United States
Environmental Protection
Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S2-86/101 Mar. 1987
Project Summary
Dioxin and Furan
Contamination in the
Manufacture of Halogenated
Organic Chemicals
Anthony Lee, Beverly Campbell, and William Kelly
The manufacture of halogenated or-
ganic chemicals results in the forma-
tion of small amounts of undesirable
side reaction by-products. These con-
taminants may be contained in the
product chemical, separated into a
processing step residue, or lost to the
air or wastewater as a pollutant. The
halogenated dibenzo-p-dioxins (diox-
ins) and halogenated dibenzofurans
(furans) are substances which may be
hazardous to human hearth or the envi-
ronment. Identification of sources of
these compounds will aid strategies to
protect the public from exposure to
these chemicals.
For several years, attention has been
focused on one member of the dioxin
family, namely 2,3,7,8-tetra-
chlorodibenzo-p-dioxin (2,3,7,8-TCDD).
In this report, a brief review of impor-
tant chlorinated organic chemicals as-
sociated with dioxin and furan contam-
ination is followed by an extensive
discussion of brominated organic
chemical manufacturing. Potential for
dioxin and furan contamination is pre-
dicted and available information on ac-
tual product analysis is presented. The
results of this study may be used to
identify sources of dioxins and furans
and to develop methods to eliminate,
reduce or isolate the occurrence of
these compounds.
This Project Summary was devel-
oped by EPA's Hazardous Waste Engi-
neering Research Laboratory, Cincin-
nati, OH, to announce key findings of
the research project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering infor-
mation at back).
Introduction
Polychlorinated dibenzo-p-dioxins
(PCDDs) have been the subject of inten-
sive study by the scientific community
for many years. Often dubbed as the
"most toxic man-made substances,"
"carcinogenic," etc., the health and en-
vironmental risks of this class of chemi-
cals are a major concern throughout the
world.
There has been much confusion as to
when PCDDs and their toxic effects first
became known to the scientific world.
The composition and toxic effects of
PCDDs were known and reported in the
scientific literature as early as 1957.
Polychlorinated dibenzofurans
(PCDFs) are another class of contami-
nants that have aroused public concern.
They are frequently found with PCDDs
in chlorophenol products and also as
contaminants in polychlorinated
biphenyls (PCBs). Fires involving PCB-
filled transformers and capacitors have
been found to generate relatively large
amounts of PCDFs.
The U.S. Environmental Protection
Agency has taken a number of regula-
tory actions to control these sub-
stances. Actions by the Office of Pesti-
cide Programs have effectively banned
the use of trichlorophenol-based pesti-
cide substances such as 2,4,5-T and Sil-
vex® in which the contaminant 2,3,7,8-
TCDD has been found. Recently, the
Office of Solid Waste and Emergency
Response, acting under the Resource
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Conservation and Recovery Act (RCRA),
has proposed new rules for PCDDs- and
PCDFs-contaminated wastes specifying
stringent waste treatment require-
ments. Additional action has also been
taken to control exposure to PCBs. Con-
cern over the generation of PCDFs and
PCDDs in PCB-containing transformer
fires has led to new regulations by the
Office of Toxic Substances for phased
removal and replacement of the PCB
transformers.
To date, scientific and regulatory in-
terests have focused primarily on
chlorinated substances, in particular the
PCDDs, of which the 2,3,7,8-tetrachloro
isomer has been the subject of greatest
study. Similar chemical reactions are
known to occur in the manufacture of
brominated chemicals and thus polv-
brominated dibenzo-p-dioxins (PBDC )
and polybrominated dibenzofurar .
(PBDFs) may be formed as undesired
contaminants in certain brominated
chemical substances.
The full report presents available data
on processes used in the manufacture
of brominated compounds which are
most likely to be contaminated with
PBDDs and PBDFs. The chemical reac-
tions involved in the synthesis of the
brominated compounds are evaluated
in light of the reaction mechanisms that
lead to the formation of polyhalo-
genated dioxins and furans. Through
this assessment, it may then be possible
to identify critical data gaps and needs,
such as product assays and process
modifications to reduce the release of
PBDDs and PBDFs into the environ-
ment.
Brominated Organic Chemicals
Table 1 gives basic information on
brominated organic chemicals which
have a potential for PBDD or PBDF con-
tamination due to the raw materials and
processes used in their manufacture.
Relatively little recent data are available
due to the confidential nature of busi-
ness information in the organic chemi-
cals industry.
Few brominated organic chemical
products have undergone chemical
analysis for the presence and concen-
tration of dioxin and furan contamina-
tion. Some information is available for
2,4,6-tribromophenol, pentabromophe-
nol and tetrabromobisphenol A. The an-
alytical procedure in each case was high
resolution gas chromatography/mass
spectrometry. No dioxins or furans
were found in the pentabromophenol.
Contaminants in the 2,4,6-tribromophe-
nol included:
• Dibromodibenzo-p-dioxin
• Tribromodibenzo-p-dioxin
• Tetrabromodibenzo-p-dioxin
(main component, —90 ppb)
• Pentabromodibenzo-p-dioxin
• Dibromodibenzofuran
• Tribromodibenzofuran
• Tetrabromodibenzofuran
• Pentabromodibenzofuran
• Hexabromodibenzofuran
• Heptabromodibenzofuran
• Octabromodibenzofuran
Contaminants in the tetrabromobisphe-
nol A were:
• Pentabromodibenzofuran
• Hexabromodibenzofuran
• Heptabromodibenzofuran
• Octabromodibenzofuran (main
component, —30 ppb)
Possible reaction pathways and most
likely dioxin and furan contaminants are
listed for many other compounds ap-
pearing in Table 1.
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Table 1. Compounds with Potential PBDD and PBDF Contamination
Name Structure
Uses
Production
BROMINATED PHENOLS
4-Bromo-2,5-dichlorophenol
- 2,5-Dichloro-4-bromophenol
- Leptophos phenol
- Phosvel phenol
o-Bromophenol
- 2-Bromophenol
OH
Cl
Br
OH
Br
N.D.
Synthesis of resorcinol, other
organics
N.D.1
N.D.
OH
m-Bromophenol
- 3-Bromophenol
p-Bromophenol
- 4-Bromophenol
2,6-Dibromo-4-nitrophenol
- 4-Nitro-2,6-dibromo-
phenol
2,4-Dibromophenol
Br
OH
Br
OH
Br^^ Br
N02
OH
.Br
• Antiseptic
• Synthesis of other compounds
- flame retardant intermediate
N.D.
N.D.
2:5,000 Ibs or
$5,000 sales
(USITC, 7984;
N.D.
Br
2,6-Dibromophenol
Pentabromophenol
- F/ammex 5BP
Tetrabromocatechol
• Tetrabromopyrocatechol
2,4,6-Tnbromo-m-cresol
- 2,4,6-Tribromo-3-methyl
phenol
- Triphysan
- Triphysol
OH
Br
o
Br
Br
OW
Br
OH
c*
N.D.
Flame retardant intermediate
Molluscicide (experimental)
N.D
N.D.
< 1,000 Ibs/yr
(EPA estimate)
N.D.
N.D.
N.D.
Br
2,4,6-Tribromophenol
- Bromkal Pur 3
- Bromol
- Flammex 3BP
- Great Lakes PH-73
- Tribromophenol
OH
Br ^^ Br
Br
• Flame retardant intermediate
• Anti-fungal agent
• Chemical intermediate
• Antiseptic germicide
>2.27 x W3 kg
(1979}
>4.54 x W3 kg
(1981)
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Table 1. (Continued)
Name
Structure
Uses
Production
BROMINATED COMPOUNDS
Bromobenzene
- Monobromobenzene
- Phenylbromide
• Solvent
• Top-cylinder compound
• Chemical intermediate
z454 kg
z450 kg (197*
s5,000 Ibs or
$5,000 sales
(USITC, 198-
o-Bromofluorobenzene
- l-Bromo-2-fluorobenzene
- o-F/uorobromobenzene
- 2-Fluorobromobenzene
- 1-Fluoro-2-bromobenzene
< 1,000 Ibs/yr
(EPA CBI
Aggregate)
Decabromodiphenyloxide
- Berkflam 81OE
- Bis (pentabromophenyl) ether
- Bromkal 81
- Bromkal 82-ODE
- Bromkal 83-1 ODE
- BR55N
-DE 83
- DE 83R
- Decabrom
- Decabromobiphenyl ether
- Decabromobiphenyloxide
- Decabromodiphenyl ether
- Decabromophenoxybenzene
- Decabromophenyl ether
- EB10FP
- EBR 700
- FR 300
- FR 300BA
- FRP 53
- FR-PE
- Planelon DB100
- Saytex 102
- Saytex 102E
Br Br Br Br
- Flame retardant
2-8 million Ibs
yr (1976)
Br Br Br Br
2,6-Dibromobenzene
- m-Dibromobenzene
- 1,3-Dibromobenzene
Br ^^ Br
0
Ingredient of fire extinguishers
Flame retardant
Ingredient of heat transfer fluids
N.D.
2,4-Dibromofluorobenzene
- 1,3-Dibromo-4-fluoro-
benzene
2,6-Dibromofluorobenzene
Hexabromobenzene
- Benzene hexabromide
-HBB
- Perbromobenzene
Intermediate for agricultural
and pharmaceutical chemicals
N.D.
- Flame retardant
N.D.
N.D.
908 kg
454 kg (1975
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Table 1. (Continued)
Name
Structure
Uses
Production
Pentabromochlorocyc/ohexane
- Chloropentabromocyclohexane
- FR 651A
- 1,2,3,4,5-Pentabromo-6-
chlorocyclohexane
c/
Br
- Flame retardant
W6-W7 Ibs/yr
(EPA estimate)
Pentabromoethylbenzene
- EB 80
- Saytex 105
Pentabromotoluene
- Flammex 5BT
- Pentabromomethylbenzene
Tetrabromophthalic Anhydride
- Bromphthal
-FG4000
- FireMaster PHT4
- Great Lakes PHT4
- Saytex RB-49
1,2,4-Tr/bromobenzene
1,3,5-Tribromobenzene
^ '
Br
Br
CH3
Br
" ~
Br
Br
°
Br 0
Br
Br
Br
- Flame retardant
Flame retardant
" Flame retardant
- Oil additive
il additive
N.D.
N.D.
--2.27 x 103 kg
(1979)
=6.87 x 103 kg
(1981)
N.D.
N.D.
BROMINATED BIS PHENOLS
1,2-Bis(tribromophenoxy) ethane
- BTBPE
- FireMaster 680
>^-\ _
Br -/ \OCH2CHzoC /^
_ y
Br
- Flame retardant
N.D.
2,6-Dibromobisphenol A
r CH
f=\ • /=\
H° \___7~ ^ \__y~°H
- Flame retardant
N.D.
Octabromodiphenyloxide
- DE-79
- FR 143
- Octabromodiphenyl ether
- 1,1'-Oxybis-octabromo-
benzene
- Tardex 80
Br Br Br Br
) — <>. ; — \
^ V 0 -T ^
\-=-' ^^Y
Br
Br
- Flame retardant
N.D.
Pentabromodiphenyloxide
-DE71
- 1,1'-Oxybis-pentabromobenzene
- Pentabromodiphenyl ether
( _ _ ,
// \.o/' \
\ ~ / \ — /
Br Br Br
- Flame retardant
N.D.
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Table 1. (Continued)
Name
Structure
Uses
Production
Tetrabromobisphenol A
-BA59
- BA 59P
- 2,2-Bis(3,S-dibromo-4-
hydroxyphenyl) propane
- Bromdian
- Fireguard 2000
- FireMaster BP4A
- 4,4'-lsopropylidene bis-
(2,6-dibromophenol)
- Saytex FtB-100
- Tetrabrodian
- Tetrabromodihydroxy diphenyl
propane
* CH3*
C^OH
Br °"3 Br
- Flame retardant
- Plasticizer (limited)
>106 Ibs/yr
Tetrabromobisphenol A, allyl ether
- 1,l-(l-Methylethyllidene)-
bis(3,5-dibromo)-4-
(2-propenyloxy)-benzene
)—\ CH3 i—<
H°\-/ ? \- /-°-
*-—' r~u ^~~<
Br CHa Br
• Flame retardant
N.D.
Tetrabromobisphenol A-bis-2,3-dibro-
mopropyl ether
Br
- 2,2-Bis[3,5-dibromo-4- BrCH2CHCH20 •(' ^}-C-(' ^\OCH£HBrCH,Br
(2,3-dibromopropoxy)
phenyl\-propane
- Fire Guard 3100
- Great Lakes PE-68
Tetrabromobisphenol A-bisethoxylate
Tetrabromobisphenol A, bismethylether
Tetrabromobisphenol A-diacrylate
- 4,4'-lsopropylidene-
bis(2,€-dibromophenyl)-
acrylate)
Tetrabromobisphenol B
PESTICIDES
Br
CH3
CH3
Br
- Flame retardant
N.D.
Br
CH3CH20 -C
CH:
Br
Br
Br
Br
Br
/-\ CHa /-A
CH30-{' V c -C XVOCW3
\^y • \-/
Br CH* Br
O
Br CH3 Br Q
^O-r' _ /- C -V _ ^OCCH=CH2
Br
Br
CH3 ^Br
Br
Br
gr
- Propane
- Flame retardant
- Flame retardant
- Flame retardant
- Flame retardant
N.D.
N.D.
N.D.
N.D.
Bromophos
- Brofene
- o-(4-Bromo-2,5-dichloro-
phenyl)-o,o-dimethyl,
phosphorothioate
- Bromofos
- Brophene
- Nexion
- Nexion 40
- SI 942
CH3O S
CH30'
Cl
- Insecticide
N.D.
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Table 1. (Continued)
Name
Structure
Uses
Production
Bromoxynil butyrate
• 2,6-Dibromo-4-cyano-
phenyl butanoic ester
Bromoxynil octanoate
- Bronate
- Buctril
• 3,5-Dibromo-4-octanoyl-
oxybenzonitrile
Br
Q ) — v
-
Br
Br
Br
- Insecticide
Herbicide
N.D.
N.D.
Profenofos
- o-(4-Bromo-2-chloro-
phenyl)-o-ethyl-S-propyl-
phosphorothioate
- CCA 15324
- Curacron
- Polycron
- Selecron
P-O/' >Br
Cl
• Insecticide
N.D.
1N.D. = No Data
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Anthony Lee, Beverly Campbell, and William Kelly are with Technical Resources,
Inc., Rockville. MD 20852.
Brian A. West fall is the EPA Project Officer (see below).
The complete report, entitled "Dioxin and Furan Contamination in the
Manufacture of Halogenated Organic Chemicals," (Order No. PB 87-119905/
AS; Cost: $13.95, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield. VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Hazardous Waste Engineering Research Laboratory
U.S. Environmental Protection Agency
Cincinnati. OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
BULK RATE
POSTAGE & FEES
EPA
PERMIT No G-
Official Business
Penalty for Private Use S300
EPA/600/S2-86/101
0000329 PS
S
CHICAGO
AGENCY
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