/ Natural fibers have been relatively easy
to treat with flame-retardant materials. However, flame retardant materials
for synthetics have not been as easily developed. Some brominated organic com-
pounds have been found to be more effective flame-retardants than chlorinated
oo /
compounds for applications 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 the flame-resistance performance requirements, and are also economi-
cally feasible* They also have the desired property of having little effect
upon the flexibility of the base compounds. For these reasons extensive in-
terest has been shown in PBB's, especially hexabromobiphenyl (HUB), octa-
bromobiphenyl (OBB), and decabromobiphenyl (DBB) as flame retardants.
The only PBB product to reach large scale commercial production is
HBB, which is marketed as Firemaster BP-6 by Michigan Chemical Company. How-
ever, several other companies have shown an interest in the use of DBB and
OBB, as well as HBB, as flame retardants. In this section, the actual uses
of BP-6 ate described, and some potential uses of PBB's are also discussed.
The final few paragraphs of the section discuss some possible substitutes for
PBB's as flame retardants.
B. Existing Uses
Little information was available concerning the use of Firemaster
BP-6. The information gathered was of two basic types. First, Michigan Chemi-
cal Company supplied some information concerning the type of final products
in which Firemaster BP-6 is used. Also, the two known domestic users of BP-6,
Borg-Warner Corporation and Standard T Chemical Company, provided limited
-------
TABLE V
DOMESTIC USES FOR FIREMASTER
Industry
Business machines
and industrial
equipment
Electrical
Fabricated products
Transportation
Miscellaneous
Approximate
Allocation of
Total
Firemaster BP-6
Produced (%)
48
35
12
Examples
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.
After it was determined that BP-6 is the only commercial PBB, an
attempt was made to identify and contact the users of BP-6. The only two
companies that were identified are Standard T Chemical Company, Chicago,
Illinois, and Borg-Warner Corporation, Parkersburg, West Virginia. Inquiries
were made to these companies requesting data concerning quantities of BP-6
used and products in which BP-6 is used. The information obtained from these
companies is summarized as follows.
Standard T Chemical Company uses BP-6 as a flame retardant as an
ingredient in coating materials which have only an industrial use; they use
an estimated 34,014 kg/year of BP-6 in their Staten Island, New York, plant..H/
Additional information concerning the products involved or the quantities of
PBB's present in the product is considered by Standard T to be of a proprietary
nature, and therefore, was not provided to MRI.2^L/ In response to questions
concerning by-product and waste stream contamination with PBB's, Standard T
reported that there are no by-products nor waste streams associated with
their process.il/
33
-------
the major user of Fireraaster BP-6 has been the Borg-Warner Corp-
oration, the BP-6 is used to produce flame retardant ABS resin in three Borg-
Warner plants: Parkersburg, West Virginia} Ottawa, Illinois; and Oxnard,
California. ABS resins are produced by polymerizing acrylonitrile, butadiene,
and styrehe monomers. A Borg-Warner representative has indicated that his com-
pany used approximately 1,179,138 kg of Firemaster BP-6 during 1974.16^
this quantity accounts for about 55% of the total BP-6 produced that year.
the process in which BP-6 is used is reported to be a dry mixing
process with no by-products or waste streams, the technical literature^/ in-
dicates that a typical concentration of BP-6 in the final mixture is about
20% by weight. Lower BP-6 concentrations (e.g., 7 or 13%) are used in plastic
formulations which include other flame-retardant additives.1Z/ the two com-
ponents are mixed in a Banbury mixer (batch charge of about 136 kg) until the
flux point of the ABS resin is reached and the flakes of BP-6 are melted, the
mixture is then cooled and pelletized. During the cooling process, the Impreg-
nated ABS resin comes into contact with cooling water. However, a spokesman
for Borg-Warner has reported that ABS is not water soluble and that PBB's are
not transferred to this water. Substantiating data were not supplied, however.
i
A Bbrg-Warner representative has also Indicated that flame-retardant
ABS produced by his company is processed in the same manner as general ABS
compounds.sS.' ABS compounds generally may be used in any of several different
processing steps, the two general categories of ABS products are injection
molded and extrusion grade. Injection molding, extruding and calendering of
ABS by 'a wide variety of techniques are possible. Both screw and ram injec-
tion molding Can be used. It is also possible to electroplate ABS, and the
resins can also be foamed by several techniques.At/ Thus, there are several
commercial processes in which the BP-6 could possibly be introduced into the
environment during secondary production stages. However, the available data
are insufficient to establish the amounts of such possible environmental con-
tamination.
In 'summary, two users of PBB's have been located who, together,
consume approximately 56% of the annual production. Data from these companies,
as well as from'Michigan Chemical, indicate that the final disposition of the
PBB's is in products which do hot come into contact with food, feed, or human
wearing apparel. It has also been reported that in the primary processing
stage', there are no waste 'streams or by-products. However, no data have been
Obtained detailing the fate of the PBB's at the fabricating stage of the ABS.
Data are particularly heeded on any PBB levels in cooling waters
used during pel let iz ing of the A!BS resins, and in other ABS products that are
fabricated in the same equipment -as flame-resistant ABS--since cross-contami-
nation 'could occur.
-------
C. Potential Uses
Three information sources were utilized to determine potential uses
of PBB's. First, a search of U.S. patent literature was conducted, and all
patents claiming the use of PBB's were obtained. A general literature search
was also conducted to find any technical articles detailing uses of PBB's.
Finally, the technical brochures of PBB manufacturers were examined to deter-
mine the recommended uses of their products.
In examining these sources, the only commercial use found for PBB's
was as a flame retardant. However, there are several types of materials for
which PBB's can be used as a flame retardant, and these are discussed In the
following paragraphs.
A search of U.S. patents revealed six patents claiming PBB's as
flame retardants. Five of these patents were issued to U.S. firms and one
was issued to a German firm. Each U.S. firm was contacted to determine present
production status under their patent. The following paragraphs detail the pro-
cess and materials involved in each patent as well as information concerning
present production status. While most of the patents discuss several alterna-
tive flame retardants, this discussion is concerned with those sections of
the patents detailing the use of brominated biphenyls.
One patent studied by MRI involves a combination of phosphonium
bromides and brominated biphenyls which can be used as a flame retardant for
olefin polymers.2^/ The specific phosphorus compound is a phosphonium bromide
having either the formula ^PR'J^Br" where R is a phenyl or 2-cyanoethyl
and R' is a lower alkyl or 2-cyanoethyl, or the formula [R3P-CH-CH-PR3]++2Br"
where R is defined as above. The specific brominated compound Is decabromo-
diphenyl (DBB), octabromobiphenyl (OBB), hexabromobiphenyl (HBB), or tetra-
bromodiphenyl (TBB).
The patent indicates that the flame retardant should consist of a
mixture of phosphonium bromide and brominated biphenyl ranging from a ratio
of 2:1 to 1:2, respectively. This mixture should be incorporated into a poly-
mer in amounts from 0 to 25% by weight, based upon the weight of the polymer.
The flame retardant may be added to the polymer as a combination or as in-
dividual components in any of the following manners: (a) by milling the
polymer and components on a two-roll mill in a Banbury mixer, etc.} (b) by
molding the components and the polymer simultaneously; (c) by extruding the
polymer and components; or (d) by blending all the materials together in a
liquid or powder form and later forming the desired end-product. Also, the
flame retardant may be incorporated during production of the polymer. In-
formation obtained from contact with the company assigned this patent indi-
cates that products are not being manufactured under this patent.—'
35
-------
Another patent: is of a broad nature and identifies many specific
components both for the flame retardant and for the base plastic* The general
formulation consists of a thermoplastic compound for the base and a flame
retardant comprising a polychloro-substituted organic compound, a polybromo-
subs.tituted .organic .compound, and if so desired, an antimony-containing com-
pound or a tin-containing compound.±2' The specific brominated biphenyl men-
tioned in this .Universal Oil Products Company patent is hexabromobiphenyl.
The invention consists of an embodiment of the polychloro-substituted compound
and hexabrpmpbiphenyl, in combination, in the final composition in the range
of 5 to 507. by weight of the finished product, the antimony-containing pr
tin-containing substitute in the range of 0.2 to 15%, and the thermoplastic
substance in amounts ranging from 50 to 94.8% by weight. These materials may
be combined by any mode of admixing known in the art. Universal Oil Products
is not presently producing flame-retardant compositions using HBB, nor does
it have any plans to produce such compounds.zi/
A patent assigned to Cities Service Company includes PBB's as a part
of a mixture yielding nondrip, self-extinguishing polyethylene.^!/ The general
formulation consists of polyethylene, a halogenated organic flame retardant,
ammonium sulfate or ammonium fluoborate, a metal compound synergist, such as
antimony trlpxlde, and silica. The particular PBB's involved are decabromo-
blphenyl (DBB), octabromobiphenyl (OBB), and hexabromobiphenyl (HBB). The
polyethylene is combined with the flame retardant so as to constitute 55 to
70% by weight of the final product. This is combined with 2 to 10% by weight
of PBB, 5 to 10% by weight of ammonium sulfate or ammonium fluoborate, 5 to
107. by weight of a metal compound synergist, and 15 to 25% by weight of silica
to obtain the final composition. These mixtures may be combined by any suit-
able technique known in the -industry. However, they are usually prepared by
mixing the flame retardant compounds .with molten polyethylene. A Cities Ser-
vice representative has indicated that PBB's are not used presently, and that
there are no plans to use PflB's.41/ All products now being manufactured under
this patent use bromineted aliphatic flame retardants.
In November of 1973, General Electric was issued a patent for the
production of a flame and moisture resistant material that can be used to im-
pregnate fibrous-insulating materials.;!/ The impregnating composition contains
halogenated rubber, halogenated polyphenyl, hydrated alumina, halogenated
phthalic anhydride, and antimony tri.oxide. The halogenated polyphenyls of in-
terest are tetrabrpraoblphenyl, hexabromobiphenyl, and octabromobiphenyl.
-------
The composition of the impregnating materials, in parts by weight,
aret
Halogenated rubber 15-25
Polybrominated blphenyl 25-35
Hydrated alumina 30-40
Halogenated phthalic anhydride 3-9
Antimony trioxide 3-9
Phosphate ester 0-9
Aluminum stearate 0-1
The ingredients are dispersed in a volatile liquid organic such as
toluene or xylene to aid in the preparation of the impregnating composition
and its later application into the fibrous materials. First, the soluble
halogenated rubber and PBB are dissolved, followed by the other soluble com-
ponents. The insoluble components such as antimony trioxide, phthalic an-
hydride, and hydrated alumina are then slurried through the liquid by ball
rolling into the rubber-biphenyl solution. The composition is then diluted
with additional solvent until concentrations of about 25 to 200 parts by
weight, of solvent to 100 parts by weight of the flame-retardant components
are reached. For the impregnating of asbestos and other inorganic fibers, 75
to 175 parts by weight of solvent to 100 parts by weight of flame retardant
are preferred.
The invention also describes the flame-resistant, moisture-resistant
insulation for wire and cable that can be produced from this flame retardant.
The wire is said to have applications in high-temperature, high-moisture ap-
pliances such as dishwashers and clothes dryers. General Electric has indi-
cated that no wiring is being produced under this patent with brominated bi-
phenyl as a flame-retardant.ZZ'
In October of 1973, Monsanto Research Corporation was issued a
patent involving the production of smoke-retardant styrene polymers.—' The
patent is basically concerned with the addition of iron, manganese or chrom-
ium 8-hydroxyquinolate to styrene polymers. However, one of the claims of
the patent involves the addition of octabromobiphenyl (OBB) as a flame re-
tardant. The specific embodiments described in the patent consist of ABS
resin combined with 24.4% by weight OBB and Fe(8-hq)3 ranging from 4.4 to
21.9% by weight. The patent did not describe the method by which the ingred-
ients were combined. A representative from Monsanto has indicated that none
of its flame-retardant ABS products has reached the commercial stage.!£/ He
also indicated that Monsanto would probably not use PBB's in its products.
37
-------
Another patent of interest is assigned to Chemische Fabrik Kalb
G.m.b.H. of Cologne-Kalb, Germany.^/ This patent describes both the produc-
tion and use of a flame retardant which is a mixture of brorainated blphenyl
and brominated biphenyi ether. The preferred product is obtained by brorainat-
ing a mixture of 26.57. by weight biphenyl and 73.5% by weight biphenyl ether
to a product containing 70 to 857. by weight of bromine. The patent describes
the use of the above product as a flame retardant for a number of plastic
resins. The flame retardant is used in quantities which provide a bromine
content between 5 and 157. by weight in the synthetic resin. It is also ad-
vantageous to incorporate 3 to 157. by weight of antimony trioxide. The flame
retardant can be added to the resin in several manners. First, it may be
added to the monomer before polymerization. Also, the addition of the flame
retardant to poly.olefins may be accomplished during their production. Finally,
the flame retardant may be admixed during the rolling, calendering, or extru-
sion of the polymers. The status of production of flame-retardant polymers
under this patent was not determined.
An examination of the literature revealed only one additional use
of PBB's as a flame retardant. Fincher et al.,—' found that polyurea shrink-
resistant coatings for wool could be made flame resistant by the addition of
large quantities of hexabromoblphenyl. The flame resistant coatings were fast
to repeated washings, but were not able to maintain the flame resistance
properties after dry cleaning. The article is of Australian origin, and no
information was obtained concerning the commercial application of this pro-
cess.
Information was obtained from White Chemical detailing the chemical
properties and suggested uses of their brominated biphenyls. They suggested
that decabrpmobiphenyl can be used as a flame retardant for ABS, polystyrene,
polyethylene, polypropylene, polycarbonates, polyester fibers, polyester resin
and polyamide fibers.!£/ Hexabromobiphenyl was suggested as a flame retardant
for polyurethane foams and synthetic latices.
In summary, all information obtained indicates that the major po-
tential uses for PBB's are as flame retardants for a variety of materials,
principally various synthetic thermoplastics. However, some data indicate
that PBB's can also be used in flame-retardant combinations for both wool
and inorganic fibers. There is no information that suggests any use for PBB's
other than as a flame-retarding agent.
P. Brominated Substitutes for PBB's
Because of public concern stimulated by the PBB contamination in-
cident in Michigan, commercial producers and consumers of flame-retardants
have become interested in the development and use of substitutes for PBB's.
A brief discussion of potential substitutes is presented here.
38
-------
The field of flame retardant additives for thermoplastic materials
is in a rapidly developing stage. Several products have been developed and
are being marketed which have flame-retardant properties similar to those of
PBB's. However, these flame retardants are not as economical as PBB's* Several
of these possible substitutes are described in the current technical litera-
ture.^/
Two of the most promising are decabromobiphenyl oxide, produced by
Dow Chemical Company, Fine Organics, and Great Lakes Chemical, and a haloge-
nated aliphatic produced by Cities Service Company. Both of these compounds
are currently priced at about $3.86/kg ($1.75/lb),££/ which is significantly
higher than the price of BP-6 (about $1.65/kg or $0.75/lb).
Decabromobiphenyl oxide (DBBO) is a compound similar in structure
to decabromobiphenyl. The difference is that it has an oxygen atom which binds
the two benzene rings. The toxicity of DBBO was studied in a Dow report men-
tioned in Section VII, p. 40; DBBO appears to be a much less toxic material than
i'BB's. However, according to Dr. Joseph Green of Cities Service Company, DBBO
has ,:• Tendency to degrade to lower brominated biphenyl oxides. These lower
order compounds may possibly pose environmental problems similar to those of
the lower brominated PBB's.^j/
The Cities Service product, Citrex BC-26, is a halogenated organic
containing 29% bromine and 40% chlorine.—' According to Dr. Joseph Green of
Cities Service Company, this product is less toxic than PBB's and does not
exhibit the property of bioaccumulation.f^/
These and several other compounds have been developed which have
flame-retardant properties equivalent to those of PBB's. However, the prob-
lem remains to develop compounds with these properties that have the same
economic advantages.
-------
IX. HEALTH AND ENVIRONMENTAL ASPECTS
A.. Introduction
In, the late 19.60's several companies began to have an interest in
polybrominated biphenyls (PBB's) because of their flame retardant capabili-
ties. However, because of the similarity of these compounds to PCB's, there
was some concern about the toxicity of PBB's. This concern, which was inten-
sified by the Michigan cattle-feeding incident of 1973, has led to several
extensive studies of the toxicological and environmental effects of PBB's.
Tfye following subsections briefly discuss the findings of these
studies under the separate headings of health aspects and environmental as-
pects. The health studies are directed to three basic areas: toxicity to
animals, effects on animal reproduction, and animal retention and excretion
of Piifl's. Th,e subsection on environmental aspects discusses physical and
chemical prpp.erties of PBB's, and the fate of Firemaster BP-6 in the environ-
ment .
B. Health Aspects.
1. Toxicity of PBB's:. Since 1970, several chemical firms have
sponsored studies of the toxicp'logical effects of PBB's. The four major re-
ports to dat^e are of the Michigan Chemical Company study conducted by Hill
Top Research, Institute, Inc. ,£Z/ the Dow study conducted by Norris et al.,Z°'
and two Du Pont studies conducted, by Aftosmis et al.^9|50/
Each of these studies covered acute oral toxicity in rats and skin
and eye irritation in rabbits. In addition, both Aftosmis et al. and Hill Top
conducted inhalation studies, on rats. Norris et al. also conducted 30 day and
2 year, rat feeding studies,, and Aftosmis et al.^i/ conducted a subacute 28
day feeding study.
In all studies of acute oral toxicity, the test sample was adminis-
tered by intragastric intubation to the rats. Both Norris and Aftosmis used
a m;aximum dosage of 2tpOQ, mg/kg4&,49./ an(j, found no signs of acute toxicity.
The Hill TOP study used h:igh;er. concentrations and found the acute LD^Q to be
in the range pf 21.5 g/kg.£Z/ The Hill; Top, study also indicated that some of
the rats exhibited; s.ignsi. o;f. systeraatic tpxicity such as diarrhea stains,
urine sta.ins an
-------
To test dermal absorption toxicity, Aftosmis et al, applied a
| paste containing either hexabromobiphenyl (HBB) or octabromobiphenyl (OBB)
, to the stomachs of rabbits for 24 hr and then removed it. The rabbits were
I .ien observed for 14 days. Hill Top ResearchfLZ/ used the same procedure us-
I ing only HBB. Both sets of data indicate that the acute dermal LD5Q of HBB
j in rabbits is in the range of 2.15 to 10 g/kg.ftlt^O/ Aftosmis et al. also
noted significant liver enlargement at dosage levels of 1.0 g/kg and larger,
and Hill Top noted ataxia and emaciation in the majority of rabbits at all
! dosage levels after the first five post exposure days.
i The skin and eye irritation studies on rabbits conducted by all
i three groups indicated only slight irritation. This slight irritation disap-
peared quickly after the removal of the PBB-treated skin patches. Aftosmis
et al AP_/ also found no evidence of irritation on 173 human volunteers who
wore a polyester fabric sample containing 67. by weight OBB.
1 To test acute inhalation toxicity, Hill Top Research exposed 10
rats to HBB at a concentration of 71.1 mg/liter for 1 hr.zZ ' Although no rats
died, ad o;;rsisted in six rats until termination. The rats showed an average
i ,,ie.i.glii: xw of 59 g and, upon termination, showed depleted body fat stores.
1 In their inhalation study, Aftosmis et al. found that rats exposed to PBB's
at levels of 13.0 and 18.4 pg/liter for 4 hr showed a significant increased
1 liver to body weight ratios. 50/ Additional tests indicated that the threshold
i level for this liver enlargement is about 2.6
Both Norris et al. and Aftosmis et al. fed rats OBB at dietary lev-
els ranging from 0 to 1% for approximately 1 month. Both found liver weight
increases at feeding levels of 0.01% and above. Aftosmis also found a buildup
of bromine in the fat, liver and muscles of rats fed at the 100 ppm level and
above. The bromine level in the fat had not decreased 18 weeks after the feed-
ing ended.
Although all three studies indicate a low acute toxicity for PBB's,
both Aftosmis et al. and Norris et al. recommend that these compounds not
be used as flame retardants because of the PBB accumulation in the liver and
in body fat.
2. Effects of PBB's on animal reproduction; Four studies have
been conducted which examine the effect of PBB's on the reproductive process.
Aftosmis et al.fL2/ have studied the embryotoxicity of PBB's in rats. Cecil
et al f 51,52/ and Lillie et al.22./ have conducted studies on laying hens which
examine the effects of PBB's on egg production, fertility and hatchability.
Aftosmis et al. administered OBB in the diet of rats at levels of
0, 100, 1,000, and 10,000 ppm from the 6th through the 15th day of the gesta-
tion period. ^9/ The pups were delivered by caesarean section on the 20th day
of pregnancy. Neither the outcome of the pregnancy nor the embryonal develop-
ment was effected by treatment. However, four fetuses^ one from each of four
41
-------
different litters, showed major abnormalities. These abnormalities were
found in two litters each at the 1,000 and 10,000 ppm levels. Further studies
would be required to determine whether these abnormalities were related; or
whether they were a chance occurrence.
In two studies primarily concerned with the effect of PCB's on lay-
c i to /
ing hens, Cecil et al. LI3Z/ also examined the effects of Firemaster BP-6
(hexabromobiphenyl) on hens. Both studies indicate that a level of 20 ppm of
EBB in feed has no effect on the hatchabillty or fertility of eggs. However,
it was found during the 2nd month of feeding that egg production was 11*5%
less than that for the control birds.JL!/ These findings were substantiated
by Llllie et al.ll/
Data from the Michigan contamination incident indicate that the PBB
in the diet of cows tends to have a dramatic effect upon their reproduction
processes.22/ Thus, there are data which indicate that PBB's in the food in-
take can have an adverse effect on the reproductive process of various ani-
mals,
3. Retention and excretion pf PBB's: Several studies have been
undertaken to determine the path of PBB's in animals' systems. G. F. Fries .
et al. studied the retention and excretion of PBB's in both hens and cows,—
and G. F. Fries and G. S. Morrow later studied the excretion of PBB's in the
milk of cows.!!/ Norrls et al. conducted ^C metabolism studies on OBB in
rats.
In their study of hens, G. F. Fries et al. fed a group of 35 hens
a diet containing 20 ppm PBB for 7 weeks.!ft/ At the end of a 9-week period,
the PBB levels in hens sacrificed were 21.5 ppm in the eggs and 69.5 ppm in
body fat. After 16 weeks the level had dropped to 2.2 ppm in eggs, but the
level in body fat had dropped only to 62.4 ppm. Fries et al. also found a
significantly higher retention of hexabromobiphenyl than heptabromobiphenyl
in the body fat of the chickens. It should also be noted that 45% of the PBB
residue was excreted through the eggs. As part of the same study, Fries et
al. incorporated excreta from the hens into the diet of a cow to give PBB
levels of 0.61 ppm in the cow's diet. After 30 days, a steady state of about
6 ppm was reached in the milk fat of the cow.lft/ After the PBB feeding was
stopped, the .concentration fell about 80% in the first 10 days, and more
slowly thereafter.
In A later study, G. F. Fries -and G. S. Morrow fed four cows 10
mg/day of PPB for 60 days.M/ After 30 days the PBB level in the milk fat
plateaued at 3.07 ppm. After the PBB feeding was stopped, the level declined
71% in the first 15 days. The decline then slowed drastically with a half-
life of 58 days
42
-------
In the C metabolism study conducted by Norris et al., rats were
dosed with 1 mg of OBB and then were tested at 24-hr intervals for 16 days.M/
Approximately 62% of the ^C activity was found in the feces at the end of
24 hr. However, after the 16th day about 26% of the l^C activity had not been
recovered. When the rats were sacrificed on the 16th day, *^C activity was
found in the adrenal, heart, adipose, skin, liver, and pancreas tissue.
C. Environmental Aspects
During 1970 to 1975, Firemaster BP-6 has been the principal PBB
flame-retardant material produced and sold domestically. The following sub-
sections discuss the properties of BP-6 and decabromobiphenyl and the fate
of BP-6 in the environment.
1. Physical and chemical properties of Firemaster BP-6
General structure and composition
n + m = 6
BP 6 is a mixture of brominated biphenyls with an average
bromine content equivalent to about six bromine atoms/biphenyl molecule.
This product is a mixture of the following brominated biphenyls.—'
JL JL
Tetrabromobiphenyl 2.0 Heptabromobiphenyl 13.8
Pentabromoblphenyl 10.6 Other bromoblphenyls 11.4
Hexabromobiphenyl 62.8
Bromine content ^ 75%
Softening point 72°C
I
Density 2.57 g/ml at 268C
Vapor pressure, mm of Hg
90CC 7.6 x 10-5
140°C 7.6 x 10-3
2208C 7.6 x 10'1
43
-------
;So:lubil*ty ;at 28°C. .g/100 ,g .solvent
P,ioxane
•Toluene
Benzene
•;Chlorp;form
:Carbon :tetrachloride
^Dimethyl formamide
Ethyl acetate
.Acetone
.^Petroleum ,e,ther
Water -solubility. ;25°C
•Thermal .stability
115
97
78
75
40
30
16
8
6
2
11 ,par,ts per billion
Decomposes at 300 to 400°C
-Chemical .and iphotolytic stability: Firemaster BP-.6 is rela-
tive'y tnert chemically. Although.-,no data /are ;aya>i:lable on the photo lytic
,stabi:i:iv:.y-p«f iF;i=remast,er -;BP--6,, .a ;atudy ,
-------
Volatility (by TGA) Less than 5% 341°C
10% 363°C
25% 388CC
Melting point (°C) 380 to 386
3. The fate of Firemaster BP-6 in the environment! Information
concerning the probable fate of BP-6 in the environment has been provided by
the manufacturer.Al' Based on their knowledge of the end-use products into
which Firemaster BP-6 is incorporated, it is assumed that the major portion
of these products (which have a useful life of 5 to 10 years) end up in a
junk pile or are buried in a sanitary landfill. The ultimate disposition of
BP-6 upon burial is uncertain. In their opinion, BP-6 eventually undergoes
oxidative/biological degradation forming carbon dioxide, water, and bromide
ion. When a chemical change in the BP-6 molecule does occur, degradation
proceeds relatively rapidly.
Although no data on soil migration of BP-6 are available, a Michigan
'.;heraical spokesman believes that migration is minimal. This opinion is based
on t actors: (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 chlori-
nated biphenyls, exhibit an extremely small migration tendency. Since BP-6
should exhibit properties similar to the higher polychlorinated biphenyls,
BP-6 does not seem to be easily leached from the soil.
-------
REFERENCES
.!. Pesticide Chemical News, p. 8, 5 June 1974.
2. •PjB8t.lc.ijde Chemical Jtews. ,p. 9, 19 June 1974.
3. Chemical and Engineering News, p. 7, 24 February 1975.
4. Personal Communication with Dr. Fred Kerst, Vice President, Michigan
Chemical Corporation, St. Louis, Michigan, May 1975.
5. 'Personal Communication with .Mr. James Dunphy, White Chemical Corpora-
tion, Bayonne, New Jersey, May 1975,
6. U.S. Department of the Army, Corps of Engineers,, Application for Permit
to Discharge in Navigable Waters, Application M1-070-OX5-2-710319,
;iled on 17 June 1971, by Michigan Chemical Corporation, St. Louis,
Michigan.
7. Personal Communication with Mr. James Spalnhower, Borg-Warner Corpora-
tion, JParkersburg, West Virginia,, 19 May 1975.
8. Nleoderaus, P^ 0., ,and H. L. Wilson, "Flame and Moisture Resisting Im-
pregnating Compositions for Fibrous Materials and Products Thereof,"
U.S. Patent 3,772,455, assigned to General Electric Company, Patented
13 November 1973.
9. Parts, L. P,, and J. T,. Miller, "Smoke Retardant Styrene Polymer Compo-
sitions," U.S, Patent 3,766,157, assigned to Monsanto Research Corp-
oration, Patented 16 October 1973.
10. Personal Communication 'with Mr. Wetzel, Monsanto Research Corporation,
St. Louis, Missouri, 14 May 1975.
11. iFincher, K. W., G. B. Guise, and M. A. White, "Machine-Washable Flame- .
.Resistant Wool," Textile Res, J.« pp. 623-625, October 1973.
12. ;PerBonal Communication with Mr. James Dunphy, White Chemical Company,
Bayonne, Wew Jersey, January 1975^
13.. 'Personal ^Communication with ,Mr, J.. L. Hesse, Michigan Department of
Natural Resources., Lansing, Michigan, April 1975.
14. Hesse, J,. L., *
-------
13. Personal Communication with Mr. James A. Cole, Chemical Samples Company,
Columbus, Ohio, January 1975.
16. Personal Communication with Mr. Fred Fields, Bromine Products Manager,
Ethyl Corporation, Baton Rouge, Louisiana.
17. Personal Communication with Mr. Phillip Lewis, Food and Drug Adminis-
tration, Washington, D.C., January 1975.
18. Moore, D. E., J. F. Mills, and J. A. Schneider, "Bromination With Bromine
Chloride Under Pressure,11 U.S. Patent 3,845,146, assigned to The Dow
Chemical Company, Patented 29 October 1974.
19. Mitchell, L. C., "Process For Production of Polybrominated Aromatics,"
U.S. Patent 3,763,248, assigned to Ethyl Corporation, Patented 2
October 1973.
20. o« .kner, H., "Process For The Production of Bromine Derivatives of Aro-
matic Compounds," U.S. Patent 3,285,965, assigned to Chemische Fabrik
Kalk G.m.b.H., Cologne-Kalk, Germany, Patented 15 November 1966.
21. Personal Communication with Dr. William C. Burnett, Regional Director
of U.S. Department of Health, Education and Welfare, Food and Drug
Administration Division, Kansas City, Missouri, February 1975.
22. Jackson, T. F., and F. L. Halbert, "A Toxic Syndrome Associated With
the Feeding of Polybrominated Biphenyl-Contaminated Protein Concen-
trate to Dairy Cattle," J, Amer. Vet. Med. Assn., 165(5):437 (1974).
23. Isleib, D. R., and G. L. Whitehead, "Polybrominated Biphenyls: An Agri-
cultural Incident and Its Consequences. I. The Agricultural Effects
of Exposure."
Humphrey, H. E. B., N. S. Haynes, and M. L. Budd, "Polybrominated Bi-
phenyls t An Agricultural Incident and Its Consequences. II. An
Epidemiclogleal Investigation of Human Exposure."
Technical Papers to be Presented at the 9th Annual Conference on Trace
Substances in Environmental Health, University of Missouri, Columbia,
9-12 June 1975.
24. Willett, L. B., and H. A. Irving, "The Distribution and Clearance of
Polybrominated Biphenyls by Cows," Technical Paper Scheduled for Pres-
entation at 70th Annual Meeting of the American Dairy Science Associ-
ation at Kansas State University, Manhattan, 22-25 June 1975.
47
-------
25. Cotane r ce , Business Dally, issue No. PSA-6276, p. 3, 11 March 1975.
26. Personal Gomnuhicat-idn with Mr. J; L. Hesse* Michigan Department of
Natural Resources* LaitBlng, Michigan, 16 January 1975.
27. Hiriseh, D. J.^ P. R;. Parrish, J. I. Lowe, A. J. Wilson, jr., and P. D.
Wilson, "GKfonic toxicity, Uptake, and Retention of a Polychlorinated
Biphehyi (Ardclof 1254) in two Estuaririe Fishes," Bull. .Environ.
i 6£2) 1 113-119 (1971),
28* Nebefeer, A. V.* F; A. PuBlls, and D. Lv Defoe, "toxicity of Polychlori-
riated Biphehyls (PGB's) to Fish and Other Aquatic Life," EPA, National
Water Quality Laboratory, Dialuth, Minnesota (1971).
29. Persona 1 Cbtiinuhicatioh with Mr. Jaime s Dunphy, White Chemical Corpora-
tion, Bayonne, Mew Jersey, 23 December 1974.
30 o Personal Communication with Mr. Patrick A. Lincoln, Waste Control Engi-
neer,! Michigan Chemical Corporation, St. Louis, Michigan, 16. May 1965.
31* M64terh\ f iaafeicis. Encycl6|iiedjta-y SJrlCIA* 197^-1975^ October 1974.
32. Lyons, Jv W*f the . .Ghemiat ry and U ses . 6 f . Fire Ret ardant s , Wiley-Inter-
scierite, a Division of John Wiley and Sons, the. , New York, New York
33. feefst, F., , "PolySrbln-ihia'te'd1 BIphenylisV1 a technical Presentation Con-
cerning Operations of Michigan Chemical Corporation, St. Louis,
Michigan, to the Hichigan Environmental Review Board, 23 September
34. Personal Gbmtiuriicatibn with Mr. Bill Ralmah, Standard t Chemical Com-
pany,1 S tat en IstaridV New Ybrlc, 3 March 11975.
35. Pe~r81ona'l' Corifeiuriicat-i;on wlthv Mr. Gerald' Shaw, Standard T Chemical Com-
pany, St«te'n island* New Yd^rlc^ 24 March 1975.
36. P;ersonall Gomtfiurill/c -Si -fdf^ WlMh: M*i Rbbeft Gilllgari, Borg-Wamer Corpora-
tiotiy Pa*Ke*siSiu*gV We'tfe V^rgiaiaV $& March 1975.
37:. B^atnag^ar; V.^MVr F^r^;.R^a^dknt\;M^litiidna ; Ha;ridbodk% Vol. I, Pro-
g'rfess1 irt F:tre" Jfte^aMiSricy £er'i:e'sy fechriomic Publishing Company, Inc.,
-------
38. Murray, R« W, "Combinations of Phosphonium Bromides and Brominated Aro-
matic Compounds as Flame Retardant Compositions for Olefin Polymers,"
U.S. Patent 3,699,077, assigned to American Cyanamld Company, Patented
17 October 1972.
39. Personal Communication with Dr. Chris Savides, American Cyanamid Com-
pany, Bound Brook, New Jersey, 21 April 1975.
40. Cyba, H. A., "Noval Flame Retardant Compositions of Matter," U.S. Patent
3,723,383, assigned to Universal Oil Products Company, Patented 27 March
1973.
41. Personal Communication with Mr. Ray Nelson, Universal Oil Products Com-
pany, Des Plaines, Illinois, 19 February 1975.
42. Green, J., and J. Versnel, "Self Extinguishing Composition," U.S. Patent
3,730,942, assigned to Cities Service Company, Patented 1 May 1973.
43. Personal Communication with Dr. Joseph Green, Cities Service Company,
New York, New York, 19 February 1975.
44. Personal Communication with Mr. Phillip Schlamt, General Electric Com-
pany, Bridgeport, Connecticut, April 1975.
45. Jenkner, H., "FUmeproofed Synthetic Resins," U.S. Patent 3,347,822
assigned to Chemlsche Fabrlk Kalk G.m.b.H., Cologne-Kalk, Germany,
Patented 17 October 1967.
46. Kolina, J. F., "There Are New Ways to Tame the Flame," Modern Plastics,
pp. 42-45, May 1975.
47. Hill Top Research, Inc., Acute Toxiclty and Irritation Studies Master
BP-6 Hexabromobiphenvl (1970).
48. Norrls, J. N., et al., "Toxicological and Environmental Factors Involved
in the Selection of Decabromobiphenyl Oxide as a Fire Retardant Chemi-
cal," Ap. Poly. Symp. No. 22. pp. 195-219 (1973).
49. Aftosmis, J. G., et al., "The Toxicity of Brominated Biphenyls. I.
Oral Toxiclty and Embryotoxicity," Presented at the Society of Toxi-
cology Meeting, March 1972.
50. Aftosmis, J. G., "Toxicology of Brominated Biphenyls. II. Skin, Eye,
and Inhalation Toxicity and an Acute Test Method for Evaluating Hepa-
totbxicity and Accumulation in Body Fat," Presented at the Society
of Toxicology Meeting, March 1972.
49
-------
51. 'Cecil, H. G. , J. pitman, G. F. Fries, L. W. Smith, and R. J. Lillie,
"PCB'B in Laying Hens," Preprint Paper, National Meeting, Division of
Water, Air, $«st,e iChe$istry, Amer. Ghem. Soc..
52. Cecil, H. C. , J. Bitman, R. J. Lillie, G. F. Fries, and J. Verrett,
^Erabryotoxic and Teratpgenic Effects in Unhatched Fertile Eggs from
Hens Fed Ppiy chlorinated Biphenyls (PCB's)," Bull. Envir. Contain.
ToxicpU. Ujc£)i489 -495 (1974). — ,— — . -•• .. , —-,-,.
53. Lillie, R. J., H. C. Cecil, j. Bitman, and G. F. Fries, Differences
in Refiponse of .Caged White Leghorn Layers to Various Pplychlprinated
Biphenyls (^GB1*) Jn the Dtiet." Poultry Sci.. 53172(5-732 (1?74).
54. Fries, G. F., L. ,W. .Smith, H. C. Cecil, J. Bitman, and R. J. Lillie,
'!Re tent ion and .Excretion of Polybrpminated Biphenyls by Hens and Cows,"
Presented at the 165th Meeting, Amerlean Chemical Society, Pallas,
Texaf, 11 April l!?73. "*""' '"' -. '"
' ".') ' *' ' ' *'*
55. Fries, p. F., ,and G, :S. .Mprrow, 'lExcretipn of Tplybrominated Biphenyls
Into the Milk ,pf C^ws,^ .^r^icjultura;! ;toy^ipental Quality Institute,
U.S. pepartment of Agriculture, unpublished document.
------- |