In order to confirm the possibility that recycled fractions from the waste electrical and electronic equipment (WEEE) stream were illegally entering the European market in black polymeric food-contact articles (FCAs), bromine quantification, brominated flame retardant (BFR) identification combined with WEEE-relevant elemental analysis and polymer impurity analysis were performed. From the 10 selected FCAs, seven samples contained a bromine level ranging from 57 to 5975 mg kg(-)(1), which is lower than expected to achieve flame retardancy. The BFRs that were present were tetrabromobisphenol A (TBBPA), decabromodiphenylether (decaBDE), decabromodiphenylethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Typical elements used in electronic equipment and present in WEEE were detected either at trace level or at elevated concentrations. In all cases when bromine was detected at higher concentrations, concurrently antimony was also detected, which confirms the synergetic use of antimony in combination with BFRs. This study describes also the measurement of rare earth elements where combinations of cerium, dysprosium, lanthanum, neodymium, praseodymium and yttrium were detected in four of the seven BFR-positive samples. Additionally, polymer purity was investigated where in all cases foreign polymer fractions were detected. Despite the fact that this study was carried out on a very small amount of samples, there is a significant likelihood that WEEE has been used for the production of FCAs.

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Achilias DS, Kanellopoulo I, Megalokonomos P, Antonakou E, Lappas AA. Chemical recycling of polystyrene by pyrolysis: potential use of the liquid product for the reproduction of polymer. Macromol Mater Eng. 2007;292:923–934.

Arias PA. Brominated flame retardants – an overview. The second international workshop on brominated flame retardants; Stockholm: AB Firmatryck; 2001. pp. 17–19.

Association of Plastics Manufacturers in Europe, Verband Kunststoffzeugende Industrie Feedstock recycling of electrical and electronic plastic waste (depolymerization and conversion into syncrude) 1997

Ballesteros-Gómez A, De Boer J, Leonards PE. Novel analytical methods for flame retardants and plasticizers based on gas chromatography, comprehensive two-dimensional gas chromatography, and direct probe coupled to atmospheric pressure chemical ionization-high resolution time-of-flight-mass spectrometry. Anal Chem. 2013;85:9572–9580. PubMed

Ballice L, Reimert R. Classification of volatile products from the temperature-programmed pyrolysis of polypropylene (PP), atactic-polypropylene (APP) and thermogravimetrically derived kinetics of pyrolysis. Chem Eng Process. 2002;41:289–296.

Becker L, Lenoir D, Matuschek G, Kettrup A. Thermal degradation of halogen-free flame retardant epoxides and polycarbonate in air. J Anal Appl Pyrolysis. 2001;60:55–67.

Becker PC, Olsson NA, Simpson JR. Erbium-doped fiber amplifiers fundamentals and technology. San Diego (CA): Academic Press; 1999.

Bergman Å, Rydén A, Law RJ, de Boer J, Covaci A, Alaee M, Birnbaum L, Petreas M, Rose M, Sakai S, van den Eede N, van der Veen I. A novel abbreviation standard for organobromine, organochlorine and organophosphorus flame retardants and some characteristics of the chemicals. Environ Int. 2012;49C:57–82. PubMed PMC

Bockhorn H, Hornung A, Hornung U, Schawaller D. Kinetic study on the thermal degradation of polypropylene and polyethylene. J Anal Appl Pyrolysis. 1999;48:93–109.

Brandsma SH, de Boer J, van Velzen MJ, Leonards PE. Organophosphorus flame retardants (PFRs) and plasticizers in house and car dust and the influence of electronic equipment. Chemosphere. 2014;116:3–9. PubMed

Cai MG, Hong QQ, Wang Y, Luo XJ, Chen SJ, Cai MH, Qiu CR, Huang SY, Mai BX. Distribution of polybrominated diphenyl ethers and decabromodiphenylethane in surface sediments from the Bering Sea, Chukchi Sea, and Canada Basin. Deep-Sea Res Part II. 2012;81-84:95–101.

Chen Y, Li J, Chen L, Chen S, Diao W. Brominated flame retardants (BFRs) in waste electrical and electronic equipment (WEEE) plastics and printed circuit boards (PCBs) Proc Environ Sci. 2012;16:552–559.

Clement RE, Reiner EJ, Bhavsar SP. Organohalogen contaminants of emerging concern in Great Lakes fish: a review. Anal Bioanal Chem. 2012;404:2639–2658. PubMed

Covaci A, Gerecke AC, Law RJ, Voorspoels S, Kohler M, Heeb NV, Leslie H, Allchin CR, de Boer J. Hexabromocyclododecanes (HBCDs) in the environment and humans: a review. Environ Sci Technol. 2006;40:3679–3688. PubMed

Czernik S, Elam CC, Evans RJ, Meglen RR, Moens L, Tatsumoto K. Catalytic pyrolysis of nylon-6 to recover caprolactam. J Anal Appl Pyrolysis. 1998;46:51–64.

Darnerud PA. Toxic effects of brominated flame retardants in man and in wildlife. Environ Int. 2003;29:841–853. PubMed

Dimitrakakis E, Janz A, Bilitewski B, Gidarakos E. Small WEEE: determining recyclables and hazardous substances in plastics. J Hazard Mater. 2009;161:913–919. PubMed

Egebäck A-L, Sellström U, McLachlan MS. Decabromodiphenyl ethane and decabromodiphenyl ether in Swedish background air. Chemosphere. 2012;86:264–269. PubMed

Entwisle J. Development of a procedure for the determination of selected brominated flame retardants (PBB, PBDE) in plastics by HPLC-ICP-MS. LGC Reference No. LGC/R/ 2010/39. 2010 http://www.nmschembio.org.uk/ PublicationArticle.aspx?m=83&amid=7093

European Commission. Directive (EC) No. 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 in electrical and electronic equipment. Off J Eur Union L. 2002;37:19.

European Commission. Regulation (EC) No. 1907/2006 of the European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), establishing a European Chemicals Agency, amending Directive 1999/45/EC and repealing Council Regulation (EEC) No 793/93 and Commission Regulation (EC) No 1488/94 as well as Council Directive 76/769/EEC and Commission Directives 91/155/EEC, 93/67/EEC, 93/105/EC and 2000/21/EC. Off J Eur Union. 2006;396:1.

European Commission. European Regulation (EC) No 282/2008 of 27 March 2008 on recycled plastic materials and articles intended to come into contact with foods and amending Regulation (EC) No 2023/2006. Off J Eur Union L. 2008;86:9.

European Commission Report of the Ad-hoc Working Group on defining critical raw materials. 2010 July 2010; http://ec.europa.eu/enterprise/policies/rawmaterials/documents/index_en.htm

European Commission. Regulation (EC) No. 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food. Off J Eur Union L. 2011a;39:41.

European Commission. Directive (EC) No. 2011/65/EU of the European Parliament and of the Council of 8 June 2011 on the restriction of the use of certain hazardous substances in electrical and electronic equipment. Off J Eur Union. 2011b;L179:88.

European Commission. Directive (EC) No. 1183/2012/EU of 30 November 2012 amending and correcting Regulation (EU) No 10/2011 on plastic materials and articles intended to come into contact with food. Off J Eur Union. 2012;L338:11.

European Commission. Regulation (EC) No. 202/2014 of 3 March 2014 amending European Commission Regulation (EU) No. 10/2011 on plastic materials and articles intended to come into contact with food. Off J Eur Union L. 2014a;62:13.

European Commission. Recommendation No. 2014/118/EU of 3 March 2014 on the monitoring of traces of brominated flame retardants in food. Off J Eur Union L. 2014b;65:39.

[CEN] European Committee for Standardization . EN 62321:2009 Electrotechnical products – Determination of levels of six regulated substances (lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers). Brussels: CEN; 2009.

Fernandez MF, Araque P, Kiviranta H, Molina-Molina JM, Rantakokko P, Laine O, Vartiainen T, Olea N. PBDEs and PBBs in the adipose tissue of women from Spain. Chemosphere. 2007;66:377–383. PubMed

Fink H, Panne U, Theisen M, Niessner R, Probst T, Lin X. Determination of metal additives and bromine in recycled thermoplasts from electronic waste by TXRF analysis. Fresen J Anal Chem. 2000;368:235–239. PubMed

Gallen C, Banks A, Brandsma S, Baduel C, Thai P, Eaglesham G, Heffernan A, Leonards PE, Bainton P, Mueller JF. 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. 2014;491–492:255–265. PubMed

Gieroń J, Grochowalski A, Chrząszcz R. PBB levels in fish from the Baltic and North seas and in selected food products from Poland. Chemosphere. 2010;78:1272–1278. doi: 10.1016/j.chemosphere.2009.12.031. PubMed DOI

Goodship V, Stevels A. Waste electrical and electronic equipment (WEEE) handbook. Woodhead Publishing Series in Electronic and Optical Materials; Cambridge: 2012.

Grob R, Bunke D, Gensch CO, Zangl S, Manhart A. Study on Hazardous Substances in Electrical and Electronic Equipment, Not Regulated by the RoHS Directive. Study made at the Öko-Institut e.V. (Head Office Freiburg) 2008

Hajšlová J, Pulkrabová J, Poustka J, Čajka T, Randák T. Brominated flame retardants and related chlorinated persistent organic pollutants in fish from river Elbe and its main tributary Vltava. Chemosphere. 2007;69:1195–1203. PubMed

Harju M, Hamers T, Kamstra JH, Sonneveld E, Boon JP, Tysklind M, Andersson PL. Quantitative structure–activity relationship modeling on in vitro endocrine effects and metabolic stability involving 26 selected brominated flame retardants. Environ Toxicol Chem. 2007;26:816–826. doi: 10.1897/06-308R.1. PubMed DOI

Hirai Y, Sakai S. Brominated flame retardants in recycled plastic products. 2007. Paper presented at BFR 2007: the 4th international symposium on brominated flame retardants; Amsterdam: 2007.

Hopewell J, Dvorak R, Kosior E. Plastics recycling: challenges and opportunities. Philos Trans R Soc Lond B Biol Sci. 2009;364:2115–2126. PubMed PMC

Hosaka A, Watanabe C, Tsuge S. Rapid determination of decabromodiphenyl ether in polystyrene by thermal desorption- GC/MS. Anal Sci. 2005;21:1145–1147. PubMed

Jakab E, Uddin MA, Bhaskar T, Sakata Y. Thermal decomposition of flame-retarded high-impact polystyrene. J Anal Appl Pyrolysis. 2003;68-69:83–99.

Jenssen BM, Sørmo EG, Bæk K, Bytingsvik J, Gaustad H, Ruus A, Skaare JU. Brominated flame retardants in North- East Atlantic marine ecosystems. Environ Healt Perspect. 2007;115:35–41. PubMed PMC

Knoop J, Opperman U, Schram J. Interference-Free Determination of REEs in Electronic Waste Using ICP Optical Emission Spectroscopy. J Chem Chem Eng. 2014;8:635–640.

Martinho G, Pires A, Saraiva L, Ribeiro R. Composition of plastics from waste electrical and electronic equipment (WEEE) by direct sampling. Waste Manag. 2012;32:1213–1217. PubMed

Miège C, Peretti A, Labadie P, Budzinski H, Le Bizec B, Vorkamp K, Tronczyński J, Persat H, Coquery M, Babut M. Occurrence of priority and emerging organic compounds in fishes from the Rhone River (France) Anal Bioanal Chem. 2012;404:2721–2735. PubMed

Oba K, Ishida Y, Ito Y, Ohtani H, Tsuge S. Characterization of branching and/or cross-linking structures in polycarbonate by reactive pyrolysis−gas chromatography in the presence of organic alkali. Macromolecules. 2000;33:8173–8183.

Oguri N, Onishi A, Uchino S, Nakahashi K, Jin X. Analysis of polyester by a combination of Curie-Point heating techniques and preparative liquid chromatography. Anal Sci. 1992;8:57–61.

Oppermann U, Schram J, Knoop J. Determination of rare earth elements in electronic waste using ICP-OES spectrometry. European winter conference on plasma spectrochemistry; Jagiellonian University of Krakow; 2013. p. 289.

Paine MR, Rae ID, Blanksby SJ. Direct detection of brominated flame retardants from plastic e-waste using liquid extraction surface analysis mass spectrometry. Rapid Commun Mass Spectrom. 2014;28:1203–1208. PubMed

Pitts JJ. Effect of antimony trioxide on flame retardation. Fire Flamm. 1972;3:51.

Pöhlein M, Bertran RU, Wolf M, van Eldrik R. Rapid identification of RoHS-relevant flame retardants from polymer housings by ultrasonic extraction and RP-HPLC/UV. J Chromatogr A. 2005;1066:111–117. PubMed

Pöhlein M, Bertran RU, Wolf M, Vaneldik R. Versatile and fast gas chromatographic determination of frequently used brominated flame retardants in styrenic polymers. J Chromatogr A. 2008;1203:217–228. PubMed

Pritchard G. Plastics additives. London: Chapman & Hall; 1998.

Puype F, Samsonek J. Evaluation of the quantitative analysis of PBDEs in plastics by thermal desorption GC-MS for soluble plastics. Dioxin 2008. Organohalogen Compounds. 2008;70:1522–1525.

Ricklund N, Kierkegaard A, McLachlan MS. An international survey of decabromodiphenyl ethane (deBDethane) and decabromodiphenyl ether (decaBDE) in sewage sludge samples. Chemosphere. 2008;73:1799–1804. PubMed

Rutkowski JV, Levin BC. Acrylonitrile-butadiene-styrene copolymers (ABS): pyrolysis and combustion products and their toxicity? A review of the literature. Fire Mat. 1986;10:93–105.

Samsonek J, Puype F. Rapid determination of certain BFRs in plastics by X-ray fluorescence spectrometry (XRF) and thermal desorption GC-MS (TD-GC-MS) for the RoHS directive. Organohalogen Compounds. 2007;69:2789–2792.

Samsonek J, Puype F. Occurrence of brominated flame retardants in black thermo cups and selected kitchen utensils purchased on the European market. Food Addit Contam A. 2013;30:1976–1986. PubMed

Schartel B. Phosphorus-based flame retardancy mechanisms—old hat or a starting point for future development? Materials. 2010;3:4710–4745. PubMed PMC

Schecter A, Haffner D, Colacino J, Patel K, Päpke O, Opel M, Birnbaum L. Polybrominated diphenyl ethers (PBDEs) and hexabromocyclodecane (HBCD) in composite U.S. food samples. Environ Health Perspect. 2010;118:357–362. PubMed PMC

Schlummer M, Brandl F, Mäurer A, van Eldik R. Analysis of flame retardant additives in polymer fractions of waste of electric and electronic equipment (WEEE) by means of HPLC-UV/MS and GPC-HPLC-UV. J Chromatogr A. 2005;1064:39–51. PubMed

Simon J, Kantor T, Kozma T, Pungor E. Thermal analysis of Sb2O3 /Organohalide-based flame retardants including atomic absorption detection of the evolved species. J Therm Anal. 1982;25:57–77.

Stapleton HM, Klosterhaus S, Keller A, Ferguson PL, van Bergen S, Cooper E, Webster TF, Blum A. Identification of flame retardants in polyurethane foam collected from baby products. Environ Sci Technol. 2011;45:5323–5331. PubMed PMC

Straus S, Madorsky SL. Pyrolysis of styrene, acrylate, and isoprene polymers in a vacuum. J Res Natl Bur Stand. 1953;50

Szymańska JA, Piotrowski JK, Frydrych B. Hepatotoxicity of tetrabromobisphenol-A: effects of repeated dosage in rats. Toxicology. 1999;142:87–95. PubMed

UNEP REPORT ISBN 978-92-807-3267-2Metal recycling: opportunities, limits, infrastructure, a report of the working group on the global metal flows to the international resource panel. Reuter. MA, Hudson C, van Schaik A, Heiskanen K, Meskers C, Hagelüken, C. 2013 http://www.unep.org/resourcepanel/Portals/24102/PDFs/Metal_Recycling_Full_Report.pdf

Vehlow J, Mark F. Electrical and electronic plastics waste co-combustion with municipal solid waste for energy recovery. 1997 www.APME.com

Vilaplana F, Karlsson P, Ribes-Greus A, Ivarsson P, Karlsson S. Analysis of brominated flame retardants in styrenic polymers. Comparison of the extraction efficiency of ultrasonication, microwave-assisted extraction and pressurised liquid extraction. J Chromatogr A. 2008;1196–1197:139–146. PubMed

Wallisch KL. Pyrolysis of random and block copolymers of ethyl acrylate and methyl methacrylate. J Appl Polym Sci. 1974;18:203–222.

Westerhout RWJ, Waanders J, Kuipers JAM, van Swaaij WPM. Kinetics of the low-temperature pyrolysis of polyethene, polypropene, and polystyrene modeling, experimental determination, and comparison with literature models and data. Ind Eng Chem Res. 1997;36:1955–1964.

Wienold J, Recknagel S, Scharf H, Hoppe M, Michaelis M. Elemental analysis of printed circuit boards considering the ROHS regulations. Waste Manag. 2011;31:530–535. PubMed

Wu H-Q, Huang X-L, Huang F, Lin X-S. Determination of polybromodiphenyl ethers and polybromobiphenyls in electrical and electronic equipments by gas chromatography-mass spectrometry. Chin J Anal Chem. 2007;35:325–329.

Zhang X-L, Luo X-J, Chen S-J, Wu J-P, Mai B-X. Spatial distribution and vertical profile of polybrominated diphenyl ethers, tetrabromobisphenol A and decabromodiphenylethane in river sediment from an industrialized region of South China. Environ Pollut. 2009;157:1917–1923. PubMed

Zhao Y, Yang L, Wang Q. Pulsed large volume injection gas chromatography coupled with electron-capture negative ionization quadrupole mass spectrometry for simultaneous determination of typical halogenated persistent organic pollutants. J Am Soc Mass Spectrom. 2007;18:1375–1386. PubMed