vvEPA
United States
Environmental Protection Agency
EPA Document** 740-Q1-4001
August 2015
Office of Chemical Safety and
Pollution Prevention
TSCA Work Plan Chemical
Technical Supplement- Physicochemical Properties and
Environmental Fate of the Brominated Phthalates Cluster
(BPC) Chemicals
Brominated Phthalates Cluster
Flame Retardants
CASRN
26040-51-7
183658-27-7
20566-35-2
77098-07-8
7415-86-3
*
*
NAME
1,2-Benzenedicarboxylic acid, 3,4,5, 6-tetrabromo-, l,2-bis(2-
ethylhexyl) ester
Benzole acid, 2,3,4,5-tetrabromo-, 2-ethylhexyl ester
1,2-Benzenedicarboxylic acid, 3,4,5, 6-tetrabromo-, l-[2-(2-
hydroxyethoxy)ethyl] 2-(2-hydroxypropyl) ester
1,2-Benzenedicarboxylic acid, 3,4,5, 6-tetrabromo-, mixed
esters with diethylene glycol and propylene glycol
1,2-Benzenedicarboxylic acid, l,2-bis(2,3-dibromopropyl) ester
Confidential A
Confidential B
* Confidential Business Information
August 2015
-------
TABLE OF CONTENTS
TABLE OF CONTENTS 2
1 INTRODUCTION 3
1.1 CHEMICAL AND PHYSICAL PROPERTIES 4
1.1.1 Reactive BPC members 4
1.1.2 Additive BPC members 5
1.2 ENVIRONMENTAL FATE AND BIOACCUMULATION 6
1.2.1 Summary 6
1.2.2 Fate in Air and the Indoor Environment 7
1.2.3 Fate in Water 8
1.2.4 Fate in Soil and Sediment 10
1.2.5 Bioaccumulation 10
1.3 ENVIRONMENTAL FATE AND BIOACCUMULATION-DATA NEEDS 13
1.3.1 Ambient Environment 13
1.3.2 Indoor Environment 14
REFERENCES 14
LIST OF TABLES
Table 1-1: Physicochemical properties of TBPH 5
Table 1-2: Physicochemical Properties of TBPA Diol 5
Table 1-3: Environmental Fate Data forthe Brominated Phthalates Cluster 11
TABLE OF FIGURES
Figure 1-1: Generic Structure of the Brominated Phthalates Cluster Chemicals 3
Figure 1-2: Generic structure of the BPC members and CASRN 7415-86-3 4
Page 2 of 17
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1 INTRODUCTION
Each chemical in this cluster has several structural features in common:
1) Multiple bromine atoms, typically attached to the aromatic ring
2) The 1,2-benzenedicarboxylate moiety (phthalate structure)1 and
3) Alkyl esters
Br O
Br
O-Alkyl
O—Alkyl
Br O
Figure 1-1: Generic Structure of the Brominated Phthalates Cluster Chemicals
Some members of the cluster have free primary or secondary alcohol functionalities. These
may impart certain properties to the chemical substance [making them more water soluble and
chemically reactive], more significantly the alcohol moiety can react to incorporate the
brominated (BFR) into the substrate via covalent bond formation. These chemicals are not
limited to that reactive form of application and they could also be mixed with substrate as an
additive flame retardant (FR).
The one cluster member is an anomaly when compared to the structure of the other cluster
member chemicals, bis (2,3-dibromopropyl) 1,2-benzenedicarboxylicacid (CASRN 7415-86-3).
The primary difference between this chemical and the other cluster members is the positioning
of the four (4) bromine atoms (on the alkyl ester moieties) as opposed to the positions on the
benzene ring.
1 The cluster member 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB; CASRN 183658-27-7) is missing one of
the phthalate carboxylate ester but is including in this cluster since the commercial product Firemaster 550
also contains the TBB/TBPH phthalate mixture. This structural anomaly should not affect the inclusion of this
chemical since phthalates often decarboxylate during metabolism and biodegradation. (Robbert
Kleerebezem*,
Page 3 of 17
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Br O
Br
0-Alkyl
O-Alkyl
Figure 1-2: Generic structure of the BPC members and CASRN 7415-86-3
1.1
CHEMICAL AND PHYSICAL PROPERTIES
1.1.1 Reactive BPC members
The reactive members of the BPC are 1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, l-[2-
(2-hydroxyethoxy)ethyl] 2-(2-hydroxypropyl) ester (TBPA-Diol; CASRN 20566-35-2) and 1,2-
Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, mixed esters with diethylene glycol and
propylene glycol (TBPA-Diol; CASRN 77098-07-8).
Because these chemicals are chemically bound to the polymer, it is far less likely they will
migrate from products or articles unless there is excess chemical present due to an incomplete
polymerization reaction. The reactive members of the brominated phthalates cluster (BPC),
including the primary degradation product tetrabromophthalic acid, have not been reported in
literature as being present in environmental or biological media.
The brominated phthalates with hydroxyalkyl esters are generally intended to react with
isocyanate monomers and become covalently bonded into the chemical backbone of the
polyurethane foams (PUF). There is no evidence of the phthalate esters based urethane
linkages ever depolymerizing under abiotic, biotic, or metabolic conditions. One may anticipate
that if depolymerization were to occur the ester linkage would cleave before the carbamate
linkage generating the tetrabromophthalate diacid as a predominant product. There has been
no monitoring data indicating the presence of hydroxyalkyl tetrabromophthalates in the
environment or biota. As such worker exposures would be the main concern during chemical
manufacturing and PUF manufacturing. The esters are liquids with negligible vapor pressure
and limited but measurable water solubility because of the hydroxyl and/or other oxygen
atoms in the molecule [one MSDS states < 1 g/L; the estimates are substantially lower than this
number but seem unreasonable). In one patent [Grain and Surma, 2010], it is noted that both
reactive and additive BPC chemicals can be added to foam, which would again lead to potential
release of one type of BPC while the reactive BPC would be self contained in the foam
backbone .
Page 4 of 17
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1.1.2 Additive BPC members
The additive members of the BPC are 1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, 1,2-
bis(2-ethylhexyl) ester (TBPH; CASRN 26040-51-7), benzoic acid, 2,3,4,5-tetrabromo-, 2-
ethylhexyl ester (TBB; CASRN 183658-27-7) and 1,2-Benzenedicarboxylic acid, l,2-bis(2,3-
dibromopropyl) ester (CASRN 7415-86-3).
Additive flame retardants are incorporated and dispersed throughout a product, but are not
chemically bound to it. Additive flame retardants are more likely than reactive flame
retardants to migrate from products or articles. Emissions from a single product or article may
be small. However, combined emissions from all sources within various indoor
microenvironments, residences, schools, public and commercial buildings, cars, trains,
airplanes, may be significant.
TBPH and TBB are liquids with negligible vapor pressure and water solubility. They have the
same functional groups and may be considered close analogs of one another.
There are few measured physicochemical properties values for Melting Point, Boiling Point,
Vapor Pressure, Water Solubility or Octanol Water Partition Coefficient for these chemicals.
The MSDS sheet (Unitex, 2006) for pure TBPH provides some range limits for the cluster as does
the water solubility [1.3 mg/L at 25°C, (ECHA, 2013)] for the unbrominated di(2-ethylhexyl)
phthalate (DEHP); while the more water soluble products [hydroxyl containing] are represented
by CASRN 77098-07-8, a submission under the HPV Challenge program (Albemarle - GLCC,
2004).
Table 1-1: Physicochemical properties of TBPH
l
TBPH
MP _
< -20 °C
__JBP_____L_^_VJL | s-H2p
> 400 °C
< 1.0 E-3 Torr
at 25 °C
insoluble
LogJi5ML__|
9.34
(ACD est.)
Source: Unitex Chemical Corp. Uniplex FRP-45 MSDS (Unitex, 2006)
Table 1-2: Physicochemical Properties of TBPA Diol
Compound
CASRN
77098-07-8
MP
NA
B
N
A
V
< 1E-6 Torr
(est.)
S-H2O
<1
g/L
MS
Log Kow
3.83
(EPI est.)
Source: EPA HPV Challenge Program submission (Albemarle - GLCC, 2004)
CASRN 7415-86-3
No data were located for this cluster member.
Page 5 of 17
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In addition to the chemicals already described, Confidential A, and Confidential B can be
considered analogous to the other cluster members described here. There was little to no
physicochemical data, and structures for these chemicals are similar enough to use read across.
1.2.1 Summary
Very little information exists on the environmental fate and bioaccumulation of the brominated
phthalates cluster (BPC) members. 1,2-Benzenedicarboxylicacid, 3,4,5, 6-tetrabromo-, l,2-bis(2-
ethylhexyl) ester (TBPH) and benzoic acid, 2,3,4,5-tetrabromo-, 2-ethylhexyl ester (TBB) are the
best studied and may be considered close analogs of one another. Based on available data,
both compounds are ranked low for persistence (PI) relative to standard criteria (EPA, 1999b).
The tetrabrominated microbial degradation and/or hydrolysis products tetrabromophthalic acid
and tetrabromobenzoic acid are expected to be much more persistent and are ranked as P3.
Estimated bioaccumulation factors (BAFs) suggest that TBPH and TBB have low (Bl) and
moderate bioaccumulation potential (B2), respectively. The phthalicand benzoic acid products
are also considered to have low (Bl) and moderate bioaccumulation potential (B2),
respectively.
TBPH and TBB are expected to have low mobility in soil. Biodegradability is not well
characterized but based on available data, half-lives for primary degradation in water may be
on the order of days. Primary biodegradation of TBPH and TBB is expected to yield the
monoethylhexyl ester of tetrabromophthalic acid and tetrabromobenzoic acid as the main
products, respectively. Abiotic hydrolysis may occur, but the low solubility of TBPH and TBB
may lower the effective rate of hydrolysis in the environment. Based on estimated half-lives
and considering the low water solubility, rates of abiotic hydrolysis are expected to be
negligible at environmental pH and temperatures. The ultimate hydrolysis products of TBPH
and TBB, 3,4,5,6-tetrabromo- 1,2-benzenedicarboxylic acid (i.e. tetrabromophthalic acid) and
tetrabromobenzoic acid, are expected to be resistant to further abiotic transformations as well
as biodegradation and may be persistent in the environment. The rate of atmospheric gas-
phase (hydroxyl radical) photo-oxidation has the potential to be moderate; however, these
substances are expected to exist primarily in the particulate phase in the ambient atmosphere,
and generally it is assumed that oxidation of particle-bound substances is slow or negligible.
Particulate-phase TBPH and TBB are expected to be removed from the atmosphere by wet and
dry deposition processes. TBPH and TBB absorb light at environmentally significant
wavelengths, but the importance of this process for environmental waters has not been
established. These chemicals have the potential to be transported far from their original point
of release, primarily in the atmospheric particle-bound form.
1,2-Benzenedicarboxylicacid, 3,4,5,6-tetrabromo-, l-[2-(2-hydroxyethoxy)ethyl] 2-(2-
hydroxypropyl) ester and 1,2-benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, mixed esters with
Page 6 of 17
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diethylene glycol and propylene glycol (CASRNs 77098-07-8 and 20566-35-2) are expected to
have high mobility in soil. Estimated abiotic hydrolysis half-lives for this substance are lower
than for TBPH and TBB (on the order of days to months depending on the estimation program),
but these values are still considered to be in the slow-to-negligible category (EPA, 2012f). No
biodegradation data were available for this substance. Given its molecular structure this
substance would not be expected to be readily biodegradable, but both abiotic hydrolysis and
biodegradation may produce the same brominated degradation product as for TBPH; namely
tetrabromophthalic acid. As for TBPH and TBB, the estimated rate of atmospheric
photooxidation is moderate; however, this is not expected to be an important environmental
degradation pathway. Given the estimated rate of hydrolysis, CASRN 77098-07-8 is expected to
have low persistence (PI) and low bioaccumulation potential (Bl). However, the degradation
product tetrabromophthalic acid is expected to have high persistence (P3) and low
bioaccumulation potential (Bl).
No measured environmental fate data exist for 1,2-benzenedicarboxylic acid, l,2-bis(2,3-
dibromopropyl) ester, CASRN 7415-86-3. Both estimated vapor pressure and volatility, based
on estimated Henry's Law constant, are low. This substance is expected to partition strongly to
environmental solid phases (in sludge, soil, etc.) and have low-to-moderate mobility in soil.
Based on chemical structure and estimated data hydrolysis may occur, but the rate is expected
to be negligible. Given its molecular structure this substance would not be expected to be
readily biodegradable. Atmospheric photooxidation is expected to be slow. This substance is
estimated to be moderately persistent (P2) and bioaccumulative (B2). Hydrolysis, if it occurs,
may yield 2,3-dibromopropanol as a product, but neither this nor any other hydrolysis products
are expected to have PBT properties.
1.2.2 Fate in Air and the Indoor Environment
BPC members have low-to-negligible vapor pressures and low-to-negligible volatility, and as a
result, inhalation of volatilized (gas phase) substances is expected to be a minor route of indoor
exposure for all BPC members. In contrast exposure via dust may be important, but little
information is available on how these compounds get into house dust. This process may
involve direct transfer from flame-retarded objects, driven by partitioning properties of the
substances. Measured concentrations of TBPH (AN et al., 2012; Allen et al., 2013a; Allen et al.,
2013b; Bradman et al., 2012; Dodson et al., 2012; Gheorghe et al., 2013; Johnson et al., 2013;
Kopp et al., 2012; Sahlstrom et al., 2012; Schlabach et al., 2011; Shoeib et al., 2012; Springer et
al., 2012; Stapleton et al., 2008a; Stapleton et al., 2009; Stapleton et al., 2008b; Van den Eede
et al., 2012) and TBB (AN et al., 2012; Allen et al., 2013a; Allen et al., 2013b; Bradman et al.,
2012; Dodson et al., 2012; Gheorghe et al., 2013; Johnson et al., 2013; Kopp et al., 2012;
Sahlstrom et al., 2012; Schlabach et al., 2011; Shoeib et al., 2012; Springer et al., 2012;
Stapleton et al., 2008a; Stapleton et al., 2009; Stapleton et al., 2008b; Van den Eede et al.,
2012) in indoor air and dust are consistent with these predictions. The relative contributions of
indoor air and dust to overall exposure indoors are expected to be similar to that reported for
polybrominated diphenyl ethers (PBDEs) in the indoor environment (Webster et al. 2013), for
which dust was considered important but indoor air not.
Page 7 of 17
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If released to the ambient atmosphere, these compounds are expected to exist primarily in the
particulate phase, given their estimated vapor pressures. Consequently, the photochemically
catalyzed vapor phase reaction with hydroxyl radicals (for which half-lives are given in Table
1-3) is not expected to be environmentally relevant. Davis and Stapleton (2009) measured half-
lives for photodegradation of TBPH and TBB by sunlight in several organic solvents. Half-lives
for photodegradation of TBPH in toluene, methanol, and tetrahydrofuran were 147, 220 and
168 min, respectively. For TBB the values were 162, 95, and 85 min. These results suggest that
both substances absorb light and photodegrade at environmentally important wavelengths,
although for water the importance of this process is not known.
In the particulate phase, they may be subject to removal from the atmosphere via wet or dry
deposition. TBB and TBPH have the potential to be transported far from their original point of
release (Harju et al., 2009), but their atmospheric transport behavior is determined by the
transport behavior of the particles to which they sorb. A study of arctic biota by Harju et al.
(2009) provides supporting evidence of long-range transport. In an air monitoring study TBPH
and TBB were detected at high frequency in samples collected from North America, Central and
South America, Europe, Africa, Asia, and Australia (Lee et al., 2010), providing additional
evidence for the ability of these substances to enter the atmosphere and undergo long-range
transport.
CASRNs 77098-07-8 and 20566-35-2, and CASRN 7415-86-3 are expected to behave similarly to
TBPH and TBB in the atmosphere. The estimated Henry's Law constants are negligibly low
(Table 1-3) and as a result, they are not expected to volatilize from water or soil. However,
even if released to the atmosphere, they are expected to exist primarily in the particulate
phase. Consequently, the photochemically catalyzed vapor phase reaction with hydroxyl
radicals is not expected to be environmentally relevant.
J^LJ^^
If released to water, TBPH and TBB are expected to adsorb to sediment and suspended
particulate matter, based upon the estimated Koc values (Table 1-3). Volatilization from water
is not expected to be an important environmental fate process given the estimated Henry's Law
constants. Abiotic hydrolysis may occur, but the low solubility of TBPH and TBB may lower the
effective rate of hydrolysis in the environment. Based on estimated half-lives and considering
the low water solubility, rates of abiotic hydrolysis are expected to be negligible at
environmental pH and temperature. The ultimate hydrolysis products of TBPH and TBB,
3,4,5,6-tetrabromo- 1,2-benzenedicarboxylic acid (i.e. tetrabromophthalic acid) and
tetrabromobenzoic acid, respectively, are expected to be resistant to further abiotic
transformation as well as biodegradation and may be persistent in the environment.
TBPH was not readily biodegradable in one test, achieving less than 4% of its theoretical oxygen
demand after 28 days in a test with inoculum from secondary effluent from a tricking filter at a
sewage treatment plant that received predominantly domestic waste (Table 1-3). It is unclear
Page 8 of 17
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whether these results represent a combination of a closed bottle test (OECD TG 301D) and a
modified Sturm test (OECD TG 301B), or two separate tests. In a separate Porous Pot test
(OECD TG 303A) conducted using a commercial mixture of TBPH and TBB, these substances did
not biodegrade but did show substantial total removal (>= 93%) by sorption to sludge.
Primary biodegradation of TBPH and TBB is expected to yield the monoethylhexyl ester of
tetrabromophthalic acid and tetrabromobenzoic acid as the main products, respectively. A
shake-flask die-away study (OCSPP 835.3170) of the same commercial mixture yielded half-lives
for disappearance of the starting material of 3.5 days and 8.5 days in active water and active
sediment test systems, respectively. Neither ultimate degradation nor other possible
metabolites were measured in this test.
Recently de Jourdan et al. (de Jourdan et al., 2013) studied the fate of TBPH and TBB in aquatic
mesocosms, which are designed to closely simulate environmental conditions. This type of
study can be considered a higher tier (more realistic) form of simulation test, in comparison to
die-away studies as summarized above. The median dissipation times (DT50) differed in the
two compartments, with more rapid disappearance in the particulate (9-30 d) than in the
sediment compartment (>100 d) for each compound. The degradation products were more
concentrated in the particulate compartment and corresponded to known photodegradation
products. The ratio of TBB to TBPH differed in the mesocosm compartments compared with
the starting test material, indicating increased degradation of TBB relative to TBPH. In the die-
away test (discussed in the preceding paragraph) the "active sediment" treatment had a low
level of suspended sediment in natural water; thus it is analogous to the "particulate phase"
treatment in the de Jourdan et al. (de Jourdan et al., 2013) mesocosm study. The reported
DTSOs of 9-30 d for the particulate compartment therefore can be compared to the 8.5-day
half-life for the "active sediment" die-away treatment. The higher DTSOs observed in the
"sediment phase" portion of the mesocosm study would be expected, given that as a rule,
organic chemicals degrade more slowly under the anaerobic conditions prevalent in benthic
sediments.
Davis and Stapleton (Davis and Stapleton, 2009) measured half-lives for photodegradation of
TBPH and TBB by sunlight in several organic solvents. Half-lives for photodegradation of TBPH
in toluene, methanol, and tetrahydrofuran were 147, 220 and 168 min, respectively. For TBB
the values were 162, 95, and 85 min. These results suggest that both substances absorb light
and photodegrade at environmentally important wavelengths, but the importance of this
process for the water environment is not known. The observation by de Jourdan et al. (2013)
that mesocosm degradation products corresponded to known photodegradation products is
consistent with Davis and Stapleton (Davis and Stapleton, 2009), but again, photodegradation
has not been directly studied under environmentally relevant conditions.
Estimated abiotic hydrolysis half-lives for 3,4,5,6-tetrabromo-l,2-benzenedicarboxylic acid,
mixed esters with diethylene glycol and propylene glycol (CASRNs 77098-07-8 and 20566-35-2)
are lower than for TBPH and TBB (on the order of days to months depending on the estimation
program), but still considered to be in the slow-to-negligible category. No biodegradation data
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were available for this substance. Given its molecular structure it would not be expected to be
readily biodegradable, but both abiotic hydrolysis and biodegradation may produce the same
brominated degradation product as for TBPH; namely tetrabromophthalic acid. The
nonbrominated ester hydrolysis product(s) of 3,4,5,6-tetrabromo-l,2-benzenedicarboxylicacid,
mixed esters with diethylene glycol and propylene glycol are expected to be rapidly
biodegradable under all conditions. l,2-(2,3-Dibromopropyl) benzene dicarboxylate (CASRN
7415-86-3) is estimated to hydrolyze abiotically more slowly than other cluster members (i.e. at
a negligible rate) but is similarly not expected to be readily biodegradable. Abiotic or
biologically catalyzed hydrolysis, if either occurs, may yield 2,3-dibromopropanol as a product.
If released to soil, TBPH and TBB are expected to have low mobility, based on their estimated
log Koc values. Estimated Koc values for l,2-(2,3-dibromopropyl) benzene dicarboxylate (CASRN
7415-86-3) are just below the threshold for low/moderate mobility, suggesting that mobility
may be characterized as low-to-moderate for this cluster member. In contrast, 3,4,5,6-
tetrabromo-l,2-benzenedicarboxylic acid, mixed esters with diethylene glycol and propylene
glycol (CASRNs 77098-07-8 and 20566-35-2) is expected to have high mobility in soil. The
biodegradation studies and other evidence discussed above suggest that ultimate degradation
of the brominated benzoic and phthalic acid degradation products of BPC members is likely to
be slow. One study is available for tetrabromophthalic anhydride (CASRN 632-79-1), which
would be quickly hydrolyzed to tetrabromophthalic acid (CASRN 13810-83-8) in the
environment, and it showed no degradation in 28 days (Butz, 1979). The nonbrominated
products that would be formed from biological or abiotic hydrolysis of the parent materials are
expected to biodegrade easily under all environmental conditions. Volatilization from moist soil
surfaces is expected to be low given the negligibly low estimated Henry's Law constants (Table
1-3). Hydrolysis may be an important environmental fate process in moist soil but this requires
experimental confirmation.
Davis (Davis, 2013) studied the fate of TBPH and TBB in greenhouse experiments. These
compounds were found to resist degradation biosolids-amended, in non-vegetated soil, but in
biosolids-amended soil planted with alfalfa, 43% of TBPH was lost in 28 days in the high
biosolids-amended pots. It was stated that no clear evidence of phytoaccumulation was
observed, suggesting that TBPH loss was due to degradation in the soil.
1.2.5 Bioaccumulation
A commercial mixture of TBPH and TBB served as the test substance in a rainbow trout
bioconcentration study. The whole-fish measured bioconcentration factor (BCF) for the
mixture was 2.02 (log BCF = 0.31). Steady state was achieved in that study, which used uptake
and depuration periods of 35 and 14 d, respectively. Estimated BAFs (BCFBAF v3.00) suggest
low bioaccumulation potential (Bl) for TBPH but moderate potential (B2) for TBB (Table 1-3).
BCFBAF calculates a metabolic transformation half-life normalized to a lOg fish and the ester
linkage has the largest negative fragment coefficient, suggesting this may be the primary site of
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transformation forTBPH and TBB. However, metabolic biotransformation via debromination in
fish could also reduce bioaccumulation (Stapleton et al., 2004). (Sagerup et al., 2010) observed
apparent trophic magnification of TBB, but not TBPH, in an Arctic food chain in Svalbard,
Norway. The food chain included one fish species, capelin (Mallotus villosus); three seabird
species: common eider (Somateria mollissima), Brunnich's guillemot (Uria lomvia), and black-
legged kittiwake (Rissa tridactyla); and three mammalian species: ringed seal (Phoca hispida),
Arctic fox (Vulpes lagopus), and polar bear (Ursus maritimus). TBB was detected in all seven
species and TBPH in five of the seven species at ng/g levels. Lipid-adjusted concentrations did
not scale with trophic level with the exception of TBB, which was detected in polar bears at
414.8 ng/g lipid weight, more than 30 times its concentration in primary prey (ringed seal).
TBPH was not detected in polar bears.
Estimated BAFsforthe possible microbial degradation and/or hydrolysis products
tetrabromophthalic acid and tetrabromobenzoic acid are below numerical thresholds for
bioaccumulation concern; i.e. they are formally Bl (Table 1-3). However, it should be noted that
for the benzoic acid the calculated BAF for upper trophic-level fish is close to the B2 criterion
(i.e. log BAF = 3.00). Without metabolism, the predicted log BAF is 5.18, which exceeds the
threshold for high concern (B3). Based on the above results this expected chief degradation
product of TBB is considered to have moderate bioaccumulation potential (B2). This is
appropriate also because this substance is judged likely to be much more persistent in the
environment than the parent, thus increasing its potential to reach and accumulate in
organisms.
There are no experimental data for 3,4,5,6-tetrabromo-l,2-benzenedicarboxylic acid, mixed
esters with diethylene glycol and propylene glycol (CASRNs 77098-07-8 and 20566-35-2), but
based on chemical structure and estimated BCF and BAF (Table 1-3), bioaccumulation potential
is considered low (Bl) for the parent substance. Bioaccumulation potential is also judged to be
low for all potential hydrolysis products.
Similarly there are no experimental bioaccumulation data for l,2-(2,3-dibromopropyl) benzene
dicarboxylate (CASRN 7415-86-3). Both estimated BCF and BAF (the latter with metabolism
included) miss the threshold for moderate concern (log=3; Table 1-3), although the regression-
based log BCF is close to the concern level. With metabolism excluded, the predicted log BAF
exceeds the threshold for high concern (B3). Based on these results, l,2-(2,3-dibromopropyl)
benzene dicarboxylate (CASRN 7415-86-3) is judged to have moderate bioaccumulation
potential (B2).
Table 1-3: Environmental Fate Data for the Brominated Phthalates Cluster
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Property
Chemical Name
CASRN
Photooxidation
Half-life
Hydrolysis Half-
life
Biodegradation
(ready
biodegradation
test data; see
text for
additional
information)
Bioconcentration
Factor
Bioaccumulation
Factor5
Log Koc
Henry's Law
Constant
(atm-m3/mol)
Brominated Phthalate Cluster Members
1,2-
Benzenedicarbox
ylic acid, 3,4,5,6-
tetrabromo-, 1,2-
bis(2-ethylhexyl)
ester1
26040-51-7
5.8 hours
(estimated)2
pH 7 = 29 days
(estimated)2;
pH 8 = 2.9 days
(estimated)2
<4%
biodegradation
after 28 day (not
readily
biodegradable)1-3
LogBCF=l.l
(estimated)2
1.7-6.2 (not log;
BFR database,
confidential data,
described as
adequate
guideline study)
Log BAF = 0.38
(estimated)2
5.9 (estimated,
MCI method)2
7.4 (estimated,
log Kow method)
2
3.1X10'7
(estimated, group
estimate)2
Benzoic acid,
2,3,4,5-
tetrabromo-, 2-
ethylhexyl ester
183658-27-7
11.7 hours
(estimated)2
pH 7 = 34 days
(estimated)2;
pH 8 = 3.4 days
(estimated)2
No data
6% in 28 days in
301D (BFR
database,
confidential data,
described as
adequate
guideline study)
Log BCF = 3.27
(estimated)2
Log BAF = 3.32
(estimated)2
4.5 (estimated,
MCI method)2
5.7 (estimated, log
Kow method)2
7.1X10'6
(estimated, group
estimate)2
1,2-
Benzenedicarboxyl
ic acid, 3,4,5,6-
tetrabromo-, l-[2-
(2-
hydroxyethoxy)eth
yl] 2-(2-
hydroxypropyl)
ester4
20566-35-2
4.2 hours
(estimated)2
pH 7 =7.9 days
(estimated)2;
pH 8 = 19 hours
(estimated)2
No Data
Log BCF = 1.94
(estimated)2
Log BAF = 0.82
(estimated)2
1.0 (estimated,
MCI method)2
2.0 (estimated, log
Kow method)2
2.2X10'21
(estimated, group
estimate)2
1,2-
Benzenedicarb
oxylic acid,
3,4,5,6-
tetrabromo-,
mixed esters
with diethylene
glycol and
propylene
glycol
77098-07-8
See 20566-35-2
See 20566-35-2
See 20566-35-2
See 20566-35-2
See 20566-35-2
See 20566-35-2
See 20566-35-2
1,2-
Benzenedicarbo
xylic acid, 1,2-
bis(2,3-
dibromopropyl)
ester
7415-86-3
5.8 hours
(estimated)2
pH 7 = 315 days
(estimated)2;
pH 8 = 31.5 days
(estimated)2
No Data
Log BCF = 2.87
(estimated)2
Log BAF = 1.10
(estimated)2
Log BAF = 4.79
(estimated;
without
metabolism)
3.5 (estimated,
MCI method)2
3.5 (estimated,
log Kow
method)2
2.8X10'14
(estimated,
group estimate)2
Page 12 of 17
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Property
Chemical Name
Fugacity
(Level III Model)2
Air (%)
Water (%)
Soil (%)
Sediment (%)
Brominated Phthalate Cluster Members
1,2-
Benzenedicarbox
ylic acid, 3,4,5,6-
tetrabromo-, 1,2-
bis(2-ethylhexyl)
ester1
0.169
11.6
88.2
<0.1
Benzole acid,
2,3,4,5-
tetrabromo-, 2-
ethylhexyl ester
0.319
11.8
86.9
0.95
1,2-
Benzenedicarboxyl
ic acid, 3,4,5,6-
tetrabromo-, l-[2-
(2-
hydroxyethoxy)eth
yl] 2-(2-
hydroxypropyl)
ester4
0.001
37
62.9
0.09
1,2-
Benzenedicarb
oxylic acid,
3,4,5,6-
tetrabromo-,
mixed esters
with diethylene
glycol and
propylene
glycol
See 20566-35-2
1,2-
Benzenedicarbo
xylic acid, 1,2-
bis(2,3-
dibromopropyl)
ester
0.00000066
11.1
87
1.9
1 Brominated Phthalate Ester Panel (BR PEP) American Chemistry Council. August 5, 2004. Revised Robust Summary
and Test Plan for Phthalic Acid Tetrabromo Bis 2-Ethylhexyl Ester (CASRN 26040-51-7). Prepared by Health &
Environmental Horizons, Ltd. Available online from: http://www.epa.gov/hpv/pubs/summaries/phthacid/cl5484tc.htm
as of June 23, 2010.
2 EPA. 2012. Estimation Programs Interface Suite™ for Microsoft® Windows, v4.11. Environmental Protection Agency,
Washington, DC, USA. Available online from: http://www.epa.gov/opptintr/exposure/pubs/episuitedl.htm.
3 Test substance used in the biodegradation study is indicated by the sponsor as Pyronil 45 with a purity of 95%.
4 ECHA: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9ea569dl-072b-18ab-e044-00144f67d031/DISS-
9ea569dl-072b-18ab-e044-00144f67d031 DISS-9ea569dl-072b-18ab-e044-00144f67d031.html; - indicates no data
or no reliable data for this endpoint
5 Estimated upper trophic log BAF from the BCFBAF program (in Estimation Programs Interface Suite™ for Microsoft®
Windows, v4.11; see footnote 2. Estimates include metabolism except as noted.
1.3 ENVIRONMENTAL FATE and BIOACCUMULATION - DATA
__NEEDS
1.3.1 Ambient Environment
Very little information exists on the environmental fate and bioaccumulation of the Brominated
Phthalates Cluster (BPC) members, and what data do exist, are forTBPH and TBB only.
Therefore, comprehensive studies are needed for many endpoints and for all cluster members.
All cluster members should be tested individually and all major degradation products should be
quantified. This means that it is necessary to test TBB and TBPH separately. There is no point in
testing using standard ready or inherent biodegradability tests. Among published guidelines,
only simulation tests such as OECD TG 307 (aerobic and anaerobic soil transformation) and
OECD TG 308 (aerobic and anaerobic transformation in aquatic sediment) are likely to yield
information useful for informing environmental exposure (therefore, risk) assessment. Based
on photodegradation studies of TBPH and TBB using organic solvents, cluster members may
undergo direct photolysis; however additional work is needed to confirm this. These studies
should measure rates and products under relevant conditions (i.e. with water as solvent). In
Page 13 of 17
-------
addition, to provide needed information on key environmentally important physical properties,
Henry's Law constant, Koc and Koa should be determined experimentally using standard
protocols and under GLP conditions. Comprehensive bioaccumulation studies are needed for all
BPC cluster members, and these should include several aquatic and terrestrial species selected
from organisms commonly used in bioaccumulation testing. Specialized protocols are available
for some of the above endpoints and may be adapted for BPC members; e.g. the aerobic/
anaerobic sediment testing methodology developed for decaBDE under the PBDE SNUR.
1.3.2 Indoor Environment
It is EPA's judgment that exposure via dust may be important, yet little information is available
on how these compounds get into house dust. This process may involve direct transfer from
flame-retarded objects, driven by partitioning properties of the Brominated Phthalates Cluster
(BPC) substances. To better understand these processes, and therefore more accurately assess
indoor exposure, it is necessary to conduct studies to determine rates of migration of cluster
members from flame-retarded indoor objects; and rates and mechanisms of partitioning into
dust and any other media that may be vectors for human exposure.
Albemarle - GLCC (Albemarle Corporation and Great Lakes Chemical Corporation). 2004. High
Production Volume (HPV) Challenge Program. Test Plan for 1,2-Benzenedicarboxylic
Acid, 3,4,5,6- Tetrabromo-,2-(2-Hydroxyethoxy)Ethyl 2-Hydroxypropyl Ester (CASRN
7709-07-8). Baton Rouge, LA and West Lafayette, IN.
http://www.epa.gov/chemrtk/pubs/summaries/12benznd/cl5091tp.pdf.
AN, N., A. C. Dirtu, N. Van den Eade, E. Goosey, S. Harrad, H. Neels, A. Mannetje, J. Coakley, J.
Douwes, and A. Covaci. 2012. Occurrence of Alternative Flame Retardants in Indoor Dust
from New Zealand: Indoor Sources and Human Exposure Assessment. Chemosphere,
88(11), 1276-1282.
Allen, J. G., H. M. Stapleton, J. Vallarino, E. McNeely, M. D. McClean, S. J. Harrad, C. B. Rauert,
and J. D. Spengler. 2013a. Exposure to Flame Retardant Chemicals on Commercial
Airplanes. Environmental Health, 12,17.
Allen, J. G., A. L. Sumner, M. G. Nishioka, J. Vallarino, D. J. Turner, H. K. Saltman, and J. D.
Spengler. 2013b. Air Concentrations of PBDEs on in-Flight Airplanes and Assessment of
Flight Crew Inhalation Exposure. Journal of Exposure Science and Environmental
Epidemiology, 23, 337-342.
Bradman, A., F. Caspar, R. Castorina, E. Tong-Lin, T. McKone, and R. Maddalena (University of
California, Berkeley). 2012. Environmental Exposures in Early Childhood Education
Page 14 of 17
-------
Environments. 08-305. Center for Environmental Research and Children's Health,
University of California-Berkeley, Berkeley, CA.
Butz, R. G. (Velsicol Chemical Corporation). 1979. Persistence of PHT-4 in Soil at 1 and 10 Ug/G.
OTS 0523288. Chicago, II.
http://www.ntis.gov/search/product.aspx?ABBR=OTS0523288.
Davis, E. F. 2013. The Environmental Fate and Transformation of Flame Retardant Chemicals
and Triclosan Following Land Application of Biosolids. (PhD dissertation), Duke, Durham,
NC. Retrieved from http://hdl.handle.net/10161/7114.
Davis, E. F., and H. M. Stapleton. 2009. Photodegradation Pathways of Nonabrominated
Diphenyl Ethers, 2-Ethylhexyltetrabromobenzoate and Di(2-
Ethylhexyl)Tetrabromophthalate: Identifying Potential Markers of Photodegradation.
Environmental Science & Technology, 43(15), 5739-5746.
de Jourdan, B. P., M. L. Hanson, D. C. Muir, and K. R. Solomon. 2013. Environmental Fate of
Three Novel Brominated Flame Retardants in Aquatic Mesocosms. Environmental
Toxicology and Chemistry, 32(5), 1060-1068.
Dodson, R. E., L. J. Perovich, A. Covaci, N. VandenEade, A. C. lonas, A. C. Dirtu, J. G. Brody, and
R. A. Rudel. 2012. After the PBDE Phase-Out: A Broad Suite of Flame Retardants in
Repeat House Dust Samples from California. Environmental Science and Technology,
46(24), 13056-13066.
ECHA. 2013. European Chemicals Agency http://echa.europa.eu/ (accessed in 2013).
EPA (US Environmental Protection Agency). 1999b. Category for Persistent, Bioaccumulative
and Toxic New Chemical Substances. 64 Federal Register 213 (November 4,1999), pp.
60194-60204.
EPA (US Environmental Protection Agency). 2012f. Estimation Programs Interface Suite™ for
Microsoft® Windows, V4.ll Office of Pollution Prevention and Toxics, Washington, DC.
http://www.epa.gov/opptintr/exposure/pubs/episuitedl.htm (June 24, 2010).
Gheorghe, A., A. C. Dirtu, H. Neels, and A. Covaci. 2013. Brominated and Organophosphate
Flame Retardants in Indoor Dust from Southern Romania. San Francisco, CA.
www.bfr2013.com.
Harju, M., E. Heimstad, D. Herzke, T. Sandanger, S. Posner, and F. Wania. 2009. Current State of
Knowledge and Monitoring Requirements - Emerging "New" Brominated Flame
Retardants in Flame Retarded Products and the Environment TA-2462/2008. Norwegian
Pollution Control Authority, Oslo, Norway.
http://www.klif.no/publikasjoner/2462/ta2462.pdf.
Page 15 of 17
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Johnson, P. I., H. M. Stapleton, B. Mukherjee, R. Mauser, and J. D. Meeker. 2013. Associations
between Brominated Flame Retardants in House Dust and Hormone Levels in Men.
Science of The Total Environment, 445,177-184.
Kopp, E. K., H. Fromme, and W. Voelkel. 2012. Analysis of Common and Emerging Brominated
Flame Retardants in House Dust Using Ultrasonic Assisted Solvent Extraction and on-Line
Sample Preparation Via Column Switching with Liquid Chromatography-Mass
Spectrometry. Journal of Chromatography A, 1241, 28-36.
Lee, S. C, E. Sverko, T. Harner, J. Schachtschneider, D. Zaruk, M. DeJong, and E. Barresi. 2010.
"New" Flame Retardants in the Global Atmosphere under the Gaps Network. . BFR
(Brominated Flame Retardants) Conference, Kyoto, Japan, http://bfr2010.com/abstract-
download/2010/90066.pdf.
Sagerup, K., D. Herzke, M. Harju, A. Evenset, G. N. Christensen, H. Routti, E. Fuglei, J. Aars, H.
Strom, and G. W. Gabrielsen (Statlig program forforurensningsovervaking). 2010. New
Brominated Flame Retardants in Arctic Biota.
http://www.klif.no/publikasioner/2630/ta2630.pdf.
Sahlstrom, L, U. Sellstrom, and C. A. de Wit. 2012. Clean-up Method for Determination of
Established and Emerging Brominated Flame Retardants in Dust. Analytical and
Bioanalytical Chemistry, 404(2), 459-466.
Schlabach, M., M. Remberger, E. Brorstrom-Lunden, K. Norstrom, L. Kaj, H. Andersson, D.
Herzke, A. Borgen, and M. Harju (Temanord). 2011. Brominated Flame Retardants (BFR)
in the Nordic Environment. . Copenhagen: Nordic Council of Ministers..
www.norden.org.
Shoeib, M., T. Harner, G. M. Webster, E. Sverko, and Y. Cheng. 2012. Legacy and Current-Use
Flame Retardants in House Dust from Vancouver, Canada. Environmental Pollution
(Series A). Ecological and Biological, 169,175-182.
Springer, C., E. Dere, S. J. Hall, E. V. McDonnell, S. C. Roberts, C. M. Butt, H. M. Stapleton, D. J.
Watkins, M. D. McClean, T. F. Webster, J. J. Schlezinger, and K. Boekelheide. 2012.
Rodent Thyroid, Liver, and Fetal Testis Toxicity of the Monoester Metabolite ofBis-(2-
Ethylhexyl) Tetrabromophthalate (TBPH), a Novel Brominated Flame Retardant Present
in Indoor Dust. Environmental Health Perspectives, 120(12), 1711-1719.
Stapleton, H., M. Alaee, R. Letcher, and J. Baker. 2004. Debromination of the Flame Retardant
Decabromodiphenyl Ether by Juvenile Carp (Cyprinus Carpio) Following Dietary Exposure
Environmental Science and Technology, 38,112-119.
Page 16 of 17
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Stapleton, H. M., J. G. Allen, S. M. Kelly, A. Konstantinov, S. Klosterhaus, D. Watkins, M. D.
McClean, and T. F. Webster. 2008a. Alternate and New Brominated Flame Retardants
Detected in U.S. House Dust. Environmental Science & Technology, 42(18), 6910-6916.
Stapleton, H. M., S. Klosterhaus, S. Eagle, J. Fuh, J. D. Meeker, A. Blum, and T. F. Webster. 2009.
Detection ofOrganophosphate Flame Retardants in Furniture Foam and U.S. House
Dust. Environmental Science & Technology, 43(19), 7490-7495.
Stapleton, H. M., A. Sjodin, R. S. Jones, S. Niehuser, Y. Zhang, and D. G. J. Patterson. 2008b.
Serum Levels of Polybrominated Diphenyl Ethers (PBDEs) in Foam Recyclers and Carpet
Installers Working in the United States. Environmental Science and Technology, 42(9),
3453-3458.
Unitex (Unitex Chemical Corporation). 2006. Uniplex FRP-45. Material Safety Data Sheet,
Greensboro, NC. http://www.unitexchemical.com/MSDS CURR/UPLXFRP45 MSDS.pdf.
Van den Eede, N., A. C. Dirtu, N. AN, H. Neels, and A. Covaci. 2012. Multi-Residue Method for the
Determination of Brominated and Organophosphate Flame Retardants in Indoor Dust. .
Talanta, 89, 292-300.
Page 17 of 17
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