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WEEE plastic sorting for bromine essential to enforce EU regulation
Waste Management xxx (2017) xxx–xxx
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WEEE plastic sorting for bromine essential to enforce EU regulation Pierre Hennebert a,⇑, Montserrat Filella b a b
INERIS (National Institute for Industrial Environment and Risks), BP 2, F-60550 Verneuil-en-Halatte, France Institute F.-A. Forel, University of Geneva, Boulevard Carl-Vogt 66, CH-1205 Geneva, Switzerland
a r t i c l e
i n f o
Article history: Received 11 July 2017 Revised 15 September 2017 Accepted 27 September 2017 Available online xxxx Keywords: Electric and electronic equipment (EEE) Brominated flame retardants (BFR) Hazard property (HP) Persistent organic pollutants (POP)
a b s t r a c t The plastics of waste of electric and electronic equipment (WEEE) are improved for fire safety by flame retardants, and particularly brominated flame retardants (BFR). As waste, the management of these plastic fractions must comply with the update of the regulation of waste hazard classification (2014, 2017), the publication of a technical standard on management of WEEE (2015), and a restriction of use for decabromodiphenylether in the product regulation (2017). Data of bromine (n = 4283) and BFR concentrations (n = 98) in plastics from electric and electronic equipment (EEE), and from WEEE processing facilities before and after sorting for bromine in four sites in France have been studied for chemical composition and for regulatory classification. The WEEE was analysed by handheld X-ray fluorescence, and the waste was sorted after shredding, by on-line X-ray transmission for total bromine content (< or > 2000 mg/kg) in small household appliances (SHA), cathode ray tubes (CRT) and flat screens plastics. In equipment (n = 347), 15% of the equipment items have no bromine, while 46% have at least one part with bromine, and 39% have all parts brominated. The bromine concentration in plastics is very heterogeneous, found in high concentrations in large household appliance (LHA) plastics, and also found in unexpected product categories, as observed by other authors. Clearly, an unwanted global loop of brominated substances occurs via the international recycling of plastic scrap. In waste (n = 65), polybromobiphenyls, polybromodiphenylethers (PBDE), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane were analysed. The most concentrated BFRs are decaBDE (3000 mg/kg) and TBBPA (8000 mg/kg). The bromine concentration of regulated brominated substances was identified in 2014 and 2015 to be up to 86% of total bromine in ‘‘old” waste (SHA, CRT), 30–50% in ‘‘younger” waste (Flat screens), and a mean of only 8% in recent products (2009–2013). Regulated substances are a minority of all the brominated substances and the only practical way to sort is to measure total bromine on-line. The sorting reduces the mean bromine concentration in the ‘‘Low Br” fraction in all sites, and reduces the decaBDE concentration to levels below the restricted use limit. After sorting, the concentration in the ‘‘High Br” fractions exceeds all present or future regulatory limits. In conclusion, sorting of small household appliances, cathode ray tubes and flat screen plastics is necessary to avoid uncontrolled dispersion of regulated substances in recycled raw material. Other categories (large household appliances, electric and electronic tools, lighting equipment) should also be considered, since their total bromine content (unweighted mean concentration) is high for some of these products. A European campaign consisting of 7 countries and 35 sites will begin in 2017, directed by WEEE Forum, the European association speaking for thirty-one not-for-profit e-waste producer responsibility organisations, to assess the mean bromine content of plastics from large household appliances after shredding. Ó 2017 Elsevier Ltd. All rights reserved.
1. Introduction In 2014, the rounded world production of plastics was 270 million tonnes (Mt), with an EU production and demand of 50 Mt ⇑ Corresponding author. E-mail address: [email protected] (P. Hennebert).
(18.5%) and 49 Mt, respectively and 2.8 Mt (5.8%) of this EU production used for electric and electronic equipment (EEE) (Plastics Europe, 2017). That year, 25.8 Mt of post-consumer plastic waste ended up in the official waste streams in the EU, and were managed by energy recovery (10.2 Mt, 39.5%), landfilling (7.9 Mt, 30.8%) and recycling (7.6 Mt, 29.7%). The amount of electric and electronic equipment on the EU market in 2013 was 8.1 Mt (17.4
https://doi.org/10.1016/j.wasman.2017.09.031 0956-053X/Ó 2017 Elsevier Ltd. All rights reserved.
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kg/inhabitant) (Eurostat, 2017). The waste of electric and electronic equipment (WEEE) separately collected in 2013 reached 3.5 Mt (6.5 kg/inhabitant), of which 2.7 Mt were recovered. The recovered amount included 2.4 Mt of recycled WEEE (i.e. reprocessed into a product) and 0.2 million tonnes that were used for energy production. The plastic fraction in European WEEE depends on categories and products and was estimated to be 2.3 Mt or about 20.6% of the weight of EEE in 2008 (Huisman et al., 2008). In new EEE appliances, the percentage has continuously increased since 1980 from scarcely 14–18% in 1992, to 22% in 2000, and was estimated to be at 23% in 2005. The mass flow of recycled plastics from WEEE separately sorted in the EU can be estimated to 0.48 Mt (= 2.4 Mt WEEE recovered ⁄ 20% plastics in WEEE). The contribution of brominated flame retardants is unsure but has been estimated to be 25% of WEEE plastics. Flame retardant additives are now found in consumer products (see below). Recent developments in regulations and technical standards have changed the framework for the management of plastics from waste of electric and electronic equipment (WEEE). The plastic fractions of WEEE can be noted as hazardous or not in the European List of Waste depending on the content of hazardous components (codes 16 02 13⁄ or 16 02 14, and 20 01 35⁄ or 20 01 36) (EU, 2014a). There is no specific entry in the list for brominated plastics. The European Directive 2012/19/EU (EU, 2012) states that plastic containing brominated flame retardants (BFR) must be removed from any separately collected WEEE (Article 8, Annex VII). If a plastic fraction contains persistent organic pollutants (POP) at concentrations higher than regulatory concentration limits, the only authorised treatments (to destroy or irreversibly transform the substances) are: (i) physico-chemical treatment, (ii) incineration on land, or (iii) use principally as a fuel or other means to generate energy, excluding waste containing PCBs (EC, 2008, Annex V). On the other hand, according to technical specification CLC/TS 50625-3-1:2015 (developed by the standardisation organisation CENELEC upon mandate of the European Commission), all the plastic fractions of WEEE may contain significant concentrations of BFR, excepted non-cooling Large Household Appliances (LHA) and cooling and freezing LHA. The operators must separate these BFR if total bromine concentration in the fraction is known to be >2000 mg/kg, or expected to be >2000 mg/kg, or if it is not declared. On the other hand, ‘‘If the concentration of bromine is <2000 mg/kg, the operator fulfills the requirement for de-pollution of BFR” (CLC/TS 50625-3-1:2015). Detailed regulatory concentration limits are presented in this paper. Numerous substances (75 according to Alaee et al., 2003) have been reported as potential brominated additives in plastics of EEE (alkanes, cycloalkanes, aromatics, alcohols, ethers, phthalates, epoxy resins, brominated polystyrene. . .). The c-octaBDE and cdecaBDE mixtures were typically incorporated into plastics at final weight loadings of 12–18% and 5–16%, respectively (Alaee et al., 2003; UNEP, 2007). The commercial PBDE mixtures are added flame retardants which are not chemically bound to the plastic polymer but are physically mixed in during manufacture (Gallen et al., 2014). A variety of chemical elements and BFRs have been reported to be present in WEEE (Schlummer et al., 2007; Dimitrakakis et al., 2009; Wäger et al., 2010). In products, they are restricted or regulated by two European Directives: Restriction of use of certain Hazardous Substances (RoHS) in EEE (EC, 2002) and restrictions on the marketing and use of certain dangerous substances and preparation (EC, 2003). These directives contribute to the organization of the distribution of recycled plastic polymers (Decottignies et al., 2014). Although the production of POP PBDEs has ceased, significant volumes of these chemicals continue to remain in circulation through the recycling of PBDE-containing products (UNEP, 2010a,b, Gallen et al., 2014). The elimination of
these chemicals from the recycling stream are recommended to avoid the unintentional contamination of products with sensitive end uses such as children’s toys (Chen et al., 2009) and food preparation products (Puype et al., 2015). The presence of BFRs in plastics is frequently estimated by the measure of total bromine, at the laboratory or with handheld or automated X-ray fluorescence spectrometry. Detailed laboratory investigations for every type of waste and every waste stream are not economically feasible, XRF being at present the only method that allows the operator to decide on the recycling suitability of the sample in real time (Aldrian et al., 2015, Guzzonato et al., 2016). Typically, the authors measure total bromine in numerous samples, and identify BFRs (substances) in some (selected) samples. Brominated flame retardants (BFRs) and antimony trioxide (a synergist of BFRs) are found in consumer plastics, WEEE or nonWEEE. Taurino et al. (2010) measured BFRs in WEEE in Italy in composite samples of TV and personal computer (PC) monitors. The grey plastics had a mean BFR content of 43,900 mg/kg. For WEEE and non-WEEE, Gallen et al. (2014) have measured bromine by Xray fluorescence (XRF) in Australian commercial products. Bromine concentrations were >1 mg/kg in 51% of the 1714 measurements, >1000 mg/kg in 18% of measurements and >10,000 mg/kg in 10% of measurements (in 9 out of the 14 product types). Five product types (which included four electronic-based product types) had maximum XRF measurements that exceeded 100,000 mg/kg. Aldrian et al. (2015) have measured bromine by the same method in Austrian TV and PC monitors (with a routine limit of detection (LD) of 300 mg Br/kg). TV waste plastics show a bromine content of about 7000–8000 mg/kg (mean value of 3006 parts), whereas PC monitor housings (n = 1598) have a content of 32,000 mg/kg. The distributions for TV plastics were: 85.5% of parts <1000 mg/ kg, 1.9% in the range 1000–3000 mg/kg, 12.6% >3000 mg/kg), and for PC plastics: 52.6% of parts <1000 mg/kg, 3.9% in the range 100 0–3000 mg/kg, and 43.5% >3000 mg/kg). The authors conclude that adequate monitoring measures are necessary, to identify the high number of pieces with a concentration of BFRs >50,000 mg/kg (7% TV and 39% PC waste plastics) to prevent the transfer of highly contaminated pieces to the recyclable fraction. Puype et al. (2015) have quantified bromine, BFRs, polymer impurity and WEEE-relevant elements in 10 black polymeric food-contact articles in the Czech Republic. They found bromine >LD (40 mg/kg) in 7 articles (from 66 to 5975 mg/kg), with BFRs in each of the 7 articles, antimony in 4 articles (from 52 to 504 mg/kg), polymeric impurities in all cases and typical rare earth elements (REE: Ce, Dy, La, Nd, Pr and Y) in electronic applications in 4 brominated samples. However, in Br-negative samples, no traces of REES were detected, clearly indicating that WEEE plastics have been used for the production of food-contact articles, despite the very small number of samples. The authors address their concern to the scientific community, policy-makers and control authorities. Turner and Filella (2017a, 2017b) investigated the levels of antimony, bromine and chlorine in plastic consumer products in the United Kingdom. The percentage of items with brominated plastics were: Electronics 58%, Clothing-upholstery 39%, Vehicle interiors 34%, Constructionplumbing 30%, Leisure-sports 25%, Office-stationery 22%, Toyshobbies 15%, Cleaning-storage 9%, Food-drinks 6%. Total: 29% (Total non-EEE: 21%). Bromine and/or antimony were found in all categories, including categories where no flame retardancy was expected. The authors conclude that many polymeric household items that have no reason to be fire-resistant are constructed, at least in part, from recycled plastic components of end-of-life electronic products, and call for reconsideration of the means of disposal and recycling of Sb-rich electronic plastic waste. For sorting, ‘‘there is no uncritical mixed plastics fraction, however there are two fractions which appear to be very critical (mixed plastics from CRT monitors and CRT TVs)” (Wäger et al., 2010).
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33 (all in triplicates = 99) Total Br analyses Total PBB PBDE analyses Total HBCDD TBBPA analyses
691 4218 43 347
4 33 parts of 22 items with brominated parts 4316 (4406 with triplicates) 98 (188 with triplicates)
219 425 88 48 39 4
4. Consumer equipment and photovoltaic panels (Audio-Video) 5. Lighting equipment (Lightings) 6. Electrical and electronic tools (with the exception of large-scale stationary industrial tools) (Tools) 7. Toys, leisure and sports equipment (Toys) Total laboratory samples
3 6 1
16 173 3. Information and telecommunications equipment (IT)
1253
32 (56 with triplicates)
32 (all 12 brominated in triplicates = 56)
CRT: 4 inflow, 9 sorted; Flat screens: 2 inflow, 4 sorted
4 inflow, 9 sorted
4 inflow, 1 fines, 9 sorted CRT: 4 inflow, 1 fines, 9 sorted; Flat screens: 2 inflow, 4 sorted 1 2 1232 310 26 14
Parameters
Equipment-products for legal compliance Br (XRF) Equipment/Samples
Parts of Equipment Br (XRF) EEE 2009–2013 Campaign
Table 1 Campaigns, samples and analyses.
Data on bromine and BFRs in plastics from electric and electronic equipment (EEE) were obtained from a service laboratory for product quality control for compliance with the RoHS directive by the importers and resellers (SGS Multilab, Saint Etienne du Rouvray, France) from 2009 to 2013. Data on bromine and BFRs in plastics from WEEE processing facilities before and after sorting for bromine in four sites of four French companies in 2014 and 2015 (Table 1) were provided by OCAD3E (the French federation of producer responsibility organisation for WEEE), in collaboration with processing companies, the French Ministry for Ecology, and the National Institute for Industrial Safety and Environmental Protection (INERIS). The first set of data is referred to as EEE 2009– 2013 and the second group as WEEE 2014 and WEEE 2015 throughout the article. In the 2009–2013 EEE campaigns, Br was determined in the visually different plastic parts, including printed circuit boards (up to 76) of equipment using a portable XRF (Niton) with Br calibration, and an in-borne instrument automatically corrected for thickness. Up to 60 parts were measured in one piece of equipment. In a second step, laboratory analyses (total bromine, total antimony, polybromobiphenyls PBB and polybromodiphenylethers - PBDE) were performed for selected items (Table 1). The weight percentage of each part is not known, and the calculated unweighted means are estimations. In the 2014 and 2015 WEEE campaigns, WEEE were sorted by categories in collection points, shredded and automatically sorted (Pellenc ST Xpert with X-ray transmission and dual energy sensor to avoid any thickness issues) on a conveyor for total bromine content in two fractions: ‘‘Low Br (<2000 mg/kg) and ‘‘High Br” (>2000 mg/kg). In one site, the latter fraction was further sorted by density with a floating bath (1.09 kg/L) into ‘‘high brominated low density” and ‘‘high brominated high density” fractions. Samples of the flow before and after the sorting for bromine were taken according to TS-50625-3-1:2015. During one day, ten samples were taken, mixed, quartered, divided in two and sent as laboratory samples for analysis. For a shredder producing particles <5 cm, 10 subsamples of 10 L were taken and reduced to a laboratory sample of 25 L, and for a shredder producing 2–5 cm particles, 10 subsamples of 5 L were taken and reduced to 12 L. In 2014, sampling of flow with >5 cm particles deviated from this
Parts of Equipment
2.1. Campaign and samples
EEE Categories (EC 2012) and short name in this paper 1. Large household appliances (LHA) 2. Small household appliances (SHA)
2. Materials and methods
Br (Laboratory), PBB, PBDE
WEEE 2015 WEEE 2014
One day composite sample (shredder and sorter) Br (Laboratory), Sb, PBB, PBDE
Clearly, an unwanted global loop of substances occurs via the international trade of plastic scrap, according to many professionals. The recyclers are aware of this question: ‘‘The Chinese government is determined to improve environmental conditions by imposing regulatory controls on the plastics recycling industry. . . . The ultimate objectives are to get rid of small recyclers who do not have proper recycling facilities; and to stop the importation and recycling of polluted scrap. . . The environmental authorities took to seizing factories, arresting owners, disconnecting utility supplies and destroying illegal workshops” (Patawari, 2017). In this study, data of bromine and BFRs in plastics from EEE, obtained from a service laboratory for commercial products quality control from 2009 to 2013, and from WEEE processing facilities before and after automated sorting for bromine in four sites of four companies in 2014 and 2015 are presented and the following subjects discussed: distribution of the different BFRs, their concentrations and relation to total bromine content, the hazard and POP classification of these plastics, the consequences for management of these fractions, and the best way to enforce EU regulation and promote sustainable recycling of WEEE plastics.
One day composite sample (shredder and sorter) Br (Laboratory), Sb, PBB, PBDE, HBCDD, TBBPA
P. Hennebert, M. Filella / Waste Management xxx (2017) xxx–xxx
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procedure when a 12 L laboratory sample was sent to the laboratory. This was corrected in 2015. For manual dismantling of cathode ray tubes (CRTs), pieces from 250 units were taken and sent to the laboratory. The EEE and WEEE are classified in ten categories in the European WEEE Directive (EU, 2012). For products, seven categories were analysed (Table 1). The WEEEs studied here were sorted at the collection points and the processing facility into small household appliances (SHA), cathode ray tubes (CRT), and flat screens (Table 1). CRTs and flat screens can be assigned to Category 3 or 4. 2.2. Analyses The analyses were performed by the ISO 17025 service laboratory SGS Multilab (Saint-Etienne du Rouvray, France). A first sorting of the laboratory samples was conducted manually to eliminate the metallic parts. Samples were repeatedly shredded with a low-speed device (Blik model BB230), producing pieces less than 10 mm in size without heating. These samples were then cryo-ground to 4 mm using a Retsch SM300 mill and quartered to 1 kg using a riffle divider and the resulting sub-samples were cryo-ground to 1 mm. For antimony determination, an aliquot of the sample was mineralised (ISO 13657, adapted) and analysed with ICP/OES (ISO 11885). Aliquots for bromine analysis were combusted in oxygen in a closed system (EN 14582) and then assayed with ionic chromatography. Brominated flame retardants were determined per IEC 62321-6 with gas chromatography coupled with mass spectrometry (GC/MS). The expression of results in congeners and the limit of quantification are presented in Table 2. For the WEEE 2014 campaign, 33 laboratory samples were ground and the resulting aliquots were analysed (extraction and analysis) in triplicate. The relative standard deviation (RSD) values of the data higher than the limit of quantification (LOQ) are presented in Table 3. The mean RSD obtained of 13.5% has been judged satisfactory for these heterogeneous samples.
2.3. Classification for waste hazardousness, POP regulation, Br separation and restriction of use for products Products and waste must comply with their respective regulations. The hazard properties (HP) of waste in Europe are defined in the Commission Regulation 1357/2014 (EU, 2014a) and the Decision 2014/955/UE (EU, 2014b), except for the most frequent HP 14 ‘Ecotoxic’. For each hazard property, the (measured) concentrations or sum of concentrations of substances with hazard statement codes (from the ‘‘Regulation on classification, labelling and packaging of substances” (CLP, 2008) tables and European Chemical Agency - ECHA site) are compared with waste-specific concentration limits (Table 4). The Decision 2014/955/UE includes persistent organic pollutant (POP) substances (use of POP concentration limit for classification of waste containing hexabromobiphenyls). For HP 14 ‘Ecotoxic’, the recently decided calculation method (EU, 2017) has been applied, with cut-off values of 1000 mg/kg for substances with H410 hazard statement code. For bromine, a separation in fraction < o > 2000 mg/kg is recommended (CLC/TS 50625-3-1:2015). For decabromodiphenylether, a restriction of use in the EU REACH system has been applied since the first semester of 2017, with a concentration limit of 0.1% (1000 mg/kg). 3. Results and discussion 3.1. Bromine content For EEE, some equipment has no bromine (<100 mg/kg, 52/347 = 15%), while many others have at least one part with bromine (>100 mg/kg, 158/347 = 46%), and a large part of the equipment consist of all brominated parts (137/347 = 39%) (Table 5). The most frequently brominated categories are large household appliances (LHA), Toys and Tools (>70% of equipment with at least one part
Table 2 List of analysed substances, expression in congeners and limit of quantification (LOQ). Parameter
Expression
CAS
LOQ EEE (mg/kg) 100 n.a.
**
LOQ WEEE (mg/kg)
Br Sb
Total Total
Monobromobiphenyls Dibromobiphenyls Tribromobiphenyls Tetrabromobiphenyls Pentabromobiphenyls Hexabromobiphenyls Heptabromobiphenyls Octabromobiphenyls Nonabromobiphenyls Decabromobiphenyl Sum of polybromobiphenyls (PBBs)
Congener BB-2 Congener BB-15 Congener BB-30 Congener BB-49 Congener BB-103 Congener BB-153 Congener BB-189 Congener BB-194 Congener BB-206 Congener BB-209 Sum of the congeners
2113-57-7 92-86-4 59080-33-0 59080-33-0 60044-24-8 59080-39-6 59080-40-9 67889-00-3 67889-00-3 13654-09-6
1 1 1 1 1 1 20 25* 25* 25 100
1 1 1 1 1 1 1 1 2 10 20
Monobromodiphenylethers Dibromodiphenylethers Tribromodiphenylethers Tetrabromodiphenylethers PentabromobiphenyletherZ Hexabromodiphenylethers Heptabromodiphenylethers Octabromodiphenylethers Nonabromodiphenylethers Decabromodiphenylether Sum of polybromodiphenylethers (PBDEs)
Congener BDE-3 Congener BDE-15 Congener BDE-35 Congener BDE-47 Congener BDE-99 Congener BDE-153 Congener BDE-183 Congener BDE-197 Congener BDE-207 Congener BDE-209 Sum of the congeners
101-55-3 2050-47-7 147217-805436-43-1 60348-60-9 68631-49-2 207122-16-5 117964-21-3 437701-79-6 1163-19-5
1 1 1 1 1 1 1 25 25 50 100
1 1 1 1 1 1 1 1 2 10 20
Hexabromocyclododecanes (HBCDD) 3,30 ,5,50 -Tétrabromobisphénol A (TBBPA)
1,2,5,6,9,10-Hexabromocyclododecane TBBPA
3194-55-6 79-94-7
n.a. n.a.
10 1
10 20
N.a.: not analysed. * Octa and nona measured together. ** XRF.
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P. Hennebert, M. Filella / Waste Management xxx (2017) xxx–xxx
Table 3 Reproducibility of the element and substances analysis on three separate laboratory samples from a daily shredder flow of the campaign WEEE 2014 (concentration, and relative standard deviation for triplicates > LOQ, total 1201 values). Parameter
Concentration of triplicates (mg/kg)
Br Sb
Relative standard deviation (standard deviation/mean)
n
min
max
mean RSD
max RSD
33 33
423 25
55375 5287
0.10 0.10
0.27 0.25
Pentabromobiphenyls (PBB 103) Hexabromobiphenyls (PBB 153) Heptabromobiphenyls (PBB 189) Octabromobiphenyls (PBB 194) Nonabromobiphenyls PBB 206) Decabromobiphenyl (PBB 209) Sum of PBBs
1
18
18
0.44
1 3 5 5
62 5 12 5
62 158 328 548
0.08 0.17 0.15 0.13
0.23 0.28 0.26
Tetrabromodiphenylethers (PBDE 47) Pentabromobiphenylethers (PBDE 99) Hexabromodiphenylethers (PBDE 153) Heptabromodiphenylethers (PBDE 183) Octabromodiphenylethers (PBDE 197) Nonabromodiphenylethers (PBDE 207) Decabromodiphenylether (PBDE 209) Sum of PBDEs
4 4 16 24 23 28 32 32
5 5 5 5 5 5 5 13
10 27 764 4410 4453 2627 16300 28600
0.23 0.20 0.12 0.17 0.15 0.13 0.15 0.14
0.50 0.32 0.30 0.64 0.36 0.28 0.42 0.36
Parameters without sums Parameters with sums
Mean (207 trip.) Mean (244 trip.)
0.135 0.135
Table 4 Classification of regulated substances: Hazard statement codes, hazard properties (HP) and POP classification, concentration limits (CL – mg/kg). Substance
CAS
Hazard statement code
Br Sb2O3
1309-64-4
H351
HexaBB -PBB TetraBDE TetraBDE PentaBDE PentaBDE HexaBDE HeptaBDE OctaBDE NonaBDE DecaBDE HBCDD HBCDD HBCDD TBBPA
36355-01-8 40088-47-9 40088-47-9 32534-81-9 32534-81-9 36483-60-0 68928-80-3 117964-21-3 69278-62-2 1163-19-5 3194-55-6 3194-55-6 3194-55-6 79-94-7
H350 H373 H400 H373 H400 H360 H360 H360
Hazard property
HP
CL
HP 7
POP
Decision 2014/955/ UE POP
CL
Rule
Separation
Restriction of use 2017
CL
2000
1B - H410 - H410 1B 1B 1B
H319 H319 - H335 - H315 H361 H400 - H410 H400 - H410
HP HP HP HP HP HP HP HP
7 5 14 5 14 10 10 10
10,000 (Sb 8400) 1000 100,000 P H410 < 2500 100,000 P H410 < 2500 3000 3000 3000
HP HP HP HP HP
4 4 10 14 14
P H319, H315 < 200,000 P H319, H315 < 200,000 30,000 P H410 < 2500 P H410 < 2500
POP1
50
POP1 POP2 POP2
50 P P
POP2 <1000 POP2 < 1000
POP2 POP2
P POP2 < 1000 P POP2 < 1000
**
**
POP3
1000*
1000
HP 4 ‘Irritant’; HP 5 ‘Specific Target Organ Toxicity (STOT)/Aspiration’; HP 7: ‘Carcinogenic’; HP 10 ‘Toxic for reproduction’; HP 14 ‘Ecotoxic’. * 1000 mg/kg subject to review by the European Commission by 20.4.2019. ** Annex D fulfilled, annex E and F in technical committee (begin 2017).
with bromine), then small household appliances (SHA) and Lighting (>50% of equipment), and finally Audio-Video and IT (±25% of equipment). Most parts of the equipment are non-brominated (B r < 100 mg/kg), and a minority of parts have bromine in high concentration (last column of Table 5). If it is assumed that all parts have the same weight, a mean concentration of Br in plastics of equipment can be calculated (penultimate column, assuming that the concentrations below the limit of quantification are equal to zero). Nevertheless, according to professionals, at least in large household appliances, there are frequently only some small parts in contact with electric circuits and motors that are brominated, and the calculated mean could be overestimated. Four categories have a calculated mean concentration surpassing the threshold of 2000 mg/kg requiring separation according to CLC/TS 50625-3-1
(in blue in the Table): three expected (Tools, Lighting and SHA), and one unexpected (large household appliances) and having an exemption for bromine sorting in CLC/TS 50625-3-1. This indicates that this exemption should be assessed by additional data. It is not the first time that bromine >2000 mg/kg has been found in large household appliances. A report (Wäger et al., 2010) commissioned by the WEEE Forum (European association speaking for thirty-one not-for-profit e-waste producer responsibility organisations) to contribute to a formulation of normative requirements with respect to depollution of WEEE, shows also that bromine concentrations >2000 mg/kg have been found in large household appliances (1 time/6 samples), small household appliances without screens (1/3), IT equipment without screens (3/3) and consumer equipment without screens (2/2) (Wäger et al., 2010). In mixed
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P. Hennebert, M. Filella / Waste Management xxx (2017) xxx–xxx Table 5 Bromine content of EEE: number of equipment with bromine per category, number of parts of equipment with bromine per category, unweighted mean bromine concentration in all parts and in brominated parts (sorted by decreasing unweighted bromine concentration in parts) (in blue, Br > 2000 mg/kg).
Table 6 Mean concentrations of Br, PBBs and PBDEs in EEE 2009–2013 and classification (data insufficient for HP 14).
All other PBBs and PBDEs < LOQ (Table 2). HBCDD and TBBPA not analysed (n.a.).
samples, bromine >2000 mg/kg was found in a mix of categories (2, 3, 4, 6, 7) (see Table 5 for categories number) 8 times/9 samples, in a mix of categories (2, 6, 7) 2 times/4 samples and mix of categories (3, 4) 3 times/3 samples. It seems unlikely that the separation of brominated plastics by using only EEE categories is possible. Due to the large concentration range in parts, the plastics should be separated and sorted (i.e. shredded in small scraps and sorted on-line for Br content).. Other authors have come to the same conclusion in recent studies (Gallen et al., 2014 in Australia, Aldrian et al., 2015 in Austria, Puype et al., 2015 in Czech Republic, Guzzonato et al., 2016 in Italy, Turner and Filella, 2017a,b in UK). For waste, all WEEE samples contain bromine (Tables 7 and 8). The mean concentrations in the inflow fraction were 9343 mg/kg and 6597 mg/kg in 2014 and 2015, respectively, which were reduced to 2075 mg/kg and 2580 mg/kg for the ‘‘Low Br” fraction after sorting. Sorting is therefore effective but needs to be improved to reach concentrations <2000 mg/kg. 3.2. Distribution of BFR substances In 2009–2013 EEE, the arithmetic mean concentration of BFRs of 33 parts (1 LHA, 2 SHA, 16 IT, 3 Consumer, 6 Lights, 4 Toys) of 22 pieces of equipment (1 LHA, 1 SHA, 10 IT, 1 Audio-video, 4 Lights, 1 Tools, 4 Toys), mainly from 2013 are shown in Fig. 1. These selected items come from a population of 4218 parts of 347 pieces (Table 1). The regulated substances (underlined, details in Table 1) account for only 18% of the identified substances (Fig. 1). There are important differences between parts of equip-
ment. For example, the bromine concentration of parts of equipment with all parts brominated range from a minimum value of 100 – 1 600 mg/kg to a maximum value of 66,000–142,000 mg/k g for the seven EEE categories. The arithmetic mean concentrations of BFRs in WEEE of all samples are shown in Figs.2 and 3 for 2014 and 2015, respectively. DecaBDE has the highest mean BDE concentration. The sum of PBB and BDE is 473 mg/kg in EEE, and 2480 and 6270 mg/kg in WEEE for 2014 and 2015, respectively. When HBCDD and TBBPA are measured (WEEE 2015), TBBPA largely dominates (±8000 mg/kg). 3.3. Bromine balance When the bromine in identified brominated compounds (calculated as the sum of the calculated bromine content in mono- to deca-BB (mass fraction of bromine 0.76–0.85), mono- to decaBDE (0.66–0.83), HBCDD (0.75) and TBBPA (0.58)) is compared with the total bromine concentration, results are inconsistent for EEE (2009–2013 campaign) (Fig. 4); the mean mass ratio being 0.08 with the highest one at only 0.33. Thus, most of the brominated compounds remain unidentified. This might be explained by the fact that HBCDD and TBBPA were not measured. Two groups of samples were found in the 2014 WEEE campaign: a first group consistently showing a mass ratio of 0.42, with mainly SHAs and CRTs, and a second group characterised by a high bromine content but low identified bromine (Fig. 5). This group is mainly formed of flat screens, probably younger than other waste. As mentioned above, neither HBCDD or TBBPA was measured in 2014 but both
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Table 7 Mean concentrations of Br, PBBs and PBDEs in WEEE 2014 from 4 sites and classification for waste hazardousness and for POP regulation (between brackets: concentration between 50% and 100% of the concentration limit).
All other PBBs and PBDEs < LOQ (Table 2). HBCDD and TBBPA not analysed (n.a.).
Table 8 Mean concentrations of Br, PBBs, PBDEs, HBCDD and TBBPA in WEEE 2015 from 4 sites and classification for waste hazardousness and for POP regulation (between brackets: concentration between 50% and 100% of the concentration limit).
All other PBBs and PBDEs < LOQ (Table 2).
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1
51
1
69
42 79 44
11 13 162
223
908
9
863
40 21
60
3601
7983 Octa nona PBB
Deca PBB
Hexa BDE*
Hepta BDE*
Octa BDE*
Nona BDE
331
Deca BDE
Hexa BB* Nona BB Penta BDE* Octa BDE* TBBPA*
Fig. 1. Concentration of brominated flame retardants in EEE 2009–2013 (mg/kg, 32 parts of 22 equipment, PBBs and PBDEs < LOQ not represented, HBCDD and TBBPA not measured; *classified substances are underlined).
41
2 18
62
Octa BB Tetra BDE* Hepta BDE* HBCDD*
Fig. 3. Concentration of brominated flame retardants in WEEE 2015 (mg/kg, n = 32, values > LOQ, PBBs and PBDEs < LOQ not represented; * classified substances are underlined).
90
7 8
Hepta BB Deca BB Hexa BDE* Deca BDE
84 Br in substances (mg/kg)
405 362 2353
Hexa BB*
Hepta BB
Octa BB
Nona BB
Deca BB
Tetra BDE*
Penta BDE*
Hexa BDE*
Hepta BDE*
Octa BDE*
Deca BDE
1000 800 600 400 200 0
0
20000
40000
60000
80000
Br (mg/kg) Fig. 4. Bromine in measured substances as a function of total bromine in EEE (2009–2013) (n = 22).
were measured in 2015. When HBCDD and TBBPA are included in the calculation of the mass ratio (Fig. 7), the first group mass ratio changes from 0.35 to 0.86. Thus, the bromine concentration of regulated brominated substances was identified as up to 86% in ‘older’ waste (SHA, CRT) but only 30–50% in ‘younger’ waste, and a mean of only 8% in recent products (2009–2013) (see Fig. 6). 3.4. Classification for waste hazardousness, POP regulation, bromine separation and DecaBDE restriction of use for products Detailed tables of concentrations and classification are presented in the following tables. 3.4.1. EEE Mean concentrations of Br and substances in a selected set of brominated samples consisting of 33 parts from 22 items are
Br in substances without HBCDD and TBBPA (mg/kg)
Fig. 2. Concentration of brominated flame retardants in WEEE 2014 (mg/kg, n = 33, values > LOQ, PBBs and PBDEs < LOQ not represented, HBCDD and TBBPA not measured; * classified substances are underlined).
35000 30000 25000 20000 SHA CRT Flat sc.
15000 10000 5000 0
0
10000
20000
30000
40000
50000
60000
Br (mg/kg) Fig. 5. Bromine in measured substances as a function of total bromine in WEEE (2014) (n = 99 with triplicates).
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Br in substances without HBCDD and TBBPA (mg/kg)
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DecaBDE had a mean concentration >1000 mg/kg in the inflow fraction of CRT and Flat screens, and in the ‘‘High Br” fraction of CRT and SHA.
35000 30000
25000 20000
SHA CRT Flat sc.
15000 10000
5000 0
0
10000
20000
30000
40000
50000
Br (mg/kg) Fig. 6. Bromine in measured substances (excepted HBCDD and TBBPA) as a function of total bromine in WEEE (2015) (n = 56 with triplicates).
Br in substances with HBCDD and TBBPA (mg/kg)
9
35000 30000 25000 20000
SHA CRT Flat sc.
15000 10000 5000 0 0
10000
20000
30000
40000
50000
Br (mg/kg)
3.4.3. WEEE 2015 Mean concentrations of bromine and other substances are presented in Table 8 with the corresponding classification results. In 2015 as in 2014, ‘‘High Br High density” CRTs and ‘‘High Br” CRTs exceeded the concentration limits of POP regulation for the sum of tetra-, penta-, hexa- and heptaBDE (in red in the table) in the four processing sites (not shown). ‘‘High Br High density” CRTs are classified HP 10 ‘Toxic for reproduction’ due to hepta- and octaBDE concentrations. ‘‘Inflow” and ‘‘High Br Low density” CRTs approached the concentration limits of POP regulation for HBCDD and the sum of tetra-, penta-, hexa- and heptaBDE (in orange in the table). It is the same case for ‘‘High Br” SHA for the sum of tetra-, penta-, hexa- and heptaBDE. No waste is classified for HP 14 ‘Ecotoxic’, but the ‘‘High Br” CRT fraction was close to the concentration limit. Classification for HP 14 is triggered by TBBPA. The inflow fractions measured consistently presented mean bromine concentrations >2000 mg/kg. The sorting for the ‘‘Low Br” fraction of CRT and Flat screens should be improved. DecaBDE had a mean concentration >1000 mg/kg in the inflow fraction of CRT and Flat screens, and in all the ‘‘High Br” fractions. For EEE, the bromine concentration limit of 2000 mg/kg was exceeded for LHA, Tools, Lighting, IT and Toys (unweighted mean, potentially overestimated). Thus, a sorting of these categories for bromine should be recommended. Waste stream classifications were very similar for 2014 and 2015. Before sorting, in 2014 and 2015, the inflow fractions of SHA, CRT and Flat screens had mean bromine concentrations >2000 mg/kg, CRT are classified HP 14, and CRT and Flat screens had decaBDE concentrations above the restriction of use concentration limit of 1000 mg/kg for products. Unsorted fractions of
Fig. 7. Bromine in measured substances (including HBCDD and TBBPA) as a function of total bromine in WEEE (2015) (n = 56 with triplicates).
these three categories cannot be recycled as such. After sorting, the mean bromine concentration in the ‘‘Low Br” fraction in all sites (not always below 2000 mg/kg: CRTs and Flat screens), and the decaBDE concentration were below the concen-
presented in Table 6 together with the corresponding results classification. The classification for HP 14 is not applicable due to the absence of measures for HBCDD and TBBPA. Few classifying substances were detected, and their concentrations were low. No EEE have been classified as hazardous or POP with these analyses. In this selected set, mean bromine was >2000 mg/kg in LHA, IT, Lights, Tools and Toys. This mean is not weighted by the mass of each part of equipment. The concentration at the output of a shredder will be lower if the brominated parts have a mass lower than the non-brominated parts. The WEEE Forum launched a measurement campaign in 2017 to clarify this point.
tration limit of restriction of use. The ‘‘Low Br” fractions of SHA,
3.4.2. WEEE 2014 Mean concentrations of bromine and other substances are presented in Table 7, with the corresponding classification results. The classification for HP 14 is not applicable due to absence of measure of HBCDD and TBBPA. Sb was consistently lower than 8400 mg/kg in 2014 and 2015. ‘‘High Br High density” CRTs and ‘‘High Br” CRTs exceeded the concentration limits of POP regulation for the sum of tetra-, penta-, hexa- and heptaBDE (in red in the table). This is observed in the four processing sites (not shown). ‘‘High Br” SHA is close to exceeding the concentration limits of POP regulation for the same sum (in orange in the table). The mean bromine concentrations of the inflow fractions were always >2000 mg/kg. The sorting for the ‘‘Low Br” fraction of CRT should be improved.
CRT and Flat screens comply with all regulatory concentration limits and can be recycled. After sorting, the ‘‘High Br” fractions have the following regulatory concerns: – SHAs are hazardous HP 14 except for the ‘‘High Br Low Density” fraction, with a restriction of use for decaBDE in the ‘‘High Br” fraction in 2014 but no restriction for the ‘‘High Br Low Density” and ‘‘High Br High Density” fractions in 2014, and a restriction of use for decaBDE for all ‘‘High Br” fractions in 2015; – CRTs are hazardous HP 14, are HP 10 ‘Toxic for reproduction’ in the ‘‘High Br High Density” in 2015, and POP for the ‘‘High Br High Density” and ‘‘High Br” fractions; – Flat screens are hazardous HP 14 and have a restriction of use for decaBDE. 4. Conclusion The EU Directive on WEEE management states that plastics containing BFRs should be sorted and managed separately from the non-brominated fraction. Existing literature and this study show that BFRs, and a practical surrogate parameter, total bromine, are found in WEEE and EEE plastics, but also in non-EEE plastics. Classification of the fractions of WEEE before and after automated sorting is conclusive. The limit for sorting at 2000 mg/kg measured by XRF has been validated, since all fractions below
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comply with regulation (except cathode ray tubes), and all fractions above this limit are of regulatory concern (bromine, decaBDE, hazardous properties, POP substances). This concentration limit can be used as a surrogate for full laboratory analysis and classification. Our results validate on-line sorting as done today in France. Sorting could be extended to categories other than small household appliances and screens, because the BFRs used in plastic compounds change faster than regulations evolve (i.e., as shown in this study, 86% of identified bromine in ‘‘old waste” versus 30–8% in recent products), and other categories than the three considered here have bromine contents higher than 2000 mg/kg. A European campaign comprised of 7 countries and 35 sites will begin in 2017, organised by the WEEE Forum, the European association speaking for thirty-one not-for-profit e-waste producer responsibility organisations (weee-forum.org/), to assess the mean bromine content of plastics from large household appliances after shredding. Sorting is essential to avoid uncontrolled dispersion of regulated substances in recycled raw material. Acknowledgement The OCAD3E, French non-profit organisation coordinating the WEEE sector, is gratefully acknowledged for the WEEE sampling and analysis campaigns. We also sincerely thank Mr François David, Head of R&D, SGS laboratory (Saint Etienne du Rouvray, France) for data on the composition of products and his technical assistance. The help of Dr. D. Slomberg on the careful improvement of this manuscript is also highly appreciated. The data interpretation was financially supported by the Ministry of Ecology, France. References Alaee, M., Arias, P., Sjodin, A., Bergman, A., 2003. An overview of commercially used brominated flame retardants, their applications, their use patterns in different countries/regions and possible modes of release. Environ. Int. 29, 683–689. Aldrian, A., Ledersteger, A., Pomberger, R., 2015. Monitoring of WEEE plastics in regards to brominated flame retardants using handheld XRF. Waste Manage. 36, 297–304. Chen, S.-J., Ma, Y.-J., Wang, J., Chen, D., Luo, X.-J., Mai, B.-X., 2009. Brominated flame retardants in children’s toys: concentration, composition, and children’s exposure and risk assessment. Environ. Sci. Technol. 43, 4200–4206. CLC/TS 50625-3-1:2015 Requirements for the collection, logistics and treatment of WEEE - Part 3-1: Specification relating to depollution - General. CENELEC, Brussels, Belgium. CLP, 2008. 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. Official Journal of the European Union 31.12.2008 L 353 1353 pp. (2008). Decottignies, V., Bourgeois, M., Mathieu, C., Zariatti, S., 2014. Characterisation of plastic shredder fractions from waste of electric and electronic Equipment. Proceedings Crete 2014. 4th International Conference on Industrial and Hazardous Waste Management. Sept 2nd-5th, 2014. Chania, Crete, Greece.. Dimitrakakis, E., Janz, A., Bilitewski, B., Gidarakos, E., 2009. Small WEEE: determining recyclables and hazardous substances in plastics. J. Hazard. Mater. 161, 913–919. EC, 2002. Directive 2002/95/EC of the European Parliament and of the Council of 27 January 2003 on the restriction of the use of certain hazardous substances (RoHS) in electrical and electronic equipment. OJEU 13.2.2003 L 37/19. EC, 2003. Directive 2003/11/EC of the European Parliament and of the Council of 6 February 2003 amending for the 24th time Council Directive 76/769/EEC
relating to restrictions on the marketing and use of certain dangerous substances and preparations (pentabromodiphenyl ether, octabromodiphenyl ether). OJEU 15.2.2003 L 42/45. EC, 2008. Regulation (EC) No 850/2004 of the European parliament and of the Council of 29 April 2004 on persistent organic pollutants and amending Directive 79/117/EEC. Official Journal of the European Union, L 158, p. 7, 30.4.2004, last amended Commission Regulation (EU) 2016/460 of 30 March 2016, Official Journal of the European Union, L 80, p. 17, 31.3.2016. EU, 2012. Directive 2012/19/EU of the European Parliament and of the Council of 4 July 2012 on waste electrical and electronic equipment (WEEE) (recast). Official Journal of the European Union 24.7.2012. L 197/38. EU, 2014a. Commission Decision 2014/955/EU of 18 December 2014 amending Decision 2000/532/EC on the list of waste pursuant to Directive 2008/98/EC of the European Parliament and of the Council. http://eurlex.europa.eu/ legalcontent/EN/TXT/PDF/?uri=CELEX:32014D0955&rid=1. EU, 2014b. Commission Regulation (EU) No 1357/2014 of 18 December 2014 replacing Annex III to Directive 2008/98/EC of the European Parliament and of the Council on waste and repealing certain Directives. Official Journal of the European Union. 19.12.2014. L 365/89. EU, 2017. Council Regulation (EU) 2017/997 of 8 June 2017 amending Annex III to Directive 2008/98/EC of the European Parliament and of the Council as regards the hazardous property HP 14 ‘Ecotoxic’. Official Journal of the European Union. 14.6.2017. L 150/1. Eurostat, 2017. Waste statistics - electrical and electronic equipment. http://ec. europa.eu/eurostat/statistics-explained/index.php/Waste_statistics__electrical_and_electronic_equipment. Gallen, C., Banks, A., Brandsma, S., Baduel, C., Thai, P., Eaglesham, G., Heffernan, A., Leonards, P.E., Bainton, P., Mueller, J.F., 2014. Towards development of a rapid and effective non-destructive testing strategy to identify brominated flame retardants in the plastics of consumer products. Sci. Total Environ. 491–492, 255–265. Guzzonato, A., Puype, F., Harrad, S.J., 2016. Improving the accuracy of hand-held Xray fluorescence spectrometers as a tool for monitoring brominated flame retardants in waste polymers. Chemosphere 159, 89–95. Huisman, J., Magalini, F., Kuehr, R., Maurer, C., Ogilvie, S., Poll, J., Delgado, C., Artim, E., Szlezak, J., Stevels, A., 2008. 2008 Review of Directive 2002/96 on Waste Electrical and Electronic Equipment (WEEE). United Nations University. Patawari, S.B., 2017. Market analysis Plastics - A final flourish to 2016. Recycling Int. 2017 (1), 42. Plastics Europe, 2017. http://www.plasticseurope.org/Document/plastics-the-facts2016-15787.aspx?FolID=2. Puype, F., Samsonek, J., Knoop, J., Egelkraut-Holthus, M., Ortlieb, M., 2015. Evidence of waste electrical and electronic equipment (WEEE) relevant substances in polymeric food-contact articles sold on the European market. Food Addit. Contam. Part A 32, 410–426. Schlummer, M., Gruber, L., Mäurer, A., Wolz, G., van Eldik, R., 2007. Characterisation of polymer fractions from waste electrical and electronic equipment (WEEE) and implications for waste management. Chemosphere 67, 1866–1876. Taurino, R., Pozzi, P., Zanasi, T., 2010. Facile characterization of polymer fractions from waste electrical and electronic equipment (WEEE) for mechanical recycling. Waste Manage. 30, 2601–2607. Turner, A., Filella, M., 2017a. Field-portable-XRF reveals the ubiquity of antimony in plastic consumer products. Sci. Total Environ. 584–585, 982–989. Turner, A., Filella, M., 2017b. Bromine in plastic consumer products – evidence for the widespread recycling of electronic waste. Sci. Total Environ. 601–602, 374– 379. United Nations Environment Programme (UNEP), 2007. Diphenyl ether, octabromoderivative (octabromodiphenylether) draft risk profile. 2007 (August). United Nations Environment Programme (UNEP), 2010a. Technical review of the implications of recycling commercial pentabromodiphenyl ether and commercial octabromodiphenyl ether. In: 6th POP reviewing committee meeting Geneva 11–15; 2010a. [October, UNEP/ POPS/POPRC.6/2]. United Nations Environment Programme (UNEP), 2010b. Supporting Document for Technical review of the implications of recycling commercial penta and octabromodiphenyl ethers. 6th POP Reviewing Committee meeting Geneva; 2010b. [11–15 October, UNEP/POPS/POPRC.6/INF/6]. Wäger, P., Schluep, M., Müller, E., 2010. RoHS Substances in Mixed Plastics from Waste Electrical and Electronic Equipment. Swiss Federal Laboratories for Materials Science and Technology (Empa). 100 p.
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WEEE plastic sorting for bromine essential to enforce EU regulation Pierre Hennebert a,⇑, Montserrat Filella b a b
INERIS (National Institute for Industrial Environment and Risks), BP 2, F-60550 Verneuil-en-Halatte, France Institute F.-A. Forel, University of Geneva, Boulevard Carl-Vogt 66, CH-1205 Geneva, Switzerland
a r t i c l e
i n f o
Article history: Received 11 July 2017 Revised 15 September 2017 Accepted 27 September 2017 Available online xxxx Keywords: Electric and electronic equipment (EEE) Brominated flame retardants (BFR) Hazard property (HP) Persistent organic pollutants (POP)
a b s t r a c t The plastics of waste of electric and electronic equipment (WEEE) are improved for fire safety by flame retardants, and particularly brominated flame retardants (BFR). As waste, the management of these plastic fractions must comply with the update of the regulation of waste hazard classification (2014, 2017), the publication of a technical standard on management of WEEE (2015), and a restriction of use for decabromodiphenylether in the product regulation (2017). Data of bromine (n = 4283) and BFR concentrations (n = 98) in plastics from electric and electronic equipment (EEE), and from WEEE processing facilities before and after sorting for bromine in four sites in France have been studied for chemical composition and for regulatory classification. The WEEE was analysed by handheld X-ray fluorescence, and the waste was sorted after shredding, by on-line X-ray transmission for total bromine content (< or > 2000 mg/kg) in small household appliances (SHA), cathode ray tubes (CRT) and flat screens plastics. In equipment (n = 347), 15% of the equipment items have no bromine, while 46% have at least one part with bromine, and 39% have all parts brominated. The bromine concentration in plastics is very heterogeneous, found in high concentrations in large household appliance (LHA) plastics, and also found in unexpected product categories, as observed by other authors. Clearly, an unwanted global loop of brominated substances occurs via the international recycling of plastic scrap. In waste (n = 65), polybromobiphenyls, polybromodiphenylethers (PBDE), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane were analysed. The most concentrated BFRs are decaBDE (3000 mg/kg) and TBBPA (8000 mg/kg). The bromine concentration of regulated brominated substances was identified in 2014 and 2015 to be up to 86% of total bromine in ‘‘old” waste (SHA, CRT), 30–50% in ‘‘younger” waste (Flat screens), and a mean of only 8% in recent products (2009–2013). Regulated substances are a minority of all the brominated substances and the only practical way to sort is to measure total bromine on-line. The sorting reduces the mean bromine concentration in the ‘‘Low Br” fraction in all sites, and reduces the decaBDE concentration to levels below the restricted use limit. After sorting, the concentration in the ‘‘High Br” fractions exceeds all present or future regulatory limits. In conclusion, sorting of small household appliances, cathode ray tubes and flat screen plastics is necessary to avoid uncontrolled dispersion of regulated substances in recycled raw material. Other categories (large household appliances, electric and electronic tools, lighting equipment) should also be considered, since their total bromine content (unweighted mean concentration) is high for some of these products. A European campaign consisting of 7 countries and 35 sites will begin in 2017, directed by WEEE Forum, the European association speaking for thirty-one not-for-profit e-waste producer responsibility organisations, to assess the mean bromine content of plastics from large household appliances after shredding. Ó 2017 Elsevier Ltd. All rights reserved.
1. Introduction In 2014, the rounded world production of plastics was 270 million tonnes (Mt), with an EU production and demand of 50 Mt ⇑ Corresponding author. E-mail address: [email protected] (P. Hennebert).
(18.5%) and 49 Mt, respectively and 2.8 Mt (5.8%) of this EU production used for electric and electronic equipment (EEE) (Plastics Europe, 2017). That year, 25.8 Mt of post-consumer plastic waste ended up in the official waste streams in the EU, and were managed by energy recovery (10.2 Mt, 39.5%), landfilling (7.9 Mt, 30.8%) and recycling (7.6 Mt, 29.7%). The amount of electric and electronic equipment on the EU market in 2013 was 8.1 Mt (17.4
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kg/inhabitant) (Eurostat, 2017). The waste of electric and electronic equipment (WEEE) separately collected in 2013 reached 3.5 Mt (6.5 kg/inhabitant), of which 2.7 Mt were recovered. The recovered amount included 2.4 Mt of recycled WEEE (i.e. reprocessed into a product) and 0.2 million tonnes that were used for energy production. The plastic fraction in European WEEE depends on categories and products and was estimated to be 2.3 Mt or about 20.6% of the weight of EEE in 2008 (Huisman et al., 2008). In new EEE appliances, the percentage has continuously increased since 1980 from scarcely 14–18% in 1992, to 22% in 2000, and was estimated to be at 23% in 2005. The mass flow of recycled plastics from WEEE separately sorted in the EU can be estimated to 0.48 Mt (= 2.4 Mt WEEE recovered ⁄ 20% plastics in WEEE). The contribution of brominated flame retardants is unsure but has been estimated to be 25% of WEEE plastics. Flame retardant additives are now found in consumer products (see below). Recent developments in regulations and technical standards have changed the framework for the management of plastics from waste of electric and electronic equipment (WEEE). The plastic fractions of WEEE can be noted as hazardous or not in the European List of Waste depending on the content of hazardous components (codes 16 02 13⁄ or 16 02 14, and 20 01 35⁄ or 20 01 36) (EU, 2014a). There is no specific entry in the list for brominated plastics. The European Directive 2012/19/EU (EU, 2012) states that plastic containing brominated flame retardants (BFR) must be removed from any separately collected WEEE (Article 8, Annex VII). If a plastic fraction contains persistent organic pollutants (POP) at concentrations higher than regulatory concentration limits, the only authorised treatments (to destroy or irreversibly transform the substances) are: (i) physico-chemical treatment, (ii) incineration on land, or (iii) use principally as a fuel or other means to generate energy, excluding waste containing PCBs (EC, 2008, Annex V). On the other hand, according to technical specification CLC/TS 50625-3-1:2015 (developed by the standardisation organisation CENELEC upon mandate of the European Commission), all the plastic fractions of WEEE may contain significant concentrations of BFR, excepted non-cooling Large Household Appliances (LHA) and cooling and freezing LHA. The operators must separate these BFR if total bromine concentration in the fraction is known to be >2000 mg/kg, or expected to be >2000 mg/kg, or if it is not declared. On the other hand, ‘‘If the concentration of bromine is <2000 mg/kg, the operator fulfills the requirement for de-pollution of BFR” (CLC/TS 50625-3-1:2015). Detailed regulatory concentration limits are presented in this paper. Numerous substances (75 according to Alaee et al., 2003) have been reported as potential brominated additives in plastics of EEE (alkanes, cycloalkanes, aromatics, alcohols, ethers, phthalates, epoxy resins, brominated polystyrene. . .). The c-octaBDE and cdecaBDE mixtures were typically incorporated into plastics at final weight loadings of 12–18% and 5–16%, respectively (Alaee et al., 2003; UNEP, 2007). The commercial PBDE mixtures are added flame retardants which are not chemically bound to the plastic polymer but are physically mixed in during manufacture (Gallen et al., 2014). A variety of chemical elements and BFRs have been reported to be present in WEEE (Schlummer et al., 2007; Dimitrakakis et al., 2009; Wäger et al., 2010). In products, they are restricted or regulated by two European Directives: Restriction of use of certain Hazardous Substances (RoHS) in EEE (EC, 2002) and restrictions on the marketing and use of certain dangerous substances and preparation (EC, 2003). These directives contribute to the organization of the distribution of recycled plastic polymers (Decottignies et al., 2014). Although the production of POP PBDEs has ceased, significant volumes of these chemicals continue to remain in circulation through the recycling of PBDE-containing products (UNEP, 2010a,b, Gallen et al., 2014). The elimination of
these chemicals from the recycling stream are recommended to avoid the unintentional contamination of products with sensitive end uses such as children’s toys (Chen et al., 2009) and food preparation products (Puype et al., 2015). The presence of BFRs in plastics is frequently estimated by the measure of total bromine, at the laboratory or with handheld or automated X-ray fluorescence spectrometry. Detailed laboratory investigations for every type of waste and every waste stream are not economically feasible, XRF being at present the only method that allows the operator to decide on the recycling suitability of the sample in real time (Aldrian et al., 2015, Guzzonato et al., 2016). Typically, the authors measure total bromine in numerous samples, and identify BFRs (substances) in some (selected) samples. Brominated flame retardants (BFRs) and antimony trioxide (a synergist of BFRs) are found in consumer plastics, WEEE or nonWEEE. Taurino et al. (2010) measured BFRs in WEEE in Italy in composite samples of TV and personal computer (PC) monitors. The grey plastics had a mean BFR content of 43,900 mg/kg. For WEEE and non-WEEE, Gallen et al. (2014) have measured bromine by Xray fluorescence (XRF) in Australian commercial products. Bromine concentrations were >1 mg/kg in 51% of the 1714 measurements, >1000 mg/kg in 18% of measurements and >10,000 mg/kg in 10% of measurements (in 9 out of the 14 product types). Five product types (which included four electronic-based product types) had maximum XRF measurements that exceeded 100,000 mg/kg. Aldrian et al. (2015) have measured bromine by the same method in Austrian TV and PC monitors (with a routine limit of detection (LD) of 300 mg Br/kg). TV waste plastics show a bromine content of about 7000–8000 mg/kg (mean value of 3006 parts), whereas PC monitor housings (n = 1598) have a content of 32,000 mg/kg. The distributions for TV plastics were: 85.5% of parts <1000 mg/ kg, 1.9% in the range 1000–3000 mg/kg, 12.6% >3000 mg/kg), and for PC plastics: 52.6% of parts <1000 mg/kg, 3.9% in the range 100 0–3000 mg/kg, and 43.5% >3000 mg/kg). The authors conclude that adequate monitoring measures are necessary, to identify the high number of pieces with a concentration of BFRs >50,000 mg/kg (7% TV and 39% PC waste plastics) to prevent the transfer of highly contaminated pieces to the recyclable fraction. Puype et al. (2015) have quantified bromine, BFRs, polymer impurity and WEEE-relevant elements in 10 black polymeric food-contact articles in the Czech Republic. They found bromine >LD (40 mg/kg) in 7 articles (from 66 to 5975 mg/kg), with BFRs in each of the 7 articles, antimony in 4 articles (from 52 to 504 mg/kg), polymeric impurities in all cases and typical rare earth elements (REE: Ce, Dy, La, Nd, Pr and Y) in electronic applications in 4 brominated samples. However, in Br-negative samples, no traces of REES were detected, clearly indicating that WEEE plastics have been used for the production of food-contact articles, despite the very small number of samples. The authors address their concern to the scientific community, policy-makers and control authorities. Turner and Filella (2017a, 2017b) investigated the levels of antimony, bromine and chlorine in plastic consumer products in the United Kingdom. The percentage of items with brominated plastics were: Electronics 58%, Clothing-upholstery 39%, Vehicle interiors 34%, Constructionplumbing 30%, Leisure-sports 25%, Office-stationery 22%, Toyshobbies 15%, Cleaning-storage 9%, Food-drinks 6%. Total: 29% (Total non-EEE: 21%). Bromine and/or antimony were found in all categories, including categories where no flame retardancy was expected. The authors conclude that many polymeric household items that have no reason to be fire-resistant are constructed, at least in part, from recycled plastic components of end-of-life electronic products, and call for reconsideration of the means of disposal and recycling of Sb-rich electronic plastic waste. For sorting, ‘‘there is no uncritical mixed plastics fraction, however there are two fractions which appear to be very critical (mixed plastics from CRT monitors and CRT TVs)” (Wäger et al., 2010).
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33 (all in triplicates = 99) Total Br analyses Total PBB PBDE analyses Total HBCDD TBBPA analyses
691 4218 43 347
4 33 parts of 22 items with brominated parts 4316 (4406 with triplicates) 98 (188 with triplicates)
219 425 88 48 39 4
4. Consumer equipment and photovoltaic panels (Audio-Video) 5. Lighting equipment (Lightings) 6. Electrical and electronic tools (with the exception of large-scale stationary industrial tools) (Tools) 7. Toys, leisure and sports equipment (Toys) Total laboratory samples
3 6 1
16 173 3. Information and telecommunications equipment (IT)
1253
32 (56 with triplicates)
32 (all 12 brominated in triplicates = 56)
CRT: 4 inflow, 9 sorted; Flat screens: 2 inflow, 4 sorted
4 inflow, 9 sorted
4 inflow, 1 fines, 9 sorted CRT: 4 inflow, 1 fines, 9 sorted; Flat screens: 2 inflow, 4 sorted 1 2 1232 310 26 14
Parameters
Equipment-products for legal compliance Br (XRF) Equipment/Samples
Parts of Equipment Br (XRF) EEE 2009–2013 Campaign
Table 1 Campaigns, samples and analyses.
Data on bromine and BFRs in plastics from electric and electronic equipment (EEE) were obtained from a service laboratory for product quality control for compliance with the RoHS directive by the importers and resellers (SGS Multilab, Saint Etienne du Rouvray, France) from 2009 to 2013. Data on bromine and BFRs in plastics from WEEE processing facilities before and after sorting for bromine in four sites of four French companies in 2014 and 2015 (Table 1) were provided by OCAD3E (the French federation of producer responsibility organisation for WEEE), in collaboration with processing companies, the French Ministry for Ecology, and the National Institute for Industrial Safety and Environmental Protection (INERIS). The first set of data is referred to as EEE 2009– 2013 and the second group as WEEE 2014 and WEEE 2015 throughout the article. In the 2009–2013 EEE campaigns, Br was determined in the visually different plastic parts, including printed circuit boards (up to 76) of equipment using a portable XRF (Niton) with Br calibration, and an in-borne instrument automatically corrected for thickness. Up to 60 parts were measured in one piece of equipment. In a second step, laboratory analyses (total bromine, total antimony, polybromobiphenyls PBB and polybromodiphenylethers - PBDE) were performed for selected items (Table 1). The weight percentage of each part is not known, and the calculated unweighted means are estimations. In the 2014 and 2015 WEEE campaigns, WEEE were sorted by categories in collection points, shredded and automatically sorted (Pellenc ST Xpert with X-ray transmission and dual energy sensor to avoid any thickness issues) on a conveyor for total bromine content in two fractions: ‘‘Low Br (<2000 mg/kg) and ‘‘High Br” (>2000 mg/kg). In one site, the latter fraction was further sorted by density with a floating bath (1.09 kg/L) into ‘‘high brominated low density” and ‘‘high brominated high density” fractions. Samples of the flow before and after the sorting for bromine were taken according to TS-50625-3-1:2015. During one day, ten samples were taken, mixed, quartered, divided in two and sent as laboratory samples for analysis. For a shredder producing particles <5 cm, 10 subsamples of 10 L were taken and reduced to a laboratory sample of 25 L, and for a shredder producing 2–5 cm particles, 10 subsamples of 5 L were taken and reduced to 12 L. In 2014, sampling of flow with >5 cm particles deviated from this
Parts of Equipment
2.1. Campaign and samples
EEE Categories (EC 2012) and short name in this paper 1. Large household appliances (LHA) 2. Small household appliances (SHA)
2. Materials and methods
Br (Laboratory), PBB, PBDE
WEEE 2015 WEEE 2014
One day composite sample (shredder and sorter) Br (Laboratory), Sb, PBB, PBDE
Clearly, an unwanted global loop of substances occurs via the international trade of plastic scrap, according to many professionals. The recyclers are aware of this question: ‘‘The Chinese government is determined to improve environmental conditions by imposing regulatory controls on the plastics recycling industry. . . . The ultimate objectives are to get rid of small recyclers who do not have proper recycling facilities; and to stop the importation and recycling of polluted scrap. . . The environmental authorities took to seizing factories, arresting owners, disconnecting utility supplies and destroying illegal workshops” (Patawari, 2017). In this study, data of bromine and BFRs in plastics from EEE, obtained from a service laboratory for commercial products quality control from 2009 to 2013, and from WEEE processing facilities before and after automated sorting for bromine in four sites of four companies in 2014 and 2015 are presented and the following subjects discussed: distribution of the different BFRs, their concentrations and relation to total bromine content, the hazard and POP classification of these plastics, the consequences for management of these fractions, and the best way to enforce EU regulation and promote sustainable recycling of WEEE plastics.
One day composite sample (shredder and sorter) Br (Laboratory), Sb, PBB, PBDE, HBCDD, TBBPA
P. Hennebert, M. Filella / Waste Management xxx (2017) xxx–xxx
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procedure when a 12 L laboratory sample was sent to the laboratory. This was corrected in 2015. For manual dismantling of cathode ray tubes (CRTs), pieces from 250 units were taken and sent to the laboratory. The EEE and WEEE are classified in ten categories in the European WEEE Directive (EU, 2012). For products, seven categories were analysed (Table 1). The WEEEs studied here were sorted at the collection points and the processing facility into small household appliances (SHA), cathode ray tubes (CRT), and flat screens (Table 1). CRTs and flat screens can be assigned to Category 3 or 4. 2.2. Analyses The analyses were performed by the ISO 17025 service laboratory SGS Multilab (Saint-Etienne du Rouvray, France). A first sorting of the laboratory samples was conducted manually to eliminate the metallic parts. Samples were repeatedly shredded with a low-speed device (Blik model BB230), producing pieces less than 10 mm in size without heating. These samples were then cryo-ground to 4 mm using a Retsch SM300 mill and quartered to 1 kg using a riffle divider and the resulting sub-samples were cryo-ground to 1 mm. For antimony determination, an aliquot of the sample was mineralised (ISO 13657, adapted) and analysed with ICP/OES (ISO 11885). Aliquots for bromine analysis were combusted in oxygen in a closed system (EN 14582) and then assayed with ionic chromatography. Brominated flame retardants were determined per IEC 62321-6 with gas chromatography coupled with mass spectrometry (GC/MS). The expression of results in congeners and the limit of quantification are presented in Table 2. For the WEEE 2014 campaign, 33 laboratory samples were ground and the resulting aliquots were analysed (extraction and analysis) in triplicate. The relative standard deviation (RSD) values of the data higher than the limit of quantification (LOQ) are presented in Table 3. The mean RSD obtained of 13.5% has been judged satisfactory for these heterogeneous samples.
2.3. Classification for waste hazardousness, POP regulation, Br separation and restriction of use for products Products and waste must comply with their respective regulations. The hazard properties (HP) of waste in Europe are defined in the Commission Regulation 1357/2014 (EU, 2014a) and the Decision 2014/955/UE (EU, 2014b), except for the most frequent HP 14 ‘Ecotoxic’. For each hazard property, the (measured) concentrations or sum of concentrations of substances with hazard statement codes (from the ‘‘Regulation on classification, labelling and packaging of substances” (CLP, 2008) tables and European Chemical Agency - ECHA site) are compared with waste-specific concentration limits (Table 4). The Decision 2014/955/UE includes persistent organic pollutant (POP) substances (use of POP concentration limit for classification of waste containing hexabromobiphenyls). For HP 14 ‘Ecotoxic’, the recently decided calculation method (EU, 2017) has been applied, with cut-off values of 1000 mg/kg for substances with H410 hazard statement code. For bromine, a separation in fraction < o > 2000 mg/kg is recommended (CLC/TS 50625-3-1:2015). For decabromodiphenylether, a restriction of use in the EU REACH system has been applied since the first semester of 2017, with a concentration limit of 0.1% (1000 mg/kg). 3. Results and discussion 3.1. Bromine content For EEE, some equipment has no bromine (<100 mg/kg, 52/347 = 15%), while many others have at least one part with bromine (>100 mg/kg, 158/347 = 46%), and a large part of the equipment consist of all brominated parts (137/347 = 39%) (Table 5). The most frequently brominated categories are large household appliances (LHA), Toys and Tools (>70% of equipment with at least one part
Table 2 List of analysed substances, expression in congeners and limit of quantification (LOQ). Parameter
Expression
CAS
LOQ EEE (mg/kg) 100 n.a.
**
LOQ WEEE (mg/kg)
Br Sb
Total Total
Monobromobiphenyls Dibromobiphenyls Tribromobiphenyls Tetrabromobiphenyls Pentabromobiphenyls Hexabromobiphenyls Heptabromobiphenyls Octabromobiphenyls Nonabromobiphenyls Decabromobiphenyl Sum of polybromobiphenyls (PBBs)
Congener BB-2 Congener BB-15 Congener BB-30 Congener BB-49 Congener BB-103 Congener BB-153 Congener BB-189 Congener BB-194 Congener BB-206 Congener BB-209 Sum of the congeners
2113-57-7 92-86-4 59080-33-0 59080-33-0 60044-24-8 59080-39-6 59080-40-9 67889-00-3 67889-00-3 13654-09-6
1 1 1 1 1 1 20 25* 25* 25 100
1 1 1 1 1 1 1 1 2 10 20
Monobromodiphenylethers Dibromodiphenylethers Tribromodiphenylethers Tetrabromodiphenylethers PentabromobiphenyletherZ Hexabromodiphenylethers Heptabromodiphenylethers Octabromodiphenylethers Nonabromodiphenylethers Decabromodiphenylether Sum of polybromodiphenylethers (PBDEs)
Congener BDE-3 Congener BDE-15 Congener BDE-35 Congener BDE-47 Congener BDE-99 Congener BDE-153 Congener BDE-183 Congener BDE-197 Congener BDE-207 Congener BDE-209 Sum of the congeners
101-55-3 2050-47-7 147217-805436-43-1 60348-60-9 68631-49-2 207122-16-5 117964-21-3 437701-79-6 1163-19-5
1 1 1 1 1 1 1 25 25 50 100
1 1 1 1 1 1 1 1 2 10 20
Hexabromocyclododecanes (HBCDD) 3,30 ,5,50 -Tétrabromobisphénol A (TBBPA)
1,2,5,6,9,10-Hexabromocyclododecane TBBPA
3194-55-6 79-94-7
n.a. n.a.
10 1
10 20
N.a.: not analysed. * Octa and nona measured together. ** XRF.
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Table 3 Reproducibility of the element and substances analysis on three separate laboratory samples from a daily shredder flow of the campaign WEEE 2014 (concentration, and relative standard deviation for triplicates > LOQ, total 1201 values). Parameter
Concentration of triplicates (mg/kg)
Br Sb
Relative standard deviation (standard deviation/mean)
n
min
max
mean RSD
max RSD
33 33
423 25
55375 5287
0.10 0.10
0.27 0.25
Pentabromobiphenyls (PBB 103) Hexabromobiphenyls (PBB 153) Heptabromobiphenyls (PBB 189) Octabromobiphenyls (PBB 194) Nonabromobiphenyls PBB 206) Decabromobiphenyl (PBB 209) Sum of PBBs
1
18
18
0.44
1 3 5 5
62 5 12 5
62 158 328 548
0.08 0.17 0.15 0.13
0.23 0.28 0.26
Tetrabromodiphenylethers (PBDE 47) Pentabromobiphenylethers (PBDE 99) Hexabromodiphenylethers (PBDE 153) Heptabromodiphenylethers (PBDE 183) Octabromodiphenylethers (PBDE 197) Nonabromodiphenylethers (PBDE 207) Decabromodiphenylether (PBDE 209) Sum of PBDEs
4 4 16 24 23 28 32 32
5 5 5 5 5 5 5 13
10 27 764 4410 4453 2627 16300 28600
0.23 0.20 0.12 0.17 0.15 0.13 0.15 0.14
0.50 0.32 0.30 0.64 0.36 0.28 0.42 0.36
Parameters without sums Parameters with sums
Mean (207 trip.) Mean (244 trip.)
0.135 0.135
Table 4 Classification of regulated substances: Hazard statement codes, hazard properties (HP) and POP classification, concentration limits (CL – mg/kg). Substance
CAS
Hazard statement code
Br Sb2O3
1309-64-4
H351
HexaBB -PBB TetraBDE TetraBDE PentaBDE PentaBDE HexaBDE HeptaBDE OctaBDE NonaBDE DecaBDE HBCDD HBCDD HBCDD TBBPA
36355-01-8 40088-47-9 40088-47-9 32534-81-9 32534-81-9 36483-60-0 68928-80-3 117964-21-3 69278-62-2 1163-19-5 3194-55-6 3194-55-6 3194-55-6 79-94-7
H350 H373 H400 H373 H400 H360 H360 H360
Hazard property
HP
CL
HP 7
POP
Decision 2014/955/ UE POP
CL
Rule
Separation
Restriction of use 2017
CL
2000
1B - H410 - H410 1B 1B 1B
H319 H319 - H335 - H315 H361 H400 - H410 H400 - H410
HP HP HP HP HP HP HP HP
7 5 14 5 14 10 10 10
10,000 (Sb 8400) 1000 100,000 P H410 < 2500 100,000 P H410 < 2500 3000 3000 3000
HP HP HP HP HP
4 4 10 14 14
P H319, H315 < 200,000 P H319, H315 < 200,000 30,000 P H410 < 2500 P H410 < 2500
POP1
50
POP1 POP2 POP2
50 P P
POP2 <1000 POP2 < 1000
POP2 POP2
P POP2 < 1000 P POP2 < 1000
**
**
POP3
1000*
1000
HP 4 ‘Irritant’; HP 5 ‘Specific Target Organ Toxicity (STOT)/Aspiration’; HP 7: ‘Carcinogenic’; HP 10 ‘Toxic for reproduction’; HP 14 ‘Ecotoxic’. * 1000 mg/kg subject to review by the European Commission by 20.4.2019. ** Annex D fulfilled, annex E and F in technical committee (begin 2017).
with bromine), then small household appliances (SHA) and Lighting (>50% of equipment), and finally Audio-Video and IT (±25% of equipment). Most parts of the equipment are non-brominated (B r < 100 mg/kg), and a minority of parts have bromine in high concentration (last column of Table 5). If it is assumed that all parts have the same weight, a mean concentration of Br in plastics of equipment can be calculated (penultimate column, assuming that the concentrations below the limit of quantification are equal to zero). Nevertheless, according to professionals, at least in large household appliances, there are frequently only some small parts in contact with electric circuits and motors that are brominated, and the calculated mean could be overestimated. Four categories have a calculated mean concentration surpassing the threshold of 2000 mg/kg requiring separation according to CLC/TS 50625-3-1
(in blue in the Table): three expected (Tools, Lighting and SHA), and one unexpected (large household appliances) and having an exemption for bromine sorting in CLC/TS 50625-3-1. This indicates that this exemption should be assessed by additional data. It is not the first time that bromine >2000 mg/kg has been found in large household appliances. A report (Wäger et al., 2010) commissioned by the WEEE Forum (European association speaking for thirty-one not-for-profit e-waste producer responsibility organisations) to contribute to a formulation of normative requirements with respect to depollution of WEEE, shows also that bromine concentrations >2000 mg/kg have been found in large household appliances (1 time/6 samples), small household appliances without screens (1/3), IT equipment without screens (3/3) and consumer equipment without screens (2/2) (Wäger et al., 2010). In mixed
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P. Hennebert, M. Filella / Waste Management xxx (2017) xxx–xxx Table 5 Bromine content of EEE: number of equipment with bromine per category, number of parts of equipment with bromine per category, unweighted mean bromine concentration in all parts and in brominated parts (sorted by decreasing unweighted bromine concentration in parts) (in blue, Br > 2000 mg/kg).
Table 6 Mean concentrations of Br, PBBs and PBDEs in EEE 2009–2013 and classification (data insufficient for HP 14).
All other PBBs and PBDEs < LOQ (Table 2). HBCDD and TBBPA not analysed (n.a.).
samples, bromine >2000 mg/kg was found in a mix of categories (2, 3, 4, 6, 7) (see Table 5 for categories number) 8 times/9 samples, in a mix of categories (2, 6, 7) 2 times/4 samples and mix of categories (3, 4) 3 times/3 samples. It seems unlikely that the separation of brominated plastics by using only EEE categories is possible. Due to the large concentration range in parts, the plastics should be separated and sorted (i.e. shredded in small scraps and sorted on-line for Br content).. Other authors have come to the same conclusion in recent studies (Gallen et al., 2014 in Australia, Aldrian et al., 2015 in Austria, Puype et al., 2015 in Czech Republic, Guzzonato et al., 2016 in Italy, Turner and Filella, 2017a,b in UK). For waste, all WEEE samples contain bromine (Tables 7 and 8). The mean concentrations in the inflow fraction were 9343 mg/kg and 6597 mg/kg in 2014 and 2015, respectively, which were reduced to 2075 mg/kg and 2580 mg/kg for the ‘‘Low Br” fraction after sorting. Sorting is therefore effective but needs to be improved to reach concentrations <2000 mg/kg. 3.2. Distribution of BFR substances In 2009–2013 EEE, the arithmetic mean concentration of BFRs of 33 parts (1 LHA, 2 SHA, 16 IT, 3 Consumer, 6 Lights, 4 Toys) of 22 pieces of equipment (1 LHA, 1 SHA, 10 IT, 1 Audio-video, 4 Lights, 1 Tools, 4 Toys), mainly from 2013 are shown in Fig. 1. These selected items come from a population of 4218 parts of 347 pieces (Table 1). The regulated substances (underlined, details in Table 1) account for only 18% of the identified substances (Fig. 1). There are important differences between parts of equip-
ment. For example, the bromine concentration of parts of equipment with all parts brominated range from a minimum value of 100 – 1 600 mg/kg to a maximum value of 66,000–142,000 mg/k g for the seven EEE categories. The arithmetic mean concentrations of BFRs in WEEE of all samples are shown in Figs.2 and 3 for 2014 and 2015, respectively. DecaBDE has the highest mean BDE concentration. The sum of PBB and BDE is 473 mg/kg in EEE, and 2480 and 6270 mg/kg in WEEE for 2014 and 2015, respectively. When HBCDD and TBBPA are measured (WEEE 2015), TBBPA largely dominates (±8000 mg/kg). 3.3. Bromine balance When the bromine in identified brominated compounds (calculated as the sum of the calculated bromine content in mono- to deca-BB (mass fraction of bromine 0.76–0.85), mono- to decaBDE (0.66–0.83), HBCDD (0.75) and TBBPA (0.58)) is compared with the total bromine concentration, results are inconsistent for EEE (2009–2013 campaign) (Fig. 4); the mean mass ratio being 0.08 with the highest one at only 0.33. Thus, most of the brominated compounds remain unidentified. This might be explained by the fact that HBCDD and TBBPA were not measured. Two groups of samples were found in the 2014 WEEE campaign: a first group consistently showing a mass ratio of 0.42, with mainly SHAs and CRTs, and a second group characterised by a high bromine content but low identified bromine (Fig. 5). This group is mainly formed of flat screens, probably younger than other waste. As mentioned above, neither HBCDD or TBBPA was measured in 2014 but both
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Table 7 Mean concentrations of Br, PBBs and PBDEs in WEEE 2014 from 4 sites and classification for waste hazardousness and for POP regulation (between brackets: concentration between 50% and 100% of the concentration limit).
All other PBBs and PBDEs < LOQ (Table 2). HBCDD and TBBPA not analysed (n.a.).
Table 8 Mean concentrations of Br, PBBs, PBDEs, HBCDD and TBBPA in WEEE 2015 from 4 sites and classification for waste hazardousness and for POP regulation (between brackets: concentration between 50% and 100% of the concentration limit).
All other PBBs and PBDEs < LOQ (Table 2).
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1
51
1
69
42 79 44
11 13 162
223
908
9
863
40 21
60
3601
7983 Octa nona PBB
Deca PBB
Hexa BDE*
Hepta BDE*
Octa BDE*
Nona BDE
331
Deca BDE
Hexa BB* Nona BB Penta BDE* Octa BDE* TBBPA*
Fig. 1. Concentration of brominated flame retardants in EEE 2009–2013 (mg/kg, 32 parts of 22 equipment, PBBs and PBDEs < LOQ not represented, HBCDD and TBBPA not measured; *classified substances are underlined).
41
2 18
62
Octa BB Tetra BDE* Hepta BDE* HBCDD*
Fig. 3. Concentration of brominated flame retardants in WEEE 2015 (mg/kg, n = 32, values > LOQ, PBBs and PBDEs < LOQ not represented; * classified substances are underlined).
90
7 8
Hepta BB Deca BB Hexa BDE* Deca BDE
84 Br in substances (mg/kg)
405 362 2353
Hexa BB*
Hepta BB
Octa BB
Nona BB
Deca BB
Tetra BDE*
Penta BDE*
Hexa BDE*
Hepta BDE*
Octa BDE*
Deca BDE
1000 800 600 400 200 0
0
20000
40000
60000
80000
Br (mg/kg) Fig. 4. Bromine in measured substances as a function of total bromine in EEE (2009–2013) (n = 22).
were measured in 2015. When HBCDD and TBBPA are included in the calculation of the mass ratio (Fig. 7), the first group mass ratio changes from 0.35 to 0.86. Thus, the bromine concentration of regulated brominated substances was identified as up to 86% in ‘older’ waste (SHA, CRT) but only 30–50% in ‘younger’ waste, and a mean of only 8% in recent products (2009–2013) (see Fig. 6). 3.4. Classification for waste hazardousness, POP regulation, bromine separation and DecaBDE restriction of use for products Detailed tables of concentrations and classification are presented in the following tables. 3.4.1. EEE Mean concentrations of Br and substances in a selected set of brominated samples consisting of 33 parts from 22 items are
Br in substances without HBCDD and TBBPA (mg/kg)
Fig. 2. Concentration of brominated flame retardants in WEEE 2014 (mg/kg, n = 33, values > LOQ, PBBs and PBDEs < LOQ not represented, HBCDD and TBBPA not measured; * classified substances are underlined).
35000 30000 25000 20000 SHA CRT Flat sc.
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0
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20000
30000
40000
50000
60000
Br (mg/kg) Fig. 5. Bromine in measured substances as a function of total bromine in WEEE (2014) (n = 99 with triplicates).
Please cite this article in press as: Hennebert, P., Filella, M. WEEE plastic sorting for bromine essential to enforce EU regulation. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.09.031
Br in substances without HBCDD and TBBPA (mg/kg)
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DecaBDE had a mean concentration >1000 mg/kg in the inflow fraction of CRT and Flat screens, and in the ‘‘High Br” fraction of CRT and SHA.
35000 30000
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0
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Br (mg/kg) Fig. 6. Bromine in measured substances (excepted HBCDD and TBBPA) as a function of total bromine in WEEE (2015) (n = 56 with triplicates).
Br in substances with HBCDD and TBBPA (mg/kg)
9
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SHA CRT Flat sc.
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Br (mg/kg)
3.4.3. WEEE 2015 Mean concentrations of bromine and other substances are presented in Table 8 with the corresponding classification results. In 2015 as in 2014, ‘‘High Br High density” CRTs and ‘‘High Br” CRTs exceeded the concentration limits of POP regulation for the sum of tetra-, penta-, hexa- and heptaBDE (in red in the table) in the four processing sites (not shown). ‘‘High Br High density” CRTs are classified HP 10 ‘Toxic for reproduction’ due to hepta- and octaBDE concentrations. ‘‘Inflow” and ‘‘High Br Low density” CRTs approached the concentration limits of POP regulation for HBCDD and the sum of tetra-, penta-, hexa- and heptaBDE (in orange in the table). It is the same case for ‘‘High Br” SHA for the sum of tetra-, penta-, hexa- and heptaBDE. No waste is classified for HP 14 ‘Ecotoxic’, but the ‘‘High Br” CRT fraction was close to the concentration limit. Classification for HP 14 is triggered by TBBPA. The inflow fractions measured consistently presented mean bromine concentrations >2000 mg/kg. The sorting for the ‘‘Low Br” fraction of CRT and Flat screens should be improved. DecaBDE had a mean concentration >1000 mg/kg in the inflow fraction of CRT and Flat screens, and in all the ‘‘High Br” fractions. For EEE, the bromine concentration limit of 2000 mg/kg was exceeded for LHA, Tools, Lighting, IT and Toys (unweighted mean, potentially overestimated). Thus, a sorting of these categories for bromine should be recommended. Waste stream classifications were very similar for 2014 and 2015. Before sorting, in 2014 and 2015, the inflow fractions of SHA, CRT and Flat screens had mean bromine concentrations >2000 mg/kg, CRT are classified HP 14, and CRT and Flat screens had decaBDE concentrations above the restriction of use concentration limit of 1000 mg/kg for products. Unsorted fractions of
Fig. 7. Bromine in measured substances (including HBCDD and TBBPA) as a function of total bromine in WEEE (2015) (n = 56 with triplicates).
these three categories cannot be recycled as such. After sorting, the mean bromine concentration in the ‘‘Low Br” fraction in all sites (not always below 2000 mg/kg: CRTs and Flat screens), and the decaBDE concentration were below the concen-
presented in Table 6 together with the corresponding results classification. The classification for HP 14 is not applicable due to the absence of measures for HBCDD and TBBPA. Few classifying substances were detected, and their concentrations were low. No EEE have been classified as hazardous or POP with these analyses. In this selected set, mean bromine was >2000 mg/kg in LHA, IT, Lights, Tools and Toys. This mean is not weighted by the mass of each part of equipment. The concentration at the output of a shredder will be lower if the brominated parts have a mass lower than the non-brominated parts. The WEEE Forum launched a measurement campaign in 2017 to clarify this point.
tration limit of restriction of use. The ‘‘Low Br” fractions of SHA,
3.4.2. WEEE 2014 Mean concentrations of bromine and other substances are presented in Table 7, with the corresponding classification results. The classification for HP 14 is not applicable due to absence of measure of HBCDD and TBBPA. Sb was consistently lower than 8400 mg/kg in 2014 and 2015. ‘‘High Br High density” CRTs and ‘‘High Br” CRTs exceeded the concentration limits of POP regulation for the sum of tetra-, penta-, hexa- and heptaBDE (in red in the table). This is observed in the four processing sites (not shown). ‘‘High Br” SHA is close to exceeding the concentration limits of POP regulation for the same sum (in orange in the table). The mean bromine concentrations of the inflow fractions were always >2000 mg/kg. The sorting for the ‘‘Low Br” fraction of CRT should be improved.
CRT and Flat screens comply with all regulatory concentration limits and can be recycled. After sorting, the ‘‘High Br” fractions have the following regulatory concerns: – SHAs are hazardous HP 14 except for the ‘‘High Br Low Density” fraction, with a restriction of use for decaBDE in the ‘‘High Br” fraction in 2014 but no restriction for the ‘‘High Br Low Density” and ‘‘High Br High Density” fractions in 2014, and a restriction of use for decaBDE for all ‘‘High Br” fractions in 2015; – CRTs are hazardous HP 14, are HP 10 ‘Toxic for reproduction’ in the ‘‘High Br High Density” in 2015, and POP for the ‘‘High Br High Density” and ‘‘High Br” fractions; – Flat screens are hazardous HP 14 and have a restriction of use for decaBDE. 4. Conclusion The EU Directive on WEEE management states that plastics containing BFRs should be sorted and managed separately from the non-brominated fraction. Existing literature and this study show that BFRs, and a practical surrogate parameter, total bromine, are found in WEEE and EEE plastics, but also in non-EEE plastics. Classification of the fractions of WEEE before and after automated sorting is conclusive. The limit for sorting at 2000 mg/kg measured by XRF has been validated, since all fractions below
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comply with regulation (except cathode ray tubes), and all fractions above this limit are of regulatory concern (bromine, decaBDE, hazardous properties, POP substances). This concentration limit can be used as a surrogate for full laboratory analysis and classification. Our results validate on-line sorting as done today in France. Sorting could be extended to categories other than small household appliances and screens, because the BFRs used in plastic compounds change faster than regulations evolve (i.e., as shown in this study, 86% of identified bromine in ‘‘old waste” versus 30–8% in recent products), and other categories than the three considered here have bromine contents higher than 2000 mg/kg. A European campaign comprised of 7 countries and 35 sites will begin in 2017, organised by the WEEE Forum, the European association speaking for thirty-one not-for-profit e-waste producer responsibility organisations (weee-forum.org/), to assess the mean bromine content of plastics from large household appliances after shredding. Sorting is essential to avoid uncontrolled dispersion of regulated substances in recycled raw material. Acknowledgement The OCAD3E, French non-profit organisation coordinating the WEEE sector, is gratefully acknowledged for the WEEE sampling and analysis campaigns. We also sincerely thank Mr François David, Head of R&D, SGS laboratory (Saint Etienne du Rouvray, France) for data on the composition of products and his technical assistance. The help of Dr. D. Slomberg on the careful improvement of this manuscript is also highly appreciated. The data interpretation was financially supported by the Ministry of Ecology, France. References Alaee, M., Arias, P., Sjodin, A., Bergman, A., 2003. An overview of commercially used brominated flame retardants, their applications, their use patterns in different countries/regions and possible modes of release. Environ. Int. 29, 683–689. Aldrian, A., Ledersteger, A., Pomberger, R., 2015. Monitoring of WEEE plastics in regards to brominated flame retardants using handheld XRF. Waste Manage. 36, 297–304. Chen, S.-J., Ma, Y.-J., Wang, J., Chen, D., Luo, X.-J., Mai, B.-X., 2009. Brominated flame retardants in children’s toys: concentration, composition, and children’s exposure and risk assessment. Environ. Sci. Technol. 43, 4200–4206. CLC/TS 50625-3-1:2015 Requirements for the collection, logistics and treatment of WEEE - Part 3-1: Specification relating to depollution - General. CENELEC, Brussels, Belgium. CLP, 2008. 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. Official Journal of the European Union 31.12.2008 L 353 1353 pp. (2008). Decottignies, V., Bourgeois, M., Mathieu, C., Zariatti, S., 2014. Characterisation of plastic shredder fractions from waste of electric and electronic Equipment. Proceedings Crete 2014. 4th International Conference on Industrial and Hazardous Waste Management. Sept 2nd-5th, 2014. Chania, Crete, Greece.. Dimitrakakis, E., Janz, A., Bilitewski, B., Gidarakos, E., 2009. Small WEEE: determining recyclables and hazardous substances in plastics. J. Hazard. Mater. 161, 913–919. EC, 2002. Directive 2002/95/EC of the European Parliament and of the Council of 27 January 2003 on the restriction of the use of certain hazardous substances (RoHS) in electrical and electronic equipment. OJEU 13.2.2003 L 37/19. EC, 2003. Directive 2003/11/EC of the European Parliament and of the Council of 6 February 2003 amending for the 24th time Council Directive 76/769/EEC
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Please cite this article in press as: Hennebert, P., Filella, M. WEEE plastic sorting for bromine essential to enforce EU regulation. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.09.031