ROHS ANNEX II DOSSIER FOR BBP

Transcription

1 ROHS ANNEX II DOSSIER FOR BBP Proposal for restriction of a substance in electrical and electronic appliances under RoHS Substance Name: Benzyl butyl phthalate EC Number(s): CAS Number(s): January 2014

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3 ROHS Annex II Dossier for BBP Contents CONTENTS CONTENTS IDENTIFICATION, CLASSIFICATION AND LABELLING Name, other identifiers and physico-chemical properties of the substance Name, other identifiers and composition of the substance Physico-chemical properties Classification and Labelling Status Legal status and use restrictions USE OF THE SUBSTANCE Use and function of BBP in general Use of BBP in EEE Quantities of BBP in EEE HUMAN HEALTH Human health hazard assessment Endpoints of concern Existing Guidance values ENVIRONMENT Environmental fate properties Environmental hazard Eco-toxicity studies Potential for secondary poisoning Existing guidance values (PNECs) WASTE MANAGEMENT OF ELECTRICAL AND ELECTRONIC EQUIPMENT WEEE categories containing BBP Relevant waste materials/components containing BBP Waste treatment processes applied to WEEE containing BBP Treatment processes applied BBP flows during treatment of WEEE Treatment processes selected for assessment under RoHS Releases from the relevant WEEE treatment processes Shredding of WEEE Summary of releases from WEEE treatment EXPOSURE ESTIMATION Human exposure January

4 ROHS Annex II Dossier for BBP Contents Exposure estimates of workers of EEE waste processing plants Exposure estimates of workers of EEE waste processing plants Environment exposure Exposure estimates for the environment due to WEEE treatment Monitoring data: WEEE treatment sites/locations IMPACT AND RISK ESTIMATION Impacts on WEEE management as specified by Article 6(1) a Risks estimation for workers and neighbouring residents Risks estimation for the environment ALTERNATIVES Availability of alternatives Hazardous properties of alternatives Conclusion on alternatives DESCRIPTION OF THE SOCIO-ECONOMIC IMPACTS Approach and assumptions Impact on producers of plasticisers and plastics Impact on EEE producers Impact on EEE users Impact on waste management Impact on administration Total socio-economic impact RATIONALE FOR INCLUSION OF THE SUBSTANCE IN ANNEX II OF ROHS REFERENCES ABBREVIATIONS LIST OF TABLES LIST OF FIGURES January 2014

5 ROHS Annex II Dossier for BBP Identification, Classification and Labelling 1 IDENTIFICATION, CLASSIFICATION AND LABELLING 1.1 Name, other identifiers and physico-chemical properties of the substance Name, other identifiers and composition of the substance Table 1: Substance identity and composition (Source: ECHA, 2008) Chemical name Benzyl butyl phthalate EC number CAS number IUPAC name Index number in Annex VI of the CLP Regulation Benzyl butyl phthalate Molecular formula C 19H 20O 4 Molecular weight range 312,35 Synonyms 1,2-benzenedicarboxylic acid, butyl phenylmethyl ester; benzyl-n-butyl phthalate; phthalic acid, butyl benzyl ester; Santicizer 160; Sicol 160; Unimoll BB Structural formula Degree of purity > 95.5% (w/w) Remarks -- January

6 ROHS Annex II Dossier for BBP Identification, Classification and Labelling Physico-chemical properties The physical chemical properties of BBP are summarised in Table 2. Table 2: Physico-chemical properties of BBP (Source: ECHA, 2008; ECB, 2007) Property Physical state at 20 C and kpa Melting/freezing point Boiling point Value liquid <-35 C 370 C at hpa Vapour pressure Pa at 20 C Water solubility 2.8 mg/l Partition coefficient n-octanol/water (log P OW) Log K ow 4.84 Flashpoint 198 C (390 F) Autoignition temperature 425 C Density (25 C) g/cm 3 Henry s law constant (calculated) Pa*m 3 mol Classification and Labelling Status The Classification, Labelling and Packaging (CLP) 1 regulation requires companies to classify, label and package their substances and mixtures before placing them on the market. The regulation aims to protect human health and the environment by means of labelling to indicate possible hazardous effects of a particular substance. It should therefore ensure a proper handling, including manufacture, use and transport of hazardous substances. BBP is listed in Annex VI of the CLP Regulation and is harmonised classified as depicted in Table 3. In accordance with Directive 67/548/EEC BBP is classified as Repr. Cat. 2; R61 (may cause harm to the unborn child); Repr. Cat. 3; R62 (possible risk of impaired fertility); N; R50-53 (very toxic to aquatic organisms-may cause long-term adverse effects in the aquatic environment) and labelled with the symbols T,N and R61, R62, R50/53; S53, S45, S60, S61. Additionally to the harmonised classification BBP is self-classified as Acute Tox. 3 (H331) by some manufactures and/or importers. This information has been obtained from the C&L inventory provided by ECHA. 2 1 Regulation (EC) No 1272/2008 of the European Parliament and of the Council on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/ for details see: 6 January 2014

7 ROHS Annex II Dossier for BBP Identification, Classification and Labelling Table 3: Harmonised classification of BBP 1 Index No International Chemical Identifi-cation BBP EC No CAS No Classification Labelling Spec. Conc. Limits, Notes M-factors benzyl butyl phthalate Hazard Class and Category Code(s) Repr. 1B Aquatic Acute 1 Aquatic Chronic 1 Hazard statement code(s) H360Df H400 H410 Pictogram, Signal Word Code(s) GHS09 GHS08 Dgr Hazard statement code(s) H360Df H400 H410 Suppl. Hazard statement code(s) Classification according to part 3 of Annex VI, Table 3.1 (list of harmonized classification and labelling of hazardous substances) of the CLP Regulation Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006 January

8 ROHS Annex II Dossier for BBP Identification, Classification and Labelling 1.3 Legal status and use restrictions REACH Regulation 3,4 BBP is included in Annex XIV - list of substances subject for authorisation - of the Regulation No. 1907/2006. Specific authorisation for BBP will be required for a manufacturer, importer or downstream user to place the substance on the market, use it in preparations or for the production of articles. BBP cannot be placed on the market or used after 21st of February 2015, unless an authorisation is granted for the specific use or the use (e.g., medical devices) is exempted for authorisation. Furthermore, there are specific restrictions for certain phthalates in toys and and childcare articles. BBP is included in Annex XVII (restrictions on the manufacture, placing on the market and use of certain dangerous substances, preparation and articles) of the Regulation No. 1907/2006 (Annex XVII, group 51). Following restriction conditions have to be taken into consideration for three phthalates, including BBP: in toys and childcare articles BBP, Bis(2-ethylhexyl)phthalate (DEHP), and Dibutyl-phthalate (DBP) shall not be used as substance or in mixtures in concentrations greater than 0.1 % by weight of plasticised material; toys and childcare articles containing BBP, DEHP, and DBP in a concentration greater than 0.1 % by weight of plasticised material shall not be placed on the market. Food Contact Material Regulation 5 In the European Union certain restrictions on the use of BBP in food contact materials are implemented. BBP can be only used as plasticiser in repeated use materials and articles. In single-use materials and articles contacting non-fatty foods BBP can be used with exemptions for articles containing foodstuffs for infant, baby and young children. However, the migration of the plasticiser should not exceed the Substance Migration Limit (SML) of 30 mg/kg food. Furthermore it can be used as technical support agent in concentrations up to 0.1% in the final product. 3 Commission Regulation (EU) No 143/2011 of 17 February 2011 amending Annex XIV to Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals ( REACH ) 4 Corrigendum to Commission Regulation (EU) No 143/2011 of 17 February 2011 amending Annex XIV to Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals ( REACH ) 5 Commission Regulation (EC) No 10/2011 of 14th January 2011 on plastic materials and articles intended to come into contact with food 8 January 2014

9 ROHS Annex II Dossier for BBP Identification, Classification and Labelling Cosmetic regulation 6 BBP is prohibited to be used for the production of cosmetic products. It is listed in Annex II list of substances prohibited in cosmetic substances- to the Cosmetic Regulation. 6 Regulation (EC) No 1223/2009 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 30 November 2009 on cosmetic products January

10 ROHS Annex II Dossier for BBP Use Of the Substance 2 USE OF THE SUBSTANCE 2.1 Use and function of BBP in general BBP is used as plasticiser in minor concentrations in flexible polymers (e.g. PVC) as well as in some non-polymers (e.g., adhesives, paints, sealants, printing inks) (COWI, 2009). It is used together with other plasticisers to add special properties to the intermediate and end product including faster gelation of the polymer or hard and stain resistant surface of the polymer. Phthalates are not bound chemically in the polymer matrix (external plasticisers). The substance group can therefore migrate from the plasticised polymer by e.g. extraction with soapy water/oils, by evaporation and by diffusion (DEPA, 2010). 2.2 Use of BBP in EEE BBP is mainly used as plasticiser in PVC flooring. The usage in EEE has not been confirmed (DEPA, 2010). However, it might be assumed that BBP is present in EEE in following applications: synthetic leather, coated textile, flexible or rigid PVC sheets, printing inks, sealants and adhesives. These applications might be used in various product types including electric devices. 2.3 Quantities of BBP in EEE The market for BBP has been decreasing over the last decades indicating that BBP is replaced by alternatives. The overall production in the EU in 2007 was below 18,000 t/y. 70% of the BBP is used in polymer production, mainly for PVC flooring. It is used in the flooring industry because of its properties to speed up production (faster gelation of polymer) and its properties to build a specific floor surface. Information on the use of BBP in the EEE production is scarce. BBP quantity in European EEE For the purpose of the present assessment the BBP quantity entering the European market via EEE was estimated as follows: DEPA (2010) estimates the amount of BBP used in EEE produced within the EU to be 20 to 200 tonnes per year. When assuming that ten times as much of BBP containing EEE is imported than produced domestically the total amount of BBP coming into use annually within EEE would be some 2,000 t/y. Thus for the scenario-analysis it is assumed that 2,000 t/a of BBP are put on the market in the EU via EEE. According to comments by vinylplus information is available about phthalate concentrations in soft PVC-waste (excluding flooring). According to this the concentration of DEHP was 7.5%, of BBP 0.1%. According to vinylplus thus the quantities of BBP in EEE entering the European market would be lower than the above figure. However, so far no detailed information on the referenced analysis was provided. 10 January 2014

11 ROHS Annex II Dossier for BBP Human health 3 HUMAN HEALTH 3.1 Human health hazard assessment In the year 2007 an in-depth evaluation of potential risks of BBP to human and/or environment has been performed within the EU Risk assessment report series (details see ECB, 2007). Hazard assessment in brief Following conclusions based on the hazard assessment have been drawn: The acute toxicity of BBP in rodents is low. The oral LD 50 ranged from g/kg bw day in rats and were 4.17 g/kg bw/day and 6.16 g kg bw/day, for male and female mice, respectively. The outcome of toxicological studies revealed that the compound is not irritating to the skin and only slightly irritating to the eye. Data indicate that BBP does not possess sensitising potential. Based on the present information BBP can be considered as a non-genotoxic and non-carcinogenic substance. Repeated dose toxicity studies with rodents indicate that BBP possess adverse effects on the liver and kidney. A NOAEL for oral exposure of 151 mg/kg bw and a NOAEL for the inhalative route of 218 mg/m 3 have been deduced from a 13-week studies with laboratory rodents. BBP is found to adversely affect the reproductive organs in rodents which may affect fertility. The developmental toxicity in offspring included prenatal mortality, reduced fetal weight, and malformed foetuses. Furthermore, the substance is found to be a developmental toxicant and to possess anti-androgen like properties in experimental animal studies. The endpoints of concern are depicted in more detail in chapter Endpoints of concern The present assessment takes into cognisance the previous the evaluation undertaken within the European risk assessment series (ECB, 2007). Detail findings of individual studies are not discussed in the present report. Instead, main findings of toxicological studies are depicted in Table 4. The effect of BBP after repeated dose application to experimental animals has been investigated in several studies. Main target organs for BBP toxicity are the reproductive system, kidney and the liver. Toxicological studies revealed that the most sensitive endpoints of BBPs toxicity profile are adverse effects on reproduction and development. In particular the male reproductive system has been identified as sensitive towards BBP. The NOAEL of reproduction and developmental studies is in the range of 20 to 100 mg/kg bw. For the endpoint fertility a NOAEL of 100 mg/kg bw/day has been deduced based on the study outcome of Nagao et al. (Nagao et al., 2000). The NOAEL is based on adverse effects on fertility parameters, like atrophy of the testis, epididymis, and seminal vesicle, and reduced reproductive organ weights have been observed in the F1 generation at 500 mg/kg bw/day. Adverse effects on reproduction and developmental system January

12 ROHS Annex II Dossier for BBP Human health For developmental effects a NOAEL of 50 mg/kg bw/day for the offspring based on adverse effects detected for anogenital distance (AGD) observed in the study of Tyl et al. (2004) has been deduced. The observed effect was doserelated in both F1 and F2 offspring. Evidences from human studies Endocrine disruption Repeated dose toxicity Duty et al. (2003) evaluated in a human study the relation between semen quality and exposure to phthalates. Altered semen quality parameters were associated with high levels of mono butyl phthalate and/ mono benzyl phthalate in the urine. Due to co-exposure of various phthalates it is difficult to draw a conclusion that the altered semen quality was related only to BBP exposure. An association between prenatal and postnatal exposure to phthalates and whether the exposure had any influence on reproductive organ development in newborn boys was studied in two epidemiological studies. Results of an epidemiological study demonstrate an association between maternal exposures to BBP as well as other phthalates and lower anogenital index (AGI) in boys (Swan et al., 2005). In another study only a marginal association was found between intake of milk contaminated with BBP and postnatal surge of reproductive hormones (SHBG, LH, testosterone and inhibin B) in new-born boys (Main et al., 2005). A recent evaluation of epidemiological studies suggests that there is an association between BBP childhood exposure and formation of asthma and eczema (Braun and Sathyanarayana, 2013). BBP is in the EU EDS database listed as one of the 66 potentially endocrine substances with classification of high exposure concern (Annex 15) 7. BBP has been classified as cat. 3 for wildlife, cat. 1 for Humans and Combined as cat. 1 (cat.1: Evidence for endocrine disruption in living organisms; cat. 2: Evidence of potential to cause endocrine disruption; cat.3: No evident scientific basis). In vivo studies indicate that BBP possess an anti-androgen-like activity. In a 13 week study with oral administration of BBP to Wistar rats in concentrations of 151, 381 and 960 mg/kg bw. a NOAEL of 151 mg/kg bw/day was derived. At the next dose level (381 mg/kg bw/day) adverse effects such as kidney weight increase, urinary ph decrease, histo-pathological changes in pancreas, gross pathological changes in the liver have been observed. A NOAEL of 218 mg/m 3 was derived from a 13 week inhalation study in Sprague-Dawley rats. At the applied dose of 789 mg/m 3 adverse effects such as increased kidney and liver weight in male and female rats and a decrease in serum glucose in male rats have been detected. 7 List of 66 identified EDS substances with high, medium and low exposure concern: 12 January 2014

13 ROHS Annex II Dossier for BBP Human health Table 4: Examples of reproductive and repeated dose toxicity studies (cited in ECB, 2007) Study type Species Application and exposure levels Outcome LOAEL NOAEL Reference Reproductive toxicity Two study generation Sprague- Dawley rats Orally; by gavage 0, 20, 100 or 500 mg/kg bw/day Atrophy of the testis, epididymis, and seminal vesicle, and reduced reproductive organ weights in F1 generation mg/kg bw/day (for effects on the reproductive organ). Nagao et al., 2000 Increased serum follicle stimulation hormone (FSH) concentrations in F0 parental. 20 mg/kg bw/day (altered hormone levels) Two generation study Sprague- Dawley rats Orally; in the diet 0, 50, 250, 750 mg/kg bw/day Reduced anogenital distance 250 mg/kg bw/day 50 mg/kg bw/day Tyl et al., 2004 Repeated dose toxicity 13 week study; repeated dose toxicity study Wistar rats Orally; in the diet 151, 381, 960 mg/kg bw/day 381 mg/kg bw/day in males: Kidney weight increase, urinary ph decrease, his- 381 mg/kg bw/day 151 mg/kg bw/day Hammond et al., 1987 topathological changes in pancreas, gross pathological changes in the liver 151 mg/kg bw/day in females: Marginal increase in relative liver and cecum January

14 ROHS Annex II Dossier for BBP Human health Study type Species Application and exposure levels Outcome LOAEL NOAEL Reference weight. 13 week repeated dose toxicity study Sprague- Dawley rats inhalative route 51, 218 and 789 mg/m 3 Increased kidney and liver weight was reported at in male and female rats; a decrease in serum glucose 789 mg/m mg/m 3 or 62.8 mg/kg bw/day Monsanto (1982) in male rats. January 2014

15 ROHS Annex II Dossier for BBP Human health Existing Guidance values An overview on derivation of national Occupational exposure limits (OELs) within the European member states as well as non member states is provided by the European Agency for Health and Safety at work (EU-OSHA website 8 ). OELs and guideline values in different countries are between mg/m 3 (GESTIS 9 ). No OEL for BBP has been derived by the European Scientific Committee on Occupational Exposure limits (SCOEL) so far 10. The tolerable daily intake (TDI), which is an estimate of the amount of a substance in air, food or drinking water that can be taken in daily over a lifetime without appreciable health risk has been settled by the Scientific Panel on Food Additives, Flavourings, Processing Aids and Materials in Contact with Food (AFC) and is 0.5 mg/kg bw/day (EFSA, 2005). Likewise, as for the DNEL derivation the study of Tyl et al. (2004) and an assessment factor of 100 has been applied. For the present assessment Derived No Effect Levels (DNELs), which have been critically deduced and reviewed within the European Risk assessment Committee in September 2013 (RAC, 2013) are going to be used for further risk characterisation. The outcome of the derivation of different DNELs is summarised in Occupational exposure limits Tolerable daily intake Derived no effect level for BBP Table 5. The point of departure for the DNEL derivation of BBP has been derived from the study of Tyl et al. (2004), in which reduced anogenital distance has been observed. A NOAEL of 50 mg/kg/day was used as point of departure. Assessment factors have been applied for inter- and intra-species difference. There are too many uncertainties to draw a conclusion whether humans are more, less or equal sensitive than rats, therefore default values for interspecies (default: 4x2.5) were used (RAC, 2013). Applying the overall assessment factor of 100 an oral DNEL of 0.5 mg/kg/day was derived by the RAC for the general population. The oral NOAEL rat was converted into a dermal corrected NOAEL by correcting for differences in absorption between routes (5% absorption is considered for the dermal route). Further correction for exposure during 5 days a week instead of 7 days a week has been applied to derive a dermal DNEL for workers. The oral NOAEL in rat (in mg/kg bw/day) was converted into an inhalatory corrected NOAEC (in mg/m3) by using a default respiratory volume for the rat corresponding to the daily duration of human exposure (RAC, 2013). For the general population the exposure is considered to be 24 hrs/per day and for workers 8 hrs. Furthermore, for workers light work was considered for the estimation of the respiratory volume. Point of the departure Assessment factors Oral DNEL Dermal DNEL DNEL inhalation 8 EU-OSHA: 9 GESTIS-GefahrenSToffInformationsSystem database of hazardous substances provided by Institute for Occupational Safety and Health of the German Social Accident Insurance (IFA); 10 SCOEL: January

16 ROHS Annex II Dossier for BBP Human health Table 5: Overview of the deduced derived no effect concentrations (DNELs) for BBP (Source: RAC, 2013) 11 Assessment Factors Workers General population (Adults& Children) Interspecies, AF* 4 4 Interspecies, remaining differences 2,5 2,5 Intraspecies 5 10 Dose response 1 1 Quality of database 1 1 Applied Factor* ORAL Absorption (%) 100% 100% NOAEL (not relevant) 50 DNELs ORAL in mg/kg/d (not relevant) 0.5 DERMAL Absorption (%) 5% 5% NOAEL (corrected) DNELs DERMAL in mg/kg/d INHALATION Absorption (%) 100% 100% Standard respiratory volume in m 3 /kg bw per day LOAEC (corrected) DNECs INHALATION in mg/m * interspecies AF was not applied when calculation inhalation DNECs 11 for details see: 16 January 2014

17 ROHS Annex II Dossier for BBP Environment 4 ENVIRONMENT An in-depth evaluation of BBP has been carried out in the frame of the European risk assessment reports published in the year 2007 (ECB, 2007). Studies regarding the environmental fate properties of BBP and also adverse effects on environmental organism have been in detail reviewed and evaluated. In the following section the environmental fate properties are and compared with the Persistence and Bio accumulative criteria (PBT criteria) settled down in Annex XIII of the REACH regulation, as well as with the criteria indicated in Annex D of the Stockholm Convention (POPs criteria). Predicted no effect concentrations (PNEC) which have been previously deduced by within the EU RAR are depicted in chapter Environmental fate properties There is evidence that BBP is readily biodegradable under aerobic conditions (fulfilling the 10 day window criterion). Under anaerobic conditions the biodegration rate is slower (e.g., sediments or deeper soil or groundwater). Hydrolysis and photolysis in water is likewise for other phthalates rather low. Biodegradation There are two important steps in the metabolic pathway of aerobic or anaerobic biodegradation of phthalates, including BBP: (1) the di-ester is hydrolysed into the mono-esters by esterases with low substrate specificity (2) the mono-esters are converted into phthalic acid Experimental data indicate a half-life for BBP in the atmosphere of app. 1.5 days. Studies indicate that primary biodegradation of BBP takes place, however, with variable half-lives. Furthermore, data indicate that metabolites, mainly monoesters and phthalic acid, are formed. A comparison with the criteria determined in Annex XIII of the REACH regulation indicates that BBP does not fulfill the P (Persistence) criteria. The determined bio-concentration factors (BCFs) are in the range of l/kg. For estimating the secondary poisoning the BCF value of 449 l/kg using 14 C-labelled BBP was considered within the EU RAR, since this value covers the parent compound and also the mono-ester metabolites (MBuP and MBeP), which are supposed to have any impact on the organisms. Persistence Bioaccumulation Table 6: Summary of selected environmental parameters of BBP and comparison with PBT and POPs criteria Parameter Outcome PB criteria (according REACH, Annex XIII) POPs criteria (Stockholm Convention) Surface water (river) (half-life) ds 40 ds >60 ds Log Kow >5 January

18 ROHS Annex II Dossier for BBP Environment Log Koc 10.5 l/kg Bioconcentration factor l/kg >2000 l/kg >5000 l/kg T Reprotoxic 1B substance meets the criteria for classification for CMR substances (categories 1A-1B) toxicity or ecotoxicity data indicating potential to damage human health or the environment The present data indicate that BBP does not fulfil Persistence and/or Bioaccumulation criteria stipulated in Annex XIII of the REACH regulation or criteria of Annex D of the International Stockholm Convention. 4.2 Environmental hazard Eco-toxicity studies Main conclusions on ecotoxicity studies To determine the possible adverse effects of BBP in the aquatic environment numerous short as well as long-term studies are available and summarised in the European Risk assessment report (ECB, 2007). A comparison of test results to that time revealed that the lowest NOAEC of 75 µg/l has been achieved from a 28-day study carried out with an invertebrate species (Mysidopis bahia), which has been considered as starting point for derivation of guidance values ( Predicted no effect concentration) within the EU RAR. However, within the EU RAR it was stated that further long-term toxicity data on fish should be available to determine possible endocrine effects in fish. A long-term fish study has been conducted in the year and is published on the ECHA dissemination site 12. The data suggest four times higher sensitivity. To determine the adverse effects on organisms in the aquatic sediments no experimental data have been available, the equilibrium method has been used to estimate possible toxic effects and guidance values (ECB, 2007). One acute toxicity earthworm test according to test guidelines has been performed to determine the possible adverse effects of BBP on the terrestrial compartment. However, no LC 50 could have been developed due to 100% survival. For the determination of toxic effects to the atmospheric compartment two separate phytotoxicity tests were carried out, in which no effects at the highest mean vapour concentration (5.7 µg/m 3 ) have been detected. 12 For details see: e f67d249/AGGR-8c7bcba7-d776-4f3d-876e-ddd347d8d83e_DISS- 9c7dab96-58cb-6886-e f67d249.html#AGGR-8c7bcba7-d776-4f3d-876eddd347d8d83e 18 January 2014

19 ROHS Annex II Dossier for BBP Environment Potential for secondary poisoning Secondary poisoning is a phenomenon related to toxic effects which might occur in higher members of the food chain resulting from ingestion of organisms from lower trophic levels that contain accumulated substances. Thus, chemicals which have bioaccumulation and biomagnification properties within the food chain may pose an additional threat. An important factor to enter the food chain is the uptake of the substance by plants. Howver, data indicate that a more important route for phthalates contamination is the air-plant route, determined probably by the high log Kow and low valour pressure. BBP has a Log Kow of 4.84 and measured BCF values in the range l/kg. Therefore, an assessment of exposure through the food chain therefore becomes relevant. Within the EU risk assessment series (ECB, 2007) a NOAEL of 50 mg/kg bw from a rat reproduction toxicity study (Tyl et al., 2004) is used for the derivation of the PNEC for prediators. Application of conversion factor of 20 and assessment factor of 30 a PNEC oral of 33 mg/kg in food has been deduced Existing guidance values (PNECs) The predicted no effect concentration (PNEC) is the concentration below which exposure to a substance is not expected to cause adverse effects to species in the environment. Therefore the determination of these values is important for further characterisation of probable risks. Based on the eco-toxicity studies PNECs (Predicted no effect concentrations) have been deduced (ECB, 2007). Table 7 gives an overview of the PNECs for different compartments. Table 7: Predicted no effect concentrations (PNECs) for different environment compartments (Source: ECB, 2007) Compartment NOAEL Safety factor PNEC Aquatic Compartment Surface water Marine 75 µg/l 75 µg/l µg/l 0.75 µg/l Freshwater-sediment* Marine-sediment* mg/kg wwt 0.17 mg/kg wwt Soil* mg/kg wwt Secondary poisoning 50 mg/kg bw 30 conversion factor: mg/kg food (prediators) *no experimental data available; PNEC derivation based on equilibrium partitioning method; January

20 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment 5 WASTE MANAGEMENT OF ELECTRICAL AND ELECTRONIC EQUIPMENT WEEE categories containing BBP According to DEPA (2010) no information on the use of BBP containing polymers, respectively PVC parts in individual EEE categories is available. As explained in Chapter 2 BBP may be used in any type of EEE in applications such as synthetic leather and coated textile in straps, flexible or rigid PVC sheet, sealants, printing inks and adhesives Relevant waste materials/components containing BBP Main materials/componen ts Given the information on the use of BBP it is assumed that this amount, i.e. 2,000 t/a, will be contained in mixed plastics streams. 5.2 Waste treatment processes applied to WEEE containing BBP Treatment processes applied Initial treatment processes Treatment of separately collected WEEE Those WEEE which are separately collected, are either manually dismantled or shredded. These may be performed in large-scale ELV-shredders, in many cases combined with automated material sorting, or specific shredders (e.g. horizontal cross-flow shredders, plants for treatment of screens etc.). In shredding processes BBP ends-up most probably in mixed plastics fractions. Given that BBP cannot be allocated to any easy to remove parts it is likely that also by dismantling BBP ends up also in an unspecific mixed fraction. Treatment of WEEE ending up in unsorted MSW WEEE ending up in unsorted municipal waste is likely to be incinerated or landfilled. In MSW especially small appliances which are easily thrown into a waste bin are found. Treatment of WEEE exported A relevant share of the potential WEEE arising be it as waste or as used goods - are supposed to be shipped to third countries. These WEEE may undergo dismantling, dumping or any kind of combustions process. Subsequent treatment processes Treatment of shredder residues Plastics containing fractions resulting from shredding of WEEE as well as from dismantling as the initial treatment are usually either: landfilled 20 January 2014

21 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment incinerated (incineration or co-incineration) in the form of mixed plastics enriched fractions For the production of solid recovered fuels required for co-incineration, PVC has to be removed to comply with limit values for Chlorine. Thus it is assumed that BBP is predominantly treated in waste incineration plants. or treated in further treatment processes for separation of materials, e.g. in so called post-shredder processes Subsequent treatment of mixed plastics in third countries will be in many cases open burning or dumping. Treatment of plastics in third BBP flows during treatment of WEEE To evaluate which waste treatment processes are of relevance with regard to potential BBP released caused by WEEE and to estimate these releases the following scenario for the treatment of BBP containing WEEE was established. It is assumed that the BBP-input into waste management by WEEE corresponds to the total quantity of BBP put on the European market via EEE 13, i.e. 2,000 tonnes annually. Actual WEEE generation at a given time, e.g. based on models taking into account the life-time of particular equipment, was not considered for the present assessment. To estimate the flows of BBP entering individual treatment processes in particular the following aspects were taken into account. the rate of separate collection of WEEE the rate of (illegal) shipment to third countries share of individual treatment processes applied to the relevant waste streams Waste management scenario for BBP containing WEEE The treatment scenario was established on the basis of European WEEE statistics (Eurostat, WEEE data for ), assumptions made by EC (2008) based on figures of 2005 and on own estimations. WEEE treated in WEEE treatment plants in the EU 44 % 15 of the total WEEE arising 16 are treated in WEEE treatment plants in the EU (i.e. 4.1 Mio t/a). Assumptions 13 Based on 9.4 Mio EEE put on the market Eurostat: Waste Electrical and Electronic Equipment (WEEE) statistics (env_waselee); extracted August WEEE reported to be collected separately, including also 11% of WEEE (particularly large household appliances) not reported to be separately collected but treated by the same processes as the comparable appliances reported as being separately collected. 16 For the purpose of the present assessment the WEEE arising is seen equal to the amounts put on the market January

22 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment Taking into account also the composition of WEEE reported to be separately collected (Eurostat, WEEE- statistics 17 ) it is assumed that this amount is composed of: 61% (2.5 Mio t/a) large household appliances (assumption treatment: 80% shredder process; 20% manual dismantling) 7% (0.29 Mio t/a) small household appliances (assumption treatment: 100% shredder) 17% (0.7 Mio t/a) IT&T appliances incl screens (assumption treatment: 70% dismantling, 30% shredder) 15% (0.65 Mio t) are consumer electronics incl. screens (assumption 30% dismantling, 70% shredder) Thus for separately collected WEEE an overall share of 71% of shredding and a 29% of manual dismantling are assumed. WEEE contained in unsorted MSW 13 % of the overall WEEE arising is not separately collected but ends up with unsorted MSW (i.e. 1.2 Mio t/a). It is assumed that two thirds of MSW in the EU are landfilled, one third incinerated 18. WEEE whose fate is not known 41 % of the overall WEEE arising (3.9 Mio t/a) are unaccounted for and are assumed to be shipped to third countries to an unknown degree. Re-use of WEEE A small share of an estimated 2% of WEEE being re-used is neglected within the present assessment. Treatment of shredder residues It is assumed that the total quantity of BBP entering WEEE shredder processes is transferred to shredder residues. It is assumed that 2/3 of shredder residues resp. mixed plastics enriched fractions are landfilled and one third 1/3 is incinerated. Treatment of mixed plastics fractions from manual dismantling It is assumed that the total quantity of BBP entering WEEE dismantling is transferred to any mixed fraction. It is assumed that 2/3 of these fractions are landfilled and one third 1/3 is incinerated. There is little indication that such mixed fractions are further separated for recycling of particular polymers. 17 The shares of individual categories in the amounts reported to be separately collected were used 18 See for example EEA (2013) 22 January 2014

23 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment Taking into consideration the material composition of WEEE and the estimates described in Chapter 2.3 Quantities of BBP used in EEE an average BBP content of % in WEEE is assumed 19. Based on these assumptions the following BBP quantities undergoing the individual treatment processes were estimated (see Table 8 below). BBP input into WEEE treatment processes Table 8: Estimated quantities of BBP entering the main treatment processes for WEEE and secondary wastes derived thereof (in tonnes per year) WEEE (2,000) Secondary wastes Separately collected WEEE WEEE in unsorted MSW WEEE shipped out of the EU Mixed plastics derived from dismantling Shredder residues Secondary wastes from uncontrolled WEEE treatment in third countries (incl. ) Re-Use 40 a 255 b (and sort- Shredding automated ing) disman- Manual tling 625 c Landfilling (EU) 172 d 169 f 413 h Incineration (EU) 86 e 84 g 206 i Uncontrolled treatment in third countries (dismantling, dumping, burning) 820 j a 2,000 t * 0.02 b 2,000 t * 0,44 * 0.29 c 2,000 t * 0.44 * 0.71 d 2,000t *0.13 * 2/3 e 2,000t *0.13 * 1/3 f 255 t * 2/3 g 255 t * 1/3 h 625 t * 2/3 i 625 t * 1/3 j 2,000 t * tonnes of BBP are contained in 9.4 Mio tonnes of EEE average BBP concentration in WEEE = 0.021% January

24 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment Treatment processes selected for assessment under RoHS In order to focus on those processes where risks for workers or the environment are most likely to be expected, the following process was selected as most relevant for the present risk assessment: Relevant processes Treatment of WEEE in shredders, because it is applied to BBP containing parts of WEEE at several stages in the overall treatment chain at a large number of installations/locations. Less relevant processes The following treatment processes were NOT taken into account for a quantitative risk determination within this assessment: Manual dismantling, because - as there is neither a mechanical nor a thermal treatment releases to air, water and soil are considered to be low (Specific information on releases from / exposure through manual dismantling is not available). Landfilling, because WEEE and materials derived thereof are not the main source for BBP in the landfilled waste usually. Incineration under controlled conditions, because WEEE and materials derived thereof are not the main source for BBP in the incinerated waste usually. Furthermore a well-functioning emission control is assumed. Treatment processes under uncontrolled conditions, because WEEE and materials derived thereof are not the main source for BBP. 5.3 Releases from the relevant WEEE treatment processes In the following information on and estimates of DEHP releases from the selected processes are summarized Shredding of WEEE Info on releases The most important route of BBP from shredding of WEEE or plastics materials thereof is considered to be via emissions of dust. Emissions from shredders are typically abated by dust removal in a cyclone and a wet scrubber. According to the BREF WTI (2006) generic emission levels for dust (PM) associated to the use of BAT are in the range of 5-20 mg/nm 3. However, treatment of metal wastes, including WEEE, in shredders has been recently included into the scope of IED-Directive. Information on the actual dust emissions from shredders under current operational conditions is scarce Dust concentrations between 1.3 and 18.7 mg/nm 3 for German shredders have been reported (BDSV, 2012) 24 January 2014

25 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment From EC (2007) estimates of the quantities of diffuse emissions of dust are available. They estimate an overall annual release of PM10 from European car shredders of 2,100 tonnes resulting from manipulation of fluff and fines 21. In order to estimate BBP releases via diffuse emissions of dust during manipulating material streams at sites where WEEE are shredded, the following assumptions were made: The total input of BBP into WEEE shredders was estimated to account to 625 t/a (compare BBP flows in Table 8) 90% of the BBP input into a shredder are transferred to fluff/fines/dust % of fluff/fines/dust are emitted diffusely via PM10 (under dry conditions, watering of the material and other measures for prevention of diffuse emissions will reduce the percentage by one order of magnitude) Assumptions concerning diffuse emissions The total quantity of BBP emissions via diffuse dust emissions from sites, where WEEE are shredded, is estimated to range from 56 kg/a 23 to for 562 kg/a 24. The actual order of magnitude will depend on the degree to which BAT for preventing diffuse emissions from handling of shredded materials including e.g. encapsulation of aggregates or wettening of materials is applied. Having in mind that not all shredders in the EU apply BAT, the estimation of BBP being emitted after de-dusting is based on the upper value for BAT-AELs, i.e. 20 mg/nm 3. Furthermore, an exhaust air flow of 20,000 Nm 3 /h 25 and a treatment quantity of 60 t WEEE per hour 26 were assumed. Furthermore, it was assumed that the BBP concentration in dust is the same than in the processed EEE. Estimates of diffuse emissions Assumptions concerning channeled emissions Based on these assumptions 27 the BBP via residual dust emissions is estimated to account for 2.06 kg/a. In order to estimate the BBP emissions per installation 28 and day processing of WEEE in large-scale metal shredders was used as a reference. The following assumption was made: Estimates channelled emissions Releases per installation and day Typical daily WEEE throughput in a large-scale metal shredder is 250 tonnes based on an assumption of 18% generation of fines/dust from materials treated in a shredder and an emission factor of the dry material (g/kg) of 1 g/kg 22 Assumption based on Morf et al. (2004) 23 RFair 0.09 g/kg 24 RFair 0.9 g/kg 25 E.g. described by Ortner (2012) 26 Umweltbundesamt (2008) 27 RFair = g/kg 28 According to EC (2007) there are 220 large scale shredders in the EU Capacities of Austrian ELV-shredders: t/h, assumption 7 working hours per day January

26 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment Based on the resulting daily BBP input per installation of 53 kg and using the release factors for BBP as illustrated above the following BBP releases per installation and day are estimated: 4.7 to 47 g of BBP are emitted diffusely via particulates 0.17 g of BBP are emitted after de-dusting. Further considerations In general there is a tendency to further process mixed shredder residues with the aim to recover valuable metals and also to achieve legally binding recycling targets. In order to obtain recyclable metal-rich concentrates, several automated sorting techniques are used. These include various types of mechanical treatments, such as shredding, milling, etc., where dust is generated. It is assumed that not all of those installations are equipped with efficient dust prevention techniques. Additional BBP releases via dust from processing of shredder residues in such installations are likely. Emissions to water and soil from shredding are considered to be negligible. Workplace description mechanical treatment of WEEE Treatment of WEEE in large-scale metal shredders is a highly automated process, where workers primarily manipulate the material outdoors using various work machines, partly sitting in closed cabins. Figure 1: Large-scale metal shredder plant (Source: Umweltbundesamt, 2008) Other mechanical processes for WEEE treatment including e.g. horizontal cross flow shredders or special drums may be completed by manual sorting of the disintegrated appliances along a conveyer belt. The air at these indoor work places may be extracted or not. Usually workers are required to use masks to prevent them from inhaling the dust. It is assumed, though, that the practical implementation leaves room for improvement. 26 January 2014

27 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment Figure 2: Manual sorting of disintegrated WEEE (Source: Umweltbundesamt, 2008) There are different options for further mechanical treatment of mixed shredder residues. There are installations where the mostly encapsulated aggregates are handled outdoors or partly encased. Thus material manipulation by workers is carried out outdoors or in partly enclosed places with natural ventilation. Figure 3: Installation for further treatment of mixed shredder fractions (Source: Umweltbundesamt, 2008) Other installations have fully encapsulated grinding and sorting aggregates situated in a closed building with indoor air extraction. The manipulation of the material is carried out both, indoors and outdoors. January

28 ROHS Annex II Dossier for BBP Waste management of Electrical and Electronic Equipment Summary of releases from WEEE treatment Table 9: Estimated total BBP releases from WEEE treatment processes in the EU (in kg per year) Air (particulates) diffuse Air (particulates) channeled Shredding (and automated sorting) of WEEE Total Table 10: Estimated local BBP releases from WEEE treatment processes in the EU (in g per installation and day) Air (particulates) diffuse Air (particulates) channelled Shredding (and automated sorting) of WEEE January 2014

29 ROHS Annex II Dossier for BBP Exposure Estimation 6 EXPOSURE ESTIMATION 6.1 Human exposure Humans are exposed to BBP via use of consumer products, indirect environmental exposure and/or due to occupational exposure. BBP has been found in air, water and soil and dietary products. Thus, human exposure can be through contaminated air, water, soil and food. For the general population, the diet is considered as major source of BBP exposure. BBP in food might originate from the environment, food processing and/or food packaging. General population In an Danish study the estimated mean exposure ranged from µg/kg bw/day (Peterson and Breindahl, 2000) and a further Danish study in which dietary exposure was based on measured and estimated concentrations the oral daily intake was 1 µg/kg bw/day in adults, 2.4 µg/kg bw/day in children aged 7 to 14, and 5.9 µg/kg bw/day in children aged 1 to 6 years (Müller et al., 2003). Additionally, the general population might be exposed through inhalation of indoor air due to the presence of BBP in PVC and non-pvc polymeric material. The maximal exposure concentration for the general population from intake of BBP from indoor air has been estimated to be mg/mg/kg bw/day (California Environmental Protection Agency, 1992). For children there might be an additional exposure through intake of BBP from baby equipment and children toys (worst case: mg/kg bw/day) (ECHA, 2008) Exposure estimates of workers of EEE waste processing plants Exposure estimates of workers of EEE waste processing plants The exposure estimation performed within this assessment is based on the assumptions and calculations provided in the chapter waste treatment and releases of BBP. Within the frame of the process of registration of substances under REACH several guidance documents and supporting tools for exposure estimation have been introduced. One of these tools, the TRA (Targeted Risk Assessment) tool has been established and developed by ECETOC to align with the expectations contained in Chapters R12-R16 of the Technical Guidance on Information Requirements and Chemicals Safety Assessment by ECHA and is frequently used by industry and also integrated in the Chesar tool, which is provided by ECHA. ECETOC TRA Within this assessment the TRA tool 3.0. has been used to estimate exposure of workers. One scenario have been selected as relevant regarding exposure due to waste management operations (see chapter 5.2.). shredding of WEEE containing BBP, where exposure mainly occurs through dermal uptake and inhalation of dust (see chapter 5.3) Limitations January

30 ROHS Annex II Dossier for BBP Exposure Estimation One limitation of the TRA model is that waste treatment processes are not indicated explicitly by the uses and processes which can be selected, as the TRA tool is intended for industrial processes such as manufacture or formulation. Therefore the most appropriate processes to describe the exposure conditions of waste treatment processes have been chosen Exposure estimates: Shredding As described above no process category for shredding is available. In order to select exposure conditions which are comparable with shredding- processes the process category 24: high (mechanical) energy work-up of substances bound in materials and/or articles has been selected. Further description of these processes is given in the REACH guidance document R.12: substantial thermal or kinetic energy applied to substance by hot rolling/forming, grinding, mechanical cutting, drilling or sanding. Exposure is predominantly expected to be to dust (ECHA, 2010). RCR- Risk Characterisation Ratio Further selected input parameters: professional use of solid substance with high dustiness, 8 hours activity (>than 4 hours), outdoors, no respiratory protection or gloves (dermal PPE - personal protective equipment). Further 100% of substance in the preparation (>25%) has been applied. The results were then corrected taking into account the calculated average BBP content of EEE (Chapter 2.3) and information on transfer of BBP to dusts from WEEE shredding (see Chapter 5.3.1). Thus the average content of BBP in the dust of WEEE shredders is estimated at 0.021%. In table 9 the results of the assessment are summarized. Table 11: Results of the ECETOC-TRA model for exposure and risk of shredding Parameter conc. solid conc. solid conc. solid BBP BBP BBP PROC Process category 24a 24b 24c 24a 24b 24c Long-term Inhalative Exposure Estimate (ppm for volatiles) / (µg/m3 for solids) Long-term Inhalative Exposure Estimate (µg/m3) Long-term Dermal Exposure Estimate (µg/kg/day) ,44 0,44 0,59 0,74 0,74 0,59 2,94 2,94 0,59 DNEC/DNEL *RCR 24a 0, , ,00004 *RCR 24b 0, , ,00007 *RCR 24c 0, , ,00030 *RCR: Risk Characterization Ratio 30 January 2014