## TSCA Work Plan Chemical

Technical Supplement – Physicochemical Properties a nd
Environmental Fate of the Brominated Phthalates Clu ster

(BPC) Chemicals

Brominated Phthalates Cluster
Flame Retardants

CASRN NAME 26040-51-7 1,2-Benzenedicarboxylic acid, 3,4,5,6-te trabromo-, 1,2-bis(2-

ethylhexyl) ester
183658-27-7 Benzoic acid, 2,3,4,5-tetrabromo-, 2-et hylhexyl ester

20566-35-2 1,2-Benzenedicarboxylic acid, 3,4,5,6-te trabromo-, 1-[2-(2-

hydroxyethoxy)ethyl] 2-(2-hydroxypropyl) ester

77098-07-8 1,2-Benzenedicarboxylic acid, 3,4,5,6-te trabromo-, mixed

esters with diethylene glycol and propylene glycol

7415-86-3 1,2-Benzenedicarboxylic acid, 1,2-bis(2,3 -dibromopropyl) ester

* Confidential A
* Confidential B
* Confidential Business Information

August 2015 United States Environmental Protection Agency EPA Document# 740-Q1-4001 August 2015 Office of Chemical Safety and
Pollution PreventionPage 2 of 17



## 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 for the Brominat ed Phthalates Cluster ............................. . 11

TABLE OF FIGURES Figure 1-1: Generic Structure of the Brominated Pht halates Cluster Chemicals ......................... .. 3 Figure 1-2: Generic structure of the BPC members an d CASRN 7415-86-3 ................................. .. 4Page 3 of 17



## 1 INTRODUCTION

Each chemical in this cluster has several structura l 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 Br

Br O Alkyl

Figure 1-1: Generic Structure of the Brominated Pht halates Cluster Chemicals

Some members of the cluster have free primary or se condary alcohol functionalities. These may impart certain properties to the chemical subst ance [making them more water soluble and chemically reactive], more significantly the alcoho l moiety can react to incorporate the brominated (BFR) into the substrate via covalent bo nd formation. These chemicals are not limited to that reactive form of application and th ey 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-benzenedicarboxylic acid ( CASRN 7415-86-3). The primary difference between this chemical and th e other cluster members is the positioning of the four (4) bromine atoms (on the alkyl ester m oieties) as opposed to the positions on the benzene ring.

1 The cluster member 2-ethylhexyl-2,3,4,5-tetrabromob enzoate ( TBB ; CASRN 183658-27-7) is missing one of the phthalate carboxylate ester but is including in this cluster since the commercial product Firemast er 550
also contains the TBB / TBPH phthalate mixture. This structural anomaly should not affect the inclusion of this chemical since phthalates often decarboxylate durin g metabolism and biodegradation. (Robbert Kleerebezem*, 1999)Page 4 of 17 Br O

Br O

O Br

Br O Alkyl

Alkyl O Br Br

O

O

O Br Br

Figure 1-2: Generic structure of the BPC members an d 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-Benzenedica rboxylic acid, 3,4,5,6-tetrabromo-, 1-[2- (2-hydroxyethoxy)ethyl] 2-(2-hydroxypropyl) ester ( TBPA-Diol; CASRN 20566-35-2) and 1,2- Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, mixe d 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 e xcess chemical present due to an incomplete polymerization reaction. The reactive members of th e brominated phthalates cluster (BPC), including the primary degradation product tetrabrom ophthalic acid, have not been reported in literature as being present in environmental or bio logical media.

The brominated phthalates with hydroxyalkyl esters are generally intended to react with isocyanate monomers and become covalently bonded in to 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 li nkage would cleave before the carbamate linkage generating the tetrabromophthalate diacid a s a predominant product. There has been no monitoring data indicating the presence of hydro xyalkyl tetrabromophthalates in the environment or biota. As such worker exposures wou ld be the main concern during chemical manufacturing and PUF manufacturing. The esters ar e 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 [Cra in 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 w ould be self contained in the foam
backbone .Page 5 of 17

1.1.2 Additive BPC members

The additive members of the BPC are 1,2-Benzenedica rboxylic 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 ac id, 1,2-bis(2,3- dibromopropyl) ester (CASRN 7415-86-3).

Additive flame retardants are incorporated and disp ersed 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. E missions from a single product or article may be small. However, combined emissions from all sou rces 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 wat er solubility. They have the same functional groups and may be considered close analogs of one another.

There are few measured physicochemical properties v alues for Melting Point, Boiling Point, Vapor Pressure, Water Solubility or Octanol Water P artition 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, 20 13)] for the unbrominated di(2-ethylhexyl) phthalate (DEHP) ; while the more water soluble pro ducts [hydroxyl containing] are represented by CASRN 77098-07-8 , a submission under the HPV Challenge program (Alb emarle - GLCC, 2004).

Table 1-1: Physicochemical properties of TBPH

C ompou n d M P B P VP s
- H 2O L o g K o w

TBPH < -20 °C > 400 °C < 1.0 E-3 Torr
at 25 °C insoluble 9.34 (ACD est.)

Source: Unitex Chemical Corp. Uniplex FRP-45 MSDS ( Unitex, 2006)

Table 1-2: Physicochemical Properties of TBPA Diol

C ompou nd M P B P V

P s
- H 2O L o g K o w

CASRN
77098-07-8 NA N

A < 1E- 6 Torr

(est.) < 1

g/L

MS 3.83

(EPI est.)

Source: EPA HPV Challenge Program submission (Albem arle - GLCC, 2004)

CASRN 7415-86-3
No data were located for this cluster member.Page 6 of 17

In addition to the chemicals already described, Confidential A, and Confidential B can be considered analogous to the other cluster members d escribed here. There was little to no physicochemical data, and structures for these chem icals are similar enough to use read across.



### 1.2 ENVIRONMENTAL FATE AND BIOACCUMULATION

1.2.1 Summary

Very little information exists on the environmental fate and bioaccumulation of the brominated phthalates cluster (BPC) members. 1,2-Benzenedicarb oxylic acid, 3,4,5,6-tetrabromo-, 1,2-bis(2- ethylhexyl) ester ( TBPH ) and benzoic acid, 2,3,4,5-tetrabromo-, 2-ethylhex yl 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 (P1) relative to standard criteria (EPA, 1999b). The tetrabrominated microbial degradation and/or hy drolysis products tetrabromophthalic acid and tetrabromobenzoic acid are expected to be much more persistent and are ranked as P3. Estimated bioaccumulation factors (BAFs) suggest th at TBPH and TBB have low (B1) and moderate bioaccumulation potential (B2), respective ly. The phthalic and benzoic acid products are also considered to have low (B1) and moderate b ioaccumulation potential (B2), respectively.

TBPH and TBB are expected to have low mobility in soil. Biodeg radability is not well characterized but based on available data, half-liv es 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 occ ur, but the low solubility of TBPH and TBB may lower the effective rate of hydrolysis in the e nvironment. 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. Th e 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 resistan t to further abiotic transformations as well as biodegradation and may be persistent in the envi ronment. The rate of atmospheric gasphase (hydroxyl radical) photo-oxidation has the po tential to be moderate; however, these substances are expected to exist primarily in the p articulate phase in the ambient atmosphere, and generally it is assumed that oxidation of parti cle-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-b ound form.

1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, 1-[2-(2-hydroxyethoxy)ethyl] 2-(2- hydroxypropyl) ester and 1,2-benzenedicarboxylic a cid, 3,4,5,6-tetrabromo-, mixed esters withPage 7 of 17

diethylene glycol and propylene glycol (CASRNs 7709 8-07-8 and 20566-35-2) are expected to have high mobility in soil. Estimated abiotic hydr olysis half-lives for this substance are lower
than for TBPH and TBB (on the order of days to months depending on the e stimation program),
but these values are still considered to be in the slow-to-negligible category (EPA, 2012f). No biodegradation data were available for this substan ce. Given its molecular structure this substance would not be expected to be readily biode gradable, but both abiotic hydrolysis and biodegradation may produce the same brominated degr adation product as for TBPH ; namely tetrabromophthalic acid. As for TBPH and TBB, the estimated rate of atmospheric photooxidation is moderate; however, this is not ex pected to be an important environmental degradation pathway. Given the estimated rate of h ydrolysis, CASRN 77098-07-8 is expected to have low persistence (P1) and low bioaccumulation p otential (B1). However, the degradation product tetrabromophthalic acid is expected to have high persistence (P3) and low bioaccumulation potential (B1).

No measured environmental fate data exist for 1,2-b enzenedicarboxylic acid, 1,2-bis(2,3- dibromopropyl) ester, CASRN 7415-86-3. Both estima ted vapor pressure and volatility, based on estimated Henry’s Law constant, are low. This s ubstance 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 hydr olysis may occur, but the rate is expected to be negligible. Given its molecular structure t his 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 bioa ccumulative (B2). Hydrolysis, if it occurs, may yield 2,3-dibromopropanol as a product, but nei ther 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) subst ances 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 (Ali et al., 2012; Allen et al., 2013a; Allen et a l., 2013b; Bradman et al., 2012; Dodson et al., 2012; G heorghe et al., 2013; Johnson et al., 2013; Kopp et al., 2012; Sahlstrom et al., 2012; Schlabac h 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 (Ali et al., 2012; Allen et al., 2013a; Allen et al ., 2013b; Bradman et al., 2012; Dodson et al., 2012; Gheorghe et al., 2013; J ohnson et al., 2013; Kopp et al., 2012; Sahlstrom et al., 2012; Schlabach et al., 2011; Sho eib et al., 2012; Springer et al., 2012; Stapleton et al., 2008a; Stapleton et al., 2009; St apleton et al., 2008b; Van den Eede et al., 2012) in indoor air and dust are consistent with t hese 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 indoo r environment (Webster et al. 2013), for which dust was considered important but indoor air not.Page 8 of 17

If released to the ambient atmosphere, these compou nds are expected to exist primarily in the particulate phase, given their estimated vapor pres sures. Consequently, the photochemically catalyzed vapor phase reaction with hydroxyl radica ls (for which half-lives are given in Table 1-3) is not expected to be environmentally relevant . Davis and Stapleton (2009) measured halflives for photodegradation of TBPH and TBB by sunlight in several organic solvents. Half-liv es 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 result s suggest that both substances absorb light and photodegrade at en vironmentally important wavelengths, although for water the importance of this process i s not known.

In the particulate phase, they may be subject to re moval from the atmosphere via wet or dry deposition. TBB and TBPH have the potential to be transported far from thei r 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 s orb. A study of arctic biota by Harju **et al**

. (2009) provides supporting evidence of long-range t ransport. In an air monitoring study TBPH
and TBB were detected at high frequency in samples collect ed 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 ent er the atmosphere and undergo long-range
transport.

CASRNs 77098-07-8 and 20566-35-2, and CASRN 7415-86-3 are expected to behave similar ly to

TBPH and TBB in the atmosphere. The estimated Henry’s Law cons tants 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 expect ed to exist primarily in the particulate phase. Consequently, the photochemically catalyzed vapor phase reaction with hydroxyl radicals is not expected to be environmentally rele vant.

1.2.3 Fate in Water

If released to water, TBPH and TBB are expected to adsorb to sediment and suspended particulate matter, based upon the estimated K oc values (Table 1-3). Volatilization from water is not expected to be an important environmental fa te process given the estimated Henry’s Law constants. Abiotic hydrolysis may occur, but the l ow solubility of TBPH and TBB may lower the effective rate of hydrolysis in the environment. B ased on estimated half-lives and considering the low water solubility, rates of abiotic hydrolys is are expected to be negligible at environmental pH and temperature. The ultimate hyd rolysis 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, achievi ng less than 4% of its theoretical oxygen demand after 28 days in a test with inoculum from s econdary effluent from a tricking filter at a sewage treatment plant that received predominantly domestic waste (Table 1-3). It is unclearPage 9 of 17

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 remov al (>= 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 d ays and 8.5 days in active water and active sediment test systems, respectively. Neither ultim ate 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 e nvironmental conditions. This type of study can be considered a higher tier (more realist ic) form of simulation test, in comparison to die-away studies as summarized above. The median d issipation 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. T he degradation products were more concentrated in the particulate compartment and cor responded to known photodegradation products. The ratio of TBB to TBPH differed in the mesocosm compartments compared wit h the starting test material, indicating increased de gradation of TBB relative to TBPH . In the dieaway test (discussed in the preceding paragraph) th e “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 a l., 2013) mesocosm study. The reported DT50s of 9-30 d for the particulate compartment the refore can be compared to the 8.5-day half-life for the “active sediment” die-away treatm ent. The higher DT50s observed in the “sediment phase” portion of the mesocosm study woul d be expected, given that as a rule, organic chemicals degrade more slowly under the ana erobic conditions prevalent in benthic
sediments.

Davis and Stapleton (Davis and Stapleton, 2009) me asured half-lives for photodegradation of

TBPH and TBB by sunlight in several organic solvents. Half-liv es 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 wavel engths, but the importance of this process for the water environment is not known. Th e observation by de Jourdan **et al** . (2013) that mesocosm degradation products corresponded to known photodegradation products is consistent with Davis and Stapleton (Davis and Sta pleton, 2009), but again, photodegradation has not been directly studied under environmentally relevant conditions.

Estimated abiotic hydrolysis half-lives for 3,4,5,6 -tetrabromo-1,2-benzenedicarboxylic acid, mixed esters with diethylene glycol and propylene g lycol (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 e stimation program), but still considered to be in the slow-to -negligible category. No biodegradation dataPage 10 of 17

were available for this substance. Given its molec ular 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-1,2-benzenedicarboxylic acid, mixed esters with diethylene glycol and propylene g lycol are expected to be rapidly biodegradable under all conditions. 1,2-(2,3-Dibro mopropyl) benzene dicarboxylate (CASRN 7415-86-3) is estimated to hydrolyze abiotically mo re 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.

1.2.4 Fate in Soil and Sediment

If released to soil, TBPH and TBB are expected to have low mobility, based on their estimated log K oc values. Estimated Koc values for 1,2-(2,3-dibromo propyl) benzene dicarboxylate (CASRN 7415-86-3) are just below the threshold for low/mod erate mobility, suggesting that mobility may be characterized as low-to-moderate for this cl uster member. In contrast, 3,4,5,6- tetrabromo-1,2-benzenedicarboxylic acid, mixed este rs with diethylene glycol and propylene glycol (CASRNs 77098-07-8 and 20566-35-2) is expect ed 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 degrada tion products of BPC members is likely to be slow. One study is available for tetrabromophth alic anhydride (CASRN 632-79-1), which would be quickly hydrolyzed to tetrabromophthalic a cid (CASRN 13810-83-8) in the environment, and it showed no degradation in 28 day s (Butz, 1979). The nonbrominated products that would be formed from biological or ab iotic hydrolysis of the parent materials are expected to biodegrade easily under all environment al 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 biosolid s-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 clea r 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 bi oconcentration factor (BCF) for the mixture was 2.02 (log BCF = 0.31). Steady state wa s 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 (B1) for TBPH but moderate potential (B2) for TBB (Table 1-3).
BCFBAF calculates a metabolic transformation half-l ife normalized to a 10g fish and the ester linkage has the largest negative fragment coefficie nt, suggesting this may be the primary site ofPage 11 of 17

transformation for TBPH and TBB . However, metabolic biotransformation via debromi nation in fish could also reduce bioaccumulation (Stapleton e t 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, c apelin ( **Mallotus villosus** ); three seabird species: common eider ( **Somateria mollissima** ), Brünnich’s guillemot ( **Uria lomvia** ), and blacklegged 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 con centration in primary prey (ringed seal).

TBPH was not detected in polar bears.

Estimated BAFs for the possible microbial degradati on and/or hydrolysis products tetrabromophthalic acid and tetrabromobenzoic acid are below numerical thresholds for bioaccumulation concern; i.e. they are formally B1 (Table 1-3). However, it should be noted that for the benzoic acid the calculated BAF for upper t rophic-level fish is close to the B2 criterion (i.e. log BAF = 3.00). Without metabolism, the pre dicted 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 pot ential (B2). This is appropriate also because this substance is judged l ikely to be much more persistent in the environment than the parent, thus increasing its po tential to reach and accumulate in organisms.

There are no experimental data for 3,4,5,6-tetrabro mo-1,2-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 B AF (Table 1-3), bioaccumulation potential is considered low (B1) for the parent substance. Bi oaccumulation potential is also judged to be low for all potential hydrolysis products.

Similarly there are no experimental bioaccumulation data for 1,2-(2,3-dibromopropyl) benzene dicarboxylate (CASRN 7415-86-3). Both estimated BC F and BAF (the latter with metabolism included) miss the threshold for moderate concern ( log=3; Table 1-3), although the regressionbased 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, 1,2-(2,3-dibromopropyl) benzene dicarboxylate (CASRN 7415-86-3) is judged t o have moderate bioaccumulation potential (B2).

Table 1-3: Environmental Fate Data for the Brominat ed Phthalates ClusterPage 12 of 17

Property Brominated Phthalate Cluster Members

Chemical Name 1,2-

Benzenedicarbox ylic acid, 3,4,5,6- tetrabromo-, 1,2- bis(2-ethylhexyl)

ester 1 Benzoic acid,

2,3,4,5- tetrabromo-, 2- ethylhexyl ester 1,2-

Benzenedicarboxyl ic acid, 3,4,5,6- tetrabromo-, 1-[2- (2- hydroxyethoxy)eth yl] 2-(2- hydroxypropyl)

ester 4 1,2-

Benzenedicarb oxylic acid, 3,4,5,6- tetrabromo-,
mixed esters with diethylene glycol and propylene glycol 1,2-

Benzenedicarbo xylic acid, 1,2- bis(2,3- dibromopropyl)

ester

CASRN 26040-51-7 183658-27-7 20566-35-2 77098-07-8 7415- 86-3
Photooxidation
Half-life 5.8 hours

(estimated) 2 11.7 hours

(estimated) 2 4.2 hours (estimated) 2 See 20566-35-2 5.8 hours (estimated) 2
Hydrolysis Halflife pH 7 = 29 days

(estimated) 2 ; pH 8 = 2.9 days (estimated) 2 pH 7 = 34 days

(estimated) 2 ; pH 8 = 3.4 days (estimated) 2 pH 7 =7.9 days

(estimated) 2 ; pH 8 = 19 hours (estimated) 2 See 20566-35-2 pH 7 = 315 days (estimated) 2 ; pH 8 = 31.5 days (estimated) 2

Biodegradation (ready biodegradation test data; see
text for
additional information) <4%

biodegradation after 28 day (not readily biodegradable) 1,3 No data

6% in 28 days in 301D (BFR database, confidential data,
described as adequate guideline study) No Data See 20566-35-2 No Data

Bioconcentration

Factor Log BCF = 1.1

(estimated) 2 1.7-6.2 (not log; BFR database, confidential data,
described as adequate guideline study) Log BCF = 3.27

(estimated) 2 Log BCF = 1.94

(estimated) 2 See 20566-35-2 Log BCF = 2.87 (estimated) 2

Bioaccumulation

Factor 5 Log BAF = 0.38

(estimated) 2 Log BAF = 3.32

(estimated) 2 Log BAF = 0.82 (estimated) 2 See 20566-35-2 Log BAF = 1.10 (estimated) 2
Log BAF = 4.79 (estimated;
without metabolism) Log K oc 5.9 (estimated,

MCI method) 2 7.4 (estimated, log Kow method)

2 4.5 (estimated,

MCI method) 2 5.7 (estimated, log Kow method) 2 1.0 (estimated,

MCI method) 2 2.0 (estimated, log Kow method) 2 See 20566-35-2 3.5 (estimated, MCI method) 2 3.5 (estimated, log Kow method) 2 Henry’s Law

Constant (atm-m 3 /mol) 3.1 × 10 -7

(estimated, group estimate) 2 7.1 × 10 -6

(estimated, group estimate) 2 2.2 × 10 -21

(estimated, group estimate) 2 See 20566-35-2 2.8 × 10 -14 (estimated, group estimate) 2Page 13 of 17

Property Brominated Phthalate Cluster Members

Chemical Name 1,2-

Benzenedicarbox ylic acid, 3,4,5,6- tetrabromo-, 1,2- bis(2-ethylhexyl)

ester 1 Benzoic acid,

2,3,4,5- tetrabromo-, 2- ethylhexyl ester 1,2-

Benzenedicarboxyl ic acid, 3,4,5,6- tetrabromo-, 1-[2- (2- hydroxyethoxy)eth yl] 2-(2- hydroxypropyl)

ester 4 1,2-

Benzenedicarb oxylic acid, 3,4,5,6- tetrabromo-,
mixed esters with diethylene glycol and propylene glycol 1,2-

Benzenedicarbo xylic acid, 1,2- bis(2,3- dibromopropyl)

ester

Fugacity (Level III Model) 2

Air (%) Water (%) Soil (%) Sediment (%) 0.169

11.6

88.2

<0.1 0.319

11.8

86.9

0.95 0.001

37

62.9

0.09 See 20566-35-2

0.00000066

11.1

87

1.9

1 Brominated Phthalate Ester Panel (BR PEP) American Chemistry Council. August 5, 2004. Revised Robus t Summary
and Test Plan for Phthalic Acid Tetrabromo Bis 2-Et hylhexyl Ester (CASRN 26040-51-7). Prepared by Hea lth & Environmental Horizons, Ltd. Available online from : http://www.epa.gov/hpv/pubs/summaries/phthacid/c154 84tc.htm as of June 23, 2010.

2 EPA. 2012. Estimation Programs Interface SuiteTM for Microsoft® Windows, v4.11. Environmental Prote ction Agency, Washington, DC, USA. Available online from: http://www.epa.gov/opptintr/exposure/pubs/episuited l.htm

. 3 Test substance used in the biodegradation study is indicated by the sponsor as Pyronil 45 with a puri ty of 95%.

4 ECHA: http://apps.echa.europa.eu/registered/data/dossiers /DISS-9ea569d1-072b-18ab-e044-00144f67d031/DISS9ea569d1-072b-18ab-e044-00144f67d031_DISS-9ea569d1- 072b-18ab-e044-00144f67d031.html ; — indicates no data or no reliable data for this endpoint

5 Estimated upper trophic log BAF from the BCFBAF pr ogram (in Estimation Programs Interface SuiteTM for Microsoft® Windows, v4.11; see footnote 2. Estimates include m etabolism 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 for TBPH and TBB only. Therefore, comprehensive studies are needed for man y endpoints and for all cluster members. All cluster members should be tested individually a nd all major degradation products should be quantified. This means that it is necessary to tes t TBB and TBPH separately. There is no point in testing using standard ready or inherent biodegrada bility 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 i n aquatic sediment) are likely to yield information useful for informing environmental expo sure (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 co nditions (i.e. with water as solvent). InPage 14 of 17

addition, to provide needed information on key envi ronmentally important physical properties, Henry’s Law constant, Koc and Koa should be determi ned experimentally using standard protocols and under GLP conditions. Comprehensive b ioaccumulation studies are needed for all BPC cluster members, and these should include sever al aquatic and terrestrial species selected from organisms commonly used in bioaccumulation tes ting. 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 fo r 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 p rocess may involve direct transfer from flame-retarded objects, driven by partitioning prop erties of the Brominated Phthalates Cluster (BPC) substances. To better understand these proces ses, 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 rat es and mechanisms of partitioning into dust and any other media that may be vectors for hu man exposure.



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