## TSCA Work Plan Chemical

Problem Formulation and Data Needs Assessment

Brominated Phthalates Cluster
Flame Retardants

Br O

Br O Alkyl

O Br

Br O Alkyl

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-Q1-4004 August 2015 Office of Chemical Safety and
Pollution PreventionPage 2 of 52



## TABLE OF CONTENTS

TABLE OF CONTENTS .................................

................................................... ......................... 2

AUTHORS / CONTRIBUTORS / ACKNOWLEDGEMENTS .........

................................................... 4

ABBREVIATIONS .....................................

................................................... ............................ 5

EXECUTIVE SUMMARY .................................

................................................... ....................... 7

1 INTRODUCTION ......................................

................................................... ..................... 9

1.1 S COPE OF THE A SSESSMENT

.................................................. ................................................... ......................... 10

1.1 R EGULATORY AND A SSESSMENT H ISTORY

.................................................. ................................................... ....... 13

2 PROBLEM FORMULATION ...............................

................................................... ........... 14

2.1 P HYSICAL AND C HEMICAL P ROPERTIES

.................................................. ................................................... ............ 14

2.2 U SES

.................................................. ................................................... ................................................... .... 14

**2.2.1 Additives .........................................** 

**................................................... ...................................................**  **.. 15**

**2.2.2 Reactives..........................................** 

**................................................... ...................................................**  **. 17**

**2.2.3 Confidential A and Confidential B .................** 

**................................................... ....................................... 17** 

2.3 F ATE AND T RANSPORT

.................................................. ................................................... ................................ 17

2.4 E XPOSURES

.................................................. ................................................... ............................................... 17

**2.4.1 Releases to the Environment .......................** 

**................................................... ........................................ 18** 

**2.4.2 Presence in the Environment .......................** 

**................................................... ........................................ 19** 

**2.4.3 Occupational Exposures ............................** 

**................................................... .......................................... 19** 

**2.4.4 General Population Exposures ......................** 

**................................................... ....................................... 20** 

**2.4.5 Consumer Exposures ................................** 

**................................................... ............................................ 20** 

2.5 H AZARD E NDPOINTS

.................................................. ................................................... ................................... 21

**2.5.1 Ecological Hazard .................................** 

**................................................... ............................................... 21** 

**2.5.2 Human Health Hazard ...............................** 

**................................................... .......................................... 22** 

2.6 R ESULTS OF P ROBLEM F ORMULATION

.................................................. ................................................... ............ 23

**2.6.1 Conceptual Model ..................................** 

**................................................... ............................................. 23** 

**2.6.2 Analysis Plan .....................................** 

**................................................... ...................................................**  **24**

**2.6.3 Sources and Pathways Excluded From Further Assessme**  **nt ................................................ ................... 26** 

**2.6.4 Uncertainties and Data Gaps .......................** 

**................................................... ....................................... 26** 

3 DATA NEEDS ASSESSMENT .............................

................................................... ............ 41

3.1 D ATA N EEDS C ONCLUSIONS

– A DDITIVE B ROMINATED P HTHALATE C LUSTER (BPC) C HEMICALS .................................... 41

3.2 D ATA N EEDS C ONCLUSIONS

– R EACTIVE B ROMINATED P HTHALATE C LUSTER (BPC) C HEMICALS .................................... 45

REFERENCES ........................................

................................................... ............................. 47

APPENDICES ........................................

................................................... ............................. 52Page 3 of 52

LIST OF TABLES
Table 1-1: Members of the Brominated Phthalates Clu ster .............................................. ........... 10
Table 2-1: Production Volumes of the Brominated Pht halates Cluster Chemicals ...................... 18 Table 3-1: Data Needs Assessment (DNA) ............

................................................... ..................... 41
Table 3-2: Data Needs Assessment ..................

................................................... .......................... 45

LIST OF APPENDIX TABLES Table_Apx A-1: Comparison of Different Polyurethane Foam Products .................................... .. 52

LIST OF FIGURES Figure 2-1: Conceptual Model for the Brominated Pht halates Cluster ................................... ..... 23 Figure 2-2: Overview of Data Needs for Hazard and E xposure to Dust during Polyurethane Foams (PUF) manufacture and use of PUF Products ...

................................................... .............. 27 Figure 2-3: Overview of Data Needs for Ecotoxicity from Environmental Exposure to Brominated Phthalates Cluster (BPC) chemicals in Polyurethane Foams (PUF). ...................................... ....... 28 Figure 2-4: Overview of Data Needs for Human Health exposure to dust and TBPH from Polyurethane Foams (PUF) ..........................

................................................... .............................. 29 Figure 2-5: Overview of Data Needs for Human Health exposure to dust and TBB from Polyurethane Foams (PUF) ..........................

................................................... .............................. 30 Figure 2-6: Overview of Data Needs for Human Health exposure to dust and Bromo Alkyl Ester from Polyurethane Foams (PUF)......................

................................................... .......................... 31 Figure 2-7: Overview of Data Needs for Human Health exposure to dust and TBPA-DIOL AND TBPA-DIOL (MIXED ESTERS) chemicals from Polyurethan e Foams (PUF) .................................... 32Page 4 of 52



## AUTHORS / CONTRIBUTORS / ACKNOWLEDGEMENTS

This report was developed by the United States Envi ronmental Protection Agency (US EPA), Office of Chemical Safety and Pollution Prevention (OCSPP), Office of Pollution Prevention and Toxics (OPPT). The Work Plan Data Needs Assessment for the brominated phthalates cluster was prepared based on currently available data. Men tion of trade names does not constitute endorsement by the EPA.

EPA Assessment Team
**Lead** : Maria Szilagyi, OPPT/Risk Assessment Division (RAD)

**Team Members** : Robert Boethling, OPPT/RAD Christina Cinalli, OPPT/Chemistry, Economics & Sust ainable Strategies Division (CESSD) Karen Eisenreich, OPPT/RAD Greg Fritz, OPPT/CESSD Jay Jon, OPPT/RAD Timothy Lehman, OPPT/CESSD Kendra Moran, OPPT/RAD Loraine Passe, OPPT/Chemical Control Division (CCD)

**Management Leads** : Mark Townsend, OPPT/RAD Stan Barone Jr., OPPT/RAD

Acknowledgements The following individuals contributed to portions o f this document H. Kay Austin, OPPT/RAD Charles Bevington, OPPT/RAD

Internal Peer Reviewers Mary C. Fehrenbacher, OPPT/RAD Nhan Nguyen, OPPT/RAD Jennifer Seed, OPPT/RAD Yvette Selby-Mohamadu, OPPT/RAD

Portions of this document and the technical supplem ents were prepared for EPA/OPPT by Abt Associates, the Syracuse Research Corporation (SRC) and Versar.

Docket Please visit the public docket (Docket: EPA-HQ-OPPT -2014-0491) to view supporting
information.Page 5 of 52



## ABBREVIATIONS

BFR Brominated Flame Retardant
BPC Brominated Phthalates Cluster CASRN Chemical Abstract Service Registry Number
CBI Confidential Business Information CDR Chemical Data Reporting CPSC Consumer Product Safety Commission DEHP bis (2-ethylhexyl) phthalate
DNA Data Needs Assessment EC European Commission ECHA European Chemicals Agency EPA Environmental Protection Agency EU European Union
FR Flame Retardant HPV High Production Volume IUR Inventory Update Reporting Rule kg Kilogram(s)

K OW Octanol:Water partition coefficient

lb Pound
LOEL Lowest Observed Effect Level Log K OW Logarithmic octanol:water partition coefficient
mg Milligram
NICNAS National Industrial Chemicals Notification and Assessment Scheme
NOAEL No-observed-adverse-effect level OCSPP Office of Chemical Safety and Pollution Pre vention OECD Organisation for Economic Co-operation and D evelopment
OPPT Office of Pollution Prevention and Toxics OSHA Occupational Safety and Health Administration PBDE Polybrominated Diphenyl Ether PentaBDE Pentabrominated diphenyl ether PFA Polyurethane Foam Association PUF Polyurethane foams (in recognition of the vari ety of polyurethane foam

formulations) PVC Polyvinylchloride REACH Registration, evaluation, authorisation and restriction of chemicals SVOCs Semi-volatile organic chemicals TBB Benzoic acid, 2, 3, 4, 5-tetrabromo-, 2-ethyl hexyl ester TBPH 1, 2-Benzenedicarboxylic acid, 3, 4, 5, 6-te trabromo-, 1, 2-bis (2-ethylhexyl) ester TBPA-Diol Generic designator that is used fo r 1, 2-Benzenedicarboxylic acid, 3, 4, 5, 6-

tetrabromo-, 1-[2-(2-hydroxyethoxy) ethyl] 2-(2-hyd roxypropyl) esterPage 6 of 52

TBPA-Diol (mixed esters)

Generic designator that is used for 3,4,5,6 tetrabr omo-1, 2-benzene dicarboxylic acid, mixed esters with diethylene glycol and propy lene glycol TCEP Tris (2-chloroethyl) phosphate
TSCA Toxic Substances Control Act
US United StatesPage 7 of 52



## EXECUTIVE SUMMARY

As part of EPA’s comprehensive approach to enhance the Agency’s management of existing chemicals, EPA/OPPT identified a work plan of chemi cals for further assessment under the Toxic Substances Control Act (TSCA) in March 2012. Chemic al risk assessments will be conducted if, as a result of scoping and problem formulation, the re are exposures of concern, identified hazards and sufficient data for quantitative analys is. If an assessment identifies unreasonable risks to humans or the environment, EPA will pursue risk reduction. This document presents the data needs assessment for the brominated phthalates cluster as part of the TSCA Work Plan.

EPA/OPPT has identified a cluster of cyclic aliphat ic bromide flame retardant chemicals, including 1,2-benzenedicarboxylic acid, 3,4,5,6-tet rabromo-, 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); 1,2-benzenedicarboxylic acid, 3,4,5,6-tetrab romo-, 1-[2-(2-hydroxyethoxy)ethyl] 2-(2- hydroxypropyl) ester ( TBPA-Diol ; CASRN 20566-35-2); 1,2-benzenedicarboxylic acid, 3,4,5,6- tetrabromo-, mixed esters with diethylene glycol an d propylene glycol [ TBPA-Diol (mixed esters) ; CASRN 77098-07-8] and 1,2-benzenedicarboxylic aci d, 1,2-bis(2,3-dibromopropyl) ester (CASRN 7415-86-3). In addition there are two other chemicals in the cluster whose name and structure are considered confidential, designated, Confidential A and Confidential B. These chemicals have similar physical and chemical proper ties and environmental fate characteristics two of these chemicals, TBPH and TBB 1 have been selected as the index chemicals for this cluster. Uses for 1,2-benzenedicarboxylic acid, 1,2 -bis(2,3-dibromopropyl) ester (CASRN 7415- 86-3) have not been identified: the remaining ident ified members of the cluster are used as flame retardants in polyurethane foams (PUF). The t oxicological hazard profile for this cluster of chemicals is incomplete.

The conclusions from Problem Formulation, as illust rated in the Conceptual Model and described by Assessment Questions, indicate that th e toxicological profile and exposure profile for this cluster of chemicals is incomplete and ina dequate to develop a TSCA work plan risk assessment. EPA/OPPT found that while the data for Firemaster®BZ-54 are sufficient to support
a determination that TBB may present an unreasonable risk in certain scenar ios, this review identified critical data gaps and uncertainties rel ated to exposure and hazard which preclude EPA/OPPT from moving forward with an assessment for any of the chemicals in the Brominated
Phthalates Cluster.

During problem formulation, EPA/OPPT identified ava ilable fate, exposure and hazard data, and characterized potential exposures, receptors and ef fects. Data adequacy were determined following published EPA/OPPT criteria 2 . EPA/OPPT reviewed the public literature (nominall y to

1 TBPH and TBB have been identified as components for Firemaster ® 550 and Firemaster ® BZ-54 for which data are being generated in the open literature

2 Generally followed guidance outlined for the High Production Volume Challenge Program at: http://www.epa.gov/chemrtk/pubs/general/datadfin.ht m and http://www.epa.gov/champ/pubs/hpv/Methodology%20for %20HBP%20under%20ChAMP_March%202009.pdf
And EPA Risk Assessment Guidance at: http://www.epa.gov/raf/Page 8 of 52

August 2013) and its own files (public and confiden tial) to explore the sources, pathways, receptors and effects for consideration in the asse ssment and identified areas of data limitation, data uncertainty and critical missing d ata elements necessary to conduct the assessment. EPA/OPPT developed a conceptual model a nd an analysis plan as a result of problem formulation.

Likely sources and pathways considered for analysis include use of BPC members as flame retardants in polyurethane foams (PUF) and PUF prod ucts found in commercial and residential environments. Monitoring studies have reported the occurrence of TBPH and TBB in various media including sludge, sediment, indoor dust and b iota. Frequent detection of TBPH and TBB in these media provides evidence of release and tra nsport of TBPH and TBB into the environment and suggests an increasing potential fo r exposure. Some data show exposures to

TBPH and TBB to remote species (e.g. seals and sea birds) indic ating the occurrence of global release and transport. The source of the chemicals is unknown. There is no evidence of environmental exposure to the other BPC members rep orted in the literature. No information on potential worker exposure or release to the envi ronment during BPC chemical manufacture, PUF manufacture or PUF processing is available. How ever, monitoring data suggest that worker exposure to BPC chemicals during the use of PUF con taining products occurs.

EPA/OPPT developed a conceptual model to outline th e assessment strategy for the PBC chemicals. Using available tools and approaches, EP A/OPPT identified the relevant TSCA use of

TBPH and TBB as flame retardants in PUF and PUF products found in residential and commercial environments. EPA/OPPT determined that t he major source of exposure to TBPH
and TBB for human health and the environment was via TBPH and TBB in dust and/or TBPH and

TBB in dust generated during the manufacture and proce ssing of TBPH and TBB and the processing and use of products containing TBPH and TBB. TBPH and TBB have been detected in house dust. In addition, there is evidence that a d iverse array of commercial and household PUF-containing articles containing TPBH and TBB can be broken down (i.e. via mechanical or physical wearing, or chemical degradation), thus co ntributing to dust/microplastic particles. During routine cleaning operations, it is thought t hat these microparticles derived from PUF and PUF products can be washed away into the sewerage s ystems where these particles containing BPC chemicals can adhere to wastewater treatment pl ant sludge or make their way into the outdoor environment by transportation through the a ir and/or washed down the drains (or storm drains) to enter waterways.

Due to the prevalence of PUF and PUF products in co mmercial and residential settings, EPA/OPPT focused the exposure scenarios on PUF manu facture and use of PUF products, and the use of PUF and PUF products by workers and cons umers in commercial and residential environments. The monitoring of TBPH and TBB in dust is considered a good indicator for the evaluation of human exposure to PUF and PUF-contain ing products.

As a result of this problem formulation, EPA/OPPT i s releasing a Data Needs Assessment for the Brominated Phthalates Cluster to guide the collecti on of additional data and information to fill the critical data gaps and reduce uncertainties ide ntified during problem formulation. As thePage 9 of 52

information is collected, EPA will continue to eval uate the adequacy of the database to conduct a risk assessment that can inform decision making.



## 1 INTRODUCTION

As a part of EPA’s comprehensive approach to enhanc e the Agency’s management of existing chemicals, in March 2012 EPA identified a work plan of chemicals for further assessment under the Toxic Substances Control Act (TSCA) 3 . After gathering input from stakeholders, EPA developed criteria used for identifying chemicals f or further assessment 4 . The criteria focused on chemicals that meet one or more of the following factors: (1) potentially of concern to children’s health (for example, because of reproduc tive or developmental effects); (2) neurotoxic effects; (3) persistent, bioaccumulative , and toxic (PBT); (3) probable or known carcinogens; (4) used in children’s products; or (5 ) detected in biomonitoring programs. Using this methodology, EPA/OPPT identified a TSCA Work P lan of chemicals as candidates for risk assessment in the next several years. In the priori tization process, the brominated phthalates cluster (BPC), was identified for assessment based on available data for the two index chemicals

TBPH and TBB . The cluster members are expected to be persistent , bioaccumulative and potentially hazardous to human health (developmenta l toxicity) and the environment (acute and chronic toxicity).

EPA/OPPT is performing risk assessments on chemical s in the work plan. If an assessment identifies unacceptable risks to humans or the envi ronment, EPA/OPPT will pursue risk management. The target audience for this risk asses sment is primarily EPA risk managers; however, it may also be of interest to the broader risk assessment community as well as US stakeholders interested in the brominated phthalate s cluster. The information presented in the risk assessment may be of assistance to other feder al, state and local agencies as well as to members of the general public who are interested in the risks of the brominated phthalates
cluster.

The initial steps in EPA/OPPT’s risk assessment dev elopment process, which is distinct from the initial prioritization exercise, includes scoping a nd problem formulation. During these steps EPA/OPPT reviews currently available data and infor mation, including but not limited to, assessments conducted by others (e.g., authorities in other countries), published or readily available reports and published scientific literatu re. During scoping and problem formulation the more robust review of the factors influencing i nitial prioritization may result in refinement – either addition/expansion or removal/contraction – of specific hazard or exposure concerns previously identified in the prioritization methodo logy.

This document includes the results of scoping and p roblem formulation for the brominated phthalates cluster. In the initial prioritization a nd scoping stages EPA/OPPT determined which

3 http://www.epa.gov/oppt/existingchemicals/pubs/work plans.html

4 http://www.epa.gov/oppt/existingchemicals/pubs/wpme thods.pdfPage 10 of 52

chemical(s) would be included and what uses would b e considered in the assessment. During problem formulation, EPA/OPPT identified available exposure and hazard data, and characterized potential exposures, receptors and ef fects. EPA/OPPT developed a conceptual model (Section 2.6.1) and analysis plan (Section 2. 6.2) as a result of problem formulation.



### 1.1 Scope of the Assessment

The members of the Brominated Phthalates Cluster (B PC) are depicted in Table 1-1.
Confidential A and Confidential B are referenced throughout the assessment and where appropriate, information that is not deemed confide ntial is included or cited as Confidential Business Information (CBI). The BPC chemicals have several structural features in common: multiple bromine atoms, typically attached to the a romatic ring; t he 1, 2-benzenedicarboxylate moiety (phthalate structure) 5 and they are alkyl esters. These common features f orm the basis of these chemicals being clustered and assessed tog ether. In addition, the overarching use of these chemicals is as flame retardants (FR) in a va riety of products with polyurethane foams (PUF) being the major use and focus of this assessm ent.

Table 1-1: Members of the Brominated Phthalates Clu ster

CASRN NAME STRUCTURE

26040-51-7 TBPH : 1,2-

Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, 1,2- bis(2-ethylhexyl) ester

183658-27-7 TBB : Benzoic acid, 2,3,4,5-

tetrabromo-, 2-ethylhexyl

ester

20566-35-2 TBPA-Diol : 1,2-

Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, 1-[2- (2-hydroxyethoxy)ethyl] 2- (2-hydroxypropyl) ester

5 The cluster member 2-ethylhexyl tetrabromobenzoate ( TBB) , CASRN [ 183658-27-7] is missing one of the phthalate carboxylate esters but is included in thi s cluster since the commercial product Firemaster®5 50 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. (Kleerebezem, 1999 )Page 11 of 52

CASRN NAME STRUCTURE

77098-07-8 TBPA Diol (mixed esters) :

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

Representative Structure

7415-86-3 Bromo Alkyl Ester : 1,2-

Benzenedicarboxylic acid, 1,2-bis(2,3-dibromopropyl)

ester

CONFIDENTIAL A * *

CONFIDENTIAL B * *

*Confidential Business Information

1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, 1,2-bis(2-ethylhexyl) ester ( TBPH ; CASRN 26040-51-7) and benzoic acid, 2,3,4,5-tetrabromo-, 2-ethylhexyl ester ( TBB ; CASRN 183658-27- 7) are used as additives in product formulations (e .g. Firemaster®550 ). 1, 2-Benzenedicarboxylic acid, 1, 2-bis (2, 3-dibromopropyl) ester ( Bromo Alkyl Ester; CASRN 7415-86-3) is also used as
an additive but hasn’t been introduced into commerc e in quantities that trigger reporting under IUR/CDR (Inventory Update Reporting/Chemical Data R eporting). 1,2-Benzenedicarboxylic 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-, mixed esters with diethylene glycol and propylene glycol [ TBPA-Diol (mixed esters) ; CASRN 77098-07-8] are primarily used as reactives in product formulations and are incorporated into the polyurethane backbone via a covalent bond. Only one of the two confidential cluster members was reported
in CDR. The stated use was claimed as CBI.

All chemicals in the cluster are listed on the TSCA Inventory. All chemicals, except for Bromo Alkyl Ester (CASRN 7415-86-3) and Confidential A , are all found in commerce at volumes greater than one million pounds. The exact producti on volume of TBB and Confidential B are considered CBI and the information cannot be shared publicly.

Monitoring data show that 1,2-benzenedicarboxylic a cid, 3,4,5,6-tetrabromo-, 1,2-bis(2- ethylhexyl) ester ( TBPH ) and benzoic acid, 2,3,4,5-tetrabromo-, 2-ethylhe xyl ester ( TBB ) are present not only in environments where chemicals ar e expected (homes, aircrafts, cars and office buildings), but also in environments where a nthropogenic chemicals are not expectedPage 12 of 52

(natural environment and wildlife) raising concerns about exposure to these chemicals. Furthermore, the TBPH / TBB ratio found in the environment is different from t hat found in the manufactured commercial product (Davis et al., 2012 ; Stapleton et al., 2008a). No evidence of environmental exposure to the other brominated phth alate cluster (BPC) members has been
found.

Using available tools and approaches, EPA/OPPT iden tified the relevant TSCA use of TBPH and

TBB as flame retardants in PUF and PUF products found in residential and commercial environments. EPA/OPPT determined that the major so urce of exposure to TBPH and TBB for
human health and the environment was via TBPH and TBB in dust and/or TBPH and TBB in dust generated during the manufacture and processing of TBPH and TBB and the processing and use of products containing TBPH and TBB. TBPH and TBB have been detected in house dust. In addition, there is evidence that a diverse array of commercial and household PUF-containing articles containing TPBH and TBB can be broken down (i.e. via mechanical or physica l wearing, or chemical degradation), thus contributing to dust /microplastic particles. During routine cleaning operations, it is thought that these micro particles derived from PUF and PUF products can be washed away into the sewerage systems where these particles containing BPC chemicals can adhere to wastewater treatment plant sludge or make their way into the outdoor environment by transportation through the air and/o r washed down the drains (or storm drains) to enter waterways.

Due to the prevalence of PUF and PUF products in co mmercial and residential settings, EPA/OPPT focused the exposure scenarios on PUF manu facture and use of PUF products, and the use of PUF and PUF products by workers and cons umers in commercial and residential environments. The monitoring of TBPH and TBB in dust is considered a good indicator for the evaluation of human exposure to PUF and PUF-contain ing products.

TBPH and TBB have been detected in dust samples in commercial a nd domestic indoor environments suggesting that the monitoring of TBPH and TBB in dust is considered a good model for the evaluation of human exposure to PUF a nd PUF containing products. The source
of TBPH and TBB in the outdoor environment is not known and so pot ential releases to the environment from PUF manufacturing and processing a re also being assessed. PBDE research for foam products as a source of FR has been well d ocumented and is the basis of EPA/OPPT’s current focus on the BPC chemicals in dust and spec ifically PUF. Hale demonstrated that FRtreated polyurethane foams were a source of PBDE ex posure up the food chain (Hale et al., 2002). In addition, TBPH / TBB were shown to increase in air samples as the marke t switched from PBDE to BPC in foam (Ma et al., 2012). FR [TCE P] concentrations in dust were directly associated with FR content in foam baby products as opposed to other FR containing products (Marklund et al., 2005).

EPA/OPPT found limited hazard data for assessing th e human health and environmental effects endpoints. In addition, only limited data are avail able for the commercial products (e.g.

Firemaster ® 550 and Firemaster ® BZ-54) which show potential toxicity to human healt h and the
environment and whose effects are difficult to attr ibute to a particular BPC chemical withoutPage 13 of 52

additional information. Further, data on the commer cial products from non-guideline studies indicate that toxicity observed for phthalates alon e may not be the same for the structurally similar brominated phthalates. Available data from environmental studies were not considered reliable as these provided conflicting results. Con sequently, EPA/OPPT determined that the available data for the BPC index chemicals, TBPH and TBB, are inadequate to characterize hazard or exposure for the purposes of risk assessm ent.



### 1.1 Regulatory and Assessment History

All chemicals in the cluster are listed on the TSCA Inventory. All chemicals, except for Bromo Alkyl Ester (CASRN 7415-86-3) and Confidential A , are all found in commerce at volumes greater than one million pounds. The exact producti on volume of TBB and Confidential B are considered CBI and the information cannot be shared publicly.

EPA/OPPT reviewed the public literature (nominally to August 2013) and its own files (public and confidential) in the preparation of this assess ment. Data adequacy was determined following published EPA/OPPT criteria 6 . Internationally, TBPH has been registered for use in the European Union (EU) and Canada is gathering informa tion for preparing a screening-level assessment. Canada is also gathering information o n TBB

. Bromo Alkyl Ester (CASRN 7415-86- 3) has been cited in the World Health Organisation’ s (WHO) programme for chemical safety (WHO, 1997). TBPA-Diol has also been registered in the EU and is cited in the WHO programme for chemical safety (WHO, 1997). In Australia, the National Industrial Chemicals Notification and Assessment Scheme (NICNAS) prepared a report on the polybrominated flame retardants which
references TBPA-Diol and TBPA-Diol (mixed esters). No hazard data were available for human health or ecotoxicity for these two chemicals (NICN AS, 2001). Hazard data have since been published for the commercial product, Firemaster®BZ -54 (Chemtura, 2012a; NICNAS, 2004),
which is a mixture of TBPH and TBB (Chemtura, 2010).

In the US, the Consumer Product Safety Commission (CPSC) has published two risk assessments on the use of flame retardants: a preliminary risk assessment of FR chemicals in upholstered furniture foam (CPSC, 2006a) and a quantitative ass essment of potential health effects from the use of fire retardant chemicals in mattresses (CPSC , 2006b). Firemaster®550 was included in this assessment; however, the associated BPC chemic als ( TBPH and TBB ) were not assessed due to the lack of toxicity data.

Screening-level data for two of the BPC chemicals [ TBPH and TBPA-Diol (mixed esters) ] were submitted to EPA/OPPT under the High Production Vol ume (HPV) Challenge Program (ACC, 2004; Albemarle - GLCC, 2004). In 2003, EPA/OPPT’s Design for the Environment (DfE) program convened a multi-stakeholder group to undertake an assessment of viable alternatives to

6 Generally followed guidance outlined for the High Production Volume Challenge Program at: http://www.epa.gov/chemrtk/pubs/general/datadfin.ht m and http://www.epa.gov/champ/pubs/hpv/Methodology%20for %20HBP%20under%20ChAMP_March%202009.pdf
and EPA Risk Assessment Guidance at: http://www.epa.gov/raf/Page 14 of 52

pentaBDE called the Furniture Flame Retardancy Part nership (FFRP), which included chemical manufacturers, furniture manufacturers, and governm ental and non-governmental organizations. At the end of 2004, industry volunta rily ceased production of pentaBDE, and EPA/OPPT issued a Significant New Use Rule (SNUR) t hat effectively prohibited further manufacture of the chemical. In 2005, the partnersh ip issued the report, "Environmental
Profiles of Chemical Flame-Retardant Alternatives f or Low-Density Polyurethane Foam (EPA, 2005). The report described the human health and en vironmental profiles of twelve pentaBDE alternatives which did not appear to pose the same level of concern as pentaBDE. DfE recently announced the development of an update to the Alter native Assessment for flame retardants in furniture foam ( http://www.epa.gov/dfe/pubs/projects/flameret/about .htm ). For the update, DfE identified nineteen flame retardants an d blends relevant to the market in 2013 that may be used in upholstered consumer product contain ing flexible polyurethane foam. The report included an assessment of TBPH and TBB based on the available science at the time ; the update will include revised profiles for these two substances and be complementary to this data needs assessment. In addition, data are availa ble for the commercial product, Firemaster® BZ -54 (Chemtura, 2012a; NICNAS, 2001) which is a m ixture of TBPH and TBB (Chemtura, 2010).



## 2 PROBLEM FORMULATION

The problem formulation stage is intended to determ ine the major factors to be considered in the assessment, including exposure pathways, recept ors and health endpoints (EPA, 1998, 2014). Accordingly, this problem formulation summar ized the exposure pathways, receptors and health endpoints EPA/OPPT has recommended for i nclusion in the risk assessment. To make this determination, EPA/OPPT conducted a preli minary data review, to identify available fate, exposure and hazard data and determine its li kely suitability for quantitative analysis and to identify exposure pathways, receptors and health endpoints for quantitative analysis. EPA/OPPT summarized the outcome of this evaluation in conceptual models that illustrate the exposure pathways, receptor populations and effects that will be considered in the risk assessment. EPA/OPPT also prepared data analysis pl ans to demonstrate the proposed approach to answering the defined assessment questi ons.



### 2.1 Physical and Chemical Properties

The physical and chemical properties are summarized in the technical supplement [EPA# 740- Q1-4001] titled “Physicochemical properties and env ironmental fate of the brominated phthalates cluster (BPC) chemicals” which can be fo und at Docket Number EPA-HQ-OPPT-2014-

0491 on www.regulations.gov

.



### 2.2 Uses

EPA/OPPT has prepared a data needs assessment (DNA) to facilitate the gathering of appropriate data needed to prepare a risk assessmen t of the BPC chemicals. To refine the scope of the DNA, use scenarios were evaluated and are su mmarized in the supporting documentPage 15 of 52

(EPA# 740-Q1-4004 on www.regulations.gov ). The major use identified for all cluster members is as a flame retardant (FR) in polyurethane foams (PUF) and PUF products. The other uses identified are considered minor in comparison to th e amount of chemical used in PUF. Therefore, the manufacture of the brominated phthal ates cluster members for use in PUF and PUF products is the focus of this assessment. As st ated above, BPC use in PUF is a potential source of FR but EPA/OPPT’s focus on dust will capt ure use in PUF products even if they cannot be directly correlated to the specific source. In a ddition, under the Commission for Environmental Cooperation (CEC), Canada, Mexico and the United States are evaluating the presence and migration of flame retardants, includi ng members of the BPC, from consumer products. The information gathered from this effort will inform future risk assessment.

EPA/OPPT distinguishes the BPC flame retardants as either reactive or additive depending on
whether or not the BPC chemical reacts with the iso cyanate monomers to become incorporated into the polymer backbone via covalent bond formation. The BPC chemicals containing free hydroxy moieties chemically react w ith the isocyanate groups to make the polyurethane linkages. This process can be utilize d to make both rigid and flexible PUF. However, the literature suggests that the reactive BPCs are more commonly used for rigid foam [(Dufton PF, 1998), US Patent 5637797 and US Patent application 20120238657]. They do not discount the use in flexible PUF products and sugge st that the reactive BPC chemical may also be used in other products as an additive brominated flame retardant (BFR). These patents also suggest that additive BFR, like TBPH/TBB , or excess unreacted reactive BFR, are needed to make certain rigid foam applications meet certain s afety requirements. In addition, both reactive and additive BPC BFR are patented for use with spray polyurethane foam applications (WO 2013003261 patent application).

According to the Polyurethane Foam Association (PFA ) literature, Penta BDE was the BFR of
choice for most all flexible PUF. The BPC chemicals were used as penta alternatives in the various flexible PUF products and alternatives to u se of any brominated combustion modifying additive (CMA). Two statements by PFA reflect the u ncertainly of making general statements, "... there is no "standard foam" which represents t he performance of the flexible polyurethane foam (FPF) product category..." and "... there is n o such thing as a "standard or real fire" by which performance of a material can be measured and projected to represent performance
under all conditions." While PFA members do not mak e rigid foam, PFA did publish a comparison of the different foam products in 2011 ( See Table_Apx A-1).

The report describes the cluster members in terms o f their application in PUF and PUFcontaining products as either additives or reactive s.

2.2.1 Additives

These chemicals are added to the flexible polyureth ane foams (PUF) formulation to function as flame retardants. It is anticipated, based on avail able monitoring data that they are migrating through the foam and being released from the foam i nto the surrounding environment.Page 16 of 52 2.2.1.1 TBPH and TBB

1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, 1,2-bis(2-ethylhexyl) ester ( TBPH ) and benzoic acid, 2,3,4,5-tetrabromo-, 2-ethylhexyl est er ( TBB ) are described together because they are the major components of the Firemaster® brand of flame retardants (e.g. Firemaster®550
and Firemaster® BZ 54). They are used as additives, primarily in th e production of polyurethane (PU) foam for use in furniture (flexible to rigid f oam). Recycled foam products are not addressed specifically because they are comprised o f the universe of foam which makes it difficult to identify the composition of the recycl ed foam or the source of the bromine present. However, carpet is considered a sink for indoor dus t which may be a source of flame retardants (and other contaminants) indoors for release during future use (Batterman et al., 2009; Muenhor and Harrad, 2012). Therefore, because this assessment addresses exposure to flame retardants in dust, use of BPC chemicals in recycle d PUF products would be captured in the

assessment.

No textile uses have been identified for TBPH/TBB ; however, TBPH/TBB were detected downstream from a textile manufacturing outfall to a municipal wastewater treatment plant (La Guardia et al., 2012). Because there are severa l foam manufacturing facilities (known
sources of TBPH/TBB ) in this area, it is uncertain that the TBPH/TBB detected in the stream can
be attributed to the textile sector.

The use of flame retardants and brominated phthalat es in plastic [e.g. polyvinyl chloride (PVC)] casings for electronics (e.g. cell phones, computer s) or household items (e.g. shower curtains) is either being phased out (Greenpeace, 2013) or consi dered to be released through the use of the items. In addition, TBPH has been used in PVC for decades without detection in the environment. It is only since its use with TBB in the Firemaster formulations in PU foams that it
has been detected in the environment. Based on its low vapor pressure, it is anticipated that

TBPH exposure would be through the incidental ingestion of inhaled particulates rather than by the inhalation of the pure substance.

Information on the use of TBPH/TBB in sealants/adhesives is scarce and the use of fla me retardant in these products is only a small amount of the overall market. There is no
information on the release of the flame retardant f rom these products. If released over time due to wear and tear, it is likely that the chemica l would be captured in the particulate matter and detected in dust, e.g. house dust.

TBPH is also used as a plasticizing flame retardant for flexible polyvinyl chloride (PVC) (CECBP SGP, 2008) and as a flame retardant additive for et hylene propylene diene monomer (EPDM) M-class rubber, styrene-butadiene rubber (SBR), and neoprene (Chemtura, 2007a, 2007b, 2007c; Unitex, 2009). Applications of TBPH as a flame retardant plasticizer are adhesives and coatings; carpet backing; coated fabrics; film and sheeting; wall coverings; and wire and cable (CECBP SGP, 2008). Generally, hard plastics contai n ‘reactive’, rather than ‘additive’ brominated phthalates.Page 17 of 52 2.2.1.2 1, 2-Benzenedicarboxylic acid, 1, 2-bis(2, 3-dibrom opropyl) ester (CASRN 7415-86-3)

Bromo Alkyl Ester (CASRN 7415-86-3) was identified as potentially us ed as a flame retardant in polyester fibers [textiles; (WHO, 1997)]; however, no uses have been identified for this cluster
member to date.

2.2.2 Reactives

These chemicals are reacted into the polymer backbo ne of rigid polyurethane foams (PUF). Based on available data (nature of chemical reactiv ity and no detection in the environment), it is not anticipated that these chemicals are release d from the PUF or PUF product. While they can be used as additives, information pertaining to this use is limited (Login et al., 1981) and available data suggest that the predominant use is as a reactive substance.

2.2.2.1 CASRNs 20566-35-2 and 77098-07-8

1,2-Benzenedicarboxylic 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 aci d, 3,4,5,6- tetrabromo-, mixed esters with diethylene glycol an d propylene glycol [ TBPA-Diol (mixed esters) ; CASRN 77098-07-8] are reacted into the polyuretha ne (PU) foam backbone for insulation use. They are typically used in rigid PU foams. Because the major use of this insulation is in appliances, such as refrigerators, it is anticipated that the release of the flame retardants is limited. However, there are no data t o support this.

2.2.3 Confidential A and Confidential B

The uses for Confidential A and Confidential B are considered confidential business information.



### 2.3 Fate and Transport

The fate and transport of the BPC chemicals is summ arized in the technical supplement [EPA# 740-Q1-4001] titled “Physicochemical properties and environmental fate of the brominated phthalates cluster (BPC) chemicals” which can be fo und at Docket Number EPA-HQ-OPPT-2014-

0491 on www.regulations.gov

.



### 2.4 Exposures

The exposure pathways and associated data for the B PC chemicals are summarized in the technical supplement [EPA# 740-Q1-4002] titled “Use and exposure of the brominated phthalates cluster (BPC) chemicals” which can be fo und at Docket Number EPA-HQ-OPPT-2014-

0491 on www.regulations.gov

.Page 18 of 52

2.4.1 Releases to the Environment

Production volumes of the BPC chemicals are summari zed in Table 2-1. Available data suggest
that TBPH/TBB are getting into the environment (Stapleton et al. , 2008a) (Lam et al., 2009) (La Guardia et al., 2012) and being globally transporte d in the atmosphere (Ma et al., 2012). However, the attribution of the chemicals in the en vironment to any particular source is unclear. There is no evidence to suggest that relea se of BPC members from landfills occurs or that they are present in leachate under normal cond itions. Some landfills now use incinerators where, at the normal functioning incineration tempe ratures (> 1000 C), it is anticipated that the TBPH/TBB will be completely destroyed and will not enter th e environment (EPA-HQ-OPPT2003-0071-0004).

There is no evidence to suggest that the debrominat ion of the BPC chemicals occurs **in vivo**

. However, under laboratory conditions, there is evid ence to suggest that debromination can occur (Davis and Stapleton, 2009; Ronen and Abeli ovich, 2000) suggesting that under photolytic or anaerobic conditions, the phthalate, namely **bis** (2-ethylhexyl) phthalate (DEHP), can be released. The EPA/OPPT action plan for phtha lates outlines the environmental effects of DEHP including adverse effects to aquatic organisms with a broad range of endpoints and at
concentrations that coincide with measured environm ental concentrations (EPA, 2012d).

TBPH and TBPA-diol (mixed esters) are High Production Volume (HPV; produced or impor ted into the US at volumes ≥ one million pounds) chemic als. Information for the other cluster
chemicals is considered confidential. The release o f TBB to water from manufacturing and processing is regulated by EPA/OPPT (40 CFR Section 721.2925).

Table 2-1: Production Volumes of the Brominated Pht halates Cluster Chemicals

Cluster Member Reporting

TBPH: CASRN 26040-51-7 2006 IUR PV ≥ 10 million pounds 2012 CDR PV = 1 to 10 million pounds

Not on TRI

TBB: CASRN 183658-27-7 2006 IUR CDR National PV information for the
chemical withheld.
2012 CDR National PV information for the chemical
withheld.

Not on TRI
TBPA-Diol : CASRN 20566-35-2 2006 IUR PV = no record 2012 CDR PV = 1 to 10 million pounds

Not on TRI TBPA-Diol (mixed esters) : CASRN

77098-07-8 2006 IUR PV = 1 to 10 million pounds
2012 CDR National PV information for the chemical
withheld.

Not on TRIPage 19 of 52 Cluster Member Reporting Bromo Alkyl Ester: CASRN 7415-86-3 2006 IUR PV = no record
2012 CDR = no record

Not on TRI Confidential A Consent Order – testing PV not trigg ered
Confidential B 2012 CDR National PV information for the chemical
withheld.
IUR = Inventory Update Reporting; CDR = Chemical Up date Reporting; PV = production volume; TRI = Toxic Releases Inventory

2.4.2 Presence in the Environment

Available data suggest that TBPH/TBB are getting into the environment (Stapleton et al. , 2008a) (Lam et al., 2009) (La Guardia et al., 2012) and be ing globally transported in the atmosphere (Ma et al., 2012). However, the attribution of the chemicals in the environment to any particular source is unclear.

2.4.3 Occupational Exposures

EPA/OPPT considers inhalation and dermal exposure t o be important exposure pathways for workers. Sometimes, the inhalation of air-suspended particulate matter that is subsequently trapped in mucous and moved from the respiratory sy stem to the gastrointestinal tract (EPA, 2011) is a contributor to aggregate exposures. This will be referred to here as incidental ingestion of inhaled particulates.

The Occupational Safety and Health Administration ( OSHA) is responsible for the oversight of various workplace exposures to workers in the chemi cal manufacture and production of foam ( https://www.osha.gov/ ). At this time, there are no specific standards fo r workers involved in the production of the cluster members or their use in products.

Generally, during chemical manufacture, occupationa l exposure via the dermal and inhalation routes is likely for many chemicals. However, the c luster members are liquid and have low vapor pressures (<1X10 -6 mm Hg) suggesting that exposure to vapors via the inhalation route is
not a cause for concern.

During polyurethane foams (PUF) (flexible to rigid) processing, there is some concern for foam handlers and the particulate matter generated durin g, for example, cutting and sizing foam for use in foam products. The OSHA Permissible Exposure Limit (PEL) for particulates not otherwise regulated (general industry) is 15 mg/m 3 TWA (time weighted average) [29 CFR 1910.1000 Table Z-1 (PNOR) and 29 CFR 1910.1000 Table Z-3 (In ert or Nuisance Dust)]. The American Conference of Governmental Industrial Hygienists (A CGIH) Guideline is 10 mg/m 3 TWA (inhalable particles).Page 20 of 52

There is limited data on the use of BPC chemicals i n spray foam insulation. Spray polyurethane foam consists of two liquid chemical components, re ferred to as "Side A" and "Side B," that are mixed at the site of installation. Side A is mostly made up of isocyanates, while Side B usually contains polyol, flame retardants and amine catalys ts (Badore, 2013). While most spray foam
insulation formulations contain chlorinated flame r etardants (Babrauskas et al., 2012) evidence from patent applications suggests that there is pot ential use of reactive BPC cluster members for this application (WIPO Patent Application WO/20 13/003261).

In addition, there is evidence to suggest that occu pational exposures to some sub-populations may lead to elevated levels of BPC member chemicals . Studies measuring polybrominated diphenyl ether (PBDE) congeners in carpet installer s (serum concentrations) (Stapleton et al., 2008b) and flight attendants (air sampling) (Allen et al., 2013b) show that they are potentially exposed to higher levels of PBDEs when compared to the general population. The trend of TBPH/TBB substituting for PBDEs would likewise potentially lead to similar elevated exposures in these worker environments. In addition, there ar e data (Carignan et al., 2013) for gymnasts that demonstrate exposure to TBPH/TBB ; however, the source of exposure is not clear. Gym s typically have foam pits which are a known source o f TBPH/TBB (Carignan et al., 2013) and are a potential source of exposure not only to gymnasts but other subpopulations (e.g. toddlers and children) using the gym or other environments ( e.g. motocross or skateboarding) containing foam pits ( http://www.foamorder.com/foam-pit.html ).

2.4.4 General Population Exposures

There is potential for the general population to be exposed to the brominated phthalates cluster (BPC) chemicals through the ingestion of po tentially contaminated wildlife and vegetation. Available physical-chemical properties of the BPC chemicals suggest that they have limited solubility in water and low volatility. Th erefore, for the general population and consumers, inhalation of volatile BPC chemicals is not anticipated to be a source of significant exposure. However, the BPC chemicals do partition i nto particulate matter (Weschler and Nazaroff, 2008, 2010) which is a potential source o f exposure via incidental ingestion of inhaled particulates. Dermal exposure is not considered a significant route of exposure from BPC chemicals from polyurethane foams (PUF) products (C hemtura, 2012a).

2.4.5 Consumer Exposures

Consumer exposure to the BPC chemicals may include dermal exposure through direct skin contact with the chemicals on the surface of object s or articles, incidental ingestion of inhaled particulates (see 2.4.3) and incidental ingestion o f indoor settled dust via hand-to-mouth behaviors. In addition, children may experience inc idental ingestion via object-to-mouth behaviors. Inhalation exposure is not expected (see 2.4.4).

TBPH and TBB have been found in house dust in Boston, MA and Ca lifornia (Stapleton et al., 2008a) (Dodson et al., 2012). The source of these f lame retardants is unclear but could be
attributed to the number of flame-retardant-contain ing consumer goods found in homes.Page 21 of 52

Flexible polyurethane foam is used in both commerci al and domestic furniture. Additional
information on use in furniture can be found in the EPA/OPPT environmental profile of
chemical flame-retardant alternatives for low-densi ty PUF (EPA, 2005). TBPH and TBB are semivolatile organic chemicals (SVOCs) with high log-KO A values. Hence, any breakdown of the consumer products **in situ** may lead to the release of the flame retardant whi ch predominantly partitions into particulate matter e.g. house dust (Weschler and Nazaroff, 2008, 2010). Carpet
in homes is considered a natural sink for house dus t (Batterman et al., 2009; Muenhor and Harrad, 2012).

EPA/OPPT recognizes that FR have been associated wi th use in polyvinylchloride (PVC) which is present in many consumer goods (e.g. children’s toy s, shower curtains, etc.). In addition, TBPH use was reported in the EPA/OPPT IUR data for decad es before the Firemaster®550 or Firemaster®BZ-54 products were used in foam; howeve r, no TBPH releases were observed. Stapleton et al., (Stapleton et al., 2008a) were no t looking for TBPH/TBB when an unknown brominated flame retardant was observed that they i dentified as the Firemaster®550 components, suggesting that if TBPH had previously been present in dust from non-foam uses, it would likely have been found in earlier sampling . Since the introduction of TBPH/TBB as a replacement for PBDEs in foam, they have been detec ted in environmental monitoring e.g. sludge in San Francisco estuaries (Klosterhaus et a l., 2009; La Guardia et al., 2010). Given that the vapor pressure of e.g. TBPH is very low, release from PVC will likely occur th rough mechanical action, again, suggesting that these par ticles will be detected in, for example, house
dust.

Although insulation has been identified as a source for TBPA-diol and TBPA-diol (mixed esters)

, if used as reactives (See 2.2.2.1), exposure is not expected; however, release from PUF needs to be confirmed. EPA/OPPT has found no evidence that t hese cluster chemicals are present in the environment suggesting that exposure to these clust er chemicals is either unlikely or below detection levels. EPA/OPPT has not identified curre nt uses for Bromo Alkyl Ester

.


### 2.5 Hazard Endpoints

The hazard data for the BPC chemicals are summarize d and tabulated in the technical supplement [EPA# 740-Q1-4003] titled “Hazard Assess ment of the brominated phthalates cluster (BPC) chemicals” which can be found at Dock et Number EPA-HQ-OPPT-2014-0491 on www.regulations.gov

.

2.5.1 Ecological Hazard

Insufficient experimental data are available to cha racterize hazard that would result from chronic exposure to wildlife population. Currently, information from experimental studies that address standard aquatic toxicity endpoints are lim ited to two chronic invertebrate studies conducted on two different species and two differen t flame retardant formulations [Firemaster® BZ-54, PM-PHT-4 Diol and TBPH (>95%)]. These studies present conflicting
conclusions. Additional studies are available that attempt to address population-level effects.Page 22 of 52

These studies would not be sufficient to support a full risk assessment, but can be used to support qualitative hazard characterization for the brominated phthalates. These studies suggest aquatic and/or sediment dwelling invertebra te populations are likely to be impacted by chronic exposure to brominated phthalate flame reta rdants and suggest high hazard concern. Acute toxicity data were available for TBPH/TBB (Firemaster® BZ-54) that also suggest aquatic invertebrates as the most sensitive species; howeve r, given the low water solubility and high Log K ow of TBPH/TBB and the use of solvents and/or test concentrations above the limit of solubility, there is concern that these effects do not represent environmental conditions. Additional brominated phthalates presented in the c luster that have lower Log K ow values may result in acute hazard, but insufficient acute toxi city information are available to characterize
the hazard to these chemicals.

2.5.2 Human Health Hazard

Structural analogy suggests the potential for repro ductive toxicity and “phthalate syndrome” associated with the structural analog, bis (2-ethyl hexyl) phthalate (DEHP). Limited toxicity data are available for the human health endpoints for th e brominated phthalates cluster members; however, EPA/OPPT has published a screening-level h azard characterization on the phthalate esters category (EPA, 2010a) which indicates a broa d range of toxicity.

No hazard data are available for TBB . Available data for some members of the BPC [ TBPH (purity > 95%)] and for Firemaster® BZ 54 ( TBPH/TBB mixture) suggest that the acute oral and dermal toxicity in animals is low. The acute inhala tion toxicity of TBPA-Diol is high.

A chronic dietary study with TBPH (purity >95%) did not identify a target organ alth ough perturbations in clinical chemistry parameters sugg ested effects on the liver. In a chronic gavage study with Firemaster® BZ 54 ( TBPH/TBB mixture), effects on the kidney were observed at all doses with females appearing to be more sens itive to exposure. Chronic toxicity data are not available for the remaining brominated phthalat e cluster members [ TBPA-diol

, TBPA-diol (mixed esters)

, Bromo Alkyl Ester

, Confidential A and Confidential B ).

Data from a two-generation reproductive toxicity st udy and a prenatal developmental toxicity study with the commercial product Firemaster® BZ 54 ( TBPH/TBB mixture) showed the potential to affect fetal development at high doses . No data are available for reproductive/developmental toxicity for the remaini ng brominated phthalate cluster members [ TBPH

, TBPA-diol

, TBPA-diol (mixed esters)

, Bromo Alkyl Ester

, Confidential A and
Confidential B ).

Genetic toxicity studies indicate that TBPH (purity >95%) is not mutagenic to bacteria but
induces chromosomal aberrations **in vitro**

. TBPH (purity >95%) did not induce mouse
micronuclei **in vivo**

. TBPA-diol and TBPA-diol (mixed esters) are not mutagenic to bacteria. No genetic toxicity data are available for the remaini ng brominated phthalate cluster members [ TBB, Bromo Alkyl Ester

, Confidential A and Confidential B ].Page 23 of 52



### 2.6 Results of Problem Formulation

2.6.1 Conceptual Model

During problem formulation, a conceptual model (see Figure 2-1) was developed to identify important sources, pathways, and receptors of expos ure. Potential exposures to the BPC chemicals (derived from the manufacture, processing and use of BPS--containing polyurethane products) in homes, offices, the environment, and o ccupational settings were linked to hazard endpoints in human and non-human receptors.

The conceptual model designed to identify important sources, pathways, and receptors of exposure, and to link potential exposures to BPC ch emicals in dust (derived from PUF and PUF products) in homes, offices, the environment, and o ccupational settings to hazard endpoints (responses) of concern is shown in Figure 2-1 7 . The schematic depicts the pathways (arrows) of potential exposure to the BPC members found in dus t generated during chemical manufacture, the manufacture of PUF and PUF products, and the us e (and disposal) of PUF and PUF products. The dotted lines designate critical areas of data u navailability/uncertainty associated with exposure pathways.

Figure 2-1: Conceptual Model for the Brominated Pht halates Cluster

7 The potential for environmental exposure to BPC ch emicals during chemical manufacture is depicted as a potential source of environmental exposure but is not being a ddressed in this assessment.Page 24 of 52

EPA/OPPT developed a conceptual model to identify i mportant sources, pathways, and receptors of exposure, and to link potential exposu res to BPC chemicals in dust [derived from polyurethane foams (PUF) and PUF products] in homes , offices, the environment, and occupational settings to hazard endpoints (receptor s/effects) of concern. The schematic depicts the pathways (arrows) of potential exposure to the BPC members found in dust generated during manufacture of PUF and PUF products. The dot ted lines designate critical data gaps/uncertainties associated with the identified e xposure pathways.

2.6.2 Analysis Plan

Based on concerns for the potential risk of the Bro minated Phthalates Cluster (BPC) chemicals to human health and the environment, EPA/OPPT, as p art of problem formulation, identified risk assessment questions to focus the assessment o n TSCA uses. The following information is
known.

• 1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, 1,2-bis(2-ethylhexyl) ester ( TBPH ) and benzoic acid, 2,3,4,5-tetrabromo-, 2-ethylhexyl ester ( TBB ) have been detected in
house dust and commercial environments.

◦ Available hazard data on commercial products and em erging data from targeted
studies with TBPH and TBB metabolites indicate disruption of thyroid hormone homeostasis and the potential for effects on testos terone levels.

• TBPH and TBB have been detected in waterways and remote species

.

◦ Available data on commercial products and TBPH indicate potential acute and chronic toxicity.

Based on the available information and keeping the focus on TSCA uses, the following assumptions were made in compiling the assessment q uestions.

• The major source of potential environmental and hum an exposure to the BPC chemicals is from the release of the BPC chemicals during pol yurethane foams (PUF) manufacture or use of PUF products. There may be other sources of exposure for some of the BPC
chemicals.

• Measuring TBPH and TBB in dust can be used to monitor potential human exp osure

The general assessment questions are as follows wit h additional tiering below:

1. Which BPC chemicals are found in dust in enviro nments where PUF and PUF products
are manufactured and used?
2. What data are needed to characterize hazard to B PC chemicals found in dust? 3. What additional exposure data, if any, are neede d to characterize exposure to BPC
chemicals found in dust?
4. What is the hazard to human health from the BPC chemicals found in dust? 5. What is the hazard to sensitive species in the environment from the BPC chemicals
found in dust?Page 25 of 52

6. Are the concentrations of BPC chemicals found in dust a risk to human health and the
environment?

**A. Environmental Exposure** 

1. How persistent and bioaccumulative are the microniz ed particles of foam containing the
BPC chemicals?

2. Are the BPC chemicals persistent and bioaccumulativ e in the environment? If not “P”, are the degradates?

3. Are non-dust releases to the environment during the manufacture of BPC chemicals more significant than BPC releases from PUF?

4. What releases to the environment occur during the p roduction of PUF and manufacture of articles containing PUF (particulates and dust)?

a. How does the type of PUF relate to the amount relea sed?
b. Is this release relevant for the BPC chemicals cova lently bound to the polymer
backbone?

5. Are there environmental releases of BPC chemicals f rom PUF during use and disposal of commercial or consumer products containing PUF?

a. Can the analogous release of non-BPC FR be used as a surrogate for BPC
releases?

6. What hazard data need to be developed to address th e potential risk to environmental species associated with any or all of these exposur es?

a. For BPC released chemicals?
b. For persistent degradation products?

**B. Occupational Exposure**  No information is available on the potential exposu re to workers during manufacture of the BPC chemicals, PUF manufacture and processing, or t he use of products containing PUF.
Available data for TBPH and TBB suggest that there is the potential for occupation al

exposure.

1. What is the potential worker exposure to BPC chemic als during their manufacture?

2. What is the potential worker exposure to BPC chemic als during the manufacture of PUF and manufacture of articles containing PUF (particu lates and dust)?

a. Does the potential worker exposure differ between B PC chemicals used as
additives versus BPC chemicals used as reactives?

3. What is the potential worker exposure to BPC chemic als from the use of commercial or consumer products containing PUF?

a. Does the potential worker exposure differ between B PC chemicals used as
additives versus BPC chemicals used as reactives?

4. What hazard data need to be developed to address th e potential risk to human health associated with any or all of these exposures?Page 26 of 52

**C. General Population and Consumer Exposure** 

TBPH and TBB have been detected in house dust. However, TBPA-diol and TBPA-diol (mixed esters) , including the primary degradation product tetrabr omophthalic acid, have not been reported in literature as being present in the envi ronment. The diols are the reactive BPC chemicals that are incorporated into the polymer st ructure via covalent bonds. This suggests
that unlike TBPH and TBB , they are not being released from the PUF or from PUF manufacturing and processing facilities; or that if emission occurs, degradation is fast enough to prevent measurable accumulation. Information on the remaining BPC chemicals, Confidential A
and Confidential B , cannot be released.

1. What is the potential consumer exposure to BPC chem icals in dust from the use of PUF and PUF products?

a. Does the potential consumer exposure differ between BPC chemicals used as
additives versus BPC chemicals used as reactives?

2. What hazard data need to be developed to address th e potential risk to human health associated with any or all of these exposures?

3. Which PUF products contain BPC chemicals?

4. How do releases to the environment contribute to le vels of TBPH or TBB found in dust from PUF potentially lead to general population exp osure (e.g. particulates/dust from PUF manufacture and use)?

5. Are there TBB / TBPH dust releases that contribute to levels in the env ironment / biota?

2.6.3 Sources and Pathways Excluded From Further Assessme nt

In general, the data gaps preclude excluding source s and pathways from further assessment. However, the potential for environmental exposure t o BPC chemicals during chemical manufacture may be a potential source of exposure. Assessment is contingent on obtaining
information on releases of FR to the environment an d the continued regulation of the releases
of TBB to water.

2.6.4 Uncertainties and Data Gaps

Data gaps and data needs have been identified for t he Brominated Phthalates Cluster (BPC) chemicals. However, data gaps are not necessarily d ata needs for a risk assessment. Figure 2-2 to Figure 2-7 outline the tiering of the data needs . Figure 2-2 depicts the overall source of dust from polyurethane foams (PUF). The BPC chemicals ca n be distinguished by the way they are predominantly used in PUF: additive or reactive use . Use as either additive or reactive in PUF is not precluded; however, the literature suggests tha t they are predominantly used as one or the
other. TBPH

, TBB and the Bromo alkyl ester are typically added to PUF. TBPA-Diol and TBPADiol (mixed esters) are typically reacted into the polymer backbone wh ere they are covalently bound. Release from the PUF is not expected and the re is no evidence from environmental monitoring that they are; however, this needs to be confirmed. The use profiles of Confidential

A and Confidential B cannot be disclosed. Questions remain as to whethe r the additive migrates out of the foam and if the reactive releas es from the foam.Page 27 of 52

If it is assumed, based on the covalent bonding, th at the reactives once reacted are not released from the polymer backbone, as suggested by environmental monitoring, then exposure to these BPC chemicals is not expected fro m their use in PUF and PUF products. When exposure isn’t expected, the characterization of ha zard is not considered a priority, and while there may be hazard data gaps there is no need to g enerate these data to determine the risk for this exposure scenario. If it is determined tha t the reactives are released from the PUF and PUF products, then data are needed to characterize hazard. The data needs are outlined in Figure 2-3 and Figure 2-7. If the additive BPC migr ates from the PUF and PUF products and exposure is likely, data needs have been identified to characterize the hazard to human health
and the environment. The data needs are outlined in Figure 2-3, Figure 2-4, Figure 2-5 and Figure 2-6 and listed in Section 2.

2.6.4.1 Overview of Data Needs for Hazard and Exposure to D ust during Polyurethane Foams (PUF) manufacture and use of PUF Products

Figure 2-2: Overview of Data Needs for Hazard and E xposure to Dust during Polyurethane Foams (PUF)
manufacture and use of PUF Products 8

Brominated Phthalate Cluster (BPC) chemicals are in Polyurethane Foams (PUF) as a chemical additive or a reactant. Use of reactant BPCs that are covalently bonded to the polymer matrix will have a slightly different release pathway than additive BPCs as additional mo re extreme conditions, such as heat, UV process woul d have to be applied in order for the reactant BPC to be r eleased from the PUF substrates. Based on dust mon itoring data, it appears the conditions for covalent bond b reakage are rare since dusts have not been found to contain the

reactive BPCs.

8 Confidential A and Confidential B not included: S ome Confidential data may be applicable to the data gaps for the
non-CBI cluster membersPage 28 of 522.6.4.2Overview of Data Needs for Ecotoxicity from Environmental Exposure to Brominated PhthalatesCluster (BPC) chemicals in Polyurethane Foams (PUF)Figure 2-3: Overview of Data Needs for Ecotoxicityfrom Environmental Exposure to Brominated Phthalates Cluster (BPC) chemicals inPolyurethane Foams (PUF).Figure 2-3depicts the relationship between the information obtained from environmental fate monitoring and dataand the need for testing in differentenvironmental compartments. The data need in an environmental compartment is directly related to the environmental fate of the BPC chemicals.Brominated flame retardants (BFR) have been found in historic Publicly Owned Treatment Works (POTW) sludge samples. The source is uncertain butpotential release from dust from drains in homes and offices cannot be discounted9. POTW sludge and land application of biosolids should be monitoredfor contamination and as source of exposure to earthworms, birds and humans through food.9(Venkatesan and Halden, 2014)Page 29 of 522.6.4.3Overview of Data Needs for Human Health Hazard fromexposure to Brominated PhthalatesCluster (BPC) chemicals in Polyurethane Foams (PUF)DustFigure 2-4: Overview of Data Needs for Human Healthexposure to dust and TBPH from Polyurethane Foams(PUF)There is evidence in the literature thatTBPHis in the environment and in dust in commercial and residential settings. Figure 2-4 shows that datafor hazardcharacterization are available for the reproductiveand developmental toxicity endpoints for the commercial mixtures of FiremasterTM550 and FiremasterTMBZ-54. Non-guideline data are available for the metabolite (TBMEHP; tetrabromomonoethylhexyl phthalate) and from ToxCastTM. The nature and extent ofreproductive and developmental effects observed asa result of exposure to commercial products that may be attributable toTBBorTBPH(or anothercomponent of the mixture) is confounded due to thelack of data with individual components. EPA/OPPThas determined that the available data neitherconclusively indicate nor discount the potential for reproductive or developmental toxicity. Additional data for hazard characterization would allow humanhealth risks from exposure toTBPHin dust derived from PUF and PUF products to be assessed.Page 30 of 52Figure 2-5: Overview of Data Needs for Human Healthexposure to dust and TBB from Polyurethane Foams (PUF)There is evidence in the literature thatTBBis in the environment or in dust found in commercial and residential settings. Figure 2-5 shows thatdata forhazard characterization are available for reproductive and developmental toxicity endpoints for the commercial mixtures FiremasterTM550 andFiremasterTMBZ-54. The nature and extent of reproductive and developmental effects observed as a resultof exposure to commercial products that may beattributable toTBBorTBPH(or another component of the mixture) is confounded due to the lack of data with individual components. Additional data forhazard characterization would allow human health risks from exposure toTBBin dust from PUF and PUF products to be assessed.Page 31 of 52Figure 2-6: Overview of Data Needs for Human Healthexposure to dust and Bromo Alkyl Ester from Polyurethane Foams (PUF)There is no information in the literature that Bromo Alkyl Ester is being used in commerce in PUF andPUF products or that Bromo Alkyl Ester is found industin commercial or residential settings. Confirmationthat Bromo Alkyl Ester is not used in PUF would bevaluable information for a risk assessment becauseifthere is no use in PUF and PUF-products, no human exposure to Bromo Alkyl Ester from its use in PUF and PUF products is anticipated and the risk can beassumed to be negligible. However, if there is evidence that Bromo Alkyl Ester is being used in PUF and PUF products, hazard and/or exposurecharacterization of Bromo Alkyl Ester would be needed for assessing risks.Page 32 of 52Figure 2-7: Overview of Data Needs for Human Healthexposure to dust and TBPA-DIOL AND TBPA-DIOL (MIXED ESTERS) chemicals fromPolyurethane Foams (PUF)There is no information in the literature that TBPA-Diols are being used in commerce in PUF and PUF products or that TBPA-Diols are found in dust incommercial or residential settings. Confirmation that TBPA-Diols are not used in PUF would be valuableinformation for a risk assessment because if thereisno use in PUF and PUF-products, no human exposure to TBPA-Diols from their use in PUF and PUF productsis anticipated and the risk can be assumed to benegligible. However, if there is evidence that TBPA-Diols are being used in PUF and PUF products, hazard and/or exposure characterization of TBPA-Diolswould be needed for assessing risks.Page 33 of 52 2.6.4.4 Releases to the Environment

2.6.4.4.1 Chemical Manufacture

Available data allow for a limited screening-level assessment of exposure to TBPH and TBPADiol . The release of TBB to water from manufacturing and processing is regu lated by EPA/OPPT (40 CFR Section 721.2925). In general, there are un certainties associated with the media type and frequency of releases of the cluster chemicals to the environment. To reduce these uncertainties, monitoring information (air, water, effluent) in and around the manufacturing
facilities would aid the risk assessment. Alternati vely, in the absence of monitoring/measured data, process specific information including site i nformation, batch size, number of hours/batch, number of batches produced/year, days/ year of operation, concentration of the chemical, release sources, estimated releases, freq uency of releases, control technologies used to mitigate/reduce the releases, and waste disposal practice would assist in the assessment of environmental exposure from the manufacturing secto r.

This information would enable EPA/OPPT to develop e nvironmental release estimates, including frequency and media of release for an “av erage" or a “typical" manufacturing site.

2.6.4.4.2 Polyurethane Foams (PUF) Manufacture

There is no readily available information on the en vironmental releases of the chemicals in this cluster during the manufacture of polyurethane foam s (PUF). The release of TBB to water from manufacturing and processing is regulated by EPA/OP PT (40 CFR Section 721.2925). An existing generic scenario for PU flexible foam manufacturing can be used to estimate releases and occupational exposures.

Available data allow for a limited screening-level assessment of releases of TBPH and TBPA-Diol to the environment, using the generic scenario and non-Confidential Business Information (CBI) Chemical Data Reporting (CDR) data.

Limited data are available for releases to the envi ronment during PUF manufacture. To reduce uncertainties, monitoring information (air, water, effluent) in and around the PU manufacturing
facilities would aid the risk assessment. Alternat ively, in the absence of monitoring/measured data, process specific information including site i nformation, batch size, number of hours/batch, number of batches/year, number of days /year of operation, concentration of the chemical, release sources, estimated releases, freq uency of releases, and control technologies used to mitigate/reduce the releases, and waste dis posal practice would aid the risk

assessment.

This information would enable EPA/OPPT to develop n on site-specific “typical facility” release estimates with frequency and media of release.Page 34 of 52 2.6.4.4.3 Manufacture of Products Containing Polyurethane Foa ms (PUF)

There is no readily available information on the en vironmental releases of the chemicals during the manufacture of products containing PUF. EPA/OPP T can use estimates following the approach taken in the New Chemicals Program to prep are a screening-level assessment based on a selected number of industries/exposure scenari os for the two chemicals for which data are available ( TBPH and TBPA-Diol ).

In addition to the inherent uncertainties of the es timates used to prepare a screening-level assessment, there would be uncertainties in the est imates of the media and frequency of releases. To reduce uncertainties, industry- wide m onitoring information (air, water, effluent) in
and around the relevant facilities would aid the ri sk assessment. Alternatively, in the absence of monitoring/measured data, process specific informat ion including site information, number of articles manufactured per hour , number of hours/da y, number of days/year, concentration of chemical in foam, release sources, estimated releas es, frequency of releases, and control technologies used to mitigate/reduce the releases, and waste disposal practice would aid the
risk assessment.

This information would enable EPA/OPPT to develop r elease estimates with frequency and media of release for one or more “generic facility” using foam containing chemicals in this
cluster.

2.6.4.4.4 Occupational Use of Products Containing Polyurethan e Foams

(PUF)

No release information is available and EPA/OPPT is unable to assess release from the uses of products containing PU foam.

Data needs for an assessment include monitoring inf ormation (air, water, effluent) in and around the use sites. Alternatively, in the absence of monitoring/measured data, use specific information including the number of use sites, deta iled description of use scenario, number of hours product is used/day, number of use days/year, concentration of chemical in the foam, amount of foam in the product, types and number of products per use site, estimated releases, frequency of releases, and control technologies use d to mitigate/reduce the releases, and waste disposal practice would aid the risk assessme nt.

This information would enable EPA/OPPT to develop a "typical" use scenario for each use and assess releases, media of release and the frequency of release.Page 35 of 52 2.6.4.4.5 Consumer Use of Products Containing Polyurethane Fo ams (PUF)

Detection of TBPH/TBB in sludge, sediment, and indoor dust indicate a po tential for exposures
to the environment. Detection of both TBPH in remote biota and environmental media indicates exposures have occurred and that global t ransport is occurring as well. Additional environmental samples from soil, sludge, sediment, and biota will provide information about the prevalence and spread of BPCs in the environmen t.

Additional data are needed to understand how, at wh at rate, and in what form TBPH and TBB migrate out of many types of products. Source char acterization, migration rates, and monitoring data are needed to demonstrate how the u se of TBPH

, TBB and Confidential A in certain products may result in subsequent exposure through migration of these chemicals into
indoor and outdoor environments.

2.6.4.5 Occupational Exposure

2.6.4.5.1 Chemical Manufacture

The chemicals in this cluster are not on the Occupa tional Safety and Health Administration’s (OSHA) list of regulated chemicals (OSHA, 2013). T here is some non-confidential CDR information on the number of manufacturing workers and concentrations (EPA, 2012a). Based on the physical-chemical properties and available i nformation, workers in cluster chemical manufacturing operations are not expected to be exp osed to the chemicals via inhalation.

Limited data are available for occupational exposur e to the cluster members leading to uncertainties in the exposure assessment. To reduce these uncertainties, workplace monitoring information (personal and/or area sampling for work ers handling the chemical) would aid the risk assessment. Alternatively, in the absence of t he monitoring data, information on manufacturing process, information on worker activi ties (activities performed during work shift, number of work hours/day, days/year of operation, c oncentration of the chemical and identification of worker activities which may resul t in inhalation exposure), and information on workplace industrial hygiene practices and control technologies would assist in the occupational exposure assessment.

This information would enable EPA/OPPT to develop a n occupational exposure assessment for the workers at manufacturing sites.

2.6.4.5.2 Polyurethane Foams Manufacture (PUF)

Based on limited monitoring data and available info rmation, limited screening-level exposure assessment may be possible. Without chemical-specif ic data, the exposure estimates would be based on particulate standards (i.e. total dust) an d/or available data on other chemicals being monitored. The exposure estimates and the number of workers exposed may not be representative of this industry.Page 36 of 52

To reduce uncertainties, industry-wide workplace mo nitoring data (personal and/or area sampling for workers handling the chemical) would a id the risk assessment. Alternatively, in the absence of the monitoring data, manufacturing proce ss information, information on worker activities (activities performed during work shift, number of work hours/day, number of days/year of operation, concentration of chemical a nd potential sources for inhalation exposure), information on workplace industrial hygi ene practices and control technologies
would aid the risk assessment.

This information would enable EPA/OPPT to develop n on site-specific “typical foam manufacturing facility” occupational exposure estim ates.

2.6.4.5.3 Manufacture of Products Containing Polyurethane Foa ms (PUF)

No data are available on occupational exposure to t he cluster chemicals during the manufacture of products containing PU foam. Based o n OSHA’s Particulates Not Otherwise Regulated (inhalable and respirable dust ) a "high-end" exposure can be determined.

To reduce uncertainties, industry-wide workplace mo nitoring information (personal and/or area sampling for workers handling the chemical) wo uld aid the risk assessment. Alternatively, in the absence of the measured data, process inform ation, information on worker activities (activities performed during work shift, number of work hours/day, days/year of operation, concentration of chemical and potential sources for inhalation exposure), information on workplace industrial hygiene practices and control technologies would aid the risk assessment.

This information would enable EPA/OPPT to develop non site-specific “typical facility” occupational exposure estimates.

2.6.4.5.4 Occupational Use of Products Containing Polyurethan es Foams (PUF)

No data are available on occupational exposure to t he cluster chemicals during the use of products containing PUF.

To reduce uncertainties, industry wide workplace ai r monitoring information would aid the risk assessment. Alternatively, in the absence of the me asured data, use information, number of use sites, information on worker activities (activi ties performed during work shift, number of work hours/day, days/year of operation, concentrati on of chemical and potential sources for inhalation exposure), information on workplace indu strial hygiene practices and control technologies would aid the risk assessment.

This information would enable EPA/OPPT to develop a "typical" use scenario for each use and assess occupational exposure assessment for each us e.Page 37 of 52 2.6.4.6 Consumer Exposure from Use of Products Containing Polyurethane Foams (PUF)

The exposure potential of TBPH and TBB is influenced by several parameters of the source
material to which these chemicals are added. One o f the major sources of exposure is considered to be certain types of polyurethane (PU) foam products based on the following criteria as compared to other product end uses: maj or use-based production volume, higher percent of flame retardant chemicals within the pro duct, long service life/product use within indoor environments, diverse set of large articles with large surface areas exposed, and multiple sources present within various indoor envi ronments.

Additional information is needed to develop source characterization which includes the type of foam linked with the type of end-use product, the p ercent weight of chemical within the product, and properties of the foam, including dens ity, rigidity, and structure. Differences in density, rigidity, and structure (closed vs. open c ell) along with the thickness of the product and its exposed surface area influence the likelihood o f migration and associated exposure potential
of TBB and TBPH over time. Lower density, thinner, open-cell flexi ble foams, with large amounts of exposed surface area have may have great er potential for additive migration over time. However, it is not clear if there may be thre shold values for one or a combination of these factors that could influence migration and exposure potential. Therefore, additional information is needed on the migration of additive chemicals out of Polyurethane Products, which include data on the thickness of product; sur face area exposed; diffusion coefficient; partition coefficient; and migration rate of FR ove r time.

Additionally, monitoring data for indoor environmen ts, homes, commercial buildings, cars, trains, where high concentrations of polyurethane p roducts are present would decrease the level of uncertainty.

2.6.4.7 Human Health Data Assessment

The potential for exposure to the brominated phthal ates cluster (BPC) members during chemical manufacture is not clearly understood. Sim ilarly, there is evidence for potential exposure to some of the cluster members during occu pational use of products containing some
of the cluster members. There is also evidence to s uggest potential consumer exposure to the BPC members during the use of some of the products containing some of the BPC members.

An overview of the data for the structural analog, bis (2-ethylhexyl) phthalate (DEHP; CASRN 117-81-7), was presented. It could be argued that c onservatively, these data could be used to characterize the hazard for the brominated phthalat es cluster (BPC) members. However, available data suggest that the mode of action of D EHP that elicits chronic (specifically reproductive and developmental) toxicity is not the same as that of the BPC members. In addition, the available data support this hypothesi s. There is uncertainty characterizing the hazard for the BPC members because the chronic (inc luding reproductive/developmental) toxicity observed in animal studies with the BPC me mbers is via a mode of action notPage 38 of 52

considered relevant to humans or at concentrations that either do not raise immediate concerns, or which are difficult to attribute to a particular chemical because the data were obtained using a commercial mixture.

Based on the available data for TBPH , there is a low hazard for acute toxicity. In the screeninglevel dietary study in rats with TBPH (described in the technical supplement), the poten tial for liver toxicity was observed by perturbations in cli nical chemistry values. However, some liver effects have been attributed to a mode of action, p eroxisome proliferation (PPARα), not considered relevant to humans (Springer et al., 201 2). The 28-day repeated-dose study, twogeneration reproductive toxicity study and a prenat al developmental toxicity study with the commercial product Firemaster® BZ 54 ( TBPH/TBB mixture), showed the potential to affect fetal development at high doses. In addition, it ap pears that the kidney is a potential target organ. The uncertainty of using these data to chara cterize the hazard for TBPH or TBB lies in the attribution of the toxicity observed to either mixt ure component. No toxicity studies with TBB alone are available; however, given that the metabo lites of TBPH and TBB are different, it is expected that any toxicity observed would not be by the same mode of action or attributable to the same chemical. (Springer et al., 2012) observed the potential for endocrine disruption with
the metabolites of TBPH and TBB suggesting that the potential for reproductive/ developmental toxicity needs to be explored further . Screening level data do not suggest a concern for carcinogenicity with TBPH and the potential for a mode of action not relevan t to humans (PPARα) further lowers the potential concern and the need for data for this chronic toxicity endpoint.

No data are available for Bromo Alkyl Ester . The acute toxicity of TBPA-Diol and TBPA-Diol (mixed esters) is considered low. No data for repeated-dose or re productive/developmental toxicity are available for TBPA-Diol and TBPA-Diol (mixed esters) . The need for human health data for these chemicals is dependent on the potent ial exposure during manufacture and the potential for at least TBPA-Diol and TBPA-Diol (mixed esters) to be released from the polymer
backbone. No uses have been identified for Bromo Alkyl Ester

.

The available toxicity data for TBPH and TBB are considered adequate for use in a screeninglevel assessment based on the criteria described by (Klimisch et al., 1997). The data for TBPH were submitted to both EPA/OPPT and the European Ch emicals Agency (ECHA) under the HPV Challenge Program 10 and REACH 11 , respectively.

The available data for TBB were submitted to EPA/OPPT as data on the commerci al product, Firemaster®BZ-54 (Chemtura, 2012a) and are consider ed adequate for use in screening-level assessments as described by (Klimisch et al., 1997)

.

10 United States High Production Volume (HPV) Challen ge Program was a voluntary chemical data program administered by EPA and is described at: http://www.epa.gov/chemrtk/index.htm

11 Registration, Evaluation, Authorisation and Restri ction of Chemicals (REACH) is the European Union ch emical regulatory program administered by ECHA and is desc ribed at: http://echa.europa.eu/web/guest/regulations/reach/Page 39 of 52

The available data for TBPA-Diol and TBPA-Diol (mixed esters) are similarly considered adequate as described above.

No data are available for Bromo Alkyl Ester

.

2.6.4.8 Environmental Data Assessment

For environmental fate and bioaccumulation, compreh ensive studies are needed for many endpoints for all cluster members. All cluster memb ers should be tested individually and all major degradation products should be quantified. Co mprehensive bioaccumulation studies are needed for all BPC cluster members, and these shoul d include several aquatic and terrestrial species selected from organisms commonly used in bi oaccumulation testing. This would assist in the determination of appropriate data needs for the ecotoxicity endpoints.

Insufficient data are available for brominated phth alates cluster members to support a category approach for assessing environmental hazard. Thus, each member will be considered independently to establish a preliminary testing ap proach. The testing approach may be subject to modifications based on the availability of fate and monitoring data that may inform on the likely routes of environmental exposure.

Even though a category approach cannot currently be supported, use information (i.e., additive or reactive flame retardants) infers certain fate c haracteristics that suggest exposure pathways likely to affect the preliminary testing strategy. The additive flame retardants all have high experimental Log K ow values (≥8.8) and predicted Log K oc values (≥4.5) suggesting predominant partitioning to sediment and soil and unlikely expo sure in the water column. Cluster members
identified as additive flame retardants include TBPH and TBB . The reactive flame retardants generally have Log K ow values <5 suggesting their presence in the water c olumn; however, use entails reacting the flame retardants into products suggesting these substances are less likely to distribute into the environment that may be better characterized with submission of fate data.
Cluster members identified as reactive flame retard ants include 2-(2-Hydroxyethoxy) ethyl 2- hydroxy propyl 3,4,5,6 tetrabromobenzene dicarboxyl ate (CASRN 20566-35-2) and 3,4,5,6 tetrabromo-1, 2-benzene dicarboxylic acid, mixed es ters with diethylene glycol and propylene glycol (CASRN 77098-07-8). Use information is limi ted for 1, 2-(2, 3-dibromopropyl) benzene dicarboxylate (CASRN 7415-86-3), Confidential A and Confidential B.

For all cluster members, experimental environmental hazard data are limited to water column organisms. Available acute toxicity data suggest aq uatic invertebrates as the most sensitive species; however, available data for this taxa are limited to the low water solubility and high Log K ow additive flame retardants TBPH and the commercial mixture, Firemaster®BZ54 (i.e.,

TBPH and TBB ) and. Available chronic aquatic toxicity data are limited to two chronic studies with two different species of invertebrates using t he additive flame retardants TBPH and the commercial mixture Firemaster®BZ54 (i.e., TBPH and TBB ). Given the low water solubility characteristics of these additive substances, futur e testing recommendations should resolve conflicting conclusions provided in chronic inverte brate toxicity testing. Testing should bePage 40 of 52

completed using the individual cluster members and not the commercial mixtures. Remaining cluster members (i.e., reactive flame retardants an d TBPA-Diols) are more likely to reside in the water column, but limited data (e.g., a single expe rimental fish acute toxicity test and no fate testing) hinder hazard determination. Thus, for the se lower Log K ow substances, testing recommendations should be based on the results of p hysiochemical and fate testing and should include preliminary acute water column toxicity tes ts.

Experimental monitoring data are available that sug gest likely exposure of TBPH and TBB to organisms that do not currently have corresponding hazard data. Since detection of these cluster members in the environment suggests potenti al for long term exposure to wildlife, chronic testing is recommended to address those org anisms likely exposed in order to characterize potential population level effects. TBPH and TBB have been detected in several species of birds, terrestrial mammals, aquatic mamm als, fish, aquatic invertebrates, and sediment-dwelling invertebrates. Proposed test stra tegies for health effects will be considered prior to testing recommendations to address detecte d concentrations in mammals. Detection in fish, aquatic invertebrates, and sediment-dwelli ng invertebrates suggest potential for exposure and uptake by organisms present in water b odies including aquatic plants and thus,
hazard and bioaccumulation characterization is need ed for these organisms. Hazard data are
needed to understand the detected concentrations in avian species, as well as exposure and fate testing given the variable exposure routes lik ely for birds and the absence of experimental
data to characterize chronic hazard. Detected conce ntrations have also been reported in sediment and biosolids suggesting potential routes of exposure. Based on concentration detected in these media, hazard characterization of terrestrial invertebrates and terrestrial plants is needed in addition to previously describe d testing of sediment-dwelling invertebrates.

Given the limitations of monitoring studies (i.e., no representation of potential degradates, availability of only TBB and TBPH data, and insufficient coverage of potentially exp osed organisms such as plants), if additional data on ph ysicochemical and fate parameters become available, additional exposure scenarios will be as sessed. Testing recommendations will focus on cluster members designated as reactive flame ret ardants, confidential substances (public information not available), and TBPA-Diols, as well as potential degradates for all cluster
members.Page 41 of 523DATA NEEDS ASSESSMENT3.1Data Needs Conclusions – Additive Brominated Phthalate Cluster (BPC) ChemicalsTable 3-1: Data Needs Assessment (DNA)Additive* BPC Chemicals:These chemicals are added to the flexible polyurethane foams (PUF) formulation and it is anticipated,based on availabledata, that they are migrating through the foams andbeing released from the foamsAVAILABLE INFORMATIONDATA GAPSDATA NEEDSBPCChemical &CASRNWorkerExposure**ReleasestoEnvironmentGeneralpopulation/ConsumerexposureWorkerexposure***ReleasestoEnvironmentGeneralpopulation/ConsumerexposureWorkerexposureReleasestoEnvironmentGeneralpopulation/ConsumerexposureEXPOSURECOMMENTTBPHandTBBhave been detected inthe home and in the environment.Rate of migration ofTBPHandTBBfromPUF and PUF productsRate of migration ofTBPHandTBBfromPUF and/or PUF productsTBPH26040-51-7Modeling and estimates availableSeefootnote•Manufacturing ProcessDescription for BPCchemical and PU foam &PU foam product•Type of PU foamassociated with PU foamproduct•Amount of PU foam usedin final PU foam product•Percent weight ofchemical in PU foam & PUfoam product•Migration of chemical outof PU foam product•Monitoring humanexposure (blood)•Source/quantity/media ofreleases•WasteDisposal•Productscontaining BPCchemical•Environmentalsampling(soil,sludge,•Manufacturing ProcessDescription for BPCchemical and PUF & PUFproduct•Type of PUF associatedwith PUF product•Amount of PUF used infinal PUF product•Percent weight ofchemical in PUF & PUFproduct•Migration of chemicalout of PUF product•Monitoring humanexposure (blood)Page 42 of 52Additive* BPC Chemicals:These chemicals are added to the flexible polyurethane foams (PUF) formulation and it is anticipated,based on availabledata, that they are migrating through the foams andbeing released from the foamsAVAILABLE INFORMATIONDATA GAPSDATA NEEDSBPCChemical &CASRNWorkerExposure**ReleasestoEnvironmentGeneralpopulation/ConsumerexposureWorkerexposure***ReleasestoEnvironmentGeneralpopulation/ConsumerexposureWorkerexposureReleasestoEnvironmentGeneralpopulation/ConsumerexposureTBB183658-27-7sediment)•BiotasamplesBromo alkylester7415-86-3HAZARD – ENVIRONMENTAL FATE & ECOTOXICITYCOMMENTTBPHandTBBhave been detected in the home and in the environment.COMMENTMost data for physical-chemicalproperties and environmental fate areestimated.Experimental data for physical –chemical properties and environmentalfateExperimental data for physical –chemicalproperties and environmental fateTBPH26040-51-7Available chronic toxicity data (TBPHpurity >95%) are inconclusiveReliable chronic toxicity dataReliable chronic toxicity data forappropriate environmentsTBB183658-27-7Available chronic toxicity data(Firemaster®BZ-54) are inconclusiveBromoAlkyl Ester7415-86-3No DataAcute and chronic toxicity data set forfish, invertebrates and algaeExposure pathways need to be determinedbefore data needs can be identified.HAZARD – HUMAN HEALTHCOMMENTTBPHandTBBhave been detected in the home and in the environment.TBPH26040-51-728-d (dietary) (TBPH purity >95%)NOAEL = 233 mg/kg-day [decreasedbody weights and effects on clinicalchemistry]•Reliable information tocharacterize the hazard forreproductive/developmentaltoxicity•Reliable information tocharacterize the hazard forreproductive/developmentaltoxicityPage 43 of 52Additive* BPC Chemicals:These chemicals are added to the flexible polyurethane foams (PUF) formulation and it is anticipated,based on availabledata, that they are migrating through the foams andbeing released from the foamsAVAILABLE INFORMATIONDATA GAPSDATA NEEDSBPCChemical &CASRNWorkerExposure**ReleasestoEnvironmentGeneralpopulation/ConsumerexposureWorkerexposure***ReleasestoEnvironmentGeneralpopulation/ConsumerexposureWorkerexposureReleasestoEnvironmentGeneralpopulation/Consumerexposure•low acute toxicity•potential long-term liver effects inanimal studies which may or maynot be by mode of action relevant tohumans•potentialreproductive/developmental effectunclear [no data on pure chemical]•potential for endocrine effects[thyroid and testes]•Additional Data for Firemaster BZ54 (see CASRN•183658-27-7)•Evaluation of endocrine effects[thyroid and testes] and potentialreproductive/developmentaltoxicityTBB183658-27-7Available data for (oral gavage)reproductive/developmental toxicity ison commercial product Firemaster®BZ54 which is a mixture ofTBPH/TBB. It isnot clear if toxicity observed isattributable toTBBorTBPHNOAEL (Firemaster®BZ-54) =50 mg/kg-day•Low acute toxicity (oral/dermal)•28-d (oral) NOAEL = notestablished LOEL =160 mg/kg-day (kidney identifiedas target organ)Acute and chronic(repeated/reproductive/developmental)toxicitydata set•Reliable information tocharacterize the hazard forreproductive/developmentaltoxicity•Evaluation of potential endocrineeffects [thyroid and testes]Page 44 of 52Additive* BPC Chemicals:These chemicals are added to the flexible polyurethane foams (PUF) formulation and it is anticipated,based on availabledata, that they are migrating through the foams andbeing released from the foamsAVAILABLE INFORMATIONDATA GAPSDATA NEEDSBPCChemical &CASRNWorkerExposure**ReleasestoEnvironmentGeneralpopulation/ConsumerexposureWorkerexposure***ReleasestoEnvironmentGeneralpopulation/ConsumerexposureWorkerexposureReleasestoEnvironmentGeneralpopulation/Consumerexposure•Evidence ofreproductive/developmentaltoxicity with Firemaster®BZ-54•potential for endocrine effectsBromoAlkyl Ester7415-86-3•acute toxicity unknown•repeated/reproductive/developmental toxicityunknownAcute and chronic(repeated/reproductive/developmental)toxicitydata setNo uses have been identified for CASRN7415-86-3. Data need dependent on thepotential for worker exposure duringchemical manufacture***The nature of Confidential A and Confidential B cannot be disclosed. Data Gaps and Data Needs shouldbe considered for both reactive andadditive uses.**Based on the available data for physical-chemical properties, worker inhalation exposure during chemical manufacture is expected to benegligible and ingestion is not anticipated in an occupational setting.***Workplace monitoring information (personal and/or area sampling for workers handling the chemical).In the absence of the monitoring data,information on manufacturing process, information on worker activities (activities performed during work shift, number of work hours/day,days/year of operation, concentration of the chemical and identification of worker activities whichmay result in inhalation exposure), andinformation on workplace industrial hygiene practices and control technologies would be useful.Page 45 of 523.2Data Needs Conclusions – Reactive Brominated Phthalate Cluster (BPC) ChemicalsTable 3-2: Data Needs AssessmentReactive* BPC Chemicals:These chemicals are reacted into the polymer backbone of rigid polyurethane foams (PUF). Based on available data (nature ofchemical reactivity and no detection in the environment), it is not anticipated that these chemicals are released from the PU foam or product. While theycan be used as additives, available data suggest that the predominant use is as a reactive substance.AVAILABLE INFORMATIONDATA GAPSDATA NEEDSBPCChemical &CASRNWorkerexposure**Releases toenvironmentGeneralpopulation/ConsumerexposureWorkerexposure***Releases toenvironmentGeneralpopulation/ConsumerexposureWorkerexposureReleases toenvironmentGeneralpopulation/ConsumerexposureEXPOSUREFOR ALLNot detected in the environment. Release from PUF unknown.Release of ‘reactives’ from PUF and/or PUFproductsTBPA-Diol20566-35-2Modelingandestimatesavailable•Not detected inenvironmentalmonitoring.•No other release dataare available (e.g.from industrialsources)See ***Footnote•Manufacturing ProcessDescription for BPCchemical and PUF andPUF products•Potential for releasefrom PUF and PUFproducts•Source/•quantity/media ofreleases•WasteDisposal•ProductscontainingBPCchemical•Manufacturing ProcessDescription for BPCchemical and PUF andPUF products•Potential for releasefrom PUF and PUFproductsTBPA-Diol(mixedesters)77098-07-8HAZARD – ENVIRONMENTAL FATE & ECOTOXICITYFOR ALLMost data for physical-chemicalproperties and environmental fate areestimated.Experimental data for physical –chemicalproperties and environmental fateExperimental data for physical-chemicalproperties and environmental fateTBPA-Diol20566-35-2Acute toxicity data for fish onlyAcute toxicity data set for invertebratesand algae and chronic toxicity data set forfish, invertebrates and algaeExposure pathways (i.e. release from PUF and PUFproducts and environmental fate) need to bePage 46 of 52Reactive* BPC Chemicals:These chemicals are reacted into the polymer backbone of rigid polyurethane foams (PUF). Based on available data (nature ofchemical reactivity and no detection in the environment), it is not anticipated that these chemicals are released from the PU foam or product. While theycan be used as additives, available data suggest that the predominant use is as a reactive substance.AVAILABLE INFORMATIONDATA GAPSDATA NEEDSBPCChemical &CASRNWorkerexposure**Releases toenvironmentGeneralpopulation/ConsumerexposureWorkerexposure***Releases toenvironmentGeneralpopulation/ConsumerexposureWorkerexposureReleases toenvironmentGeneralpopulation/ConsumerexposureTBPA-Diol(mixedesters)77098-07-8No DataAcute and chronic toxicity data set for fish,invertebrates and algaedetermined beforespecific data needs can beidentified.HAZARD – HUMAN HEALTHTBPA-Diol20566-35-2•low acute toxicity•potential repeated/reproductive/developmental toxicity unknownRepeated-dose andreproductive/developmental toxicityPotential for worker and consumer exposureneeds to be evaluated to determine specific dataneeds.TBPA-Diol(mixedesters)77098-07-8*The nature of Confidential A and Confidential B cannot be disclosed. Data Gaps and Data Needs shouldbe considered for both reactive and additive uses.**Based on the available data for physical-chemicalproperties, worker inhalation exposure during chemical manufacture is expected to be negligible andingestion is not anticipated in an occupational setting.*** Workplace monitoring information (personal and/or area sampling for workers handling the chemical). In the absence of the monitoring data,information on manufacturing process, information on worker activities (activities performed during work shift, number of work hours/day, days/year ofoperation, concentration of the chemical and identification of worker activities which may result ininhalation exposure), and information on workplaceindustrial hygiene practices and control technologies would be useful.Page 47 of 52



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