ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 1 of 108



## DATA ON MANUFACTURE, IMPORT, EXPORT, USES

AND RELEASES OF HBCDD

AS WELL AS INFORMATION ON POTENTIAL

ALTERNATIVES TO ITS USE

The technical work on this report has been led by I OM Consulting,

supported by BRE, PFA and Entec under framework contract ECHA/2008/2 (specific cont ract

ECHA/2008/02/SR4/ECA.226 )ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 2 of 108

Executive Summary

Information sources

The information presented on manufacture import and export and uses and re lases from uses is based on the RAR with additional data supplied by th e HBCD Industry User Group in October 2008. This additional data comprises summary data for the total sales and consumption of HBCDD across the EU for each year from 2003 until 2007, a breakdown of the consumption of HBCDD by the two main uses (XPS a nd EPS) and an indication of how many sites manufacture XPS or EPS i n each member

state.

The information on possible alternatives to HBCDD presented in Work Pa ckage 3 has been taken from a wide variety of sources including reviews undertak en by both industry and regulators that have aimed to identify candidate substances/techni ques.

As agreed with ECHA, this report does not cover cyclododecane as the Member State Committee has unanimously agreed that there was not sufficient scientific data to justify identification under Article 57 of the REACH Regulation.

Information on manufacture, import and export and releases from manufactu re

HBCDD is presently only produced at one site in the Netherlands. T he production volume varies from year to year. In 2006, it was about 6,000 tonnes. The EU- wide consumption of HBCDD in 2007 was 11,000 tonnes, implying net imports to the E U of about 5,000 tonnes. It is unclear how much HBCDD is actually import ed and exported to and from the EU. There was a general trend towards i ncreasing use of HBCDD between 2003 and 2007. Although, it seems likely that 2008 levels of production and importation will be slightly greater than in 2006, the expec ted recession may depress demand in 2009. In the longer term, there are moves to phase out the use of brominated compounds in the Nordic countries.

About 1,000 tonnes per annum are “micronised” in the EU to produce fine partic les for specific applications. This was undertaken at a plant in Belgi um. It is possible that micronising is also undertaken at other locations. It is unlikely t hat the increased use of HBCDD in the EU will have created an increased requirement f or micronisation and the reduced use of HBCDD in textile coating may have led to a reduction in the amount being micronised.

Releases of HBCDD to the environment from manufacturing are sma ll. It is estimated that about 3 kg a year are released from the workplace plus a further 2 kg to air and 0.1 kg to waste water. It is estimated that less than 1 kg per y ear is released from the working environment and that emissions to air are <1 kg/year. The estimated releases from manufacturing are based on the RAR. It is possible that, with increased production, release rates have increased.

Information on uses and releases from uses

HBCDD is solely used as an additive flame retardant. HBCDD i s used in four principal product types:ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 3 of 108

• Expanded Polystyrene (EPS)

• Extruded Polystyrene (XPS)

• High Impact Polystyrene (HIPS)

• Polymer dispersion for textiles

The HBCDD Industry Users Group have been unable to supply information on t he proportions of HBCDD currently used for different purposes in the EU. M ost is used in EPS and XPS and in 2006, there was a slightly greater proportion us ed in XPS than in EPS (ratio about 52:48). These products are used widely across the E U in the workplace and in consumer products. The use of XPS and EPS insulation product s increased between 2003 and 2007. As a first approximation, it has been a ssumed that

all Masterbatch has been used in XPS manufacture. Masterbatc h production accounts

for 12% of HBCDD use.

It is believed that the use of HBCDD in HIPS is small, less than 10% of total use a nd

that the use in textiles is also small. The use of HBCDD in textiles is beli eved to have fallen substantially in recent years. Although industry initially provided a n estimate of use in textiles in 2007 as 2% of total use, they subsequently indicated that they were uncertain as to the reliability of this estimate. In the absence of other infor mation, however, we have based our estimates of releases on the estimated use level or iginally provided. Textile formulators are based largely in Belgium, Germany and the U K. XPS and EPS are manufactured throughout much of Europe: Austria, Belgium, Czech Republic, Finland, France, Germany, Greece, Hungary, Italy, Netherlands, Pol and, Portugal, Serbia, Spain, Sweden and the United Kingdom.

The estimated releases of HBCDD to the environment during the man ufacture and formulation of HBCDD are 41 kg to air, 60 kg to waste water and 35 kg t o surface water per year based on consumption figures for 2006 supplied by the HBCD Industry Users Group.

The release of HBCDD from products during end use is small. Som e dust containing HBCDD will be released during the installation of EPS or XPS i nsulation and ultimately during the refurbishment or demolition of buildings containing these products. Most of the HBCDD released is from coating textiles. The estimated annual release to the environment is 530 kg to air, 1,140 kg to waste water a nd 560 kg to

surface water. The end use releases to waste water and surfa ce water are dominated by textile coating. These estimates are based on consumption fi gures for 2006 supplied by the HBCD Industry Users Group. The quantities of waste product sent for disposal are uncertain.

Estimated releases of HBCDD during the consumer use of products are highly uncertain. Releases from waste disposal are difficult to estim ate because of the long lifetime of XPS and EPS once installed in buildings (potentially up to 50 years) combined with an increasing trend towards the recycling of electri cal equipment. The release estimates for consumer use are 54 kg to air, 24 kg to wa stewater and 5 kg to surface water. These estimates are based on the RAR, adjusted for recent consum ption figures supplied by the HBCD Industry Users Group. They exclude waste disposa l.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 4 of 108

Information on Alternative substances and techniques

A number of alternative fire retardants are available to repla ce HBCDD in HIPS but they all require to be used at considerably higher loadings. At pre sent, no suitable flame retardant is available to replace HBCDD in its main end uses in XPS or EPS as the required loadings of alternative flame retardants impair t he structure and properties of the finished product to the extent that is no longer suit able for use. There

are however a number of alternative forms of insulation that can be used in place of XPS or EPS. These alternative insulation systems have different characteristics to XPS and EPS and may be less appropriate for some specific use sc enarios or may incorporate different environmental issues such as increased energy costs during transportation. Given that HBCDD is not widely used in HIPS, it is perhaps reasonable to assume that some technically and economically feas ible alternatives are already on the market, although it is uncertain whether the human hea lth and environmental impacts of these alternatives are any less th an those associated with HBCDD products.

There are a wide range of different flame retardant formula tions in textile coatings and, as with HIPS, it seems likely that some technically and ec onomically feasible alternatives are already on the market, although it is similar ly uncertain whether the human health and environmental impacts of these alternatives are an y less than those associated with HBCDD products.

The table below summarises the health and environmental information ava ilable for the suggested alternatives to HBCDD.

Use Alternative Human health Environment

Antimony trioxide (ATO) Potential human

carcinogen and reproductive toxicant Not readily biodegradable, low to

moderate bioaccumulation potential

Decabromodiphenylether/ATO Neurotoxicant Not readily biodegradable, low to

moderate bioaccumulation potential

Decabromodiphenylethane/ATO Limited data, but likely to

be of low toxicity Not readily biodegradable, may be persistent

Ethylenebis- (tetrabromo phthalimide)/ATO Low toxicity Not biodegradable and is persistent. Non-toxic.

Triphenyl phosphate Chronic toxicant with

effects on liver Readily biodegradable, toxic to aquatic organisms

Resorcinol bis (biphenyl phosphate) Chronic toxicant with

effects on liver Inherently biodegradable, may be persistent and bioaccumulative

Bis phenol A bis (biphenyl phosphate) Limited data, likely to be

of low toxicity Poorly biodegradable. Non-toxic

and is not bioaccumulative HIPS

Diphenyl cresyl

phosphate Chronic toxicant with

effects on liver, kidney

and blood. Effects on fertility Readily biodegradableECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 5 of 108

Use Alternative Human health Environment Polyethylene with

Magnesium Hydroxide Insufficient data but likely

to be of low toxicity Polythene particles are highly persistent in the aquatic environment and may contribute to reduced nutritional intake by organisms; the release of large quantities of magnesium hydroxide

to the environment could cause localised problems of water/soil alkalinity.

Decabromodiphenylether Neurotoxicant Not readily biodegradable, low to

moderate bioaccumulation potential Chlorinated paraffins Reproductive toxicant,

chronic toxicity with

effects of liver and kidneys, potential carcinogen LCCPs are considered to potentially meet the persistent or very persistent criterion. They do

not meet the toxic or

bioaccumulative criterion. Textiles

Ammonium

polyphosphates Low toxicity Not an ecotoxicant

Phenolic Foam Low toxicity in use but

manufactured from

materials toxic and carcinogenic Highly persistent material, long term disposal to landfill with potential for dust emissions to air and surface water, no recycling at

present Polyurethane and polyisocyanurate products May emit toxic fumes if

burnt, otherwise low toxicity in use, but

manufacture involves the use of isocyanates – potent respiratory

sensitisers Highly persistent material, long term disposal to landfill with potential for dust emissions to air and surface water, no recycling at

present EPS/XPS

Alternative insulation

- Thermal barriers

- Loose-fill insulation

- Blanket insulation May incorporate glass wool, rock wool, gypsum board Relatively minor health

issues - Inhalation of low toxicity dust generated during installation and removal; no significant

emissions while in use in buildings Materials can be recycled postconsumer use

This report has been produced according to a format and structur e provided by ECHA. Draft reports have been reviewed and commented on by ECHA a nd this final report has been accepted by ECHA.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 6 of 108

INFORMATION ON MANUFACTURE, IMPORT AND EXPORT AND
RELEASES FROM MANUFACTURE .......................... ...................................8

1.1 Manufacturing sites and manufacturing processes ....................................8

1.1.1 Production ............................................................................................8

1.1.1.1 Locations ...........................................................................................8

1.1.1.2 Tonnage .............................................................................................8

1.1.2 Micronising ...........................................................................................8

1.1.2.1 Process ...............................................................................................8

1.1.2.2 Locations ...........................................................................................8

1.1.2.3 Tonnage .............................................................................................8

1.2 Import and export of HBCDD on its own or in preparations .....................9

1.2.1 On own ..................................................................................................9

1.2.1.1 Imports ..............................................................................................9

1.2.1.2 Exports ..............................................................................................9

1.2.2 In preparations .....................................................................................9

1.2.2.1 Imports ..............................................................................................9

1.2.2.2 Exports ..............................................................................................9

1.3 Import and export of articles containing HBCDD ......................................9

1.4 Releases from manufacture ........................................................................10

1.4.1 Production ..........................................................................................10

1.4.1.1 Releases to working environment .................................................10

1.4.1.2 Releases to environment ................................................................11

1.4.2 Micronising .........................................................................................12

1.4.2.1 Releases to working environment .................................................12

1.4.2.2 Releases to environment ................................................................12

1.5 Unintentional formation .............................................................................13
INFORMATION ON USES AND RELEASES FROM USES ......... ................14

2.1 Identification of uses ...................................................................................14

2.1.1 Masterbatch ........................................................................................14

2.1.2 Expanded Polystyrene .......................................................................14

2.1.3 Extruded Polystyrene ........................................................................15

2.1.4 High Impact Polystyrene ...................................................................16

2.1.5 Textile Coating ...................................................................................17

2.2 Quantification of uses .................................................................................18

2.2.1 Inventory Table ..................................................................................18

2.3 Quantification of releases from uses ..........................................................20

2.3.1 Masterbatch ........................................................................................20

2.3.1.1 Releases into working environment .............................................20

2.3.1.2 Release into environment ..............................................................21

2.3.1.3 Releases into working environment .............................................22

2.3.1.4 Release into environment ..............................................................24

2.3.2 XPS ......................................................................................................28

2.3.2.1 Releases into working environment .............................................28

2.3.2.2 Release into environment ..............................................................30

2.3.3 HIPS ....................................................................................................31

2.3.3.1 Releases into working environment .............................................31

2.3.3.2 Release into environment ..............................................................32

2.3.4 Textile coating ....................................................................................33

2.3.4.1 Releases into working environment .............................................33ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 7 of 108 2.3.4.2 Release into environment ..............................................................35

2.3.5 Total emissions ...................................................................................38 INFORMATION ON ALTERNATIVE SUBSTANCES AND TECHNIQUE S ..39

3.1 Identification of alternative substances and techniques ...........................39

3.1.1 Halogenated flame retardants in conjunction with Antimony

Trioxide 39

3.1.2 Organic aryl phosphorous compounds ............................................39

3.1.3 Textile alternatives .............................................................................39

3.1.4 Phenolic Foam and Phenolic Resins .................................................40

3.1.5 Polyurethane and Polyisocyanurate Products .................................40

3.1.6 Mineral wools, other mineral products and cellulose fibre ............40

3.1.7 Intumescent systems ..........................................................................41

3.2 Information on alternatives ........................................................................41

3.2.1 Human health and environmental effects ........................................42

3.2.1.1 Halogenated flame retardants in conjunction with Antimony

Trioxide 42

3.2.1.2 Organic aryl phosphorous compounds ........................................53

3.2.1.3 Textile alternatives .........................................................................61

3.2.1.4 Phenolic Foam ................................................................................70

3.2.1.5 Polyurethane and Polyisocyanurate Products .............................72

3.2.1.6 Mineral wools and other mineral products .................................74

3.2.1.7 Cellulose fibre .................................................................................74

3.2.1.8 Intumescent systems ......................................................................75

3.2.1.9 Polyethylene with Magnesium Hydroxide ...................................75

3.2.2 Technical and economical feasibility and availability ....................76

3.2.2.1 Halogenated flame retardants in conjunction with Antimony

Trioxide 76

3.2.2.2 Organic Aryl Phosphorous Compounds ......................................78

3.2.2.3 Textile Alternatives ........................................................................79

3.2.2.4 Overview .........................................................................................80

3.2.2.5 Phenolic Foam ................................................................................80 Polyurethane and Polyisocyanurate Products .............................................81

3.2.2.6 Mineral wools and other mineral products .................................81

3.2.2.7 Cellulose fibre .................................................................................81

3.2.2.8 Intumescent systems ......................................................................81

3.2.2.9 Polyethylene with Magnesium Hydroxide ...................................81

3.3 Summary table .............................................................................................82

References ...............................................................................................................88

Disclaimers ..............................................................................................................94
ANNEX 1: LIST(S) OF INFORMATION REQUIREMENTS FOR PRIORITY
SETTING AND SPECIFICATION OF CONDITIONS FOR AUTHORI SATION
95

ANNEX 2: ...........................................

................................................... ......108ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 8 of 108

INFORMATION ON MANUFACTURE, IMPORT AND EXPORT AND

RELEASES FROM MANUFACTURE

1.1 Manufacturing sites and manufacturing processes

1.1.1 Production The production of HBCDD is a batch-process. Elementary bromine is added to cyclododecatriene in the presence of a solvent. The process temperatur e is 20 to 70°C, and the reaction takes place in closed systems. These materials are mixed to form a slurry that must be extensively washed in order to generate hig h purity HBCDD. The slurry is centrifuged, the liquids removed for reprocessing and th e solid faction is dried, stored in a silo and packed. According to one producer, production and transportation of the material to silo and the packaging are done i n a closed system. The product is delivered as powder or pellets.

The production method as described in general terms in the IUCLID Data Sheet i s as follows:

• Loading of raw materials

• Bromination

• Filtering

• Drying

• Storage in silo

• Packaging

1.1.1.1 Locations HBCDD is presently only produced at one site in the Netherlands. Two other production sites were closed for production in the autumn of 2003 and June 1997 respectively (RAR, EC 2008a).

1.1.1.2 Tonnage The reported amount of HBCDD produced at the production site in the Nethe rlands varies from one year to another. The total annual (2005) production of HB CDD was assumed to be 6,000 tonnes in the RAR (EC, 2008a).

1.1.2 Micronising

1.1.2.1 Process The HBCDD particles in some applications (e.g. for use in text ile back-coating) need to be very small. Therefore some quantities of HBCDD are microni sed in a grinding

process.

1.1.2.2 Locations No information on where micronising takes place is available, but is the RAR assumed that it occurs at a very limited number of sites.

1.1.2.3 Tonnage The total amount of HBCDD used for micronising was about 1,000 tonnes per y ear between 2000 and 2004, based on information from the textile industry (RAR). The main use for micronised HBCDD was textile coating. The industr y has informed us that this use has dropped by 80% and it is likely that the production of micronised HBCDD has also reduced. Up to date production figures are not, however, available.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 9 of 108

1.2 Import and export of HBCDD on its own or in preparations

1.2.1 On own

1.2.1.1 Imports

The HBCDD Industry working group has provided data on the consumption of HBCDD in the EU that includes all EU27 countries (Table 1.1).

Table 1.1: Sales and consumption of HBCDD in the EU in 2007 (HBCDD Industry Users Group, 2008)

Year Sales in EU Countries

tonnes Estimated EU Consumption

tonnes 2003 9,448 9,600
2004 10,123 9,750
2005 10,622 11,000
2006 10,075 11,580
2007 11,186 11,000

There was an increase in HBCDD sales between 2003 and 2007 of about 18 %. It is unclear whether this trend would be likely to continue given the growin g concern about the presence of brominated fire retardants in the environment and the moves in Nordic countries to phase out their use. Production of HBCDD between 2003 and 2007 was fairly static at 6000 tonnes, implying an increase in net im ports of almost 50% over this period. Estimates of EU consumption are slightly diff erent. They imply an increase of almost 15% between 2003 and 2007 with net imports inc reasing by almost 40%. The best estimate of imports of HBCDD in 2006 is 5,580 tonnes.

1.2.1.2 Exports

It is unclear whether any HBCDD is exported out of the EU as a simple substance. Given the proximity of the production plant to major port facilities, it is likely that some HBCDD would be exported outwith the EU as well as transported within the

EU.

1.2.2 In preparations

1.2.2.1 Imports

It is unclear whether HBCDD is imported into the EU in the form of masterbatch and plastic compounds.

1.2.2.2 Exports It is unclear whether HBCDD is exported out of the EU in the form of masterbatch and plastic compounds. Some export to other European countries that are not part of the EU would seem likely.

1.3 Import and export of articles containing HBCDD HBCDD contained in expanded polystyrene (EPS) and extruded polystyre ne (XPS) for the construction industry is not likely to be transported long dist ances due to theECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 10 of 108

bulkiness of the material. Furthermore, the extrusion and expansion proces ses are relatively straightforward industrial processes, which allow them to be carried out in the region where the products are needed. Transport of compounded polysty rene (PS) with HBCDD (granules, masterbatch or beads) over long distances ca nnot be excluded, but information on this is lacking.

Packaging material containing HBCDD (e.g. EPS) to protect se nsitive equipment is likely to be transported worldwide. High impact polystyrene (HIPS ) containing HBCDD is likely to be imported to the EU in electrical and ele ctronic equipment, but

no data on this has been submitted. Textile that is back-coated with aHBCDDcontaining layer is imported from the US and other countries in unknown qua ntities. Import of polymer dispersions for textiles containing HBCDD cannot be excluded. In summary, import (and export) of HBCDD in articles is likely to occur but has not been possible to quantify.

No up to date information on the export of HBCDD from the EU is available.

1.4 Releases from manufacture

1.4.1 Production

1.4.1.1 Releases to working environment During production of HBCDD, there is potential for exposure to HBCDD during packing, compaction (to form granules), when process operators have to ent er the centrifuge or dryers, and, to a lesser extent, during handling of pa ckaged HBCDD in

the warehouse.

Personal exposures to dust and HBCDD were measured in the production f acility in the Netherlands by Searl and Robertson (2005) using the methods for re spirable 1 and

inhalable 2 dust described in MDHS 14/3 (UK Health and Safety Executive, 2000).

The results of the monitoring are summarised in Table 1.2. A tot al of 10 measurements of personal exposures were made during packing, compa ction process operations and warehouse work. In this exercise, compaction gave the hi ghest dust and HBCDD concentrations. The plant does not produce HBCDD continuously throughout the year and the proportion of shifts on which workers are expose d to HBCDD varies from year to year. It is believed that exposure oc curs on less than 1 in

4 shifts.

Table 1.2: Personal exposure concentrations measured for workers producing

HBCDD

Dust concentration (mgm -3 ) HBCDD concentration (mgm -3 ) All Production Workers

Respirable Inhalable Respirable Inhalable
Mean (Standard deviation) 0.4 (0.2) 3.2 (1.2) 0. 18 (0.16) 1.23 (0.76)

Median 0.25 2.50 0.05 0.89

90 th Percentile 0.70 4.29 0.40 1.86

1 That part of airborne dust that can be deposited w ithin the gas-exchange region of the lung

2 That part of airborne dust that can deposited with in the respiratory systemECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 11 of 108

Dermal exposure during production was assessed in the RAR (EC, 2008a) using the EASE occupational exposure model (Tickner et al., 2005). It is assumed t hat exposure at the manufacture of HBCDD occurs principally during packing and compaction of the product. It was assumed that both hands are exposed. The calculated de rmal exposure was 840 mg/day when handling powders and 84 mg/day when handl ing granules which are coarser and less dusty. Protective suits and gloves are reported to be used in these production processes (Searl and Robertson, 2005) and it is r easonable to reduce these exposures by a factor of 5 to 170mg/day and 17 mg/day t o take account of the protection offered by the protective gloves.

1.4.1.2 Releases to environment Site-specific information on the annual release of HBCDD to air and wastewater is available for the one remaining manufacturing site in the EU, loca ted in the

Netherlands.

The annual release 2001 was 6.2 kg mainly via wastewater to a STP (Sanders, 2002). The annual release to wastewater has been reported to be 0.73 kg (2002), 0.13 kg (2003) and 0.20 kg (2004) (Tange, 2005). The highest release figure (0.73 kg/ye ar) from year 2002-2004 was taken in the RAR as a reasonable measure of t he emissions

to wastewater from this site. It is not clear whether the inc rease in sales in the EU comes from increased production or greater imports. From the RAR ( EC, 2008) the emissions from the production site to water decreased over the period 2002 to 2004, during which time the sales of HBCDD increased. As a worst cas e estimate the emissions from the risk assessment report could be retained.

The emission to air is 21.7 kg/year, according to site-specifi c data (Tange, 2003). The site has installed an “absolute filter” for outgoing air. Firs t measurements indicate that particulate emissions to air now are lower than 0.03 mg/m 3 . Using a worst-case assumption (assuming all dust would be HBCDD) this would correspond to l ess than 2 kg/year emissions to air.

No information has been submitted on the formation of solid waste contai ning HBCDD, but information is provided noting that waste from the production, including sludge from the STP, is disposed of by incineration or reused in the process.

Since there is only one active producer in the EU, the emissions fr om this site were used in the RAR for the estimation of regional background concentrat ions. The resulting total, regional and continental emissions from production of H BCDD are given in Table 1.3.

Table 1.3: Total, regional and continental emissions from pro duction of HBCDD.

Total (kg/year) Regional

(Netherlands) (kg/year) Continental (kg/year)

Air 2 2 0

Wastewater 0.73 0.73 0

Surface

water 0 0 0ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 12 of 108

1.4.2 Micronising

1.4.2.1 Releases to working environment Searl and Robertson (2005) measured personal exposures to HBCDD during micronising in one plant. Dust exposure occurred mainly during the loa ding and unloading of the grinding rig and when spills were cleaned up using a brush and shovel. The plant handled a variety of materials and micronising HBC DD was only one of several activities undertaken by workers. Exposure to HBCDD therefore did not occur on every shift, although no quantitative information about the proportion of shifts on which HBCDD was handled is available. It is believed that exposure i s likely

to occur on less than 1 in 4 shifts.

Four samples were collected and the measured personal exposure conc entrations of inhalable dust and HBCDD were high, with inhalable HBCDD concentrat ions averaging 22.7 mgm -3 (Table 1.4). HBCDD accounted for virtually all the inhalable dust. Only a small proportion of inhalable dust was within the respirable size fracti on.

Table 1.4 : Personal exposure concentrations for workers involved in grinding HBCD

Dust concentration (mgm -3 ) HBCD concentration (mgm -3 )

Respirable Inhalable Respirable Inhalable
Mean (standard deviation) 0.78 (0.21) 23.8 (11.8) 1.43 (0.64) 22.7 (12.3)

90 th Percentile 0.94 34.8 1.98 34.6

Dermal exposure during micronising was estimated in the RAR using the EASE model. The reasonable worst-case dermal exposure was estimated as 4,200 mg/day, when no PPE is used. Gloves and protective clothing, which were worn during surveys undertaken by Searl and Robertson (2005), will reduce that f igure to 840 mg/day.

1.4.2.2 Releases to environment Data from one site with micronising have been submitted from Industr y (Esser et al.

, 2003). According to industry this site uses the major part of the amount of HBCDD processed by micronising.

Local emissions No water is used in the process; except for the cleaning-wate r, which is collected in a tank and disposed of via a “waste management treatment company”. It is therefore

assumed that there are no emissions to wastewater or surface-water.

The emission to air from the site that submitted data was det ermined to be 0.3 kg/year based on site-specific data (Esser et al. , 2003). No data on the number of emission days per year are given so the RAR used the TGD (Technical Guidance Document) default value from the B-tables (300 days/year).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 13 of 108

Regional and continental emissions Based on the information given by industry that the site for which data are give n is the by far largest microniser, it is assumed that the emissions f rom possible other sites involved in micronising are negligible. Thus, the continental release i s assumed to be

zero.

The resulting total, regional and continental emissions of HBCDD for micronising are given in Table 1.5.

Table 1.5 : Total, regional and continental emissions of HBCDD from micronising

Total (kg/year) Regional

(kg/year) Continental

(kg/year)

Air 0.28 0.28 0

Wastewater 0 0 0

Surface

water 0 0 0

1.5 Unintentional formation There is no information on the unintentional formation of HBCDD during incineration, by transformation/degradation, or through other processes. Any unintentional formation of HBCDD is likely to be in negligible amounts.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 14 of 108

INFORMATION ON USES AND RELEASES FROM USES

2.1 Identification of uses HBCDD is solely used as an additive flame retardant. HBCDD i s used in four principal product types:

• Expanded Polystyrene (EPS)

• Extruded Polystyrene (XPS)

• High Impact Polystyrene (HIPS)

• Polymer dispersion for textiles

The HBCDD Industry Users Group have been unable to supply information on the proportions of HBCDD currently used for different purposes in the EU. Most is used in EPS and XPS and in 2006, there was a slightly greater proportion used in XPS than in EPS (ratio about 52:48). It is believed that the use of HBCDD in HIPS is small, l ess than 10% of total use and that the use in textiles is also small. The use of HBCDD in textiles is believed to have fallen substantially in recent years. The use of HBCDD in textiles is believed to have fallen substantially in recent years. Althoug h industry initially provided an estimate of use in textiles in 2007 as 2% of total use, they subsequently indicated that they were uncertain as to the reliability of this estimate. In the absence of other information, however, we have based our estimates of releases on the estimated use level originally provided. As a first approximation, it has bee n assumed that all Masterbatch has been used in XPS manufacture. Masterbatch production accounts for 12% of HBCDD use.

2.1.1 Masterbatch Masterbatch is a concentrated mixture of HBCDD encapsulated dur ing a heat process into a carrier resin (polystyrene) which is then cooled and cut into a granular shape. It is used to manufacture end products such as XPS or HIPS. Masterbatc h contains a higher concentration of HBCDD than the final product made from it.

2.1.2 Expanded Polystyrene Expanded Polystyrene (EPS) is a rigid cellular plastic, which i s used in a multitude of applications such as packaging. HBCDD-containing EPS is mainly us ed for the following purposes:

• insulation panels/boards in the construction sector

• automobile cushions for children (KemI, 1994) to meet the needs of the

FMVSS 302 standard

• rigid packaging material for fragile equipment (minor use)

• packaging material such as “chips” and shaped EPS-boards (minor use)

• in props for theatre and film, and in exhibitions (minor use)

Expanded polystyrene is produced in a batch process by suspension polymeri sation of styrene in water. Prior to combining the water with the organic phase, additives are introduced such as suspension agents, free-radical forming initiat ors and HBCDD. HBCDD powder, most often delivered in 25kg paper bags with a plastic liner, is suspended at low temperatures in styrene prior to the addition of the w ater phase. Normally the bags are emptied into an intermediate storage cont ainer from where theECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 15 of 108

HBCDD is transported via pipes and a weighing station prior to the a ddition to the

styrene.

In the reactor, styrene forms the disperse phase as small monom er droplets in the continuous water phase. Final droplet size (0.01 to 0.5 mm) is determine d by the ratio of disperse to continuous phase (typically 50:50) and by stirrer speed. Within the monomer droplets (bulk), polymerisation occurs while the reactor content is heated up and held at its reaction temperature. During this free-radical polymerisation an expansion agent (e.g. pentane) is added to the reactor under pressur e, where it is absorbed in the polymer droplets.

HBCDD is incorporated as an integral and encapsulated component wit hin the polymer matrix with uniform concentration throughout the bead.

After complete conversion of the styrene monomer to EPS-beads, the r eactor is cooled down and the beads are separated from the water by centrifu gation. The decanted water, which could contain dissolved and dispersed HBCDD, is reus ed and exchanged on an annual basis or less frequently. The EPS beads are dri ed and

classified into various size fractions and surface coated. These di fferent grades are packed in bins, bags, or transported in bulk trucks to the EPS-converters. T he

maximum concentration of HBCDD in EPS beads is assumed to be 0.7 %.

EPS foam is produced from EPS beads through pre-expansion of the beads with dry saturated steam, drying with warm air and shaping in shape moulds or in a continuous moulding machine. First, the raw material beads are pre-expanded in loose form with the help of dry saturated steam in pre-expanders. The raw mater ials are transported via pipes or tubes from the packaging containers to these stirred vessels. After expansion the beads are partly dried in fluid bed driers with warm air. The beads are subsequently stored in large permeable silos to “mature” for up to 24 hours. During this stage the beads dry further and reach equilibrium with the a mbient atmosphere around them. In the third phase the beads are transported/blown, via pipes/tube s into block or shape moulds or in a continuous moulding machine in which the product gets its shape. The foam can then be further formed by cutting, sawing or other machine operations.

2.1.3 Extruded Polystyrene Extruded polystyrene (XPS) is a plastic foam based on polystyrene that is formed by adding gas during extrusion. HBCDD-containing XPS is mainly used for the following purposes:

• Cold bridge insulation

• Sandwich Panels and Laminates

• Cavity Insulation

• Floors

• Basement Walls and Foundations

• Inverted Roofs

• Ceilings

The manufacture of XPS materials is carried out in the following way:ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 16 of 108

1. The polystyrene, the additives such as processing aids, flame ret ardant, dye and blowing agent are fed continuously to an extruder.

2. The polymer is melted; the blowing agent is mixed with the melte d polymer and a “foamable gel” is formed.

3. The gel is then cooled before it exits through an orifice called a die, where the blowing agent volatilises, causing the plastic to assume a foam structure. The blowing agent is usually a volatile, chemically stable compound, and by its introduction into the molten polymer, it reduces the density of the produc t by the formation of a myriad of closed cells within its structure.

4. The foam is then trimmed to desired shape. The boards are packed int o shrinkwrapped bundles and palleted. The pallets are stored for curing (usual ly 1 week) and are then ready for shipment.

5. A remainder of about 25 % of the material is recycled to the e xtruder. This material is mainly “skin” from the surface, with higher densi ty. The recycled

material comes in contact with water.

The HBCDD is supplied either in powder or in low-dust granulated f orm in either 25 kg bags or in 1 tonne supersacks or “big bags”. The supersacks are em ptied into hoppers designed to minimise dust emissions. The HBCDD is then carried to the point of mixing with screw or air driven metering equipment. The compounded polystyrene is extruded and cut into granules, and packaged. The extrudate is either air-cooled or cooled by running in a water bath.

One technology usually known as the UCI technology uses a vacuum in a ddition to blowing agents to produce lighter (lower density) foams. In this tec hnology, the product comes into contact with water in a water pond directly after the extrusi on.

2.1.4 High Impact Polystyrene Most flame-retarded High Impact Polystyrene (HIPS) products a re used in electrical and electronic appliances. For example:

• audio visual equipment cabinets (video and stereo equipment)

• distribution boxes for electrical lines in the construction sector

• refrigerator lining

HIPS pellets are produced either in a batch or continuous polymerisat ion process. HBCDD powder, delivered in plastic bags, is filled in intermedia te storage containers. HBCDD and other ingredients required for the particular HIPS form ulation are weighed and transported to the feeding hopper of the extrusion equipment where they undergo further mixing, homogenisation and granulation into pellets.

An alternative route for HIPS pellet production is via an intermedia te-compounding route. Masterbatch (as detailed in section 2.1.1) is compounded with non flam eretarded HIPS material in a conversion step.

After the molten mass at the end of the extruder is pressed thr ough a plate with holes (die/plate), different granulation processes take place, for example:

• face cutting in air; a rotating knife directly after the plat e cut the extruded “strands” into pellets cooled by air.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 17 of 108

• under water face cutting; a rotating knife directly after the plate in a w ater bath cuts the extruded strands in pellets cooled by water.

• strand cutting; the molten strands are passed through a water bath t o solidify and cool and are cut in a granulator.

After the granulation process the HIPS pellets are dried and pac ked, either in bulk silos/containers or 25 kg bags, ready for conversion into HIPS products.

HIPS materials can be converted into HIPS products using various extrusion techniques and injection moulding. HIPS products can also be manufactured vi a a compounding route, i.e. mixing non flame-retarded HIPS raw material w ith a HBCDD masterbatch during the extrusion or injection moulding process.

The HBCDD content of flame-retarded HIPS is 1 - 3 % (w/w) (BASF, 1996) or in other cases 5 or 7 % (Albemarle, March 1996). In the RAR (Swedish Chemicals Agency, 2008), it was assumed for the calculations of exposure, as a realistic worst case, that HIPS contains 7 % HBCDD.

2.1.5 Textile Coating Flame retardant systems are used in textile applications t o comply with British

Standard and German DIN flame retardant standards. HBCDD is fo rmulated to polymer-based dispersions (e.g. acrylic or latex) of variable vi scosity in the polymer industry. The dispersions are then processed in the textile finis hing industry. The textiles with the back-coating containing HBCDD are mainly used for:

• flat and pile upholstered furniture (residential and commercial furniture)

• upholstery seating in transportation

• draperies, and wall coverings

• bed mattress ticking

• interior textiles e.g. roller blinds

• automobile interior textiles and car cushions.

The HBCDD particles used for textile back-coating need to be ve ry small and micronised (see chapter 2.1.2). Flame retarded formulations containing H BCDD are prepared as water-based dispersions that can contain a binder system and HBCDD as well as up to 20 other ingredients. These flame retarded formulations , mostly custom tailored, are supplied as a dispersion to back-coaters. In this scena rio, formulation is carried out in an open batch system. HBCDD is added to a dispersion c ontaining water, a polymer e.g. synthetic latex, acrylates or PVC, thi ckener and dispersion agent. The chemical preparation can also contain other brominated f lame-retardants such as decabromodiphenyl ether. In addition, synergists such as antim ony trioxide and antimony pentoxide may also be included in the end-product. According to industry information, the concentration of HBCDD in the dispersion may range from 5 to 48 %. However, additional product information indicates that a likel y concentration of HBCDD in the coated layer may be about 25 % corresp onding to 10 - 15 % in the final dilution of the dispersion. Water and solvents will leave the preparation when dried and concentrations of flame-retardants in t he coating layer will be higher than in the preparation. Preparations with the high est concentration of

HBCDD are assumed to be diluted before use.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 18 of 108

The water based dispersion used by the back-coaters needs to be sta ble (no precipitation and no viscosity change) and should not contain particles tha t could clog the coating system. Therefore, the particle size of the soli ds is very important. Particles that are too fine act as a thickener, whereas par ticles that are too large will lead to a non-stable dispersion (precipitation) and an applied coated fil m with an unacceptable rough surface.

Back-coating to textile can be applied in the following ways:

1. as a paste where a layer is “glued” to the textile and a sc ratch knife defines the final thickness depending on the flame retardant standard, the texti le used and the flame retardant concentration in the dispersion; or

2. as a foam, where a foam layer is pressed on the textile throug h a rotating screen. Once applied the foam cells will break resulting in a thin coating f ilm.

The coating is dried and fixated in an oven at temperatures betwe en 140 to 180 °C, (Delgado and (EIPPCB, 2003).

The formulated product is used on technical textile and furniture fabr ic, on cotton fabrics, and on cotton polyester blends. For the calculations of exposure , the RAR assumed that the backcoating layer of the finished textile conta ins 25 % HBCDD. HBCDD is usually applied with antimony trioxide as a back-coat ing in a mass ratio of 2:1 (i.e. about 6-15 % HBCDD and 4-10 % antimony oxide by weight) (Na tional Research Council, 2000).

2.2 Quantification of uses

2.2.1 Inventory Table

The figures in Table 2.1 below are taken from the risk assessment report (EC, 2008). They relate to the EU-15 countries. The values come from a range of years, but were considered in the RAR (EC, 2008a) to be representative of the period 2000-2004.

Table 2.1: Inventory of HBCDD use in the EU15 in 2000-2004 (Swedish Chemicals Agency, 2008)

Use Tonnes/year No. of users Geographical

distribution

EPS formulators 3392 18 Unknown EPS industrial users 3392 100s Across Europe XPS formulators 1730 14 approx 9 in Italy 1 in Germany

1 in Austria

1 in UK 1 in Belgium

1 unknown XPS industrial users 4962 35 Across Europe

HIPS formulators 210 3 Unknown

HIPS industrial users 210 18 Unknown Textile coating

formulators 1050 16 7 in UK 5 in Belgium 4 in Germany Textile coating

industrial users 1050 24 15 in Belgium

9 in UKECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 19 of 108

Masterbatch quantities are included under the relevant polystyrene type. Most HBCDD used in XPS is used as powder at the industrial use stage, rather than being included in a compound at the formulation stage.

More recent data for EPS and XPS in the EU27 in 2007 has been provided b y the HBCDD industry user group (31/10/2008). The total tonnage of HBCDD used in XPS and EPS in the EU as a whole has increased over the last 5 ye ars which presumably reflects the growing use of XPS and EPS in construction (Table 2.2).

Table 2.2: Use of HBCDD in EPS and XPS in the EU (tonnes)

Year EPS XPS

2002 3,452 3,954

2003 4,053 4,350

2004 4,270 4,617

2005 4,690 5,123

2006 5,301 5,859

2007 5,652 N/A

Industry data also stated that 2% of HBCDD production went to te xtile manufacture in 2007, implying that a little over 200 tonnes of HBCDD was used in t extiles in

2007.

For the purposes of the estimation of releases to the environment, the 2006 usage figures for EPS and XPS and a 2007 estimate of 210 tonnes for textil e coating were used. These figures are used in tables 2 and 3 in Annex 1.

Industry data for 2007 also show that HBCDD is widely used to manufacture EPS a nd XPS across the EU (Table 2.3).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 20 of 108

Table 2.3: Distribution of EPS and XPS manufacturing sites in Europe

Number of sites Country EPS XPS

Austria 1 1 Belgium 2 1 Czech Republic 2

Finland 1

France 1 3 Germany 4 6

Greece 1 1 Hungary 1 1 Italy 1 5

Netherlands 4 1 Norway 1

Poland 1 Portugal 1

Serbia 1 Spain 2 4

Sweden 1 Turkey 3 United Kingdom 2

The use of XPS and EPS may be slightly reduced in the immedia te future (2008-9) because of the downturn in house-building currently affecting much of Eur ope, but the insulation industry is confident that sales of insulation products wi ll continue to increase in coming years in response to the increasing relative cost of energy and growing awareness of climate change (Global Insulation (internat ional trade association) http://www.propubs.com/GI/Articles/eGI_May08_ExaneBNPParibas.pdf).

2.3 Quantification of releases from uses

2.3.1 Masterbatch

2.3.1.1 Releases into working environment Exposure to airborne HBCDD during the production of masterbatch is mos t likely during the mixing of HBCDD product with polystyrene and other additives prior to melting of the mixture. Exposure is also possible during the extrusion of the melt and subsequent processing into granular form for packing.

Searl and Robertson (2005) measured HBCDD during masterbatch product ion in one plant. Measured personal exposure concentrations were variable. Peak c oncentrations during the task of mixing and weighing were quite high, but shift mean concentrati ons were much lower as these dusty tasks were only performed for part of the shift. The extruder operator was exposed to relatively low concentrations of dust and HBCD (Table 2.4). No information is available about patterns of shift rotation and the proportion of shifts on which workers might be exposed.

Table 2.4: Personal exposure concentrations associated with the production of Masterbatch (Searl and Robertson, 2005)ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 21 of 108 Dust Concentration (mgm -3 ) Concentration of HBCD (mgm -3 ) Task No of

samples Duration

(minutes) Respirable Inhalable Respirable Inhalable

Mean 0.54 9.24 0.16 1.89

Standard

deviation 0.30 5.43 0.10 2.45

Median 0.45 7.25 0.17 0.83 Mixing and weighing 10

90 th percentile 0.72 14.57 0.25 5.35

Mean 0.38 1.73 0.05 0.12

Standard

deviation 0.05 0.19 0.02 0.05

Median 0.40 1.65 0.05 0.10 Extruder

operator 4

90 th percentile 0.40 1.91 0.06 0.16

For dermal exposure, there are no measured data and EASE was there fore used by in the RAR to assess exposure levels. The reasonable worst-case dermal exposure level during the use of fine and standard grade HBCDD was estimated to be 0.1 mg/cm 2 /day. It was assumed that both hands are exposed in Masterbatch-product ion, corresponding to an exposed area of 840 cm 2 , respectively. This leads to an exposure to 84 mg/day in Masterbatch production. For granules, the exposure is thoug ht to be 10 % of that with powder because it is less dusty. Gloves were r outinely worn when pure HBCDD was handled at all plants surveyed by Searl and Robert son (2005). Gloves will reduce dermal exposure and figures of 17 mg/day and 1.7 m g/day are reasonable worst cases for Masterbatch production with powder and gra nules, respectively.

2.3.1.2 Release into environment The emissions from the formulation of EPS beads and HIPS compound are de alt with

in the same scenario. This is because information received from mos t of the sites cannot be separated between these two activities.

The emission estimates shown in Tables 2.5 and 2.6 are based largely on site specific information, applying the largest emission factor from actual si tes to the use quantity not covered by the specific information. They are taken from the ri sk assessment report (EC, 2008) and are based on the tonnages used in the period 2000-2004 in the EU15. For the geographical distribution of these uses see Section 2.2.1. The y include any emissions from masterbatch. The more recent information on the amounts of HBCDD used in EPS and XPS indicates an increase over the figur es from 2000-2004, by 56% for EPS and by 18% for XPS for the 2006 figures. Assuming that the emissions would increase pro rata, the revised emissions would be as in Tables 2.7

and 2.8.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 22 of 108

Table 2.5: Total, regional and continental emissions of HBCDD from formulat ion of EPS beads and HIPS compound (Point sources< RAR)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 19.5 0.4 19.1

Wastewater 48 0 48

Surface water 212 113.4 98.6

Table 2.6: Total, regional and continental emissions of HBCDD from formulat ion of XPS compound (Point sources, RAR)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 11.4 5.7 5.7

Wastewater 71.2 35.6 35.6

Surface water 8.6 4.3 4.3

Table 2.7: Total, regional and continental emissions of HBCDD from formulat ion of EPS beads and HIPS compound (Point sources, 2006 values)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 30.4 0.6 29.8

Wastewater 75 0 75

Surface water 330 177 154

Table 2.8: Total, regional and continental emissions of HBCDD from formulat ion of XPS compound (Point sources, 2006 values)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 13.5 6.7 6.7

Wastewater 84 42 42

Surface water 10 5 5

EPS

2.3.1.3 Releases into working environment Release during industrial use Exposure to HBCDD occurs primarily during the production of EPS when it is added

to the reactor.

The RAR (EC 2008a) reported that personal exposures to inhalable dust for five operators at one plant were 0.5 mgm -3 for respirable dust (0.5-5 μ m) and 2.0 mgm -3 for total inhalable dust. Exposures to organic dusts were measured at a nother European EPS plant. All 22 measurements were less than 6 mgm -3 (Ransbotyn, 1999).

In addition, Searl and Robertson (2005) measured inhalation short and long te rm exposures to HBCDD during the production of EPS in four plants.

Measured short term personal exposure concentrations at two plants for dust and HBCDD during the period of addition of HBCDD were high (Table 2.9).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 23 of 108

When these short-term measurements were recalculated into 8 hour average concentrations, the mean and 90th percentile HBCDD concentrations were 1 and 1.3

mgm -3 of inhalable HBCDD, respectively. Full shift measurements were conducted (Table 2.7) with the mean and 90 th percentile inhalable HBCDD concentrations being 1.39 and 4.91 mgm -3 respectively.

Table 2.9: Summary of measured personal exposure concentrations, representative of average exposure over a full shift for process operators undertaking addition of

HBCDD to the reactor.

Dust concentration (mgm -3 ) HBCDD concentration (mgm -3 )

Number of

measurements (plants) Respirable Inhalable Respirable Inhalable

Mean 0.42 2.59 0.33 1.18

Standard

deviation 1.25 4.01 1.21 3.39

Median 0.10 1.40 0.03 0.27

90 th Percentile 17 (3)

0.36 4.29 0.12 1.10

Short term personal exposure concentrations during addition of HBCDD to t he EPS reactor were higher, with mean and 90 th percentile inhalable dust concentrations of 6.98 and 10.46 mgm -3 , respectively. The task lasted 10 to 15 minutes and took place up to four times per shift and these results are not inconsistent wi th the full shift

measurements.

There were no observations recorded regarding the exposure pattern for process workers

Four personal samples collected during weighing of HBCDD for additi on to the reactor gave mean and 90th percentile inhalable HBCDD concentra tions of 7.2 and 10.5 mgm -3 respectively. Although individuals spent up to the whole working day doing this task, a few hours of weighing provides sufficient HBCDD to last for 2 weeks production.

For dermal exposure, there is no measured data and EASE (Tickner et al., 2005) was therefore applied in the RAR to assess exposure levels during indus trial use of HBCDD as an additive. The same process was followed as for M asterbatch resulting in figures of 17 mg/day and 1.7 mg/day as reasonable worst cases f or EPS production with powder and granules, respectively.

Release during professional and private use

There is no information about occupational exposure to HBCDD during the installation of EPS during construction and other activities. It is likely that inhalable dust concentrations arising from the board will not exceed 10 mgm -3 and, as the proportion of HBCDD in EPS is around 1% exposure, inhalable HBCDD concentrations are unlikely to exceed 0.1 mgm -3

.

Dermal exposure is very likely to be less than the level of 1.7 mg/day during manufacture of EPS with granules.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 24 of 108

Release during service life There is insufficient information regarding exposure to HBCDD f rom disturbance of products made from EPS during normal service life. Any exposure fr om disturbance is likely to very occasional and very low as dust generation is unlikely and the vapour pressure of HBCDD is low.

Consumer exposure to HBCDD from construction boards (EPS or XPS) wa s calculated in the RAR to be 11.6 μ g or 0.11 μ g depending on the emission factor used. If the body weight is 60 kg and, if the uptake is 100 %, the internal e xposure will be

0.19 or 0.002 μ g/kg bwt/day. This exposure was considered insignificant and was not
included in the risk assessment.

Release during disposal Removal of EPS insulation board at the end of its life is likely to be a dusty operation. In buildings, inhalable dust concentrations of more than 10 mgm -3 are likely but this will not be a continuous process. It is likely that occupants will not be present during

removal. Concentrations will be lower outside. HBCDD constitutes a round 1% of this insulation board and, assuming inhalable dust concentrations average 10m gm -3

, the exposure concentration of HBCDD to which workers will be exposed w ill be 0.1

mgm -3

.

Insulation boards form the majority of HBCDD containing waste. I t is understood that most goes to landfill or incineration. Swan et al (2004) and Kra jewski et al (2002) reported personal exposures to inhalable dust on several landfill si tes to be between 0.3 and 9.0 mgm -3 . EPS boards contain around 1% of HBCDD. Given the multitude of dust sources on landfill sites, it is inconceivable that there will be

measurable levels of HBCDD attributable to treated insulation boa rds in these dusts. Exposure to HBCDD from boards at managed incinerator sites is likely to be s imilarly

low.

2.3.1.4 Release into environment Release during industrial use

The emission estimates shown in Table 2.10 have been taken from the RAR and were derived using the approach in the OECD Emission Scenario Document on Plastics Additives (OECD, 2004) and are based on the use data for the EU15 in 2000-2004. For the geographical distribution of these uses see Section 2.2.1.

Table 2.10: Total, regional and continental emissions of HBCDD from industrial use of EPS compound in the manufacture of flame retarded EPS (Point sou rces, RAR data)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 102 10.2 92

Wastewater 82.2 8.2 74

Surface water 20.4 2 18

The more recent information on the amounts of HBCDD used in EPS indicates an increase over the figures from 2000-2004, by 56% for the 2006 figures. Assuming that the emissions would increase pro rata, the revised emissions would be as in Table

2.11.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 25 of 108

Table 2.11: Total, regional and continental emissions of HBCDD from industrial use of EPS compound in the manufacture of flame retarded EPS (Point sou rces, 2006 figures)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 159 16 144

Wastewater 128 13 115

Surface water 31 3.1 28

Release during professional and private use HBCDD is used as a flame retardant in polystyrene. The predomi nant use of polystyrene is in rigid insulation panels/boards for building constructi on (EPS and XPS).

The private use of articles (e.g. insulation boards) containing HBC DD is small compared to professional use. Emissions from private use are conside red to be covered by the calculation of emissions during professional use.

The professional use of insulation boards during construction and renovation of buildings is assumed to result in releases to the environment.

The release of particles from cutting EPS-boards was estimated in the RAR to be 100 g particles per tonne of EPS. A total of 3,392 tonnes of HBCDD was used in EPS each year. The RAR concluded that a worst-case estimate theref ore results in a yearly release of 339 kg HBCDD from the use of EPS in insulation boards.

In the RAR it was assumed that a total of 4,926 tonnes of HBCDD is used in XPS each year. The release of particles from sawing XPS-boar ds is estimated to be 5.0 g particles per tonne of XPS. This results in a yearly release of 25 kg HBCDD from the

use of XPS in construction.

The RAR estimated that the total yearly release figure is 364 kg of HBCDD from the

use of installation boards in construction. The distribution of the releas e was estimated to be 50% to surface water and 50% to air (Table 2.12).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 26 of 108

Table 2.12 : Total, regional and continental emissions of HBCDD from install ation of professional insulation boards (Diffuse sources, RAR)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 182 18 164

Wastewater 0 0 0

Surface water 182 18 164

The emission estimates shown in Table 2.12 are taken from the RAR (EC, 2008a) and are based on the tonnages used in the period 2000-2004. For the geographical distribution of these uses see Section 2.2.1. They relate to the EU-15 countries.

The more recent information on the amounts of HBCDD used in insulation boa rds in EU27 indicates an increase over the figures from 2000-2004, by 30% for the 2006 figures. Assuming that the emissions would increase pro rata, the r evised emissions

would be as in Table 2.13.

Table 2.13 : Total, regional and continental emissions of HBCDD from install ation of professional insulation boards (Diffuse sources, 2006 figures)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 236 23 213

Wastewater 0 0 0

Surface water 236 23 213

Release during service life

The emission estimates shown in Table 2.14 are based on the results of experiment measuring the loss of HBCDD from a sample of foamed polystyre ne, assuming an average service life of 30 years.

Table 2.14: Total, regional and continental emissions of HBCDD from building insulation (EPS and XPS) (Diffuse sources)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 54 5.4 48.6

Wastewater 0 0 0

Surface water 0 0 0

These emissions are taken from the RAR (EC, 2008a) and are based on the tonnages used in the period 2000-2004. They relate to the EU-15 countries, and there is no information regarding use in specific countries. As noted above, there is significant use in Eastern European countries, and so the emissions from the EU-27 may be greater. Applying the same market figures as above, the incre ased use could be up to

1.3 times that assumed for the calculation in the risk assessment report, or 70 kg/year (to air). Again as noted above, if some of the products used in Easter n Europe come from the Western European production, then the increase would not be as muc h. The

more recent information on the amounts of HBCDD used in insulation boards indicates an increase over the figures from 2000-2004; however, as the estimate of losses from service life is based on a lifetime of 30 years, t his increase will not significantly affect the emission estimates for some time.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 27 of 108

Release during disposal Waste generated during the industrial use scenario is generally recycled into the process, put into landfill or incinerated. Emissions from this kind of wa ste generation

are assumed to be included in the release estimates of the TGD for the corresponding life-cycle step. There are no data available.

There may be releases of HBCDD when buildings insulated with flam e retarded EPS are demolished. Estimates of possible future emissions from insula tion boards to the wider environment at disposal are included in the risk assessment ( EC, 2008a). The

basis for the estimates is as follows.

For boards which are recovered, possible losses of particulates were based on tests on manual breaking of board samples (information no referenced in EC, 20 08a). There were no particulate losses for XPS, and 90 g particulates per tonne for EPS. The proportion of demolition waste recycled was taken as 30% (from RTD information). A quantity of 4,000 tonnes per year of HBCDD in EPS was assumed (a s 50% of the 8,000 tonnes of HBCDD used in insulation boards). The resulting emission was 108 kg per year.

For the 70% of boards assumed not to be recycled, an emission factor of 0.1% was used. (This is referenced to Anonymous, 1998 in the risk assessment, but this source does not appear in the reference list. In an earlier draft of the assessment, this source was given as a draft version of the OECD ESD on Plastics Addit ives (OECD, 2004). However, no such emission factor could be found in that source.) Applying this factor to 70% of the 8,000 tonnes gives an emission of 5,600 kg per year.

The same approaches can be applied to the tonnages for 2006. For use of 5,301 t onnes of HBCDD in EPS, an emission of 143 kg per year (in EPS parti culates) is estimated (assuming 30% recycling). For the use of 12,160 tonnes in EPS and XPS, an emissions of 8,5112 kg per year of HBCDD can be estimated for the 70% not recycled.

These estimates assume that the equivalent of one year’s production is present in demolition waste each year. The figures apply to the EU27. The e stimate of 30% of material recycled has been retained. It could be foreseen that in the future a higher percentage could be recycled (no specific evidence, but based on genera l trends in recycling). Emissions from recycled material are lower, and hence the above

estimates should be a worst case. There are considerable uncerta inties in these estimates and it is likely that a substantial proportion of building s in which flame retarded EPS has been used are less than 30 years old and not likely to be subject to demolition at present or in the near future. EC (2008) suggested that such products had not yet been in use for 30 years. Therefore emissions from this source are unlikely to be significant at present, but may grow in the future, particular ly from about 2025 onwards as increasing numbers of buildings containing HBCDD-treated EPS become subject to refurbishment or demolition. There have been no studies of pre dicted

current or future emissions.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 28 of 108

2.3.2 XPS

2.3.2.1 Releases into working environment

Release during industrial use Potential exposure to HBCDD during XPS manufacture occurs when it is added to a hopper that feeds into the polystyrene melt. Further potential exposur e to HBCDD contained within polystyrene dust may also occur during secondary proce ssing of XPS and during the shredding and reprocessing of process waste.

Searl and Robertson (2005) measured inhalation exposures to HBCDD in duri ng the production of XPS in four plants. Masterbatch was used as a feedstoc k in three of

these. Results are summarised in Table 2.15 below.

Table 2.15 : Data summary for personal exposure measurements made in XPS plants handling Masterbatch (Searl and Robertson, 2005)

Dust concentration (mgm -3 ) Concentration HBCD (mgm -3 ) Task Number of

measurements (plants) Measure Respirable Inhalable Respirable Inhalable

Mean 0.16 1.41 0.01 0.03 Process
operators handling

Master-batch 24

(3) 90 th

Percentile 0.20 2.95 0.01 0.03

Mean 0.10 1.68 0.01 0.03 Other process

control

operators 4

(1) 90 th

Percentile 0.10 2.07 0.02 0.03

Mean 0.13 0.86 0.01 0.08 Secondary processing of

boards 9

(2) 90 th

Percentile 0.31 1.33 0.02 0.22

Mean 0.09 0.75 0.06 0.02 Reclamation 5

(1) 90 th

Percentile 0.16 1.50 0.14 0.02

Searl and Robertson (2005) also made exposure measurements at an XPS plant that used HBCDD granules. Measured exposures to HBCDD were all les s than 0.1 mgm -3
and the highest inhalable dust concentration was 2.1 mgm -3 . It was also noted that shift rotation meant that exposure occurred on between only one in five and one in 3

shifts.

The RAR described exposure measurement from eight surveys of the manufacturing of extruded polystyrene (XPS) foam described by Abbot (2001). 95 % of the inhalable and respirable HBCDD concentrations were below 0.47 mgm -3

.

Thomsen et al. , 2007 analysed HBCDD concentrations in the workplace air and in the workers’ serum Ten workers working in the “reactor” or “mixer” areas and ten persons from the general Norwegian population were selected for s tudy. The HBCDD concentrations in air ranged from 0.24 μg.m -3 to 150 μg.m -3 . The concentrations in the mixer area (mean 0.5 μg.m -3 ) were significantly lower than those in the reactor area (mean 15 μg.m -3 , median). The mean serum concentrations were 162 ng/g lipids and 218 ng/g lipids, for mixer area and reactor area workers, respectively. HBCDD was not detected above the limit of detecti on (LOD = 0.5 ng/g lipid) in any serum samples from the control group.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 29 of 108

For dermal exposure, there are no measured data and EASE was there fore used by in the RAR to assess exposure levels during industrial use of HBC DD as an additive. The same process was followed as for Masterbatch resulting in figures of 17 mg/day and 1.7 mg/day as reasonable worst cases for XPS production with powder and granules, respectively. As Masterbatch contains around 50% HBCDD, a reasonable worst case for XPS production using Masterbatch would be 0.9 mg/day, hal f of that for XPS production using HBCDD granules.

Release during professional and private use

There is no information about occupational exposure to HBCDD during the installation of EPS during construction and other activities. It is likely that inhalable dust concentrations arising from the board will not exceed 10 mgm -3 and, as the proportion of HBCDD in EPS is around 1% exposure, inhalable HBCDD concentrations are unlikely to exceed 0.1 mgm -3

.

Dermal exposure is very likely to be less than the level of 1.7 mg/day during manufacture of EPS with granules.

Release during service life Any exposure to HBCDD from disturbance of products made from XPS dur ing normal service life is likely to very low and very occasional as dust generation is unlikely and the vapour pressure of HBCDD is low.

Consumer exposure to HBCDD from construction boards (XPS or EPS) wa s calculated by the RAR to be 11.6 μ g/day or 0.11 μ g/day depending on the emission factor used. If the body weight is 60 kg and, if the uptake is 100 %, t he internal exposure will be 0.19 or 0.002 μ g/kg bwt/day. This exposure was considered insignificant and was not included in the risk assessment.

Release during disposal Removal of XPS insulation board at the end of its life is likely to be a dusty operat ion. Assuming there is approximately 1% HBCDD in XPS board and t hat inhalable dust concentrations would average 10mg m -3

, the concentration of HBCDD to which workers will be exposed will be 0.1 mgm -3 . It is likely that occupants will not be present during removal.

Insulation boards form the majority of HBCDD containing waste. I t is understood that most goes to landfill or incineration. Swan et al (2004) and Kra jewski et al (2002) reported personal exposures to inhalable dust on several landfill si tes to be between 0.3 and 9.0 mgm -3 . XPS boards may contain up to a few percent of HBCDD. Given the multitude of dust sources on landfill sites, it is inconcei vable that there will

be measurable levels of HBCDD attributable to treated insulation boards in these dusts. Exposure to HBCDD from boards at managed incinerator sites is likely to be similarly low.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 30 of 108

2.3.2.2 Release into environment Release during industrial use The sites producing flame retarded XPS use HBCDD either as pow der or as a compound. The emission estimates shown in Tables 2.16 and 2.17 have been take n from the RAR and are based on site specific information, applying t he largest emission factor from actual sites to the use quantity not covered b y the specific information. They are based on the tonnages used in the period 2000-2004. For the geographical distribution of these uses see Section 2.2.1 and relate t o the EU-15

countries. The more recent information on the amounts of HBCDD used in X PS indicates an increase over the figures from 2000-2004, by 18% for the 2006 figures. Assuming that the emissions would increase pro rata, and that the dis tribution between compound and powder remains the same, the revised emissions would be as in Table 2.18 and 2.19. The best estimate of the current total rele ase to the environment during the manufacture of flame retarded XPS is the sum of the figures

in tables 2.18 and 2.19.

Table 2.16: Total, regional and continental emissions of HBCDD from industrial use of XPS compound in the manufacture of flame retarded XPS (Point sources)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 100 20 80

Wastewater 27 5.4 21.6

Surface water 7 1.4 5.6



### Table 2.17: Total, regional and continental emissions of HBCDD at sites involved in industrial use of HBCDD powder for flam e retarded XPS (Point sources)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 23.6 2.1 21.5

Wastewater 26.4 16.9 9.5

Surface water 6.6 4.2 2.4

Table 2.18: Total, regional and continental emissions of HBCDD from industrial use of XPS compound in the manufacture of flame retarded XPS (Point sour ces, 2006 figures)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 118 24 94

Wastewater 32 6.4 25

Surface water 8.3 1.7 6.6ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 31 of 108

Table 2.19: Total, regional and continental emissions of HBCDD at sites involved in industrial use of HBCDD powder for flame retarded XPS (Point sources, 2006 figures)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 28 2.5 25

Wastewater 31 20 11

Surface water 7.8 5 2.8

Release during professional and private use HBCDD is used as a flame retardant in polystyrene. The predomi nant use of polystyrene is in rigid insulation panels/boards for building constructi on (EPS and XPS).

The private use of articles containing HBCDD (e.g. insulation boar ds) is small compared to professional use. Emissions from private use are conside red to be covered by the calculation of emissions during professional use.

Please see Section 2.3.2.2 for details on the release of HBCDD from the professional

use of XPS boards and EPS boards in construction.

Release during service life Please see Section 2.3.2.2 for the total, regional and continental emi ssions of HBCDD from building insulation (EPS and XPS).

Release during disposal Waste generated during the industrial use scenario is generally recycled into the process, put into landfill or incinerated. Emissions from this kind of wa ste generation

are assumed to be included in the release estimates of the TGD for the corresponding life-cycle step.

The discussion on emission at disposal for EPS in Section 2.3.1.4 is also relevant for

XPS.

2.3.3 HIPS

2.3.3.1 Releases into working environment Release during industrial use

There are few direct measurements associated with the industr ial use of high impact polystyrene (HIPS). The mixing processes used are comparable to those used for the preparation of EPS and XPS. Following the approach of the RAR (EC 2008a) it is assumed that inhalation exposure of HBCDD during preparation of HIPS would be

the same as for EPS.

For dermal exposure, there is no measured data and EASE was theref ore used by in the RAR to assess exposure levels during industrial use of HBC DD as an additive. The same process was followed as for Masterbatch resulting in figures of 17 mg/day and 1.7 mg/day as reasonable worst cases for HIPS production with powder and granules, respectively.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 32 of 108

Release during professional and private use There is insufficient information regarding exposure to HBCDD f rom handling products made from HIPS. Handling HIPS containing HBCDD during ass embly of electrical equipment is likely to be limited and result in much lower exposure levels than the scenarios arising during production of HIPS.

Release during service life Handling HIPS containing HBCDD during service and repair of electr ical equipment is likely to result in much lower exposure levels than the scenari os arising during production of HIPS.

Any exposure to HBCDD from products made from HIPS during normal service life is likely to be low and very occasional as dust generation is unli kely and the vapour pressure of HBCDD is low.

Release during disposal The removal of electrical equipment from premises for disposal and the transport of electrical equipment to recycling or waste disposal sites a re unlikely to cause any significant occupational or consumer exposure to HBCDD. Occupati onal exposures to HBCDD at managed landfill sites and managed incinerators are likely to be very low. Recycling of electrical equipment is unlikely to generate significant amounts of dust and it is expected that occupational exposure levels will be low. Julander et al (2005), for example, measured concentrations of polybrominated diphenyl et her (the most abundant brominated fire retardant present) of much less than 1 μgm -3 in a recycling plant.

2.3.3.2 Release into environment Release during industrial use

The emission estimates shown in Table 2.20 have been taken from the R AR and were derived using the approach in the OECD Emission Scenario Document on P lastics Additives (OECD, 2004). They are based on 2000-2004 production data and related to

the EU15. The limited more recent information on the amounts of HBCDD used in HIPS indicate a similar amount to that in the risk assessment, and so the figures are not changed.

Table 2.20: Total, regional and continental emissions of HBCDD from industrial use of HIPS compound in the manufacture of flame retarded HIPS (Point sources)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 6.3 0.63 5.7

Wastewater 5.0 0.5 4.5

Surface water 1.3 0.13 1.2

Release during professional and private use HBCDD is used as a flame retardant in high impact polystyre ne (HIPS) which is used in electrical and electronic parts (e.g. distribution boxes for e lectrical lines, video cassette and VCR housings).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 33 of 108

No quantitative information is given in the RAR. This life cycle s tep involves the assembly of electrical and electronic equipment, and so appears unli kely to lead to significant emissions to the environment.

Release during service life No quantitative information is given in the RAR. Emissions to air m ay occur in a similar way to those from EPS/XPS as described in the previous two sections. The quantity of HBCDD used for this purpose is around 2% of that used in EP S/XPS, and the likely lifetime of articles containing HIPS is shorter t han those with EPS/XPS.

Hence the emissions from the service life in HIPS can be consi dered to be negligible in comparison to those estimated in Section 2.3.2.2.

Release during disposal Waste generated during the industrial use scenario is generally recycled into the process, put into landfill or incinerated. Emissions from this kind of wa ste generation

are assumed to be included in the release estimates of the TGD for the corresponding life-cycle step.

Articles containing HIPS treated with HBCDD may be returne d to the manufacturers under the requirements of the WEEE directive, which will increase the potential for recycling of the materials in these articles. No specific information relating to the possible emissions of HBCDD from such recycling has been located. M aterial which cannot be used in recycling will be disposed of to landfill or incine ration. Other articles will be disposed of into municipal waste, and the eventual fate of this material will also be to landfill or incineration. The proportion which is dispose d of by each route will depend on the Member State in which this occurs (no infor mation on the geographical distribution has been located) – the overall figures (2006 ) for the EU-27 are 68% to landfill, 32% to incineration (Eurostat, 2008). For landfill, the risk assessment report (EC, 2008a) concludes that HBCDD has a very low mobility in soil, with strong sorption to organic matter. Hence is it very unlikel y that HBCDD will be leached in significant quantities from landfills. The r isk assessment considers that incineration leads to only very low levels of products such as brominated dioxins, and that operated correctly it is a suitable method for the disposal of HBCDD.

2.3.4 Textile coating

2.3.4.1 Releases into working environment Release during industrial use Searl and Robertson (2005) reported inhalation exposures to HBCDD in dur ing the production of textile coatings in one plant. Laboratory staff were primarily exposed to HBCDD when making up liquid formulations. Micronised HBCDD powder was added to some, but not all, of the products and this was the most importan t source of exposure for production workers.

Measured personal exposure concentrations to HBCDD for laboratory staff and production workers are in Table 2.21.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 34 of 108

Table 2.21: Personal exposure concentrations for workers involved in the preparation of textile coatings (Searl and Robertson, 2005)

Concentration of dust (mgm -3 ) Concentration of HBCDD (mgm -3 ) Task Duration

(minutes) Respirable Inhalable Respirable Inhalable

Mean (standard deviation) 0.26 (0.26) 0.85 (0.36) 0.09 (0.09) 0.23 (0.34) Laboratory

staff

90 th

percentile 0.50 1.25 0.19 0.53

Mean (standard

deviation 0.75 (0.44) 9.23 (6.64) 0.12 (0.11) 1.35 (11.94) Production using

HBCDD

90 th

percentile 1.16 15.47 0.23 3.12

For dermal exposure, there is no measured data and EASE was theref ore used in the RAR to assess exposure levels during industrial use of HBCDD as an additive, assuming dermal exposure depends on the form of HBCDD (fine, standa rd grade and granules) used in the production rather than the product. Dermal exposure to HBCDD when making textile coatings occurs principally during manual addi ng of the substance to the process. It was assumed that both hands and face are exposed in textile coating. This gives 120 mg/day as a reasonable worst ca se for texture coating production. Protective clothing was not rigorously worn in the plant surv eyed (Searl and Robertson, 2005).

Only 15 to 20% of textiles are coated with HBCDD (Searl and Rober tson, 2005) and it is likely therefore that exposure occurs at the above levels f or <25% of time

worked.

Release during professional and private use Dermal exposure to HBCDD may occur during sewing textiles w ith latex backcoating containing HBCDD. Due to the low vapour pressure the release to air from products is assumed to be relatively low at room temperature, but the release may be larger because of a temporary rise in temperature or because of weathering and abrasion. The RAR estimated that the inhalation exposure concentra tion will be 0.5

mgm -3 and the total dermal dust exposure to HBCDD will be 840 mg/day. This exposure is likely to be intermittent as a result of the wide r ange of flame retardants

used with textiles.

Release during service life Several studies have demonstrated the presence of brominated fire retardants in household, office and vehicle dust (eg Stapleton et al., 2008, Takigami et a l., 2008, Stuart et al. 2008). House dust is the most important source of exposure t o brominated fire retardants for the general population (Lorber, 2008). The Polyme r Research Centre at the University of Surrey and the Bolton Institute undertoo k studies to

determine the release of flame-retardants from backcoated t extiles (Thomas and Stevens, 2006). It was estimated that if a 10 kg child ate all the dust generated from the sofas in their home, the daily exposure would be 1.2 μg/kg/day by t he RAR who considered this exposure insignificant. The RAR also calculated tha t the internalECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 35 of 108

exposure from inhalation of HBCDD from house dust will be 1.5 μ g/kg bwt/day, using the results from Thomas and Stevens (2006).

On the basis of measured concentrations of HBCDD in house dust, Abdal lah Mohamed et al (2008) estimated that UK adults and toddlers are expos ed to respectively, to 1.1 and 4.4 μg HBCD/day (ie 0.015 and 0.44 μg/kg/day) from ingesting house dust.

The extraction of HBCDD from fabric by simulating oral suckling or mouthing and aqueous phase dermal exposure was also investigated by Thomas and Stev ens (2006). In the RAR, the average daily mouthing was estimated to be 30 μ g/kg bwt/day if the

back coated side is available and 3 μ g/kg/day if it is not.

Textile on mattress ticking may be flame-retarded with HBC DD but there is no information on how common this could be. Individuals could be exposed by lying on such a mattress with bedding. This exposure is assumed to be via der mal route, with an uptake of 4 % of the external exposure. The exposure was estimate d to be 0.01 μg/kg bwt/day (EC, 2008a). This exposure level was considered insigni ficant by the

RAR.

Exposures during sewing and repair of textiles are likely to be similar in intensity to those described in the sewing scenario above, but occur only occasionall y, perhaps

once per year.

Release during disposal There is little information currently available to fully asse ss exposure levels during disposal. The removal of curtains or furnishings by consumers may le ad to a short term small exposure but this is a “one off” for each item and, g iven the 10 or 20 year projected lifetime, is too small to be significant.

Coated textiles form a relatively low proportion of HBCDD contai ning waste. It is understood that most goes to landfill or incineration. Swan et al (2004) and Krajewski et al (2002) reported personal exposures to inhalable dust on several landfill sites to be between 0.3 and 9.0 mgm -3 . It is inconceivable that that there will

be measurable levels of HBCDD attributable to treated texti les in dusts on a mixed landfill site. Exposure to HBCDD from textiles at managed i ncinerator sites is likely to be similarly low.

2.3.4.2 Release into environment Release during industrial use

The emission estimates shown in Tables 2.22 and 2.23 have been taken from the RAR and are based on site specific information, applying the largest emission factor from actual sites to the use quantity not covered by the specific information. These emissions estimates are based on the tonnages used in the period 2000-2004. For the geographical distribution of these uses see Section 2.2.1. They relate to the EU-15

countries.

Table 2.22 : Total, regional and continental emissions of HBCDD from formulati on of polymer dispersions for textiles (Point sources, RAR).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 36 of 108

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 6.8 2.3 4.5

Wastewater 220 74 146

Surface water 55 18 37

Table 2.23 : Total, regional and continental emissions of HBCDD at sites involved in industrial use of textile back-coating (Point sources, RAR)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 0.64 0.32 0.32
Wastewater 5,653 2,826 2,826
Surface water 1,413 706.5 706.5

The more recent information on the amounts of HBCDD used in textil e coatings indicates a decrease over the figures from 2000-2004, by 80% for the 2007 f igures. Assuming that the emissions would decrease pro rata, the revised e missions would be

as in Table 2.24 and 2.25.

Table 2.24 : Total, regional and continental emissions of HBCDD from formulati on of polymer dispersions for textiles (Point sources, 2007 figures).

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 1.4 0.5 0.9

Wastewater 44 15 29

Surface water 11 3.6 7.4

Table 2.25 : Total, regional and continental emissions of HBCDD at sites involved in industrial use of textile back-coating (Point sources, 2007 figures)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 0.12 0.06 0.06

Wastewater 1130 565 565

Surface water 283 141 141

Release during professional and private use No quantitative information is given in the RAR.

Release during service life The release estimates shown in Table 2.26 were developed using the results of wearing and leaching tests on aged samples of treated textiles

Table 2.26 : Total, regional and continental emissions of HBCDD from textil es during service life (wearing the fabric) (Diffuse sources).

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 0 0 0

Wastewater 107 27 80

Surface water 27 7 20

The estimates shown in Table 2.27 are derived using the methods for service life releases from indoor service for organic flame retardants in OECD (2004).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 37 of 108

Table 2.27: Total, regional and continental emissions of HBCDD from washing of textiles (Diffuse sources).

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 0 0 0

Wastewater 10.5 2.6 7.9

Surface water 0 0 0

These emissions are taken from the risk assessment report (EC, 2008a) and are based on the tonnages used in the period 2000-2004. For the geographical distribution of these uses see Section 2.2.1. Specific information on the geographical distribution has not been located. However, most of the use of these textiles is ex pected to be in those countries which have specific regulatory requirement for use of flame-retarded textiles, namely the UK and Ireland. Therefore most of the above em issions are expected to occur in those two countries.

The reduced figure for use in textiles leads to reduced emission e stimates from the service life of textiles, as in Tables 2.28 and 2.29.

Table 2.28 : Total, regional and continental emissions of HBCDD from textil es during service life (wearing the fabric) (Diffuse sources, 2007 figures).

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 0 0 0

Wastewater 21.4 5.4 16

Surface water 5.4 1.4 4

Table 2.29: Total, regional and continental emissions of HBCDD from washing of textiles (Diffuse sources, 2007 figures).

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 0 0 0

Wastewater 2.1 0.5 1.6

Surface water 0 0 0

Release during disposal Waste generated during the industrial use scenario is generally recycled into the process, put into landfill or incinerated. Emissions from this kind of wa ste generation

are assumed to be included in the release estimates of the TGD for the corresponding life-cycle step.

Disposal of used furniture containing treated textiles is most l ikely to occur to municipal waste, and through that to landfill or to incineration. As note d above, most of the use of these treated materials is likely to be in the U K and Ireland. In these countries the main route of disposal for municipal solid waste is la ndfill (86% in the UK, 100% in Ireland). The possible emissions of HBCDD from landfil l and incineration are considered in Section 2.3.3.2, with the conclusion that such e missions are negligible.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 38 of 108

2.3.5 Total emissions

Table 2.30 shows estimated total releases of HBCDD as estimated in the RAR as outlined above. These figures are based on an estimated EU wide consumption of HBCDD of 9618 tonnes/year compared with the HBCDD Industry Users’ Group estimate of EU wide consumption in 2007 of 11,000 tonnes. Using the revised production and use figures for 2006/2007, the total emissions are as in Table 2.31.

Table 2.30: Estimated total releases of HBCDD from uses in the EU15

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 508.4 67.4 441
Wastewater 6,251 2,998 3,253
Surface water 1,933 875 1,058

Table 2.31: Estimated total releases of HBCDD from uses in the EU27 (2006/7 figures)

HBCDD emissions Total (kg/year) Regional (kg/year) Continental (kg/year)

Air 649 82 568

Wastewater 1553 669 884

Surface water 924 361 563

Note on uncertainty The basis of the emission estimates for each step is indicate d in the sections above.

Most of the formulation and industrial use estimates make use of a ctual measured emissions at sites, applying the worst case values from these to the quantities not covered by the sites providing information. These can be considered to have a reasonable degree of reliability. Other estimates are based on generic emission factors from the plastics additives emission scenario document (OECD, 2004); these are less specific to the substance (although the selection of some factors i nvolves considering the volatility of the substance) and so will have a higher degre e of uncertainty. The

emission estimates over the service life are considered to have the highest degree of uncertainty.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 39 of 108

INFORMATION ON ALTERNATIVE SUBSTANCES AND TECHNIQUES

3.1 Identification of alternative substances and techniques Manufacturers have identified certain requirements that should be m et before substitution of HBCDD can be made (Scheifers, 2004). These requirements include:

• Equal or better flame retardance for the product/part

• Equal or better performance and physical properties for the product/part

• Less risk to environment and human health

• Cost

• Commercial availability

Different applications require different levels of flame reta rdancy, which results in a large number of flame retardants for each specific purposes. The al ternatives listed below are unlikely to represent a comprehensive list but are intended to give an overview of what possible alternative to HBCDD may be availabl e. There are other alternatives to HBCDD in different applications, however little i nformation is

available on their environmental and health hazards or their technical and economic feasibility. The alternative substances and techniques described be low have largely been identified from previous reviews of the availability of alterna tives to brominated fire retardants undertaken by regulatory authorities including KEMI (2006) and the Illinois Environmental Protection Agency (2007). Further information about the technical feasibility of suggested alternatives was obtained by visiting the websites of the manufacturers and suppliers of these products and relevant trade a ssociations representing manufacturers of insulation products and plastics.

ALTERNATIVE FIRE RETARDANTS FOR USE IN HIPS, EPS AND XPS

3.1.1 Halogenated flame retardants in conjunction with Antimony Trioxide As an alternative substance for use in HIPS, other halogenated flame retardants in connection with antimony trioxide (ATO) are available:

• Decabromodiphenylether/ATO

• Decabromodiphenylethane/ATO

• Ethylenebis(tetrabromo phthalimide)/ATO

3.1.2 Organic aryl phosphorous compounds As an alternative substance for use in HIPS, organic aryl phosphor ous compounds are

available:

• Triphenyl phosphate

• Resorcinol bis (biphenyl phosphate)

• Bis phenol A bis (biphenyl phosphate)

• Diphenyl cresyl phosphate

ALTERNATIVE FIRE RETARDANTS FOR USE IN TEXTILE BACKINGS

3.1.3 Textile alternatives For the use of HBCDD in textiles, alternative substances are commercially available.

These are:

• chlorinated paraffins

• decabromodiphenylether (please see Section 3.1.1 above for details)

• ammonium polyphosphatesECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 40 of 108

• reactive phosphorus constituents

ALTERNATIVES TO EPS AND XPS INSULATION

At present, no suitable flame retardant is available to replace HBCDD in XPS or EPS as the required loadings of alternative flame retardants impair t he structure and properties of the finished product to the extent that is no longer suit able for use. There

are however a number of alternative forms of insulation that can be used in place of XPS or EPS. These alternative insulation systems have different characteristics to XPS and EPS and may be less appropriate for some specific use sc enarios or may incorporate different environmental issues such as increased energy costs during transportation

.

3.1.4 Phenolic Foam and Phenolic Resins Closed cell phenolic foam is available as an alternative technique to EPS/XPS for some insulation applications in the building and construction industry,. It has been used in the building industry for various applications such as roofing, cavi ty board, external wall board, and floor insulation. Phenolic resins are used to bi nd glass fibre, mineral wool, or shredded waste to make insulation products. Glass fi bre is the most commonly used material, accounting for 88% of all phenolic insulation pr oducts. Phenol and formaldehyde are the raw materials used to make the phe nolic resin

monomer.

3.1.5 Polyurethane and Polyisocyanurate Products Polyisocyanurate modified urethane foams are available ss an a lternative technique to EPS/XPS for some insulation applications in the building and constructio n industry. They are used in a variety of construction applications, and are commonl y referred to as “polyiso” products. Polyiso insulation products use the following flam e retardant chemicals: tris monochloropropyl phosphate (TMCPP), tris chloroethyl phosphate (TCEP), and RB-79 (diol made from tetrabromo phthalic anhydride).

3.1.6 Mineral wools, other mineral products and cellulose fibre

Mineral wools including glasswool and rockwool and products such as gypsum board are widely used in building insulation. Cellulose fibres, commonly manufactured from recycled paper, are less widely used and must be treated with flame retardants and pesticides such as boron salts before use. These products may be us ed in insulation products as part of the following systems:

Thermal barriers Reflective insulation systems are available as an alternati ve technique to EPS/XPS for some insulation applications in the building and construction. These insulati on systems include foils, films, or papers that are fitted between studs, joists, and beams. Common reflective system materials include foil-faced paper, f oil-faced polyethylene bubbles, foil-faced plastic film, and foil-faced cardboard. The resist ance to heat flow depends on the heat flow direction, and this type of insulation is most ef fective in reducing downward heat flow. When using alternative building insulati on materials, the necessary flame retardancy is often provided by use of a the rmal barrier. Thermal barriers are fire resistant coverings or coatings that separ ate the insulation material from the building interior. Thermal barriers can be used to increase the fire retardantECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 41 of 108

performance for various types of insulation. Commonly used thermal ba rriers include: gypsum board, gypsum or cement plasters, perlite board, spray-applied ce llulose, mineral fibre, or gypsum coatings, and select plywoods.

Loose-fill insulation Loose-fill insulation that can be blown into place or be spray-applied by special equipment can be used as an alternative to EPS?XPS in some buildi ng and construction applications. It is particularly suited for filling ex isting wall cavities and for irregularly shaped areas. Materials used for blown-in or s pray-applied insulation include rock wool, fibre glass, cellulose, or polyurethane foam. Loose-f ill cellulose insulation is commonly manufactured from recycled newsprint, cardboard, or other forms of waste paper. The blown-in loose-fill insulation can provide additional

resistance to air infiltration if the insulation is sufficientl y dense. Loose-fill insulation can also be poured in place by using materials such as vermiculit e or perlite. These materials are produced by expanding naturally occurring minerals in a furn ace.

Blanket insulation As an alternative to EPS/XPS in certain insulation applications in the building and construction industry, blanket insulation is available. It is usually ma de of fibre glass or rock wool and can be fitted between studs, joists, and beams. They ar e available in widths suited to standard spacings between wall studs or floor joists . Continuous rolls can be hand cut and trimmed to fit various spaces. The blankets are ava ilable with or without vapour retardant facings. Batts with special flame re sistant facing are available where the insulation will be left exposed.

3.1.7 Intumescent systems An intumescent system is a combination of various compounds that in the event of fire react together as a result of the temperature increase to form a carbon foam. This foam attains a thickness of 10 to 100 times of the originally appl ied coating and insulates the substrate material through its low thermal conductivity.

Intumescent systems include use of expanded graphite impregnated foa ms, surface treatments and barrier technologies of polymer materials.

Almost all intumescent systems comprise, in general, of three basic components • a dehydrating component, such as APP • a charring component, such as pentaerythritol (PER) • a gas source, often a nitrogen component such as melamine

Whatever the detailed mechanisms for intumescents systems are, the formation of a thick char layer, high carbon concentration, high viscosity of pyrolyzin g melt and low penetration capability for propagation of heat, makes intumescent sys tems efficient to reduce flammability and the exposure of fume gases (Swaraj 2001), (Posner 2004).

ALTERNATIVES TO HIPS

3.1.8 Polyethylene with Magnesium Hydroxide As an alternative technique to flame-retarded HIPS, it is poss ible to use polyethylene in conjunction with magnesium hydroxide.

3.2 Information on alternativesECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 42 of 108

3.2.1 Human health and environmental effects

ALTERNATIVE FIRE RETARDANTS FOR USE IN HIPS, EPS AND XPS

3.2.1.1 Halogenated flame retardants in conjunction with Antimony Trioxide Human health effects Antimony Trioxide Antimony trioxide has an oral LD50 in rats of >34,600 mg/kg and LD50 value s for administration by intraperitoneal and subcutaneous injection are 3,250 a nd 7,904 mg/kg respectively (RTECS). The lowest reported toxic dose in repeated dose experiments listed in RTECS are summarised in Table 3.1.

Table 3.1 Lowest reported toxic dose of antimony trioxide in repeated dose experiments

Species Duration

of experiment Exposure

Route Dose Effects

Rat 90 days Oral 1690 mg/kg/day Liver - changes in liver weight Blood - other changes Biochemical - Enzyme inhibition, induction, or change in blood or tissue levels - phosphatases Rat 21 days oral 1000 mg/kg/day Nutritional and Gro ss Metabolic - weight loss or decreased weight gain Rat 17 weeks Inhalation 72 ugm -3 (24 hours/day) Blood - pigmented or nucleated red

blood cells Biochemical - Enzyme inhibition, induction, or change in blood

or tissue levels - true cholinesterase

Biochemical - Metabolism (Intermediary) - lipids including

transport Rat 1 year Inhalation 4.5 mgm -3 (6 hours/day) Sense Organs and Special Senses (Eye) -

effect, not otherwise specified Lungs, Thorax, or Respiration - other changes Rat 20 days Inhalation 2.6 mgm -3 (6 hours/day) Lungs, Thorax, or Respiration - other

changes Lungs, Thorax, or Respiration - changes in lung weight Rat 13 weeks Subcutaneous 282 mg/kg/day Cardiac – o ther changes

Guinea pig 10 weeks Inhalation 45 mgm -3 Lungs, Thorax, or Respiration - fibrosis, focal (pneumoconiosis) Liver - fatty liver degeneration Related to Chronic

Data - death

In one year inhalation studies in rats, lung tumours have been reported in animals exposed at concentrations ranging between 1.6 and 50 mgm -3 (RTECS). Data from animal experiments seem to indicate that females are more s ensitive concerning developing lung neoplasms than males. Antimony trioxide induced DNA dama ge in bacteria (IARC, 1989).

In experiments in pregnant rats, inhalation exposure to antinomy oxide at concentrations of 82 and 270 ugm -3 throughout gestation have given rise to postimplantation mortality and foetal toxicity (RTECS).

There are epidemiological indications that antimony trioxide cause s dermatitis and has an impact on reproduction in female workers (IARC, 1989).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 43 of 108

Antimony trioxide is classified in the EU as "Harmful (Xn)" and must be labelled with the risk-phrase "Possible risk of irreversible effects" ( R40) as a possible carcinogen.

The UK Workplace Exposure Limit for antimony and its inorganic compounds is 0.5

mgm -3

. Name of substance Antimony Trioxide

Abbreviation

CAS No. 8452-53-9

Endpoint Value Reference

LD50 rat oral >34600 mg/kg RTECS

NOAEL mg/kg bw

Reproductive toxicity
Foetal toxicity and postimplantation mortality, LOEL rat
inhalation 82 ugm -3 RTECS

Repeated dose Toxicity, LOAEL

Rat oral

Rat inhalation 1000 mg/kg/day
72 ugm -3 (24 hour exposure) RTECS

Genotoxicity

Carcinogenicity

LOEL rat inhalation Possible human carcinogen
1.6 mgm -3 IARC

Critical endpoint Effects on general health (oral exposure) LOEL
Lung cancer LOEL in rats

OEL 1000 mg/kg/day
1.6 mgm -3

0.5 mgm -3

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 50 mg/day Intake equivalent to workpl ace exposure limit

General population, oral 0.25 mg/day Intake equival ent to inhalation DNEL

Workers, inhalation 0.5 mgm -3 Workplace exposure limit

General population, inhalation 0.0025 mgm -3 Default assessment factor for worker/general population exposure, adjustment to allow for difference in duration of exposure (x10 for lifetime exposure)
Based on workplace exposure limit

Decabromodiphenylether/ATO Studies of toxicokinetics of Decabromodiphenyl ether (decaBDE) rev eal that the chemical can be absorbed by the oral route to a limited extent, doe s not accumulate in tissues, and undergoes clearance, largely as a result of metaboli sm in the liver and

excretion in the bile.

Short-term and subchronic studies demonstrated low toxicity from ora l exposure to decaBDE with NOAELs of 3,000 mg/kg-day or higher. NTP (1986) conducted a chronic toxicity and carcinogenicity dietary study in F344 rats. De caBDE caused an increase in the incidence of thrombosis in the liver in high-dose male rats (2,240 mg/kg-day). A dose-dependent, but insignificant, increase in the inci dence ofECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 44 of 108

degeneration of the liver was also observed in treated male rats. I n the spleen, a dosedependent increase (statistically significant in the high-dose group) in the incidence of fibrosis was observed in males. In the mandibular lymph node, lymphoid hype rplasia increased in males in a dose-dependent manner, but the incidence reach ed statistical significance only at the high dose. Histopathology examination also re vealed a dosedependent increase in the incidence of neoplastic nodules in the liver in both male and female rats. Female rats appeared to be refractory to the sys temic toxicity of decaBDE at the doses used in this study.

The observed toxicity of decaBDE in the 2-year study in rats is further supported by the 2-year mouse study conducted by NTP (1986). Significant increas es in the incidence of centrilobular hypertrophy were observed in the liver o f treated male mice. In the thyroid gland, a dose-dependent and statistically si gnificant increase (at all dose levels) in the incidence of follicular cell hyperplas ia was observed in male mice. In the females, the incidence increased in the low- and high -dose groups compared with the control group, but the increase was not statistical ly significant at any dose level. Female mice in the high-dose group exhibited a sig nificant increase in the incidence of stomach ulcers. In addition, there were significant increases in the combined incidence of hepatocellular adenomas or carcinomas at both low and high doses in male mice. In the thyroid gland, follicular cell adenom as or carcinomas (combined) were slightly, but not significantly, increased in tre ated mice of both sexes. Similar to female rats, female mice appeared to be r efractory to the systemic toxicity of decaBDE.

DecaBDE also has been shown to induce behavioural changes in several studies in mice and rats (Viberg et al., 2007, 2003a; Rice et al., 2007). In the principal study selected, Viberg et al. (2003a) investigated the neurotoxic effects of decaBDE on spontaneous motor behaviour of adult NMRI male mice when these anima ls were exposed to a single oral dose as neonates on PND 3, 10, or 19 (i.e., at diff erent stages of neonatal mouse brain development). Pair-wise testing between adult mice exposed on PND 3 and control groups indicated significant dose-related changes in all three spontaneous behaviour variables at 2, 4, and 6 months of age. Adult mice exp osed neonatally up to 20.1 mg on either PND 10 or 19 did not show any significant differences in any of the variables. These data suggested t hat there was a critical window for the induction of behavioural disturbances, and the neurotoxic effec t of neonatal decaBDE exposure was persistent and also worsened with age in male mic e.

The appropriate hazard descriptor for decaBDE is ‘suggestive evide nce of carcinogenic potential’ (U.S. EPA, 2005a, b). DecaBDE was not mutagenic or genotoxic in several in vitro studies. In the International Agency for Research and Cancer (IARC, 1990) evaluation, it was concluded there was limited evidence for the carcinogenicity of decaBDE in experimental animal and classif ied it as Group 3: "Not classifiable as to its carcinogenicity to humans". In the EU RA R for DecaBDE, a cautious approach was followed, and a LOAEL for carcinogenicity of 1,120 mg/kg/day was stated based on the increased incidence of liver neoplastic nodules from the lowest tested dose (1,120 mg/kg/day).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 45 of 108 Name of substance Decabromodiphenylether

Abbreviation DecaBDE

CAS No. 1163-19-5

Endpoint Value Reference

LD50 (rat, oral) 2000 mg/kg RTECS

NOAEL mg/kg bw

Reproductive toxicity

Effects on neurobehavioural development 20.1 mg/kg/day Viberg et al (2007)

Repeated dose Toxicity, LOAEL
in male rats 2,240 mg/kg-day

Genotoxicity

Carcinogenicity LOAEL for carcinogenicity of 1,120 mg/kg/day in animals

“not classifiable in humans” RAR

IARC, 1990

Critical endpoint Effects on neurobehavioural development Dose 20.1 mg/kg/day

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 5.6 mg/day Default assessment factors plus x5 for
LOEL rather than NOEL

General population, oral 2.8 mg/day

Workers, inhalation 0.56 mgm -3

General population, inhalation 0.07 mgm -3

Decabromodiphenylethane/ATO Ethane, 1,2-bis(pentabromophenyl) (EBP; CAS no. 8452-53-9) dose levels of 0, 100, 320 and 1000 mg/kg/day administered to rats by gavage in corn oil for 90 consecutive days produced no compound-related clinical signs of systemic toxici ty, ocular lesions, or alterations in urinalysis, clinical chemistry, and haematol ogy values in the treated or recovery groups. No biologically or toxicologically significant differences were observed in body weights, body weight gains, and food consumption. Statistic ally significant differences were found between control and high-dose anima ls in mean absolute or relative liver weights. Histomorphological evaluation showed in male rats low-grade liver changes consisting of minimal to slight hepatocellul ar vacuolation (high-dose males) and minimal to slight centrilobular hepatocytomeg aly (high- and possibly mid-dose males). These changes had resolved by the end of the 28-day recovery period. No treatment-related changes were found in t he livers of female rats. No treatment-related histomorphologic changes were present in a ny of the other tissues examined in either sex, except for evidence of aspirate d test article in individual rats. The 90-day EBP NOAEL in the rat was 1000 mg/kg/day, and was consistent with that of the preceding 28-day study (no-effect lev el 1250 mg/kg/day). EBP’s lack of toxicity is likely related to poor bioavailability due to its hi gh molecular weight and low solubility (Hardy, 2002).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 46 of 108 Name of substance Ethane, 1,2-bis(pentabromophenyl)

Abbreviation DecaBDEthane

CAS No. 8452-53-9

Endpoint Value Reference

LD50 No information

NOAEL mg/kg bw No information

Reproductive toxicity No information

Repeated dose Toxicity, NOAEL

rat ≥ 1000 mg/kg bw Hardy, 2002

Genotoxicity No information

Carcinogenicity No information

Critical endpoint Not known

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 700 mg/day Default assessment factors
Based on NOEL in repeated dose experiments

General population, oral 350 mg/day

Workers, inhalation 70 mgm -3

General population, inhalation 17.5 mgm -3

Ethylenebis(tetrabromo phthalimide)/ATO

The information in this section is taken from the HPV Data Summar y and Test Plan for 1H-Isoindole-1,3(2H)-dione, 2,2’-(1,2-ethanediyl)bis(4,5,6,7-terabromo-) (a.k.a. Ethylene bis tetrabromophthalimide) prepared by Abermarle (2004).

In studies of uptake and elimination, Ethylenebis(tetrabromophthalimide) (EBTBP) was mainly excreted in the faeces (65% of dose), urine (15% of dose ), and breath (1% of dose) twenty-four hours after oral dosing in laboratory rats. Th e organs containing the highest concentrations of the compound were the liver, kidney, and muscl es. Lower levels were detected in the brain and fat.

The acute oral LD 50 in the rat was greater than 7.5 g/kg. The dermal LD50 in rabbit s was > 2,000 mg/kg and the inhalation LC50 in rats was > 203 mg/L for 1 hour.

No dermal irritation or reactivity was observed in rabbits trea ted with 0.5 g or 2.0 g/kg ethylenebis(tetrabromophthalimide). Ethylenebis(tetrabromophtha limide) was determined to be an eye irritant when tested in rabbits at a dose of 100 mg/eye. It was mildly toxic to rats when inhaled.

Repeated Dose Toxicity: In a 28-day experiments in rats EBTBP was fed to male rats (n=10/group) at 0, 0.01, 0.1 and 1% of the diet for 28 days. No mortality occur red during the study. No clinical signs of toxicity were observed. Mea n body weights, body weight gains, food consumption and organ weights, haematology and serum chemistry parameters were not affected by treatment. No gr oss or microscopic lesions attributable to test article were detected at necropsy or on light microscopy. The 28- day NOEL was ∞ 1% of the diet. This is estimated to be ~ 1,000 mg/kg/ ay.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 47 of 108

In a 90-Day study in rats EBTBP was administered to four gro ups of rats (n=15/sex/group) at 0, 0.01, 0.1 and 1.0% of the diet for 90 days followed by 46 day s during which the rats were fed control diet. No changes in haematolo gy or serum chemistry values related to treatment were detected on study days 0, 45, 92. No effect of treatment was found on urinalysis (d 0, 45 and 90). The mean rela tive and absolute organ weights of the liver, kidney, heart, and thyroids from the contr ol and 1.0% groups were statistically comparable. Several animals died on t est from non-test article related causes (most deaths were related to collec tion of blood for haematology and serum chemistry evaluations). Gross necropsy from animals di eing on test and sacrificed on days 92, 134, 135 and 136 revealed no test article-related gr oss lesions. No test article related lesions were detected on histopathology. The 90-day NOEL was 1% of the diet. This was estimated to be ~ 1,000 mg/kg/day.

Developmental: EBTBP was administered to four groups of 25 pregnant r ats by gavage in corn oil at doses of 0, 100, 500 or 1000 mg/kg/d on gestation day s 6-15. No maternal mortality or clinical signs of toxicity were obser ved during the study. No treatment-related differences were noted among the groups with re spect to maternal body weights, food consumption, necropsy or caesarean section data. No tr eatmentinduced fetal malformations or developmental variations were detecte d. The maternal and foetal NOEL was 1,000 mg/kg/day.

EBTBP was administered to two groups of 20 pregnant rabbits each by ga vage in methyl cellulose at dose of 0 or 1,000 mg/kg/d on gestation days 7-19. No m aternal mortality, abortions or clinical signs of toxicity were observed duri ng the study. Maternal body weights, weight gain, food consumption, necropsy observations and cesarean section data were generally comparable among the g roups. No treatmentrelated malformations or developmental variations were observed. Th e maternal and foetal NOEL was 1,000 mg/kg/day.

Genetic Toxicity - Mutagenicity In the Ames assay, the tester strains used were Salmonella T A98, TA100, TA1535, TA1537, and TA1538 and E. coli, WP2 uvrA. Each strain was tested with and without a source of exogenous metabolic activation of Arochlor-induced rat li ver microsomes. EBTBP dose levels were 0, 1, 10, 100, 500, 1,000 and 5,000 ug/plate. Positive and negative controls were included, and performed as expected. No increase in revertant colonies was found at any EBTBP dose level either in the presence or absence of microsomal enzymes. EBTBP was not genetically active in this assay. (Mutagenicity Evaluation of Ethylene-1,2-bis(3,4,5,6-tetrabromophthalimie) in the Ames Salmonella/Microsome Assay. February 18, 1982. Chemical Inspection & Testing Institute, Japan, Induced Mutation Division).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 48 of 108 Name of substance Ethylenebis(tetrabromo phthalimide)

Abbreviation EBTBP

CAS No. 32588-76-4

Endpoint Value Reference

LD50 – rat oral >750 mg/kg HPV data summary (2004)

NOAEL mg/kg bw

Reproductive toxicity No reported effects on fertil ity or foetal development; NOEL 1000 mg/kg/day HPV data summary (2004)

Repeated dose Toxicity, NOAEL rat, 90 day oral 1000 mg/kg HPV data summary (2004)

Genotoxicity Not genotoxic HPV data summary (2004)

Carcinogenicity No information

Critical endpoint Not determined

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 700 mg/day Default assessment factors Based on NOEL in repeated dose experiments

General population, oral 350 mg/day

Workers, inhalation 70 mgm -3

General population, inhalation 17.5 mgm -3ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 49 of 108

Environmental effects Diantimony trioxide

Identity and properties

CAS number 1309-64-4 Water solubility 2.76 mg/l in reconstituted water (=ISO 6341 medium) at 22°C (EC, 2008) Vapour pressure 133 Pa (1 mm Hg) at 574°C (EC, 2008 ) Log Kow Not relevant for this type of substance

Fate data Biodegradability Not readily biodegradable (EC, 200 8). Bioconcentration factor Bioaccumulation potential s eems to be low to moderate* (EC, 2008).
* No reliable bioaccumulation studies are available. Measured data from differ ent aquatic organisms have been used to calculate tentative BCF values which range from <5 – 15,000. It should be noted that there is considerable uncertainty in these values (EC, 2008).

Aquatic effects Species Effect Value Reference Marine fish ( Pargus major ) 96 hr LC 50 6.9 mg Sb/l # EC, 2008 Freshwater fish ( Pimephales promelas ) 96 hr LC 50 14.4 mg Sb/l EC, 2008

Freshwater fish ( Pimephales promelas ) 28 d NOEC/LOEC (growth; length) 1.13/2.31 mg Sb/l EC, 2008

Invertebrate ( Chlorohydra

viridissimus ) 96 hr LC 50 1.77 mg Sb/l EC, 2008

Invertebrate ( Daphnia magna ) 21 d NOEC/LOEC (reproduction) 1.74/3.13 mg Sb/l EC, 2008

Algae ( Raphidocelis subcapitata ) 72 hr E

r C 50 (growth rate) 72 hr NOEC/LOEC (growth rate) > 36.6 mg Sb/l 2.11/4.00 mg Sb/l EC, 2008

The PNEC for freshwater aquatic organisms based on the above data is 0.113 mg Sb/l, derived by applying an assessment factor of 10 to the lowest NOEC for freshwater fish (EC, 2008b).

# This was the only reliable study for marine aquatic organisms. Therefore the PNEC for marine water had to be derived by applying an assessment fa ctor of 100 to the lowest NOEC for freshwater fish; PNEC marine water 11.3 μg Sb/l (EC, 2008).

There is currently no agreed approach to perform a PBT-assessm ent of a metal; therefore a PBT-assessment has not been performed. Diantimony tr ioxide is classified as a dangerous substance and is listed in Annex 1 of Directive 67/548/EEC.

Given that the ESR process involved a rigorous data searching and re view process, with the possibility of the generation of new data through tests , the values reported in the RAR for diantimony trioxide can be considered to have little uncertainty.

The vapour pressure of diantimony trioxide at ambient temperature is considered t o be negligible. In the environment, antimony trioxide will slowly dissolve and trans form into Sb(OH) 3 , which is oxidised to Sb(OH) 6 - under oxic conditions. Antimony, beingECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 50 of 108

a natural element cannot by definition be degraded. However, it can be transformed between different speciation forms and oxidation states.

Decabromodiphenylether

Identity and properties

CAS number 1163-19-5 Water solubility <0.1  g/l at 25°C (EC, 2002) Vapour pressure 4.63×10 -6 Pa at 21°C (EC, 2002) Log Kow 6.27 (measured value) (EC, 2002))

Fate data
Biodegradability Not readily biodegradable (EC, 200 2). Bioconcentration factor Appears to have a low bioac cumulation potential, although there is a lack of consistent evidence (ECB, 2007).

Aquatic effects
Species Effect Value Reference Fish ( Oryzias latipes ) 48 hr LC 50 >500 mg/l (well in excess of substance’s solubility). EC, 2002

Fish ( Oncorhynchus mykiss ) 120 day feeding experiment (dose of 7.5-10 mg/kg bw/day) Increased liver weights and

lactate levels in blood after 120 days. Significance of these

effects unknown. EC, 2002

Invertebrates ( Daphnia

magna ) 21 d NOEC No information for deca-. Study

carried out for octa-. No effects on survival, growth or reproduction up to 2 μ g/l. EC, 2002

Algae ( Skeletonema

costatum and

Thalassiosira pseudonona )

Chlorella sp. 72 hr E

r C 50

96 hr E

r C 50 At the highest concentration tested (1mg/l), growth reduced by <50%. Not clear if any toxic

effects were seen. EC 50 cannot
be determined. EC, 2002

It is not possible to derive a true PNEC for the aquatic compa rtment as no effects are expected at concentrations up to the water solubility of decabromodiphenylether

.

A tentative PNEC of >1 μ g/l can be estimated based on an EC 50 >1 mg/l from the algal studies, using an assessment factor of 1,000. Alternatively, a tentative PNEC of

>0.2 μ g/l can be derived based on the 21 d NOEC for Daphnia magna with octabromo-diphenylether (no effects were seen up to the solubility limit of 2 μ g /l). This approach assumes that deca- has a similar toxicity to oc ta- in long-term tests and the derived PNEC is of the same order of magnitude as that est imated using the algal data(EC, 2002).

Given that the ESR process involved a rigorous data searching and re view process, with the possibility of the generation of new data through tests , the values reported in the RAR for decabromodiphenylether can be considered to have little uncertainty.

Decabromodiphenylether is persistent. No significant toxicity has been observed. A conclusion on bioaccumulation cannot be drawn based on the current evidence (EC B, 2007). This substance is not currently classified for environmental or he alth effects according to Directive 67/548/EEC.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 51 of 108

Relative emissions: the emissions of HBCDD from industrial use in HIPS are related to the vapour pressure. Decabromodiphenylether has a lower vapour pressure and so emissions from the same processes would be expected to be lower. Losses of HB CDD from articles during their service life are also related t o the vapour pressure; hence emissions from service life would be expected to be lower. Deca bromodiphenylether is not readily biodegradable, so is not expected to be degraded signi ficantly in wastewater treatment plants (wwtps) or to degrade in the environment.

The emission estimates for HBCDD from use in textiles are based largely on specific measurements. Therefore it is not appropriate to make an estimat e of the relative emissions for decabromodiphenylether based on a comparison of the phys icochemical properties.

Decabromodiphenylether is used in HIPS and in flame retarded text ile coatings (EC, 2002).

Decabromodiphenylethane

Identity and properties

CAS number 84852-53-9 Water solubility ~ 0.72 μ g /l at 25°C (measured value) (EA, 2007) #

Vapour pressure ~ 1×10 -6 Pa at 25°C (nominal value to indicate low volatility) (EA, 2007) Log Kow No value selected (a more reliable measurement is needed) (EA, 2007)

# There is evidence from predictive models and analo gues that the true water solubility of this substance could be much lower (EA, 2007).

Fate data
Biodegradability Not readily biodegradable (EA, 200 7). Bioconcentration factor 25 l/kg (limit value used i n calculations for the assessment for illustrative purposes) (EA, 2007).

Aquatic effects Species Effect Value Reference Fish ( Oncorhynchus mykiss ) 96 hr LC 50 No effects seen at the highest loading rate of 110 mg/l*. EA, 2007

Fish ( Cyprinus carpio ) 8 wk bioaccumulation study No abnormalities observed at exposure concentrations of 0.5 and 0.05 mg/l. EA, 2007

Invertebrates ( Daphnia

magna ) 48 hr EC 50 No effects seen at the highest loading rate of 110 mg/l*. EA, 2007

Algae ( Selenastrum capricornutum ) 96 hr EC 50 No effects seen at the highest loading rate of 110 mg/l*. EA, 2007

* Given the excess of substance used to prepare the WAF in these st udies, it is assumed that the water solubility limit of ~ 0.72 μg/l at 25°C was reached.

No toxic effects were seen in any of the tests with fish, i nvertebrates or algae. Therefore, it is not possible to derive a PNEC for aquatic organis ms (freshwater or marine).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 52 of 108

Based on screening information only, decabromodiphenylethane is consider ed to be potentially persistent. A firm conclusion on bioaccumulation potential ca nnot be

drawn due to the lack of reliable data. The substance does not mee t the toxicity criterion. Decabromodiphenylethane is not classified for either envi ronmental or human health hazards on Annex 1 of Directive 667/548/EEC (EA, 2007).

Relative emissions: the emissions of HBCDD from industrial use in HIPS are related to the vapour pressure. A vapour pressure of 1×10 -6 Pa at 25°C was assumed in the risk assessment for decabromodiphenylethane to indicate low volatili ty. However, the vapour pressure of this substance could be even lower. Therefore emiss ions from the same processes would be expected to be lower than for HBCDD. Losse s of HBCDD from articles during their service life are also related t o the vapour pressure; hence emissions from service life would be expected to be lower. Decabromodiphenyl ethane is not readily biodegradable, so is not expected to be degraded signifi cantly in wwtps or to degrade in the environment.

Ethylene bis(tetrabromophthalimide)

Identity and properties

CAS number 32588-76-4 Water solubility <1.63 mg/l (measured), 3x10 -9 mg/l (calc) – from ECB (2008) Vapour pressure 3.3×10 -20 Pa (calc)(ECB, 2008) Log Kow 9.8 (calc) (ECB, 20082)

Fate data
Biodegradability Not readily biodegradable (ECB, 20 08).

Bioconcentration factor Does not meet the B criteri on based on indicators of low bioaccumulation potential (ECB, 2008).

Aquatic effects
Species Effect Value Reference Fish ( Oryzias latipes ) 48 hr LC 50 >500 mg/l (well in excess of substance’s solubility). ECB, 2008

The EU PBT Working Group (2008)_ concluded that it is not possible to deri ve a true PNEC for the aquatic compartment as no effects are expec ted at concentrations up to the water solubility. Although the data can be considered reliabl e, they are insufficient to derive a PNEC, and so there is uncertainty over wha t level should be used to assess exposures.

The PBT Working Group concluded that the substance meets the P/vP cr iteria, does

not meet the B criterion based on indicators of limited bioaccumulati on, and does not meet the T criterion in mammals. According to the ESIS databas e, this substance is not classified in the Annex I of Directive 67/548/EEC as such, but it may be included in one of the group entries.

Relative emissions: the emissions of HBCDD from industrial use in HIPS are related to the vapour pressure. The substance has a very much lower estimat ed vapour pressure and so emissions from the same processes would be expecte d to be lower. Losses of HBCDD from articles during their service life a re also related to the vapour pressure; hence emissions from service life would be expected to be lower. EthyleneECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 53 of 108

bis(tetrabromophthalimide) is not readily biodegradable, so is not expect ed to be degraded significantly in wwtps or to degrade in the environment.

3.2.1.2 Organic aryl phosphorous compounds Health effects Triphenyl phosphate

The information in this section is drawn from the SIDS (UNEP, 2002).

Acute toxicity data exist for several species of animals and indicate low toxicity via the oral and dermal routes (1320 to 10 800 mg/kg and >7900 mg/kg, respective ly). No inhalation data are available. TPP also exhibits low toxicity in short-term studies and is not an irritant to mouse skin. In repeated dose experiments i n rats, reduced body weights and an increase in liver weights were observed in a 35 day experiment at an oral dose of 350 mg/kg/day with an estimated NOEL of 70 mg/kg . In two 4 month studies, the NOEL for effects on weight was estimated as 161 mg/kg.

There are limited data that suggest an absence of genotoxic act ivity and no indication of carcinogenic potential was observed in the mouse lung ademona assay.

No effects on fertility or foetal development were observed followi ng repeated dietary exposure of 166-690 mg/kg per day for a period of 91 days, including mating a nd gestation periods.

The neurotoxicity of TPP has been debated since the early studies of Smith et al. (1930, 1932), which reported delayed neuropathy in cats and monkeys exposed to TPP in acute and short-term studies. However, Wills et al. (1979) could demonstrate no ataxia or neuropathic damage in cats exposed to 99.9%-pure TPP. Conse quently, the validity of the Smith studies has been questioned. Other toxicity studies using behavioural and morphological end-points have demonstrated that TPP administ ered short-term to cats and chickens fails to produce neuro-toxic changes . A mixture of triaryl (including cresyl and phenyl) phosphates produced neurochemica l changes and minor peripheral nerve pathology in the caudal nerve of rats; acute i ntraperitoneal injection of 150 mg or less produced neither biochemical nor morphological c hange. It has been suggested that small concentrations of impurities may explain the

neurotoxic effects observed in some studies.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 54 of 108 Name of substance Triphenyl phosphate

Abbreviation TPP

CAS No. 115-86-6

Endpoint Value Reference

LD 50 mouse oral 1320 mg/kg SIDS (2002)

NOAEL mg/kg bw

Reproductive toxicity No effects on fertility or de velopment
have been observed SIDS (2002)

Repeated dose Toxicity, NOAEL

rat 161 mg/kg/day SIDS (2002)

Genotoxicity Limited evidence suggesting an absence of genotoxic activity SIDS (2002)

Carcinogenicity Limited evidence suggesting an absence of carcinogenic potential SIDS (2002)

Critical endpoint Liver toxicity Dose: 161 mg/kg/da y - NOEL

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 112.7 mg/day Default assessment facto rs

General population, oral 56.35 mg/day

Workers, inhalation 11.27 mgm -3

General population, inhalation 2.82 mgm -3

Resorcinol bis (biphenyl phosphate)

The Illinois Environmental Protection Agency (2007) provided a summary of the toxicology of resorcinol bis (biphenyl phosphate) in a report on alternatives to decaBDE. Their findings are tabulated below:

Endpoint Data Chronic toxicity 28-day LOAEL for increased liver weight=100 mg/kg/d (lowest dose tested); NOAEL for immune system effects=5000 mg/kg /d (highest dose tested); no other short- or long-term data. Irritation and sensitisation Minimal skin and eye i rritation; not a sensitizer Mutagenicity No cancer data; not mutagenic (1 assay ); no chromosomal abnormalities (1 assay); Reproductive/developmental

effects Rat 2-generation study NOAEL=20000 mg/kg/d (highest dose tested)

Limited additional data are listed by RTECS. The oral LD 50 in rats is reported to be >5000 mg/kg. The LC 50 is greater than 4860 mgm -3 . Exposure led to lowered activity levels and breathing difficulties. Lowered activity levels were al so observed following dermal application to rats and the LD 50 by this route is >2000 mg/kg.

RTECS also lists two additional repeated dose experiments. The low est reported toxic dose by inhalation in rats is 500 mgm -3 (6 hours/day) in a four week experiment. Effects included changes in lung and liver weights. In a 28 day expe riment in mice, the lowest reported toxic dose was 5000 mg/kg/day which was associat ed with metabolic changes.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 55 of 108 Name of substance resorcinol bis (biphenyl phosphate)

Abbreviation RBBPP

CAS No. 57583-54-7

Endpoint Value Reference

LD 50 rat oral >5000 mg/kg RTECS

NOAEL mg/kg bw

Reproductive toxicity No adverse effects reported o n fertility or development at 20000 mg/kg/day IEPA

Repeated dose Toxicity, LOAEL
rat oral – increased liver weight

rat inhalation 100 mg/kg/day
500 mgm-3 (6 hours/day) IEPA

Genotoxicity Limited data suggest absence of genotoxicity IEPA

Carcinogenicity No data IEPA

Critical endpoint

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 9.3 mg/day

General population, oral 4.7 mg/day Default assessment factors plus x5 for
LOEL rather than NOEL
Based on oral LOEL in repeated dose experiments

Workers, inhalation 0.34 mgm -3

General population, inhalation 0.084 mgm -3 Default assessment factors plus x5 for
LOEL rather than NOEL
Based on inhalation LOEL in repeated dose experiments

Bis phenol A bis (biphenyl phosphate) (BPA-BDPP) 5945-33-5

NICNAS (2000) summarise the limited available data that are av ailable for this substance. It has a low toxicity following oral administration w ith the rat LD 50 being > 2000 mg/kg. The dermal LD 50 is also >2000 mg/kg. It does not cause irritation to the eyes or skin in experiments in rabbits and is non sensitising in an assay in guinea pigs.

There are no cancer data and the available data suggest an absence of geno toxicity.

In a 28-day experiment in rats the NOAEL was 1000 mg/kg/d (highes t dose tested, includes neurotoxicity evaluation).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 56 of 108 Name of substance Bis phenol A bis (biphenyl phosphate)

Abbreviation BPA-BDPP

CAS No. 5945-33-5

Endpoint Value Reference

LD 50 rat oral >2000 mg/kg NICNAS

NOAEL mg/kg bw

Reproductive toxicity

Repeated dose Toxicity, NOAEL

rat 1000 mg/kg/day NICNAS

Genotoxicity Not genotoxic NICNAS

Carcinogenicity No information

Critical endpoint Not known

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 467 mg/day Default assessment factors
Based on NOEL in repeated dose experiments

General population, oral 233 mg/day

Workers, inhalation 46.7 mgm -3

General population, inhalation 11.7 mgm -3

Diphenyl cresyl phosphate

The following information is provided in the SIDS initial assessment profile (UENP, 1998).

Acute toxicity

Oral/Rat: LD 50 : 6,400 mg/kg Inhalation/Sheep: LC 50 : > 0.37 mg/l/1h

Dermal/Rabbit: LD 50 : > 5,000 mg/kg

Repeated dose toxicity In an OECD Combined Repeated Dose and Reproductive/Developmental Scree ning Toxicity Test in rats, salivation, reduced body weight gain and inc reased water intake were observed in both sexes, and increased food consumption was observed in male rats at 300 mg/kg/day. This was combined with enlargement and cortic al vacuolation of the adrenals, enlargement of the liver, and fatty change of the pr oximal tubular epithelium were found in both sexes. In addition, reduction of fatty change of the hepatocytes, increase in hyaline droplets and basophilic changes i n the proximal tubular epithelium, erosion or focal necrosis in mucosa of stomach and at rophy of seminiferous tubular were found in male rats, and clear cell chan ge of hepatocytes, atrophy of thymus, hypertrophy and hyperplasia of the interstiti al cells in the ovaries were found in female rats. Anaemia, and an increase of leukocytes w ere also observed in male rats at 300mg/kg together with an increase in total chol esterol and decreases in GOT, albumin, A/G ratio, cholinesterase activity and triglycer ides. In urinalysis, decreases in pH and specific gravity, an increase of urine volum e were found at 300 mg/kg in male rats. At 60 mg/kg/day, reduced body weight gain wa s observed in females and enlargement and cortical vacuolation of the adrenal s were found in both sexes. In addition, an increase of total cholesterol, a decrease of cholinesterase activity, and enlargement of the liver were found in male rats , and histopathologicalECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 57 of 108

changes in the liver, kidneys and the thymus were found in female r ats. The NOELwas identified as12 mg/kg/day.

Reproduction/developmental toxicity In an OECD Combined Repeated Dose and Reproductive/Developmental Scree ning Toxicity Test in rats, reduced fertility and implantation rate s were observed at 300 mg/kg/day. These were probably caused by dysspermatogenesis . A birth index tended to low. There were no effects on the reproductive or developmental para meters of copulation, pregnancy, parturition or lactation. In an observation of neonates , no effects were found on the values for live pups, mean pup weights, sex ra tio, abnormal pups or loss of offspring.

These results indicate that the no effect levels for reproduction or development are 60 mg/kg for sires, and 300 mg/kg for dams and offsprings. NOEL for P generation: 60 mg/kg NOEL for F1 generation: 300 mg/kg NOEL for F2 generation: not applicable

Genetic toxicity Bacterial test: Negative results in S. Typhimurium TA100, TA1535, TA98, TA1537

and E. coli WP2 uvrA with and without metabolic activation (Japanese TG). Chromosomal Aberration in vitro: Marginal positive result in Chinese hamster liver (CHL) cells with metabolic activation (Japanese TG). Micronucleus Test: Negative result (Japanese TG).

Name of substance Diphenyl cresyl phosphate

Abbreviation

CAS No. 26444-49-5

Endpoint Value Reference

LD50 6400mg/kg (rat, oral) SIDS, 1998

NOAEL mg/kg bw No information

Reproductive toxicity Reduced fertility at 300 mg/k g/day, NOEL 60 mg/kg/day SIDS, 1998

Developmental toxicity None (NOEL 300 mg/kg/day) SI DS, 1998

Repeated dose Toxicity, NOEL rat 12 mg/kg/day SIDS, 1998

Genotoxicity Negative SIDS, 1998

Carcinogenicity No information

Critical endpoint Toxicity to liver, kidney and blo od Dose (NOEL) 12 mg/kg/day

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 8.4 mg/day Default assessment factors
Based on NOEL in repeated dose experiments

General population, oral 4.2 mg/day

Workers, inhalation 0.84 mgm -3

General population, inhalation 0.21 mgm -3ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 58 of 108

Environmental effects Triphenyl phosphate

Identity and properties

CAS number 115-86-6 Water solubility 1.9 mg/l at room temperature (Saeg er et al. , 1979) Vapour pressure 2.4x10 -3 Pa at 25°C (estimated from several values at elevated temperatures) Log Kow 4.63 (Saeger et al. , 1979)

Fate data
Biodegradability Readily biodegradable (CERI,2003) Bioconcentration factor 420 (Muir et al ., 1983)

Aquatic effects
Species Effect Value Reference Fish ( Oncorhynchus mykiss ) 96 hr LC 50 0.31 mg/l Sittichaikasen, 1978

Fish ( Oncorhynchus mykiss ) 30d EC 10 (growth in sac fry) 0.037 mg/l Sittichaikasen, 1978

Invertebrates ( Gammarus ) 96 hr EC 50 0.25 mg/l Huckins et al. , 1991 Algae 26 hr IC 50 0.2-0.5 Wong and Chau, 1983 Algae NOEC 0.1 mg/l Wong and Chau, 1983

The PNEC for aquatic organisms based on the above data is 0.74 μg/l, de rived by applying an assessment factor of 50 to the EC 10 value for fish. Although the source data were compiled during preparation of a draft ESR risk asses sment was prepared for triphenyl phosphate and can be considered reliable, there is uncer tainty in the

derived PNEC which is reflected in the use of an assessment factor.

Based on the above data, the substance does not meet the P, B or T c riteria. Triphenyl phosphate is included on Annex 1 of Directive 67/548/EEC, with the classifi cation

R50/53.

Relative emissions: the emissions of HBCDD from industrial use in HIPS are related to the vapour pressure. Triphenyl phosphate has a significantly higher vapour pressure and so emissions from the same processes would be expected to be hig her. Losses of HBCDD from articles during their service life are also rel ated to the vapour pressure; hence emissions from service life would be expected to be higher. T riphenyl phosphate is readily biodegradable, so is expected to be degraded signifi cantly in wwtps and to degrade in the environment.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 59 of 108

Tetraphenyl resorcinol diphosphate

Identity and properties

CAS number 57583-54-7 Water solubility 0.69 mg/l at room temperature (Akz o Nobel, 2003) Vapour pressure 2.7x10 -6 Pa at 25°C (calculated using MPBPWIN v 1.28) Log Kow 7.41 (calculated using KOWWIN v 1.60)

Fate data
Biodegradability Inherently biodegradable (van Gink el and Stroo, 1996)

Bioconcentration factor No reliable measured data

Aquatic effects
Species Effect Value Reference Fish ( Danio rerio ) 96 hr LC 50 No effect at solubility Geurts et al. , 2006

Invertebrate ( Daphnia

magna ) 48 hr LC 50 0.76 mg/l IUCLID, 2001

Invertebrate ( Daphnia

magna ) 21 d NOEC (reproduction/mortality) 0.021 mg/l Wetton and Mullee, 2001

Algae 72 hr Slight effect at solubility Kluskens et al, 2006

The PNEC for aquatic organisms based on the above data would be 0.42 μg/l, derived by applying an assessment factor of 50 to the Daphnia NOEC. Although the source data were compiled during preparation of a draft ESR risk asses sment was prepared for tetraphenyl resorcinol diphosphate and can be considered reliabl e, there is uncertainty in the derived PNEC which is reflected in the use of an assessment fac tor.

Based on the above data, the substance does not meet the T criterion, but may meet the P or vP criteria and the B or vB criteria. Tetraphenyl r esorcinol diphosphate is not

included on Annex 1 of Directive 67/548/EEC.

Relative emissions: the emissions of HBCDD from industrial use in HIPS are related to the vapour pressure. Tetraphenyl resorcinol diphosphate has a simila r vapour pressure and so emissions from the same processes would be expecte d to be similar. Losses of HBCDD from articles during their service life a re also related to the vapour pressure and so emissions from service life would be expected to be similar. Tetraphenyl resorcinol diphosphate is inherently biodegradable, so is e xpected to be degraded to a greater extent than HBCDD in wwtps and in the environment.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 60 of 108

Bisphenol A bis (diphenyl phosphate)

Identity and properties*
CAS number 5945-33-5 (sometimes given as 181028-79- 5) Water solubility Practically insoluble (MSDS - Supr esta, 2006) Vapour pressure 24 Pa at 25°C (MSDS - Supresta, 200 6) Log Kow

- The vapour pressure value seems very high for a sub stance of this structure and molecular weight .

EPIWIN estimates a value of 3x10 -6 Pa, which seems more realistic.

Fate data*
Biodegradability Not readily biodegradable Bioconcentration factor Not expected to bioaccumula te in fish

Aquatic effects*
Species Effect Value Reference Fish ( Oncorhynchus mykiss ) 96 hr LC 50 >1 mg/l MSDS (Supresta, 2006)

Invertebrates ( Daphnia

magna ) 48 hr EC 50 >1 mg/l MSDS (Supresta, 2006)

Invertebrates ( Daphnia

magna ) 21 d NOEC >1 mg/l MSDS (Supresta, 2006)

Algae 72 hr EC 50 >1 mg/l MSDS (Supresta, 2006) * The property, fate and effects data given above are taken from an MSDS for this substance (Supresta, 2006).

No PNEC has been derived for bisphenol A bis (diphenyl phosphate). There is therefore uncertainty over whether it will have effects on aquatic organisms

.

Bisphenol A bis (diphenyl phosphate) is listed in ELINCS (EC number 425-220-8).

There is no information in ESIS for this substance and an IUCLID da ta set is not available. According to ELINCS, this substance is not classified in the Annex I of Directive 67/548/EEC as such, but it may be included in one of the group entries.

Trade names include: ADKSTAB FP-600

CR-741

FYROLFLEX BDP

NCENDX P-30

According to a European Flame Retardants Association fact sheet on bisarylphosphates (no date given) downloaded from the Internet, this subst ance is poorly biodegradable, but not toxic to fish, daphnia and algae. Bisphenol A bis (diphenyl phosphate) is not expected to bioaccumulate in fish.

Relative emissions: the emissions of HBCDD from industrial use in HIPS are related to the vapour pressure. Bisphenol A bis (diphenyl phosphate) has a predicte d vapour pressure lower than HBCDD and so emissions from the same processe s would be expected to be lower. Losses of HBCDD from articles during thei r service life are also related to the vapour pressure; hence emissions from service l ife would be expected to be lower. Bisphenol A bis (diphenyl phosphate) is not readi ly biodegradable, so is not expected to be degraded significantly in wwt ps or to degrade

in the environment.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 61 of 108

Diphenyl cresyl phosphate

Identity and properties

CAS number 26444-49-5 Water solubility 2.6 mg/l at room temperature (Saeg er et al., 1979) Vapour pressure 6.3x10 -5 Pa at 25°C (estimated from several values at elevated temperatures) Log Kow 4.51 (Saeger et al., 1979)

Fate data
Biodegradability Readily biodegradable (IUCLID, 200 0) Bioconcentration factor 200 (Bengtsson et al., 1983 )

Aquatic effects
Species Effect Value Reference Fish ( Oryzias latipes ) 96 hr LC 50 1.3 mg/l UNEP, 2002 Invertebrate ( Daphnia

magna ) 24 hr LC 50 3.7 mg/l UNEP, 2002

Invertebrate ( Daphnia

magna ) 21 d NOEC (reproduction) 0.12 mg/l UNEP, 2002

Algae 72 hr EC 50 0.99 mg/l UNEP, 2002 Algae 72 hr NOEC 0.55 mg/l UNEP, 2002

The PNEC for aquatic organisms based on the above data would be 2.4 μg /l, derived by applying an assessment factor of 50 to the Daphnia NOEC.

Based on the above data, the substance does not meet the P, B or T cr iteria. Cresyl diphenyl phosphate is not included on Annex 1 of Directive 67/548/EEC.

Relative emissions: the emissions of HBCDD from industrial use in HIPS are related to the vapour pressure. Cresyl diphenyl phosphate has a higher vapour pressure and so emissions from the same processes would be expected to be higher. L osses of HBCDD from articles during their service life are also re lated to the vapour pressure and so emissions from service life would be expected to be higher. Cresyl diphenyl phosphate is readily biodegradable, so is expected to be degraded signifi cantly in wwtps and to degrade in the environment.

ALTERNATIVE FIRE RETARDANTS FOR USE IN TEXTILE BACKINGS

3.2.1.3 Textile alternatives Health effects Chlorinated paraffins/ATO The acute oral toxicity of chlorinated paraffins of various chain l engths is low. Toxic effects such as muscular incoordination and piloerection were most e vident following single exposure to short chain length chlorinated paraffins. On the bas is of very limited data, the acute toxicity by the inhalation and dermal rout es also appears to be low. Mild skin and eye irritation has been observed after applicat ion of short and intermediate (skin irritation) chain length chlorinated paraffins. Results of several studies indicate that short chain chlorinated paraffins do not induce skin sensitizati on.

In repeated dose toxicity studies by the oral route, the liver, kidney and thyroid are the primary target organs for the toxicity of the chlorinated para ffins. For the short chain compounds, increases in liver weight have been observed at lowest dos es (lowestobserved-effect level is 50 to 100 mg/kg body weight per day and no-obs erved-effectECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 62 of 108

level is 10 mg/kg body weight per day in rats). At higher doses, increases in the activity of hepatic enzymes, proliferation of smooth endoplasmic ret iculum and peroxisomes, replicative DNA synthesis, hypertrophy, hyperplasia and necrosis of the liver have also been observed. Decreases in body weight gain (125 mg /kg body weight per day in mice), increases in kidney weight (100 mg/kg body w eight per day in rats), replicative DNA synthesis in renal cells (313 mg/kg body weig ht per day) and nephrosis (625 mg/kg body weight per day in rats) have also been observe d. Increases in thyroid weight, and hypertrophy and hyperplasia of the thyroid (LOEL of 100 mg/kg body weight per day in rats) and replicative DNA synthe sis in thyroid follicular cells (LOEL of 313 mg/kg body weight per day) have bee n reported. At higher doses (1000 mg/kg body weight per day), thyroid function is affec ted, as determined by free and total levels of plasma thyroxine and incre ased plasma thyroidstimulating hormone in rats.

For the medium chain compounds, effects observed at lowest doses are gene rally increases in liver and kidney weight (LOEL in rats of 100 mg/kg bod y weight per day; NOAEL in rats of 10 mg/kg body weight per day). Increases in serum cholesterol and "mild, adaptive" histological changes in the thyroid have been reported at similar doses in female rats (NOAEL of 4 mg/kg body weight pe r day).

For the long chain compounds, effects observed at lowest doses are mult ifocal granulomatous hepatitis and increased liver weights in female ra ts (LOAEL of 100 mg/kg body weight per day).

In the only identified reproduction study, no adverse reproductive effe cts were reported following exposure of rats to an intermediate chain length chlorinated paraffin with 52% chlorine. However, survival and body weights of the e xposed pups were reduced (LOEL for non-significant decrease in body weight of 5.7-7.2 mg/kg body weight per day; LOAEL for decreased survival of 60-70 mg/kg body weight per day). In a limited number of studies of the developmental effects of the short, medium and long chain chlorinated paraffins, adverse effects in the offspring were observed for the short chain compounds only, at maternally toxic doses in rats ( 2000 mg/kg body weight per day). For the medium and long chain compounds, no effect s on the offspring were observed even at very high doses (1000 to 5000 mg/kg body w eight per day).

Chlorinated paraffins do not appear to induce mutations in bacteria. Howe ver, in mammalian cells, there is a suggestion of a weak clastogenic pot ential in vitro but not in vivo. Chlorinated paraffins are also reported to induce cell transformation in vitro.

Long term carcinogenicity studies by oral gavage in rats a nd mice have been conducted on a short chain chlorinated paraffin (C12; 58% Cl) and a long cha in chlorinated paraffin (C23; 43% Cl). For the short chain compound in mice, there were increases in the incidence of hepatic tumours in males and f emales and tumours of the thyroid gland in females. In rats exposed to the short chain c ompound, there were increases in hepatic tumours in males and females, renal t umours (adenomas or adenocarcinomas) in males, tumours of the thyroid in females and m ononuclear cell leukaemias in males. For the long chain chlorinated paraffin, the inc idences of malignant lymphomas in male mice and tumours of the adrenal gland in female rats

were increased.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 63 of 108

In spite of the widespread use of chlorinated paraffins, there are no case reports of skin irritation or sensitization. This is supported by results of a limited number of studies in volunteers in which chlorinated paraffins have induced minimal irritancy in the skin, but not sensitization. (EHC).

Name of substance Medium Chain Chlorinated Paraffins

Abbreviation MCCPs

CAS No. 85535-84-9

Endpoint Value Reference

NOAEL mg/kg bw No data

LD 50 No data

Reproductive toxicity
Adverse effects on pup body weight and condition in rats (LOEL)
Foetal toxicity in rabbits NOEL 5 mg/kg/day

100 mg/kg/day Serrone et al., 1987

IRDC, 1983b; 1984

Repeated dose Toxicity, NOAEL
Effects on liver and kidney in rats 10 mg/kg/day Serrone et al., 1987; Birtley et al. 1980

Genotoxicity Negative Serrone et al., 1987; Birtley et al. 1980

Carcinogenicity No information

Critical endpoint Effects on newborn in rats Dose 5 mg/kg/day - LOEL

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 1.4 mg/day Default assessment factors plus x5 for
LOEL rather than NOEL

General population, oral 0.7 mg/day

Workers, inhalation 0.14 mgm -3

General population, inhalation 0.35 mgm -3ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 64 of 108 Name of substance Long Chain Chlorinated Paraffins

Abbreviation LCCPs

CAS No. 85535-86-0

Endpoint Value Reference

LD50 No information

NOAEL mg/kg bw No information

Reproductive toxicity
Foetal toxicity observed at dose causing maternal toxicity LOAEL
in rabbits 100 mg/kg/day IRDC, 1983c; 1981d; 1983d; 1982

Repeated dose Toxicity

Granulomatous inflammation of
the liver in female rats LOEAL

NOAEL in mice 275 mg/kg/day

7500 mg/kg/day NTP, 1986b; Bucher et al ., 1987

Genotoxicity Negative Birtley et al., 1980; NTP, 19 86b; ICI, 1982b; Serrone et al., 1987

Carcinogenicity
LOEL – benign lesions in the spleen - rats Carcinogenic in animals
100 mg/kg/day NTP, 1986b; Bucher et al ., 1987

Critical endpoint Possible carcinogenicity and reproductive effects Dose - 100 mg/kg/day - rats

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 28 mg/day Default assessment factors plus x10 for LOEL rather than NOEL (to take account of severity of endpoint)

General population, oral 14 mg/day

Workers, inhalation 2.8 mgm -3

General population, inhalation 0.7 mgm -3

Ammonium polyphosphates 68333-79-9

The Subcommittee on Flame-Retardant Chemicals, Committee on Toxi cology, Board on Environmental Studies and Toxicology, National Research Council (2000) reviewed the toxicology of ammonium polyphosphates and their findings a re summarised below.

No oral toxicity data for APPs were located for humans. Typical human dietary phosphorous levels are not harmful, especially in the presence of adequa te calcium and vitamin D intake. The mean daily phosphorus dietary intake for a dult males and females is estimated to be 1,500 mg/d and 1,000 mg/d, respectively. Howeve r, if the intake of phosphorus from processed foods was included in these values, the estimated dietary intake of phosphorous would be up to 20% higher.

It is known that high doses of ammonium ions can cause metabolic acidos is; persons with compromised liver function are at highest risk. Exposure to oral doses of 3.2 or 4.8 g ammonium/d as ammonium chloride for 5 d caused metabolic acidosis i n two humans with compromised liver function (Sartorius et al. 1949). Effects secondary to acidosis include renal enlargement and demineralization of bone (ATSDR 1990).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 65 of 108

The oral LD 50 for a commercially available ammonium polyphosphate in rats was estimated to be >5,000 mg/kg (Inveresk 1990b). No deaths or clinical signs of toxicity were observed among five male and five female Sprague-Dawle y rats given a single gavage dose of 5,000 mg/kg in distilled water and observed for 14 d. Weight-gain was normal in females during the second wk of the 2-wk observation period, but weightgain in exposed males was reduced during the second wk. Gross post-mortem analysis

of all dosed animals revealed no abnormalities.

No deaths or toxicity symptoms were observed among five male a nd five female Sprague-Dawley rats treated with a single gavage dose of 2,000 mg/kg in distilled water (Safepharm 1993f). Body weight gain was normal for all anim als during both wk of the observation period and no gross abnormalities were detecte d at necropsy. Therefore, it was concluded that the LD 50 for in rats is >2,000 mg/kg.

JECFA (1974) summarized a number of toxicity studies on phosphates and polyphosphate. The primary effect identified in these studies is kidney calcification (nephrocalcinosis), resulting from the precipitation of calcium phosphat e due to an upset in phosphate homeostasis. JECFA (1974) noted that it is difficult t o identify an effect level for nephrocalcinosis in toxicity studies because r enal calcification occurs naturally to some extent in control rats which is determined b y dietary intake of

calcium and vitamin D.

Studies by van Esch et al. (1957, as cited in JECFA 1974) and Hodge (1964a , 1964b) suggest that chronic exposure of rats to 0.5% (sodium) polyphosphates in the diet may cause increased kidney weight but no kidney histopathology, while higher concentrations may cause kidney calcification when mineral levels are not equalized. Based on standard food intakes, 0.5% in the diet corresponds to a dose of about 200 mg/kg.

Reproductive and Developmental toxicity No information was found regarding the reproductive or developmental effe cts of APPs following oral exposure. Information on reproductive and developmental effect s of ammonium ions was also not located.

A study conducted by van Esch et al. (1957, as cited in JECFA 1974) found dec reased fertility in rats that were treated with a mixture of one-t hird Kurrol’s salt and twothirds diphosphate at a dietary concentration of 5%. No reproductive effec ts were reported at lower concentrations.

Lang (1959, as cited in JECFA 1974), found no effects on reproduction in thre e generations of rats, each fed diets containing 0.4% or 0.75% phosphoric acid for 90

wk.

No effects on fertility, litter size, neonate growth, or neonate sur vival was observed in a three-generation reproduction study in groups of rats administered 0.5% sodium tripolyphosphate or 0.5% sodium hexametaphosphate (Hodge 1964a, 1964b, and BIBRA 1964). There was also no apparent effect on the histopathology of major organs of the third generation.

GenotoxicityECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 66 of 108

LR2 was not found to be mutagenic in 5 strains of Salmonella typhimurium (TA1535, TA1537, TA1538, TA98, TA100) exposed at concentrations of 25, 75, 250, 750, 2,500, or 5,000 μg LR2/plate in the presence or absence of exogenous metaboli c activation (rat liver S9) (Safepharm 1995). No other genotoxicity data were located for APPs or for other polyphosphates.

Carcinogencity No data are available on the carcinogenic effects of APPs by any route of exposure. Because of the absence of carcinogenicity data, the subcommittee concluded that the carcinogenic potential of APPs cannot be determined. Carcinogenicity data on ammonium ion or polyphosphates were not located. However, based on the physiological roles of these compounds they would not be expected to be carcinogenic.

Name of substance Ammonium Polyphosphate

Abbreviation

CAS No. 68333-79-9

Endpoint Value Reference

LD 50 >5000 mg/kg Subcommittee on flame retarded
chemicals

NOAEL mg/kg bw 2000 mg/kg Subcommittee on flame re tarded
chemicals

Reproductive toxicity No information

Repeated dose Toxicity, NOAEL

rat 200 mg/kg/day Subcommittee on flame retarded
chemicals

Genotoxicity Limited data suggest not genotoxic

Carcinogenicity No information

Critical endpoint Possible kidney toxicity

Preliminary DNEL DNEL for critical endpoint Remarks

Workers, oral 56 mg/kg

General population, oral 28 mg/kg

Workers, inhalation 5.6 mgm -3

General population, inhalation 1.4 mgm -3 Default assessment factors plus additional uncertainty factor of x5 to allow for use of
test data for sodium rather than aluminium polyphosphate
Based on NOEL in repeated dose experiments with sodium polyphosphateECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 67 of 108

Environmental effects

Chlorinated Paraffins

Medium chain chlorinated paraffins (MCCPs)

Identity and properties

CAS number 85535-85-9 (C 14-17 ) Water solubility 0.027 mg/l for 51% wt. Cl (measure d)* (EC, 2005) Vapour pressure 2.7×10 -4 Pa at 20°C for 45 and 52% wt. Cl* (EC, 2005) Log Kow 5.52 - 8.21 for 45% wt. Cl

5.47 - 8.01 for 52% wt. Cl 7 (middle point of range of measured values)* (EC, 2005)

Fate data
Biodegradability Not readily biodegradable (EC, 200 5).

Bioconcentration factor BCF 1,087 l/kg* (EC, 2005).

* Values used in the risk assessment as representative values for a commerc ial product (EC, 2005).

Aquatic effects
Species Effect Value Reference Fish ( Oncorhynchus mykiss ) 60 d NOEC No adverse effects at 4.5 mg/l over 60 days for C 14-17 52% wt. Cl mixed with n-pentadecane-8- 14 C 51% wt. Cl. EC, 2005

Fish ( Oryzias latipes) 20 day embryolarval study No adverse effects on embryos or

larvae up to 1.6 and 3.4 mg/l over 20 days (two substances tested:

C 14 H 23.3 Cl 6.7 55% wt. Cl and

C 14 H 24.9 Cl 5.1 48% wt. Cl). EC, 2005

Invertebrates ( Daphnia

magna ) 21 d NOEC (reproduction) 10 μg/l for C 14-17 52% wt. Cl mixed

with n-pentadecane-8- 14 C 51% wt. Cl. EC, 2005

Crustacean ( Gammarus pulex ) 96 hr LC 50 >1.0 mg/l for C 14-17 52% wt. Cl. EC, 2005

Harpacticoid ( Nitocra spinipes ) 96 hr LC 50 9.0 mg/l for C 14-17 45% wt. Cl >10,000 mg/l for C 14-17 52% wt. Cl. EC, 2005

Mussel ( Mytilus edulis ) 60 d NOEC 0.22 mg/l or C 14-17 52% wt. Cl mixed with n-pentadecane-8- 14 C 51% wt. Cl. EC, 2005

Algae ( Selenastrum capricornutum ) 96 hr NOEC (biomass)

72 hr NOEC (growth rate) 0.1 mg/l for C 14-17 52% wt. Cl mixed

with n-pentadecane-8- 14 C 51% wt. Cl (96 hr E b C 50 >3.2 mg/l) 0.049 mg/l for C 14-17 52% wt. Cl mixed with n-pentadecane-8- 14 C 51% wt. Cl. (72 hr E

r C 50 >3.2 mg/l). EC, 2005

Long-term no observed effect concentrations (NOECs) have been report ed for fish, Daphnia , mussels and algae. Effects have almost exclusively been observed on Daphnia (EC, 2005).

A PNEC of 1 μg/l has been derived for aquatic organisms by appl ying an assessment factor of 10 to the long-term NOEC of 10 μg/l obtained from the 21-day reproductive study with Daphnia magna on the basis that it is the most sensitive substance (EC, 2005).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 68 of 108

Given that the ESR process involved a rigorous data searching and re view process, with the possibility of the generation of new data through tests , the values reported in the RAR for MCCP can be considered to have little uncertainty.

MCCPs are currently classified with respect to their effe cts on human health and the environment as follows (as of September 2008):

• R64 (may cause harm to breastfed babies)

• R66 (repeated exposure may cause skin dryness or cracking)

• N; R50-53 (dangerous for the environment; very toxic to aquatic organisms

– may cause long-term adverse effects in the aquatic environment)

No PBT assessment is included in the published version of the risk as sessment (EC, 2005).

Relative emissions: the emission estimates for HBCDD from us e in textiles are based largely on specific measurements. Therefore it is not appropria te to make an estimate of the relative emissions based on a comparison of the physico-chemical properti es.

MCCPs are not readily biodegradable, so are not expected to be degrad ed significantly in wwtps or to degrade in the environment.

Long chain chlorinated paraffins (LCCPs)

Identity and properties

CAS number 85422-92-0 (C ≥ 18 ) and 63449-39-8 (C 18-32 ) Water solubility 5  g/l at 20°C for all LCCPS (EA, 2008) Vapour pressure 2.5×10 -4 Pa at 25°C for C 18-20 liquids (typically 40-52% wt. Cl)

2.5×10 -5 Pa at 25°C for C >20 liquids (typically 40-54% wt. Cl)

1.5×10 -14 Pa at 25°C for C >20 solids (typically 70% wt. Cl) (EA, 2008)* Log Kow 9.7 for C 18-20 liquids (typically 40-52% wt. Cl)

10.3 for C >20 liquids (typically 40-54% wt. Cl)

17 for C >20 solids (typically 70% wt. Cl) (EA, 2008)*

* Vapour pressure and log kow values given above have been selected for use in the risk assessment for the three groups of long chain chlorinated paraffins cons idered (EA, 2008).

Fate data
Biodegradability Unlikely to be readily or inherent ly biodegradable (EA, 2008) Bioconcentration factor BCF 1,096 l/kg for C 18-20 liquids BCF 192 l/kg for C >20 liquids BCF < 1 l/kg for C >20 solids (estimated values) (EA, 2008)ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 69 of 108

Aquatic effects
Species Effect Value Reference Fish ( Alburnus alburnus ) 14 d NOEC ≥ 125 μg/l for C 18-26 49% wt. Cl (no effects were seen at solubility). EA, 2008

Fish ( Oncorhynchus mykiss ) 60 d NOEC ≥ 4 mg/l for C 22-26 43% wt. Cl

≥ 3.8 mg/l for C >20 70% wt. Cl (no effects were seen at solubility). EA, 2008

Invertebrates ( Daphnia

magna ) 21 d NOEC 29 μg/l for C 18-20 liquid 52% wt. Cl EA, 2008

Invertebrates ( Daphnia

magna ) 21 d NOEC (reproduction) ≥ 55 μg/l for C >20 liquid 43% wt. Cl (no

effects were seen on reproduction). EA, 2008

Based on the above data, the following PNECs have been derived for aqua tic organisms using the long term NOECs from studies with Daphnia magna , and an

assessment factor of 10:

C 18-20 liquid PNEC water = 2.9 μg/l

C >20 liquid PNEC water, screening = 5.5 μg/l

C >20 solids PNEC water, screening = 5.5 μg/l

LCCPs are considered to potentially meet the persistent or very persistent criterion. They do not meet the toxic or bioaccumulative criterion. LCCPs are not listed in Annex 1 of Directive 67/548/EEC (EA, 2008). Given that the EA review invol ved a rigorous data searching and review process as undertaken for MCCP s, the values reported by the EA for LCCPs can be considered to have little uncertainty.

Relative emissions: the emission estimates for HBCDD from us e in textiles are based largely on specific measurements. Therefore it is not appropria te to make an estimate of the relative emissions based on a comparison of the physico-chemical properti es.

LCCPs are currently used in flame retardant textile coatings (EA, 2008).

Ammonium polyphosphates

Identity and properties

CAS number 68333-79-9 Water solubility 100% at 25°C (OECD, 2007) Vapour pressure Negligible* (OECD, 2007) Log Kow Not applicable to inorganic salts (OECD, 20 07) *Ammonium polyphosphate is an inorganic salt and w ill have negligible vapour pressure. Any measurable vapour pressure is due to the decomposit ion and release of ammonia gas.

Fate data
Biodegradability Standard biodegradation tests are not applicable to inorganic salts. The ammonium present in APP may be nitrified (OECD, 2007). Bioconcentration factor APP is not expected to bioa ccumulate as it has high aqueous solubility and will exist in a dissociated form in solution (OECD, 2007).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 70 of 108

Aquatic effects
Species Effect Value Reference Fish ( Oncorhynchus mykiss ) 96 hr LC 50 >101 mg/l OECD, 2007

Based on the above data, it is not possible to calculate a PNEC f or the aquatic compartment. Given that these data come from an OECD SIAR, th at has been reviewed internationally, it is assumed that there are no more data readily available. In the absence of a PNEC, there is uncertainty over what level should be used to assess

exposures.

According to the ESIS website, this substance is not classified in the Annex I of Directive 67/548/EEC as such, but it may be included in one of the group entries.

Based on the above data, ammonium polyphosphate does not meet the P, B or T criteria, so is not a PBT substance.

Reactive phosphorous constituents

We have been unable to determine exactly what these substances ar e and there is no readily available information on their toxicity or environmental ef fects. It appears to have been assumed by KEMI (2006) and others that these compounds will have less impact on human health and/or the environment than brominated compounds, but there appear to be few data to support this assertion.

ALTERNATIVES TO EPS AND XPS INSULATION

3.2.1.4 Phenolic Foam Health effects The health issues associated with the use of phenolic foam are ex pected to be minimal. Toxic gas emission from phenolic foam is generally li mited to carbon dioxide and carbon monoxide with very low levels of other gases. Phe nolic foams can achieve very low toxic gas ratings in tests such as UK Nav al Engineering Standard NES 713 and Scandinavian NordTest NT036. Phenolic foam has good fire resist ance. There is a limited potential for dust inhalation during the installa tion of phenolic foam or during the removal of phenolic foam during building renovation or demolition.

Phenolic foams are made by a reaction of phenol and formaldehyde in t he presence of a catalyst. There are potential health issues for workers involved in the manufa cture of phenolic foam who may be exposed to these chemicals. Formaldehyde is irritating to mucous membranes at low levels of exposure and has been identified as a human carcinogen by IARC (2006). Phenol causes kidney and developmental toxic ity in animals. IPCS (1994) identified NOAELS in rat studies in the ra nge of 12-40 mg/kg body weight per day and recommended that the upper limit of total hum an daily intake should be in the range of 60-200 μg/kg body weight per day, equivale nt to workplace exposure concentrations of 0.4-1.4 mgm -3 for an 8 hour shift. The UK Workplace exposure limits for formaldehyde and phenol are respect ively as 8 hour time weighted averages. Formaldehyde is labelled as R23/24/25, 34, 40, 43 (Toxic by inhalation, in contact with the skin and if swallowed, limited evidence of a carcinogenic effect, may cause sensitisation by skin contact) a nd phenol is labelled as R23/24/25, 34, 48/20/21/22, 50/53 (Toxic by inhalation, in contact with the skin and if swallowed, danger of serious damage to health by prolonged exposur e byECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 71 of 108

inhalation, in contact with the skin or if swallowed, very toxic to aqua tic organisms, may cause long-term serious effects in the aquatic environment).

Environmental effects Formaldehyde

Identity and properties

CAS number 50-00-0 Water solubility 95% (w/w) at 120°C (theoretical so lubility)* (UNEP, 2002) Vapour pressure 5,185 hPa at 25°C (measured) (OECD, 2002) Log Kow 0.35 (measured) (UNEP, 2002) *At room temperature, pure aqueous solutions contai n formaldehyde as methylene glycol and its oligomers. Aqueous solutions containing more than 3 0% (w/w) formaldehyde become cloudy at room temperature due to formation of larger poly(oxymeth ylene)glycols.

Fate data
Biodegradability Readily biodegradable (UNEP, 2002) Bioconcentration factor Unlikely to occur (UNEP, 20 02)

Aquatic effects

Species Effect Value Reference Fish ( Ictalorus melas ) (freshwater) 96 hr LC 50 24.8 mg/l UNEP, 2002 Fish ( Morone saxatilis ) (marine) 96 hr LC 50 6.7 mg/l UNEP, 2002 Invertebrates ( Daphnia pulex ) 48 hr EC 50 5.8 mg/l UNEP, 2002 Invertebrates ( Daphnia pulex ) 48 hr EC 50 29 mg/l UNEP, 2002 Algae ( Scenedesmus subspicatus ) 24 hr EC 50 24 hr EC 10 (endpoint: oxygen production and consumption) 14.7 mg/l 3.6 mg/l UNEP, 2002

The PNEC for aquatic organisms based on the above data would be 5.8 μg /l, derived by applying an assessment factor of 1,000 to the lowest valid effec t value (48 hr EC 50 of 5.8 mg/l) for Daphnia pulex.

Based on the above data, formaldehyde does not meet the P, B or T criteria, so is not a PBT substance.

Classification according to Annex 1 (ESIS website) for formaldehyde: Carc. Cat 3; R40 T; R23/24/25 C; R34, R43

Formaldehyde is mainly used as an intermediate in the chemical industry for the production of condensed resins for the wood, paper and textile processi ng industries. Urea-formaldehyde foam insulation and formaldehyde disinfectants are important sources of formaldehyde exposure (OECD, 2002).

As this substance is used in a completely different way to HBC DD, an estimation of relative emissions is not appropriate.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 72 of 108

Phenol

Identity and properties

CAS number 108-95-2 Water solubility 84 g/l at 20°C (EC, 2006) Vapour pressure 0.2 hPa at 20°C (measured) (EC, 200 6) Log Kow 1.47 (measured) (EC, 2006)

Fate data
Biodegradability Readily biodegradable (EC, 2006) Bioconcentration factor 17.5 l/kg (EC, 2006)

Aquatic effects

Species Effect Value Reference Fish ( Oncorhynchus mykiss ) 96 hr LC 50 5.02 mg/l EC, 2006 Fish ( Cirrhina mrigala ) MATC (related to survival and growth of larvae) 60 d NOEC (derived from MATC) 77-94 μg/l

77 μg/l EC, 2006

Invertebrate ( Cerodaphnia

dubia ) 48 hr LC 50 3.1 mg/l EC, 2006

Invertebrate ( Daphnia magna ) 16 d EC 10 (growth reduction) 0.46 mg/l EC, 2006 Algae ( Selenastrum capricornutum 96 hr E

r C 50 (growth inhibition) 61.1 mg/l EC, 2006

The PNEC for aquatic organisms based on the above data would be 7.7 μg /l, derived by applying an assessment factor of 10 to the lowest NOEC (77 μg /l) for Cirrhina mrigala. [The NOEC is derived from a MATC of 77-94 μ g/l with the assumption that the MATC is given as the range between the NOEC and the LOEC].

Annex I of Directive 67/548/EEC does not currently contain any environment ally relevant classifications for phenol. Classification according to Annex I (E C, 2006): T; R 23/24/25 C; R 34

R 48/20/21/22 Muta. Cat. 3, R 68

Based on the above data, phenol does not meet the P, B or T criter ia so is not a PBT

substance.

Phenol is mainly used as an intermediate in organic synthesis for t he production of bisphenol A, phenol resins, alkylphenols, caprolactam, salicylic acid, nit rophenols, diphenyl ethers, halogen phenols and other chemicals.

As this substance is used in a completely different way to HBC DD, an estimation of relative emissions is not appropriate.

3.2.1.5 Polyurethane and Polyisocyanurate Products Health effects These products do not give off volatile substances which in use and would not be expected to give rise to toxic exposures during use. There is a limited potential for dust inhalation during the installation or these products or during their during building renovation or demolition. These foams may be treated with brominated fi re retardants to achieve required levels of fire resistance.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 73 of 108

When subjected to burning, polyurethane foam systems will yield toxi c fumes consisting of various gases, which may include, but not limited to, c arbon monoxide, carbon dioxide and oxides of nitrogen, which may also present a risk to respiratory tract and eyes.

The manufacture of polyurethane and polyisocyanurate products involves the use of isocyanates which are potent respiratory sensitisers. There ar e potential health issues for workers involved in the manufacture of polyurethane foam who may be ex posed to these chemicals. The UK workplace exposure limits for isocyana tes calculated in terms of the mass of NCO groups present are 0.02 and 0.07 mgm -3 for an 8 hour shift or 15 short term exposure respectively.

Environmental effects Tris(2-chloro-1-methylethyl) phosphate (TCPP) This substance is used as a flame retardant additive for polyure thane. The main use of the treated polyurethane is in rigid foams for construction applicat ions such as blocks and panels for insulation (EC, 2008c).

Identity and properties

CAS number 13674-84-5 Water solubility 1,080 mg/l at 20°C (measured) (EC, 2008b) Vapour pressure 1.4×10 -3 Pa at 25°C (measured) (EC, 2008b) Log Kow 2.68 (measured) (EC, 2008b)

Fate data
Biodegradability Inherently biodegradable, not fulf illing the criteria (EC, 2008b). Bioconcentration factor 0.8-4.6 l/kg (2.7 l/kg, ari thmetic mean) (EC, 2008b).

Aquatic effects
Species Effect Value Reference Fish ( Pimephales promelas ) 96 hr LC 50 51 mg/l EC, 2008b Invertebrate ( Daphnia magna ) 48 hr EC 50 131 mg/l EC, 2008b Invertebrate ( Daphnia magna ) 21 d NOEC (reproduction) 32 mg/l EC, 2008b Algae ( Pseudokirchneriella subcapitata ) 72 hr E

r C 50 (growth rate)

72 hr EbC 50 (biomass) 82 mg/l 33 mg/l EC, 2008b

Algae ( Pseudokirchneriella subcapitata ) 72 hr E

r C 10 (growth rate)

72 hr E b C 10 (biomass)

72 hr NOEC 42 mg/l 14 mg/l 13 mg/l EC, 2008b

The PNEC for aquatic organisms based on the above data would be 0.64 mg/l, derived by applying an assessment factor of 50 to the long-term NOEC f or Daphnia magna. Given that the ESR process involved a rigorous data searching and re view process, with the possibility of the generation of new data through tests , the values reported in the RAR for this substance can be considered to have little uncertainty.

Tris(2-chloro-1-methylethyl) phosphate is not currently included on Annex I of Directive 67/548/EEC. Based on the above data, tris(2-chloro-1-methyle thyl) phosphate is not a PBT substance.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 74 of 108

This substance is used in a different material to HBCDD, and the processes involved may be different, hence it is not possible to make an estimate of the relative level of emissions through comparison of the substance properties with HBCDD.

3.2.1.6 Mineral wools and other mineral products Health effects These systems employ inert materials such as fibre glass, glass wool, rock wool and gypsum that do not represent a hazard to building occupants when used as insul ation. Although formaldehyde and phenolic resins may be used to bind these product s, emissions to indoor air are extremely low and do not impact on indoor air quality. These materials are innately fire and heat resistant. Ther e is potential for dust inhalation during the installation of these products or during building ren ovation or demolition. In the UK, the workplace exposure limit for all machine-m ade mineral fibres is 5 mgm -3 as inhalable dust or 2 fibres/ml, which ever is reached firs t. These materials are not classified as carcinogenic. Gypsum is a low toxicity dust and the UK workplace exposure limits would be 4 and 10 mgm -3 for the respirable and inhalable fractions respectively.

Environmental effects

The industry (EUROSIL: http://www.eurisol.com/pages/waste_sustainability.htm claim that for each tonne of CO2 generated in the manufacturing process of mineral wool, about 200 tonnes of CO2 are saved by its thermal insulation properti es over a 50-year period and that producing mineral wool requires only half the e nergy needed to manufacture other types of insulation. EUROSIL also claim tha t there has been a steady decrease in energy inputs and emissions during production over t ime. In addition, the industry claim to be using increasing amounts of recycle d materials in manufacture. Depending on the quality and availability of local suppl ies recycled glass now makes up 30% to 60% of the raw material input. In some pla nts this is as high as 80%.

Following end of life removal from buildings, there is an increasing trend to recycle these materials, otherwise they may be disposed of as inert cons truction waste and are unlikely to have a major adverse impact on the environment.

3.2.1.7 Cellulose fibre

Insulation products based on cellulose recovered from the recycling of paper and similar materials have been promoted as a green alternati ve to traditional insulation systems. Cellulose fibres are believed to represent a relat ively low health hazard for humans and the UK workplace exposure limits for respirable and inhala ble dust are 4 and 10 mgm -3 respectively as an 8 hour time weighted average. There is al so a 15 minute exposure limit for inhalable dust of 10 mgm -3

.

In order to meet fire safety standards and also in order to preve nt rodent or other pest damage, cellulose fibre insulation must be treated with fire ret ardant and persistent pesticides to be effective in use. Potentially, the presence of t hese added chemicals would lead to human health hazards and potential environmental effects that were at least as serious as those associated with EPS or XPS. Some (pe rhaps all) cellulose insulation products marketed in the EU contain inorganic boron salts that ha ve beenECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 75 of 108

added in sufficient quantity to meet fire safety regulations a nd to provide adequate pest protection. The IPCS (1998) report that animal experiments have shown that boron in the form of inorganic salts (borates) gives rise to re productive and developmental toxicity in animals and calculated that the tolerable intake (TI) of boron for humans as 0.4 mg/kg body weight per day, equivalent to 28 mg/day for a 70 kg adult. The American Conference of Industrial Hygienists (ACGIH ) recommend Threshold Limit Values for inorganic borates of 2 mgm -3 and 6 mgm -3 as an 8 hour time weighted average and 15 minute maximum exposure concentrations respecti vely. The 8 hour limit would give a daily intake equivalent to 20 mg. The U S EPA oral reference dose (ie dose at which repeated exposure would be expected to cause no significant hazard to health) for boron is 0.2 mg/kg/day (equivalent to an adult intake of 14 mg/day) to protect against reproductive and developmental effec ts (http://www.epa.gov/NCEA/iris/subst/0410.htm). The US ATSDR indicate that the

short and intermediate term Minimal Risk Levels for oral intake are 0.2 mg/kg/day and also give a draft inhalation minimal risk level for acute res piratory effects of 0.01

mgm -3 (for community rather than workplace exposure; http://www.atsdr.cdc.gov/mrls/index.html).

The IPCS (1998) indicate that boron has a low aquatic toxicity.

3.2.1.8 Intumescent systems

We have been unable to find relevant health or environmental information.

ALTERNATIVES TO HIPS

3.2.1.9 Polyethylene with Magnesium Hydroxide Health effects The available data is not sufficient to conduct a health screening of magnesium hydroxide, but indicate that the substance can be regarded as relat ively harmless in small quantities as the substance is used as food additive.

Repeated or prolonged human exposure to larger quantities of the substanc e may imply adverse impact on human health, such as general irritation and malaise. There may be lung effects at high particulate concentrations and centr al nervous system depression at very high doses.

The ISCS on polyethylene indicates low toxicity.

Environmental effects

Polyethylene is a persistent waste material, although an incre asing quantity is being recycled. Ingestion of polyethylene particles by animals is a growing problem, particularly in marine ecosystems. Organisms may ingest plas tics in preference to food. The release of small quantities of magnesium hydroxide to the environment would not be expected to cause toxicity. The disposal of large quantities in a rest ricted area of water or disposal onto soil could have a substantial impact on alkalinity levels with consequent impacts on flora and fauna.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 76 of 108

3.2.2 Technical and economical feasibility and availability ALTERNATIVE FIRE RETARDANTS FOR USE IN HIPS, EPS AND XPS

3.2.2.1 Halogenated flame retardants in conjunction with Antimony Trioxide

Technical feasibility Diantimony trioxide is an effective flame retardant synergis t used in conjunction with a source of halogen such as halogenated flame-retardants or PVC. I t is used in plastics, rubber and textiles (EC, 2008). Diantimony trioxide has a w ide range of applications and is used in polymers such as polypropylene, polyethyle ne, EDPM, ABS, HIPS (electrical components, appliance housings etc), flexibl e polyurethane, TPU, unsaturated polyesters, epoxies, phenolics and engineering therm oplastics such as PBT (Great Lakes, http://www.e1.greatlakes.com/corp/common/jsp/index.jsp ).

Decabromodiphenylethane is a general purpose additive flame retar dant for a variety of polymer applications and textiles. It is used in ABS, HIPS, poly propylene and polyethylene, polycarbonate, polybutylene terephthalate and polyethylen e terephthalate, PVC, thermoplastic elastomers, epoxy resins and unsa turated polyesters. Applications include building insulation and roofing materials , wire and cable insulation, coatings, and electrical and electronic applicati ons (particularly those made from HIPS such as TV housings) (EA, 2007). Ehylene bis(tetrabromophthalimide) is used as a flame retardant in a range of applications including HIPS, ABS, thermoplastic polyester, polycarbonate, polypropy lene and polyethylene, polyolefin, PVC and elastomers (Albemarle, http://www.albemarle.com/ ).

HBCDD provides effective flame retardant properties at low loa dings in HIPS, EPS and XPS that do not adversely impact the mechanical properties of these materials. Other fire retardants are only effective at much higher loadings which adversely affect the mechanical properties of HIPS, EPS and XPS. The higher loadi ngs would also lead to greatly increased manufacturing costs (KEMI, 2006).

The EPS sector group of Plastics Europe which represents 90% of t he EPS producers in Europe has been involved in a five year investigation to identify alt ernatives to HBCDD in EPS. They concluded that there are currently no candidate m olecules, either commercially available or “novel” compounds which are seen a s feasible alternatives to HBCDD in EPS. A similar research project under taken for XPS foams has drawn the same conclusions (Briefing note provided to IOM by the HBCD Industry User Group, October, 2008).

In a review of the use of various hazardous substances in consumer pr oducts the Norwegian Pollution Control Authority concluded that although no other flam e retardant that can fully replace HBCDD in all areas, but ther e are other different

brominated and non-brominated flame retardants that can be used in electrical/electronic products (SFT, 2007).ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 77 of 108

Economic feasibility

The Danish EPA (2007) provide indicative prices for HIPS containing de ca-BDE and alternative flame retardants (i.e. compounded), as shown in the table below.

Polymer/compound European price range ( € /kg)

Standard HIPS 0.95-1.25

HIPS + deca-BDE 1.50-1.80

HIPS + other BFR

- UL 94 V-0

- UL 94 V-1 1.90-2.10

1.70-1.90 HIPS/PPE + halogen-free FR 2.30-2.90

In addition, RPA (2002) cite information from IVL ( 1997) on prices of various types of flame retardants, as shown below.

Based on these sources of information, the following broad conclusions can be drawn:

Raw material costs for deca-BDE appear to be less than for othe r brominated flame retardants. Therefore, it is likely that the purchase price of this potential alternative

would be less than that for HBCDD.

There is insufficient available information to make distinctions bet ween HBCDD and other brominated flame retardant costs. They may be expected to be broadly sim ilar.

Chlorinated alternatives and particularly chlorinated paraffins ar e expected to be less expensive than HBCDD.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 78 of 108

For use of any alternative flame retardant, there would be addi tional one-off costs of substitution associated with, for example, product testing and changes to processing equipment which cannot readily be quantified.

3.2.2.2 Organic Aryl Phosphorous Compounds

These compounds are not generally regarded as technically or ec onomically viable alternatives to HBCDD in HIPS, EPS or XPS for the reasons des cribed above for antimony trioxide based systems. They may be technically viable alternatives to HBCDD for some specific product types.

Technical feasibility

HBCDD is used in four principal product types; EPS (insulation), XP S (insulation), HIPS (electrical and electronic parts) and polymer dispersion for textiles. Producers’ websites have been checked to see if they recommend HBCDD is used in four principal product types; EPS (insulation), XPS (insulation), HIPS (el ectrical and electronic parts) and polymer dispersion for textiles. Producers’ websites have been checked to see if they recommend triphenyl phosphate, tetraphenyl re sorcinol disphosphate, cresyl diphenyl phosphate or bisphenol A bis (diphenyl phosphate) for use in the same areas as HBCDD. According to the producers’ webs ites, triphenyl phosphate is recommended for use in HIPS, consumer electronics, applian ce housings and TV housings. Tetraphenyl resorcinol disphosphate is recommended for use in consumer electronics, appliance housings, TV housings, construction, insulat ion and mattresses. It is also used in engineered resins such as m odified PPO, polycarbonate/styrenic blends, polyesters and HIPS. HBCDD is used i n four principal product types; EPS (insulation), XPS (insulation), HIPS (electric al and electronic parts) and polymer dispersion for textiles. Cresyl diphenyl phosphate is recommended for use in construction, insulation, furniture, mattresses, textiles, a nd wall and floor coverings. Bisphenol A bis (diphenyl phosphate) is recommended for use in the electrical and electronics industry, enclosures made out of ABS/P C blends, thermosplastics including ABS and HIPS, and engineered resin applic ations such as polyphenylene oxide alloys and PC/ABS.

Economic feasibility

Based on information from RPA (2002), organophosphorus compounds could be expected to be broadly similar in price to that of HBCDD per unit mass of flame

retardant.

However, the Bromine Science and Environment Forum (quoted in Kemi, 2006) indicate that greater quantities of non halogen flame retardants a re required to achieve the same overall level of fire protection. This would tend to suggest that the overall raw material cost would be higher than for HBCDD. This is supporte d by data from the Danish EPA (2007) (above) which suggests significantly higher compound costs for HIPS/PPE with halogen-free flame retardant ( € 2.3- € 2.9 per kg compound compared to € 1.7- € 2.1 kg for a brominated flame retardant). Whilst the price per unit of compound is relatively moderate, this implies a potentially signi ficant increase inECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 79 of 108

cost of flame retardant 3 . The Danish EPA (2007) estimated that the cost of producing HIPS with a halogen-free flame-retardant rather than a brominat ed flame-retardant (other than Deca-BDE) would increase the raw material price w ith about 4-5 EUR for a full enclosure of an average TV-set.

Again, there would be additional one-off costs of substitution associated with, for example, product testing and changes to processing equipment which can not readily be quantified.

ALTERNATIVE FIRE RETARDANTS FOR USE IN TEXTILE BACKINGS

3.2.2.3 Textile Alternatives

Technical feasibility

KEMI (2006) indicate that reactive phosphorus constituents, ammonium polyphosphate, diammonium phosphate and intumescent systems are commercia lly available alternatives to HBCDD but do not provide information about per formance

or cost.

Ammonium polyphosphate is primarily used as a fertiliser (OECD, 2007) . An Internet

search revealed that this substance is used as a flame re tardant in textiles for fabric back coating and in the production of flame retardant furnishing and ma ttress ticking. Ammonium polyphosphate is also used as the catalyst component in intumes cent formulation. Aqueous solutions of ammonium polyphosphate can be used in the fla me retardant treatment of cellulosic materials ( http://www.albemarle.com/ ).

The use of fire retardant systems involving antimony trioxide i s restricted by the white pigmenting behaviour of ATO which means that it is unsuitable for applications where a transparent backing is required.

Although median-chain chlorinated parafins have been identified as a pote ntial alternative to HBCDD for textile coating, the EC (2005) reported that there was no use of medium-chain chlorinated paraffins in textiles in the EU at that time; however the report did identify that some of the medium-chain chlorinated par affins supplied to the PVC industry was used for coating applications, including text iles. Long-chain chlorinated paraffins are used for backcoating textiles. A limit ation on the use of MCCPs in this area may be that the maximum chlorine content achi evable is lower

than for SCCPs and LCCPs.

In their review of the use of various hazardous substances in consumer products the Norwegian Pollution Control Authority concluded that there are other di fferent brominated and non-brominated flame retardants that can be used in place of HBCDD for textile coatings (SFT, 2007).

Economic feasibility

3 For example, even taking a conservative assumptio n that 1kg of compound contains 7% HBCDD and assuming a price increase per kg of compo und from € 2.1 to € 2.3 per kg, this would imply a price increase of around € 3 per kg of flame retardant, assuming use in equiva lent quantities.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 80 of 108

As indicated above, the costs of deca-BDE are expected to be comparable or slig htly lower than that for HBCDD and the cost of chlorinated paraffins is expected to be

lower than that for HBCDD.

Again, there would be additional one-off costs of substitution associated with, for example, product testing and changes to processing equipment which cannot readily be quantified.

ALTERNATIVES TO EPS AND XPS INSULATION

3.2.2.4 Overview

A wide range of insulation products are available. KEMI (2007) reporte d that there are different views have been given on the economic impact of int roducing a

restriction on the use of HBCDD in EPS and XPS. Producers of EPS/X PS, building industry and authorities in 33(40) countries with little use, e g Swe den and Denmark indicate little or no consequences, whereas in countries with a lar ge use, e g Poland and Germany, respondents indicate potentially severe consequences, i n particular on small and medium sized enterprises (SMEs).

3.2.2.5 Phenolic Foam

Phenolic foam insulation is commercially available in the EU but does not appear to have a significant share of the insulation market. The European EPS t rade association (EUMEPS) claim to have a 35% share of the total construction ins ulation market in Europe ( http://www.propubs.com/GI/Articles/eGI_Sep07_EPS.pdf ) and it seems likely that the XPS market share will be of similar size. In addition, the Global Insulation trade association only consider EPS, XPS and mineral woo l in their recent(2008) review of market trends, which suggests that the marke t share for phenolic foam is low (http://www.propubs.com/GI/Articles/eGI_May08_ExaneBNPParibas.pdf). T he European Phenolic Foam Association (EPFA; http://www.epfa.org.uk/Pdfs/eng.pdf ) claim that phenolic foam has exceptional fire performance with ve ry low flame spread, negligible smoke emission and a very low level of toxic ga s emissions and that it meets the fire certification requires of UK Class 0, Dutch NEN 6065/6055 Class 1, German B1, Belgian A1, French M1 and Scandinavian NT 036 Class 1. It has an excellent strength/density ratio and offers a range of t hermal conductivity performance and is up to 50% more thermally efficient than competing products. In terms of environmental performance, EBPF claim low embedded ener gy costs compared with other insulation materials, a potentially significa nt contribution to reducing carbon emissions and availability free of CFCs and HCFCs.

The relatively small market share held by phenolic foam insulati on may indicate that it is a relatively expensive product to use. Although no information ab out relative costs was identified in our searches, there is, a substantial mar ket for these products in the US suggesting that it may be a economically feasible alte rnative for some applications. The US consumption of phenolic resins for insulation products i n 2001 was 106 thousand metric tonnes. This consumption was anticipated to increa se to 115

thousand metric tonnes in 2006.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 81 of 108

Polyurethane and Polyisocyanurate Products

Insulation products based on polyurethane and polyisocyanurate foams are commercially available but are less widely manufactured in the EU than EPS/XPS or mineral wool products (www.propubs.com/GI/Articles/eGI_May08_ExaneBNPParibas.pdf). They a re used for a range of building insulation applications including cavity wall insulation, roof insulation (but not loft insulation) and in timber frame/stud walls.

UBA (2000) provide a comparison of relative costs of material per a rea unit insulated to a specific insulation performance. If EPS = 1, mineral wool = 1.3, polyurethane = 2.8 and XPS = 3 (raw material costs only). Therefore, the raw m aterial cost of polyurethane may be expected to be slightly less than that for XP S but more than that for EPS. This includes only the materials costs and dose not take a ccount of any required changes in construction techniques or supporting construction materials.

3.2.2.6 Mineral wools and other mineral products

Fibre glass, rockwool and other mineral wools have a large share of the insulation market in Europe (>30%) and there would appear to be economically and tec hnically viable alternatives to EPS and XPS for many applications. Diffe rences in mass density and in resistance to water damage might influence technical feasibility in some applications. Based on the above comparison in UBA (2000), the raw ma terial cost of mineral wools may be expected to be slightly more than that for EPS but less

than that for XPS.

3.2.2.7 Cellulose fibre

Insulation products based on cellulose fibre are commercially avail able but not widely used. It is available in the UK for use in loft insulation, applica tion to sloping ceilings/between rafters and in timber frame/stud walls/dry l ining and suspended floors but not for cavity wall insulation, It is most effective wh ere “breathable” insulation is required as it has the capacity to absorb and release moisture. It does however have a poor moisture resistance and will degrade in damp c onditions. Given the high prevalence of building dampness, poor moisture is likely to limit the range of building insulation applications for cellulose fibre in much of European except in the most southerly member states. We have been unable to find informatio n about the

cost of cellulose fibre insulation relative to XPS/EPS.

3.2.2.8 Intumescent systems

We have been unable to find relevant information on technical and economic feasibility.

ALTERNATIVES TO HIPS

3.2.2.9 Polyethylene with Magnesium Hydroxide

KEMI (2006) indicate that polyethylene with magnesium hydroxide is a commerc ially available alternative to HIPS for the housing of electronic produc ts and wiring partsECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 82 of 108

but do not provide any information about its performance or cost relative to that of

HIPS.

In general, based for example on information from RPA (2002), it coul d be expected that use of polyethylene containing magnesium hydroxide would be les s expensive in terms of raw material costs than HIPS containing HBCDD. Howev er, there would be additional one-off costs of substitution associated with, for example, pr oduct testing and changes to processing equipment which cannot readily be quantified.

3.3 Summary table

For the major uses of HBCDD, namely in EPS/XPS there does not appe ar to be a fire retardant available that will provide equivalent performance. The main benefit of HBCDD is that it offers unique performance in polystyrene foams because it is effective at low levels (around 0.7% in EPS, 2.5% in XPS) (EC RAR, 2008). Higher quantities of non-halogen flame-retardants are required in order to ge t the same level of fire protection. This means that the qualities of the polymer (e .g. thermal insulation) are not as impaired using HBCDD as they would be with a flame retardant used in higher quantities. Higher production of non-halogen alternatives would lead to increase in manufacturing and transportation costs. In addition, the str uctural performance of EPS and XPS is impaired at higher fire retardant loadings.

There are commercially available alternatives to EPS/XPS f or use in building insulation that represent technically feasible substitutes in man y, but not necessarily all applications. Mineral wools are already in wide use and have a share of at least 30% in the European building insulation market indicating that they repres ent technically and economically viable alternatives to EPS/XPS in many applications. There may, however, be applications where the lower mass density or better moisture resistance of EPS/XPS are important. Phenolic foam is another co mmercially available product that meets relevant fire safety standards a nd has a low density, is moisture resistant and highly thermally efficient. It is prim arily used in applications where moisture resistance or thickness are important and has only a small share of the European market for insulation. This may indicate that it is rela tively expensive. These alternative insulation materials are not particularly ha zardous for human health or environment, although the chemicals used in the manufacture of phenoli c foam are hazardous to human health. There may also be significant differences between the various insulation products in terms of the net carbon savings that ari se over the life cycle from manufacturing to disposal.

There are commercially available alternative fire-retarda nts available to the use of HBCDD in HIPS and textile coatings, including non-halogenated fla me retardants that provide the same level of fire protection and performance. The relatively small quantity of HBCDD used in these applications may reflect the a vailability of competing products that do not contain HBCDD, but are equally effective in use.

Table 3.2 summarises the health, environment and feasibility informa tion available

for alternatives to HBCDD.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 83 of 108Table 3.2:Summary of alternatives to HBCDDUse Alternative Toxicity Ecotoxicity Cost Availability Use pattern PerformanceAntimony trioxide (ATO) Potential humancarcinogen andreproductivetoxicantNot readilybiodegradable ,low to moderatebioaccumulationpotentialNot directlycomparable(synergist)CommerciallyavailableUsed as a synergistwith other flameretardantsTechnicallyviable alternativeDecabromodiphenylether/ATONeurotoxicant Not readilybiodegradable ,low to moderatebioaccumulationpotentialComparableor slightlylower rawmaterialprice.Additionalone-offcosts.CommerciallyavailableUsed in HIPS atapprox 10-15% byweight, and threeparts to 1 part ATOTechnicallyviable alternativeDecabromodiphenylethane/ATOLimited data, butlikely to be of lowtoxicityNot readilybiodegradable,may be persistentComparableraw materialprice.Additionalone-offcosts.CommerciallyavailableUsed in HIPS atapprox 10-15% byweight, and threeparts to 1 part ATOTechnicallyviable alternativeEthylenebis(tetrabromophthalimide)/ATOLow toxicity Notbiodegradableand is persistent.Non-toxic.Comparableraw materialprice.Additionalone-offcosts.CommerciallyavailableUsed in HIPS atapprox 10-15% byweight, and threeparts to 1 part ATOTechnicallyviable alternativeFireretardants inHIPSTriphenyl phosphateChronic toxicantwith effects onliverReadilybiodegradable,toxic to aquaticorganismsLikelyhigher rawmaterial costAdditionalone-offcosts.Commerciallyavailable11-13% by weight Technicallyviable alternativeECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 84 of 108Use Alternative Toxicity Ecotoxicity Cost Availability Use pattern PerformanceResorcinol bis (biphenylphosphate)Chronic toxicantwith effects onliverInherentlybiodegradable,may be persistentandbioaccumulativeLikelyhigher rawmaterial costAdditionalone-offcosts.Not currentlyin widespreaduse as a flameretardantTechnicallyviable alternativeBis phenol A bis (biphenylphosphate)Limited data,likely to be of lowtoxicityPoorlybiodegradable.Non-toxic and isnotbioaccumulativeLikelyhigher rawmaterial costAdditionalone-offcosts.CommerciallyavailableDiphenyl cresyl phosphate Chronic toxicantwith effects onliver, kidney andblood. Effects onfertilityReadilybiodegradableLikelyhigher rawmaterial costAdditionalone-offcosts.CommerciallyavailableTechnicallyviable alternativeAlternativesto HIPSPolyethylene with MagnesiumHydroxideInsufficient databut likely to be oflow toxicityPolystyreneparticles are anissue in aquaticenvironmentsLikely lowerraw materialcost.Additionalone-offcosts.CommerciallyavailableTechnicallyviable alternativeTextiles decabromodiphenyletherNeurotoxicant Not readilybiodegradable ,low to moderatebioaccumulationpotentialComparableor slightlylower rawmaterialprice.Additionalone-offcosts.Commerciallyavailable25% by weight (inconjunction withATOTechnicallyviable alternativewheretransparency isnot requiredECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 85 of 108Use Alternative Toxicity Ecotoxicity Cost Availability Use pattern Performancechlorinated paraffinsReproductivetoxicant, chronictoxicity witheffects of liver andkidneys, potentialcarcinogenLCCPs areconsidered topotentially meetthe persistent orvery persistentcriterion. They donot meet the toxicorbioaccumulativecriterion.Likely lowerraw materialcost.Additionalone-offcosts.CommerciallyavailableTechnicallyviable alternativeammonium polyphosphatesLow toxicity Not anecotoxicantLikelyhigher rawmaterial costAdditionalone-offcosts.ammoniumpolyphosphatesTechnicallyviable alternativeEPS/XPS Phenolic Foam Low toxicity in usebut manufacturedfrom materialstoxic andcarcinogenicExpensive? Commerciallyavailable, butonly a smallshare ofinsulationmarketExtremely highthermal efficiencyECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 86 of 108Use Alternative Toxicity Ecotoxicity Cost Availability Use pattern PerformancePolyurethane and polyisocyanurateproductsMay emit toxicfumes if burnt,otherwise lowtoxicity in use, butmanufactureinvolves the use ofisocyanates –potent respiratorysensitisersMaterial costlikely lessthan XPS;more thanEPSCommerciallyavailable, butless widelymanufacturedin EU thanEPS/XPSThese products usethe following flameretardant chemicals:trismonochloropropylphosphate(TMCPP), trischloroethylphosphate (TCEP),and RB-79 (diolmade fromtetrabromo phthalicanhydride)Widely used asbuildinginsulation –aseffective asEPS/XPS in manyapplicationsMineral wools Dust inhalationhazard duringinstallation andremoval;negligibleemissions duringuseMinimal Material costlikely lessthan XPS;more thanEPSCommerciallyavailable withsubstantialshare ofinsulationmarketWidely used asbuildinginsulation –aseffective asEPS/XPS in manyapplications;transport costs,building loadconsiderationsand moistureresistance mayfavour XPS/EPSunder somecircumstancesECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 87 of 108Use Alternative Toxicity Ecotoxicity Cost Availability Use pattern PerformanceCellulose fibre Exposure to lowtoxicity dustduring installationand removal ;potential exposureto flame retardantsand pesticides;inorganic boronsalts are widelyused and arepotentialreproductive anddevelopmentaltoxinsPotential releaseof flameretardants andpesticides; boronis a widely usedadditive tocellulose fibreinsulation and isbelieved to have alow aquatictoxicity and isnaturally presentin theenvironmentMoreexpensivethantraditionalinsulationmethodsCommerciallyavailable butnot widelyusedMoisturesensitivity is apossible issue inmany buildinginsulationapplicationsIntumescent systemsInadequate data Inadequate data InadequatedataInadequatedataInadequate data Inadequate dataECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 88 of 108

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### Disclaimers

Third Party Disclaimer Any disclosure of this report to a third party is subject to this disclaimer. The re port was prepared at the instruction of, and for use by, our client named on the front of the report. It does not in any way constitute advice to any third party who is able to access it by any means. Entec excludes to the fullest extent lawfully per mitted all liability whatsoever for any loss or damage howsoever arising from reli ance on the contents of this report. We do not however exclude our liability (if any) for personal injury or death resulting from our negligence, for fraud or any other matter in rel ation to which we cannot legally exclude liability.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 95 of 108Annex 1: List(s) of information requirements for priority settingand specification of conditions for authorisationThe formats provided in this Annex serve as examples of possible templates that may be used by the contractor to report the requested data andinformation. Other formats (containing the requested data and information) are acceptable after consultation with ECHA..Table 1: Overview on tasks related to work package 1 (grey shaded fields not relevant)Manufacture, trade andformationProcess(narrativedescription)Locations(number of M sites;spatial distribution)2Tonnage manufactured, imported,exported or formedReleases to workingenvironment3Releases to environment(t/y released to air, wastewateror to waste)Manufacture EU Process ABatch-process:Elementarybromine added tocyclododecatrienein solvent.1; Netherlands t/y6000Production workers:Inhalable HBCDD:1.2 mgm-3Dermal exposure powder:170 mg/dayDermal exposure granules17 mg/dayProcess runs intermittently,exposure occurs <25% oftime.t/y0.002 (a)1x10-4(ww)Manufacture EU Process B Micronising small number,Belgium, unknown1000 Inhalable HBCDD:23 mgm-3Dermal exposure:840 mg/dayProcess runs intermittently,exposure occurs <25% oftime.<0.001 (a)Total Manufacture∑EU manufacture Uncertainty of estimate:∑releases (t/y) <0.004,ECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 96 of 108(t/y ; uncertainty; trend, incl. shiftsbetween manufacturing processes)t/y varies between years; trend: Likelyto have increased between 2005 and2007 in response to 10% increase insales in the EU over this period, mayreduce in future between of growingconsumer awareness of theenvironmental issues associated withbrominated fire retardants pluseconomic recessionMean inhalation exposurelevels, quite tight range forprocess workers; exposurecontrol problems atmicronising plant, now notoperating.EASE model for dermalexposure is not reliable.uncertainty of estimate: good,low emissions from sites;trends, declining throughongoing controlImport subst. on its own5580t/yImport subst. in preparationsunknownImport subst. in articles2unknownImport into EU (total)∑t/y Unknown: trends: Increasing usebetween 2003 and 2007Export subst. on its own1882t/yExport subst. in preparationsunknownExport subst. in articles1unknownExport from EU (total)∑t/y Unknown; uncertainty:Unknown; trends: UnknownGlobal manufacture∑t/y: Unknown; uncertainty:Unknown; trends: UnknownUnintentional formation duringincineration (EU)00 0Unintentional formation inprocesses (EU)00 0Unintentional formation bytransformation/degradation (EU)00 0Total unintentionalformation (EU)∑t/y 0; uncertainty: none;trends: flat∑t/y 0; uncertainty: none;trends: flat1A list of article types in which the substance is included shall be provided in addition.2In quantitative or geographical terms exact specifications are only required if the number of sites islow. If there are many sites a semi-quantitative or qualitative description of the manufacturing structure andspatial distribution of manufacturing sites (e.g. in which Member States, regions, etc.) may suffice.ECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 97 of 1083In case a quantification of releases is not possible a qualitative description of the emission situation at the workplace(s) shall be given and a semi-quantitative estimate of the exposure situation provided (e.g. noexposure – very high exp.).(a) – air; (ww) – waste waterECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 98 of 108Table 2: Overview on tasks related to work package 2 (grey shaded fields not relevant)Uses Use Process(description: narrative andby use descriptor system)Amount used(t/y)Number ofsites of use1(#)Spatial distribution ofemission sites1Releases to workingenvironment3(t/y)Releases to environment(t/y released to air, wastewateror to waste)FormulationFormulation 1Production of ExpandedPolystyrene (EPS);PROC4 Use in batchand other process(synthesis) whereopportunity forexposure arises,Industrial setting5301 21 I in Austria2 in Belgium2 in Czech Republic1 in Finland1 in France4 in Germany1 in GreeceI in Hungary1 in Italy4 in Netherlands1 in Poland2 in SpainProcess workers:Inhalable HBCDD:1.2 mgm-3Dermal exposure powder:17 mg/dayDermal exposure Granules1.7 mg/dayShift pattern not recordedDuring weighingInhalable HBCDD:7.2mgm-3Dermal exposure powder:17 mg/dayDermal exposure Granules1.7 mg/day15 days per year0.03 (a)0.08(ww)0.33 (sw)Formulation 2Production of (XPS)PROC4 Use in batchand other process(synthesis) whereopportunity forexposure arises,Industrial setting5859 281 in Austria1 in Belgium3 in France6 in Germany1 in Greece1 in Hungary5 in Italy1 in Netherlands1 in Portugal1 in SerbiaProcess workers:Inhalable HBCDD:0.03 mgm-3Dermal exposure powder:17 mg/dayDermal exposure Granules1.7 mg/dayShift rotation results inexposure on 33% of shifts orless.0.01 (a)0.08 (ww)0.01 (sw)ECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 99 of 1084 in Spain1 in Sweden2 in UKFormulation 3Production of HIPSPROC4 Use in batchand other process(synthesis) whereopportunity forexposure arises,Industrial setting210 3 unknown Process workers:Inhalable HBCDD:1.2 mgm-3Dermal exposure powder:17 mg/dayDermal exposure Granules1.7 mg/daySmall scale, exposure likelyto be occasionalincluded in Formulation 1Formulation 4Textile CoatingproductionPROC4 Use in batchand other process(synthesis) whereopportunity forexposure arises,Industrial setting210 (2007estimate)167 in UK5 in Belgium4 in GermanyProcess workers:Inhalable HBCDD:1.35 mgm-3Dermal exposure:120 mg/dayMany other formulationsused, exposure likely on<25% of shiftsLaboratory staff:Inhalable HBCDD:0.23 mgm-3Dermal exposure:unknownMany other formulationshandled, exposure likely tooccur on <25% of shifts0.001 (a)0.044 (ww)0.011 (sw)∑Formulation∑t/y: 11580;uncertainty:2006 figuresexcept textilecoating; trends:sales increasedevery year bar∑#: 47, trend:unknownOverall geographicalpattern; trend:widespread across Europe;increased used in recentyears, pressure to reduce inNordic countriesUncertainty of estimate:Mean inhalation exposurelevels, quite tight range forprocess workers.EASE model for dermalexposure is not veryaccurate.∑t/y 0.041 (a), 0.060 (ww),0.35 (sw); uncertainty: :notknown; trends not knownECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 100 of 1082006 between2002 and 2007,may be adecline inNordiccountries,economicuncertaintyaffectingconstructionand use ofinsulationEnd usesEnd Use 1Application of coating totextilePROC10:Rollerapplication or brushingof adhesive and othercoating Industrial ornon-industrial setting210 (2007estimate)24 15 in Belgium9 in UKProcess workers:Inhalable HBCDD:1.35 mgm-3Dermal exposure:120 mg/dayMany other formulationsused, exposure likely on<25% of shiftsLaboratory staff:Inhalable HBCDD:0.23 mgm-3Dermal exposure:unknownMany other formulationshandled, exposure likely tooccur on <25% of shifts<0.001 (a)1.1 (ww)0.28 (sw)End Use 2Production of EPS articlesPROC4 Use in batchand other process(synthesis) whereopportunity forexposure arises,5301 28 across Europe Process workers:Inhalable HBCDD:1.2 mgm-3Dermal exposure powder:17 mg/dayDermal exposure Granules0.16 (a)0.012 (ww)0.03 (sw)ECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 101 of 108Industrial setting1.7 mg/dayShift pattern not recordedEnd use 3Production of HIPSarticlesPROC4 Use inbatch and other process(synthesis) whereopportunity forexposure arises,Industrial setting210 unknown unknown Process workers:Inhalable HBCDD:1.2 mgm-3Dermal exposure powder:17 mg/dayDermal exposure Granules1.7 mg/daySmall scale, exposure likelyto be occasional.0.006 (a)0.005 (ww)0.001 (sw)End use 4Production of XPS articlePROC4 Use in batchand other process(synthesis) whereopportunity forexposure arises,Industrial settings5859 21 unknown Process workers:Inhalable HBCDD:0.08 mgm-3Dermal exposure powder:17 mg/dayDermal exposure Granules1.7 mg/dayShift rotation results inexposure on 33% of shifts orless.0.14(a)0.06 (ww)0.02 (sw)End Use 5Use of Insulation Boardsin construction (XPS +EPS)PROC21: Lowenergy manipulation ofsubstances bound inmaterials and/or articlesPROC23: High(mechanical) energywork-up of substancesbound in materialsand/or articlesAlreadyincluded above1000s across Europe Inhalable HBCDD:<0.1 mgm-3Dermal Exposure:<1.7mg/dayExposure pattern unknown0.24 (a)0.24 (sw)∑End Uses∑t/y11580;uncertainty:∑# 1000s,trend notOverall geographical patternacross Europe; trend: trendUncertainty of estimate:Mean inhalation exposure∑t/y 0.53 (a), 1.14 (ww), 0.56(sw); uncertainty: majority ofECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 102 of 1082007 estimatefor textilecoating, 2006figures forother uses,excludesimports ofinsulationboards; sales ofHBCDD forEPS and XPSincreasedbetween 2002and 2006,Helconcountriesdiscouraginguseknown increased use over recentyears; Pressure to reduceuse in the Helcon countrieslevels, quite tight range forprocess workers. Inhalationexposure to HBCDD onconstruction sites assumesdust concentrations arisingfrom the board are less than10 mgm-3(likely).EASE model for dermalexposure is not reliable.release is from textile coating;excludes disposal of allmaterials; trends: assumedincrease with increasingproduction.Consumer useSubstance in articles2(service life of articles)C12.1:Constructionalarticles andbuildingmaterial forindoor use: wallconstructionmaterialceramic, metal,plastic andwoodconstructionmaterial,insulatingmaterialC12.2:Constructional articles andbuildingnot appropriate textiles used mainly in UKand Ireland0.05 (a)0.02 (ww)0.005 (sw)ECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 103 of 108material foroutdoor use:wallconstructionmaterial, roadsurfacematerial,ceramic,metal, plasticand woodconstructionmaterial,insulatingmaterialAC5: Fabrics,textiles andapparel:bedding andclothing;curtains,upholstery,carpeting/flooring, rugsAC3:Electrical andelectronicproducts, e.g.computers,officeequipment,video andaudiorecording,communication equipment;HouseholdappliancesECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 104 of 108(white ware)Substance in preparations∑consumer use of subst.in articles andpreparations∑t/y notmeaningful asmost uses ofHBCDD have alifetime of 10or more years;uncertainty:huge; trends:amount ofHBCDD inconsumers’premisesincreases everyyear asinsulation isinstalledfurniturereplaced etc∑t/y 0.05 (a), 0.12 (ww), 0.03(sw); uncertainty: excludesdisposal, EU15 not EU27;trends unknown1 In quantitative or geographical terms exact specifications are only required if the number of sitesis low. If there are many sites a semi-quantitativeor qualitative description of the use structure and spatialdistribution of sites of release (e.g. in which Member States, regions, etc.) may suffice.2 A list of article types with the substance included and used by consumers shall be provided as well.3 In case a quantification of releases is not possible a qualitative description of the emission situation at the workplace(s) shall be given and a semi-quantitative estimate of the exposure situation provided (e.g. noexposure – very high exp.).(a) – air; (ww) – waste water; (sw) – surface waterECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 105 of 108Table 3: Overview of quantitative information requested at MemberState level for individual years.Production data for individual memberstates is not availableYEAR 2000-2004 Manufacturing(t/y)Manufacturing# sitesFormulation(t/y)Formulation# sitesUse 1(t/y)Use 1# sitesUse 2(t/y)Use 2# sitesMember stateAustriaBelgium...Total 6000 16382 >501050 24 3392 100sYEAR 2000-2004 Use 3(t/y)Use 3# sitesUse 4(t/y)Use 4# sitesUse 5(t/y)Use 5# sitesMember stateAustriaBelgium...Total 210 unknown 4962 35 ~7500 1000sECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 106 of 108YEAR 2006 Manufacturing(t/y)Manufacturing# sitesFormulation(t/y)Formulation# sitesUse 1(t/y)Use 1# sitesUse 2(t/y)Use 2# sitesMember stateAustria21Belgium32Czech Republic22Finland11France41Germany104Greece21Hungary21Italy61Netherlands6000 154Norway1Poland11Portugal1Spain62Sweden1United Kingdom2Total 6000 111580 49210 24 5301 21ECHA_2008_2_SR04_HBCDD_report_12_01_2009.docPage 107 of 108YEAR 2006 Use 3(t/y)Use 3# sitesUse 4(t/y)Use 4# sitesUse 5(t/y)Use 5# sitesMember stateAustria1Belgium1Czech RepublicFinlandFrance3Germany6Greece1Hungary1Italy5Netherlands1Norway1PolandPortugal1Spain4Sweden1United Kingdom2Total 210 unknown 5859 28 11000 1000sECHA_2008_2_SR04_HBCDD_report_12_01_2009.doc Page 108 of 108 

# ANNEX 2: