ANNEX XV – IDENTIFICATION OF SVHC

Annex XV dossier

PROPOSAL FOR IDENTIFICATION OF A PBT/vPvB SUBSTANCE

Substance Name:

Bis(pentabromophenyl)ether (decabromodiphenyl ether; decaBDE)

EC Number:

214-604-9

CAS Number:

1163-19-5

Submitted by:

Health & Safety Executive, Redgrave Court, Bootle, Merseyside L20 7HS United Kingdom (with support from the Environment Agency, Chemicals Assessment Unit)

Version:

PUBLIC VERSION

August 2012

ANNEX XV – IDENTIFICATION OF SVHC

CONTENTS PROPOSAL FOR IDENTIFICATION OF A PBT/VPVB SUBSTANCE ..................................................................V PART I..........................................................................................................................................................................1 JUSTIFICATION .........................................................................................................................................................2 1 IDENTITY OF THE SUBSTANCE AND PHYSICAL AND CHEMICAL PROPERTIES .................................2 1.1 Name and other identifiers of the substance ...................................................................................................2 1.2 Composition of the substance .........................................................................................................................3 1.3 Name and other identifiers of transformation products ..................................................................................4 1.4 Physico-chemical properties ...........................................................................................................................6 2 HARMONISED CLASSIFICATION AND LABELLING ....................................................................................6 3 ENVIRONMENTAL FATE PROPERTIES...........................................................................................................7 3.1 Degradation ....................................................................................................................................................7 3.1.1 Abiotic degradation .............................................................................................................................7 3.1.1.1 Hydrolysis .............................................................................................................................7 3.1.1.2 Phototransformation/photolysis.............................................................................................7 3.1.1.2.1 Phototransformation in air ................................................................................7 3.1.1.2.2 Phototransformation in water ...........................................................................19 3.1.1.2.3 Phototransformation in soil ...............................................................................29 3.1.1.2.4 Other abiotic transformation routes.................................................................30 3.1.1.3 Summary of abiotic degradation ...........................................................................................32 3.1.2 Biodegradation ....................................................................................................................................33 3.1.2.1 Biodegradation in water ........................................................................................................33 3.1.2.1.1 Estimated data ....................................................................................................33 3.1.2.1.2 Screening tests.....................................................................................................33 3.1.2.1.3 Simulation tests...................................................................................................33 3.1.2.2 Biodegradation in sediments .................................................................................................33 3.1.2.3 Biodegradation in sewage sludge ..........................................................................................63 3.1.2.4 Biodegradation in soil ...........................................................................................................68 3.1.2.5 Summary and discussion on biodegradation .........................................................................87 3.1.3 Transformation in an aquatic mesocosm .............................................................................................88 3.1.4 Summary and discussion on degradation ............................................................................................97 3.2 Environmental distribution .............................................................................................................................98 3.2.1 Adsorption/desorption .........................................................................................................................98 3.2.2 Volatilisation .......................................................................................................................................98 3.2.3 Distribution modelling ........................................................................................................................99 3.2.3.1 Fugacity modelling................................................................................................................99 3.2.3.2 Long-range transport potential ..............................................................................................99 3.3 Bioaccumulation .............................................................................................................................................103 3.3.1 Transformation in aquatic species .......................................................................................................105 3.3.1.1 Field studies ..........................................................................................................................105

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ANNEX XV – IDENTIFICATION OF SVHC 3.3.1.2 Laboratory studies .................................................................................................................108 3.3.1.3 Modelling studies ..................................................................................................................120 3.3.1.4 Summary of transformation in aquatic species......................................................................120 3.3.2 Transformation in terrestrial species ...................................................................................................121 3.3.2.1 Birds ......................................................................................................................................121 3.3.2.2 Mammals...............................................................................................................................123 3.3.3 Summary and discussion of transformation in biota ...........................................................................130 3.4 Secondary poisoning.......................................................................................................................................131 4 HUMAN HEALTH HAZARD ASSESSMENT.....................................................................................................131 5 ENVIRONMENTAL HAZARD ASSESSMENT ..................................................................................................132 6 CONCLUSIONS ON THE SVHC PROPERTIES .................................................................................................137 6.1 PBT, vPvB assessment ...................................................................................................................................137 6.1.1 Assessment of PBT/vPvB properties – comparison with the criteria of Annex XIII ..........................137 6.1.2 Summary and overall conclusions on the PBT, vPvB properties ........................................................140 PART II ........................................................................................................................................................................141 INFORMATION ON USE, EMISSIONS AND ALTERNATIVES............................................................................141 1 MANUFACTURE AND IMPORT/EXPORT ........................................................................................................141 2 USE .........................................................................................................................................................................142 2.1 End uses for decaBDE ....................................................................................................................................143 2.1.1 Plastics/polymers.................................................................................................................................143 2.1.2 Textiles ................................................................................................................................................148 2.1.3 Transport .............................................................................................................................................153 2.1.4 Other....................................................................................................................................................157 2.2 Future demand for decaBDE ..........................................................................................................................157 2.2.1 Fire safety............................................................................................................................................158 2.2.2 Legislation...........................................................................................................................................158 2.2.3 Ecolabelling initiatives and green procurement policies .....................................................................160 2.2.4 Views from stakeholders .....................................................................................................................160 3 EMISSIONS ...........................................................................................................................................................162 3.1 Emission estimates from the ESR RARs ........................................................................................................162 3.2 Emission estimates based on data gathered from participants in the VECAP ................................................163 3.3 Environmental monitoring data ......................................................................................................................164 3.4 Current use of controls to minimise emissions to the environment ................................................................164 3.5 Summary.........................................................................................................................................................165 4 CURRENT KNOWLEDGE ON ALTERNATIVES ..............................................................................................167 4.1 Introduction ....................................................................................................................................................167 4.2 Chemical flame retardants ..............................................................................................................................167 4.2.1 Polymers..............................................................................................................................................169 4.2.2 Textiles ................................................................................................................................................174 4.2.3 Transport .............................................................................................................................................176

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ANNEX XV – IDENTIFICATION OF SVHC 4.2.4 Hazard classification and registration status of some alternatives.......................................................177 4.3 Use of inherently flame retardant materials and product design.....................................................................183 4.3.1 Plastics/polymers.................................................................................................................................183 4.3.2 Textiles ................................................................................................................................................184 4.4 Summary.........................................................................................................................................................185 APPENDIX 1: PBT PROFILE OF PBDES OTHER THAN DECABDE....................................................................186 APPENDIX 2: PBDE CONGENER NOMENCLATURE...........................................................................................203 APPENDIX 3: PBT PROFILE OF SOME HYDROXYLATED AND METHOXY-PBDES .....................................204 APPENDIX 4: TECHNICAL INFORMATION ON SOME ALTERNATIVES FOR DECABDE ............................214 APPENXIX 5: ABBREVIATIONS .............................................................................................................................222 OTHER INFORMATION ............................................................................................................................................229 ANNEX 1: STAKEHOLDER CONTACTS ................................................................................................................255

List of tables Table 1: Substance identity...........................................................................................................................................2 Table 2: Constituents in the currently supplied commercial substance ........................................................................3 Table 3: Impurities........................................................................................................................................................3 Table 4: Identifiers for PBDE congeners......................................................................................................................5 Table 5: Overview of relevant physicochemical properties..........................................................................................6 Table 6: Mass balance for the anaerobic degradation of 14C-labelled decaBDE ..........................................................45 Table 7: Results of trace analysis for PBDE congeners from the anaerobic degradation of decaBDE (Schaefer & Flaggs, 2001b)...........................................................................................................................................................................46 Table 8: Formation of lower PBDE congeners from the anaerobic degradation of decaBDE (nominal 500 mg/kg treatment, composite sample) (Schaefer & Flaggs, 2001b) ..........................................................................................50 Table 9: Concentrations of PBDEs in soil after 60 days, on a µg/kg dry weight basis (± 95% confidence interval), from Huang et al. (2010) .......................................................................................................................................................70 Table 10: Concentration trends of decaBDE in sludge-amended soil, from Nyholm (2011) .......................................77 Table 11: Level III fugacity modelling for decaBDE ...................................................................................................99 Table 12: Distribution of PBDEs in sediment and biota downstream of a waste water treatment plant (from La Guardia et al., 2007) ...................................................................................................................................................................107 Table 13: Weight percentage formation of PBDE congeners in soil from the study of Huang et al., 2010 .................138 Table 14: Examples of fire safety standards applicable to end uses for plastics/polymers (based on RPA, 2003).......146 Table 15: Use of decaBDE in textiles (RPA 2003) ......................................................................................................149 Table 16: Examples of national fire safety regulations for furniture and textiles in domestic and public buildings in some Member States (based on DG SANCO, 2011; DEFRA, 2010) ...........................................................................150 Table 17: Examples of fire safety standards that are applicable to private and public transport ..................................154 Table 18: Summary of release estimates in ESR RARs ...............................................................................................162 Table 19: Possible alternatives and compatible plastics/polymers (based on RPA, 2003; Danish EPA, 2006; ECB, 2007b; Weil and Levchik, 2009; DG SANCO, 2011 and supplier’s literature including a product selector published by PINFA) .........................................................................................................................................................................170 Table 20: Hazard classification and REACH registration status of some alternative substances .................................178

iii

ANNEX XV – IDENTIFICATION OF SVHC List of figures Figure 1: Formation of PBDEs during photolysis of decaBDE adsorbed to HIPS (after Kajiwara et al., 2008)..........12 Figure 2: Formation of dibenzofurans during photolysis of decaBDE adsorbed to HIPS (after Kajiwara et al., 2008) 13 Figure 3: Preliminary results of the in situ debromination of decaBDE under different conditions after 12 days (Experiment B) .............................................................................................................................................................37 Figure 4: PBDE debromination pathways, taken from Robrock et al. (2008) ..............................................................82 Figure 5: Concentrations of decaBDE and tri- to nonaBDE homologue groups in replicate sediment samples (a – d) from the “high” mesocosm in May 2008, i.e. 8 months post-treatment (Experiment 1) ..............................................89 Figure 6: Concentrations of PBDE homologue groups in individual yellow perch carcasses from the control, “low”, “medium” and “high” mesocosm, captured in October 2008 (units are ng/g dw) .......................................................93 Figure 7: Distribution of tetra- to nonaBDE homologue groups in sediment, zooplankton and fish from the control, “low”, “medium” and “high” mesocosm in the first year after treatment....................................................................95 Figure 8: Primary life cycle stages for decaBDE (ECB, 2004) ....................................................................................144 Figure A1.1: Plot of measured log BCF against predicted log Kow ..............................................................................190

iv

ANNEX XV – IDENTIFICATION OF SVHC

PROPOSAL FOR IDENTIFICATION OF A PBT/VPVB SUBSTANCE Substance Name: Bis(pentabromophenyl)ether (decabromodiphenyl ether; decaBDE) EC Number: 214-604-9 CAS Number: 1163-19-5

•

It is proposed to identify the substance(s) as PBT according to Article 57 (d).

•

It is proposed to identify the substance(s) as vPvB according to Article 57 (e).

Summary of how the substance meets the PBT or vPvB criteria DecaBDE is widely detected in the European environment, residing mainly in sediments and soils at concentrations up to several milligrams per kilogram (parts per million) on a dry weight basis. It is also present in many types of aquatic and terrestrial wildlife species (including tissues of sensitive life stages such as bird eggs) at numerous geographical locations; although tissue concentrations are often low (close to the limits of analytical detection, or below), it can attain concentrations up to a few hundred micrograms per kilogram (parts per billion) on a wet weight basis in some top predators. Primary degradation half-lives in sediment and soil significantly exceed 180 days, indicating that decaBDE is ‘very persistent’ according to the Annex XIII criteria. On the basis of the available data, it can also be concluded that there is a high probability that decaBDE is transformed in soil and sediments to form substances which either have PBT/vPvB properties, or act as precursors to substances with PBT/vPvB properties, in individual amounts greater than 0.1% over timescales of a year. Transformation to such substances within biota provides an additional pathway for the exposure of organisms. High persistence combined with wide distribution in the environment creates a high potential for lifetime exposure and uptake in organisms, and a pool of the substance in many localities that will act as a long-term source of degradation products through both abiotic and biotic transformation. On the basis of all of the evidence that is now available, decaBDE is considered to meet the definition of a PBT/vPvB-forming substance in accordance with Annex XIII of the REACH Regulation, and thereby fulfils the criteria in Articles 57(d) and (e).

Registration dossiers submitted for this substance? Yes

v

ANNEX XV – IDENTIFICATION OF SVHC

PART I This Annex XV report provides justification for identifying decabromodiphenyl ether (decaBDE) as a substance that transforms under environmentally relevant conditions to lower molecular weight polybromodiphenyl ether (PBDE) congeners that are considered to be PBT/vPvB substances. It is therefore targeted to environmental end points, and does not consider human health hazards. An enormous amount of data has already been reviewed on this substance in a European regulatory context: one risk assessment report and two addenda under the Existing Substances Regulation (ESR) (EC, 2002; ECB, 2004; ECB, 2007a), and a further report produced by the Environment Agency in the UK (EA, 2009). These four risk assessment reports cover the main literature published up to the middle of May 2009. The UK Advisory Committee on Hazardous Substances (ACHS, 2010) also evaluated additional studies published up to about May 2010 (including a Canadian State of Science Report (Environment Canada, 2010)). More recently, a draft fact sheet has been compiled for environmental quality standard setting purposes under the Water Framework Directive (EC, 2011), and the European Food Safety Authority has also delivered a Scientific Opinion on PBDEs in food (EFSA, 2011). Reviews have also been prepared under the auspices of the United Nations (UNEP, 2008, 2010 & 2011). Given these extensive and detailed previous reviews, only a very limited amount of additional (ad hoc) literature searching has been performed for this dossier. Whilst it is possible that some relevant references might have been missed using this approach, the weight of available information means that such omissions are unlikely to be important. Some of the available data are in the form of extended abstracts from conference proceedings and these do not always contain full experimental details. Relevant references are indicated by the term “[ABST]”. The results should be treated with caution until the full details have been formally published in the peer-reviewed scientific literature. Where the full paper has been located this has been reviewed and included in this dossier along with the extended abstract. Given the range of information, it is considered appropriate to present all relevant data, even where not fully reported in the peer-reviewed literature, to allow a conclusion to be drawn on the basis of the weight of evidence. Unless otherwise stated, all of the cited data in this report have previously been presented and agreed in existing EU risk assessment reports. A robust study summary has only been prepared for one of the key studies (Huang et al., 2010), since the Canadian mesocosm experiment is not yet fully reported. All other data are presented as supporting information. Relevant fate and toxicity data for the other PBDEs have been discussed at length at the United Nations and elsewhere (see Appendix 1), and the underlying data are not summarised in the technical dossier either.

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ANNEX XV – IDENTIFICATION OF SVHC

JUSTIFICATION 1

IDENTITY OF THE SUBSTANCE AND PHYSICAL AND CHEMICAL PROPERTIES

1.1

Name and other identifiers of the substance

Table 1: Substance identity EC number:

214-604-9

EC name:

Bis(pentabromophenyl) ether

CAS number (in the EC inventory):

1163-19-5

CAS number:

1163-19-5

CAS name:

Benzene, 1,1'-oxybis[2,3,4,5,6-pentabromo-]

IUPAC name:

1,1'-Oxybis(pentabromobenzene)1

Index number in Annex VI of the CLP Regulation

Not applicable

Molecular formula:

C12Br10O

Molecular weight:

959.2 g/mole

Synonyms:

decabromodiphenyl ether; decabromodiphenyl oxide; bis(pentabromophenyl) oxide; decabromo biphenyl oxide; decabromo phenoxybenzene; benzene 1,1’ oxybis-, decabromo derivative; decaBDE; DBDPE; DBBE; DBBO; DBDPO

Note: The abbreviation decaBDE is used throughout this document to refer to the substance for brevity2. The molecule is also known by a specific congener number (BDE-209) in the IUPAC PBDE nomenclature system (Appendix 2 provides a full list of these). This congener number is referred to where comparison with the other congeners is important.

1

The IUPAC name disseminated with registration information is different to the IUPAC names notified in the Classification and Labelling (C+L) inventory. The following IUPAC names have been notified to the C+L inventory: 2,3,4,5,6-pentabromo-1-(2,3,4,5,6-pentabromophenoxy) benzene, bis(pentabromophenyl) ether, decabromodiphenyl ether, decabromdiphenylether, decabromodiphenyl oxide.

2

Individual groups of PBDE congeners are also referred to in abbreviated form (e.g. hexaBDE for hexabromodiphenyl ethers).

2

ANNEX XV – IDENTIFICATION OF SVHC Br

Structural formula:

Br O

Br

Br

Br

Br

Br

Br

Br

1.2

Br

Composition of the substance

Name: bis(pentabromophenyl) ether Degree of purity: The composition of the commercial product from different manufacturers/importers is marked as confidential in the Chemical Safety Reports. However, it is generally consistent with the information given in Tables 2 and 3 (as reported in the original ESR assessment). Table 2: Constituents in the currently supplied commercial substance Constituents Decabromodiphenyl

Typical concentration

Concentration range

97.4%

97-98%

Typical concentration

Concentration range

2.5%

0.3-3%

ether

Remarks EC, 2002

Table 3: Impurities Impurities Nonabromodiphenyl ether Octabromodiphenyl ether

Remarks

EC, 2002 0.04%

Not known

The individual congener groups may consist of more than one isomer. For example, Timmons and Brown (1988) detected three nonaBDE and three octaBDE congeners in a commercial decaBDE product using a high resolution gas chromatography – mass spectrometry (GC-MS) method. Trace amounts of other compounds, thought to be hydroxybrominated diphenyl compounds were also tentatively identified as impurities. EC (2002) also indicated that lower molecular weight PBDE congeners may be present at concentrations up to 0.005% w/w. This finding was supported by Hamm et al. (2001), who performed a trace analysis of a composite sample of commercial decaBDE from three suppliers. Total tri-, tetra-, penta-, hexa- and heptaBDEs were each present at concentrations below 0.0039 % w/w. The composition of older products or products from other sources may be different. For example, a product that is no longer supplied in the EU had a composition of 77.4% decaBDE, 21.8% nonaBDE and 0.85% octaBDE (EC, 2002). There are no stated additives incorporated into the commercially available forms of this substance (EC, 2002).

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ANNEX XV – IDENTIFICATION OF SVHC 1.3

Name and other identifiers of transformation products

The principal transformation products that are the focus of this report are listed in Table 4.

4

ANNEX XV – IDENTIFICATION OF SVHC

Table 4: Identifiers for PBDE congeners

EC number: EC name:

TetraBDE

PentaBDE

HexaBDE

HeptaBDE

OctaBDE

NonaBDE

254-787-2

251-084-2

253-058-6

273-031-2

251-087-9

264-565-7

diphenyl ether, tetrabromo derivative

diphenyl ether, pentabromo derivative

diphenyl ether, diphenyl ether, heptabromo hexabromo derivative derivative

diphenyl ether, pentabromo(tetrabro octabromo derivative mophenoxy)benzene

CAS number (in the EC inventory):

40088-47-9

32534-81-9

36483-60-0

68928-80-3

32536-52-0

63936-56-1

CAS number:

40088-47-9

32534-81-9

36483-60-0

68928-80-3

32536-52-0

63936-56-1

CAS name:

Index number in Annex VI of the CLP Regulation Molecular formula: Molecular weight:

tetrabromodiphenyl pentabromodiphenyl hexabromodiphenyl heptabromodiphenyl octabromodiphenyl ether ether ether ether ether

nonabromodiphenyl ether

-

602-083-00-4

-

-

602-094-00-4

-

C12H6Br4O

C12H5Br5O

C12H4Br6O

C12H3Br7O

C12H2Br8O

C12HBr9O

485.82

564.72

643.62

722.48

801.42

880.27

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ANNEX XV – IDENTIFICATION OF SVHC

1.4

Physico-chemical properties

The data in Table 5 are taken from the original ESR assessment (EC, 2002). Unless otherwise stated, they are also cited in the registration dossiers for the substance (as summarised on the ECHA website3). No new literature search has been conducted for physico-chemical data. Table 5: Overview of relevant physicochemical properties REACH ref Annex, §

Property

Value

Reference

V, 5.1

Physical state at 20°C and 101.3 kPa

Fine, white to off-white crystalline powder

EC (2002)

V, 5.2

Melting/freezing point

300-310°C

Dead Sea Bromine Group, 1993, cited in EC (2002)

V, 5.3

Boiling point

Decomposes at >320°C

Dead Sea Bromine Group, 1993, cited in EC (2002)

V, 5.5

Vapour pressure

4.63×10-6 Pa at 21°C

Wildlife International Ltd, 1997, cited in EC (2002)

V, 5.7

Water solubility

applicability domain NonaBDE, mono-methoxy: Log Kow > applicability domain

OctaBDE, di-hydroxy: log Kow > applicability domain OctaBDE, mono-hydroxy: log Kow > applicability domain

207

ANNEX XV – IDENTIFICATION OF SVHC OctaBDE, mono-methoxy mono-hydroxy: log Kow > applicability domain OctaBDE, mono-methoxy: log Kow > applicability domain

HeptaBDE, di-hydroxy: log Kow > applicability domain HeptaBDE, mono-hydroxy: log Kow > applicability domain HeptaBDE, mono-hydroxy, mono-methoxy: log Kow > applicability domain HeptaBDE, mono-methoxy: log Kow > applicability domain

HexaBDE, mono-hydroxy: log Kow > applicability domain HexaBDE, mono-hydroxy, mono-methoxy: log Kow > applicability domain HexaBDE, mono-methoxy: log Kow > applicability domain

HexaBDE, di-hydroxy Phenols:

Fish

30-day ChV

0.005

Phenols:

Fish

90-day ChV

0.003

Phenols:

Daphnid

21-day ChV

0.004

Log Koa estimate (KOAWIN v1.10 from KOWWIN and HENRYWIN)

NonaBDE, mono-hydroxy: log Koa = 20.6 NonaBDE, mono-methoxy: log Koa = 18.4

OctaBDE, di-hydroxy: log Koa = 22.8 OctaBDE, mono-hydroxy: log Koa =19.3 OctaBDE, mono-methoxy mono-hydroxy: log Koa = 20.7 OctaBDE, mono-methoxy: log Koa = 17.2 OctaBDE, di-methoxy: log Koa = 18.5

HeptaBDE, mono-hydroxy: log Koa = 18.1 HeptaBDE, mono-hydroxy, mono-methoxy: log Koa = 19.4 208

ANNEX XV – IDENTIFICATION OF SVHC HeptaBDE, mono-methoxy: log Koa = 15.9 HeptaBDE, di-hydroxy: log Koa = 21.6

HexaBDE, mono-hydroxy: log Koa = 16.8 HexaBDE, mono-hydroxy, mono-methoxy: log Koa = 18.1 HexaBDE, mono-methoxy: log Koa = 14.6 HexaBDE, di-hydroxy: log Koa = 20.3

BIOWIN v4.10 Results

P screening criteria in REACH guidance R11 (table R. 11.2) 1. Biowin2 (Non-Linear Model Prediction):