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Understanding the listed PBDEs

1. Enabling Activities to Review and Update the National Implementation Plan for the Stockholm Convention on Persistent Organic Pollutants 4-5 March 2013, Antalya, Turkey. Understanding the listed PBDEs. Roland Weber POPs Environmental Consulting,

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Understanding the listed PBDEs

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  1. 1 Enabling Activities to Review and Update the National Implementation Plan for the Stockholm Convention on Persistent Organic Pollutants 4-5 March 2013, Antalya, Turkey Understanding the listed PBDEs Roland Weber POPs Environmental Consulting, Ulmenstrasse 3, 73035 Göppingen, Germany

  2. 2 Polybrominated diphenyl ethers (PBDEs) • Polybromodiphenyl ethers (PBDEs) are a group of industrial chemicals which have been widely used as additive flame retardants since 1970s. • PBDEs were produced at three different degrees of bromination: • commercial Pentabromodiphenyl ether (c-PentaBDE), • commercial Octabromodiphenyl ether (c-OctaBDE) • commercial Decabromodiphenyl ether (c-DecaBDE) (still produced and not listed in the convention)

  3. 3 POP-PBDEs in the Stockholm Convention Prominent POP-PBDE congeners • The COP decided at the fourth meeting to list in Annex A certain congeners contained in c-PentaBDE and/or c-OctaBDE (POP-PBDEs) including: • tetrabromodiphenyl ether, • pentabromodiphenyl ether, • hexabromodiphenyl ether, and • heptabromodiphenyl ether BDE-47 BDE-154 BDE-183

  4. 4 Distribution of POP-PBDEs in commercial PBDE mixtures Listed in Convention Not Listed in Convention Sellstrom et al., 2005; La Guardia et al., 2006

  5. 5 POP-PBDEs in the Stockholm Convention The Convention prohibits the use of POP-PBDEs but contains a time-limited exemption for the recycling of articles that may contain PBDEs and the use and final disposal of articles manufactured from such recycling.

  6. 6 Obligation under the Convention Production and use of POP-PBDE is not allowed. Recycling of articlescontaining POP-PBDEs and the use and final disposal of articles produced from these recycled materials are allowed where the Party has notified the Secretariat to make use of the exemptions and the provisions in Part IV and V of Annex A. Trade of articles in use containing POP-PBDEs is allowed if the Secretariat has been notified by the exporting Party and importing Party for exemptions of recycling.

  7. 7 Production/Use history of POP-PBDEs tons/year Annual Consumption BFRs in Japan 70,000 Others 60,000 TBBP-A epoxy oligomer/polymer Brominated polystyrene 50,000 TBBP-A polycarbonate oligomer Bis(tribromophenoxy)ethane (BTBrPE) 40,000 Tribromophenol (TBrP) Bis(tetrabromophtalimido)ethane (BTBrPIE) 30,000 Hexabromocyclododecane (HBrCD) Pentabromodiphenyl ether (PentaBDP) 20,000 Octabromodiphenyl ether (OctaBDP) Decabromodiphenyl ether (DecaBDP) 10,000 Tetrabromobisphenol-A (TBBP-A) 0 1988 1992 1995 1996 1986 1987 1989 1990 1991 1993 1994 1997 Production and use of POP-PBDEs has stopped: e.g. in Europe or Japan already in the 1990s. In North America in 2004.

  8. 8 POP-PBDE and DecaBDE Commercial Mixture Tonnes c - PentaBDE 91,000 to 105,000 c - OctaBDE 102,700 to 118,500 c-DecaBDE 1,100,000 to 1,250,000 • The total production of all PBDEs from 1970 to 2005 is estimated between 1,300,000 and 1,500,000 tonnes • While the production of c-PentaBDE and c-OctaBDE have been discontinued, the production of not-listed DecaBDE continues. • The debromination of DecaBDE to lower PBDE is assessed by the POP Reviewing Committee. • EU: DecaBDE is restricted for electrical & electronic equipment (Directive 2002/95/EC + 2005/717/EC) but not for other uses.

  9. 9 Hexabromobiphenyl (HBB) • Only approximately 6000 tonnes of commercial HBB were produced in the United States from 1970 to 1976. • Due to the early and relatively small production and use of HBB, the chemical is of minor relevance since most of HBB containing materials have been disposed off already decades ago. • This minor relevance is also reflected in the low HBB/PBB levels in food and the related low exposure: E.g. in European countries (having used PBB to some extent in the past) HBB/PBBs were mostly below detection levels in food (EFSA 2010).

  10. 10 PBDE material flows and major use areas to be addressed by inventory & BAT/BEP • Polymers containing c-OctaBDE • Largest amount used in plastic electrical and electronic equipment (EEE) and now in related wastes (WEEE) • Minor amount in e.g. polymers in transport sector • Polyurethane (PUR) foam containing c-PentaBDE • Large amount in transport (car. bus, truck, train etc.) • In countries with flame retardant standards also used in furniture and construction and minor use in mattresses • Minor use c-PentaBDE: e.g. in textiles and rubber

  11. 11 Material flow c-OctaBDE containing articles

  12. 12 Former uses of c-OctaBDE in polymers, the applications and products

  13. The legacy of 20 years E-waste recycling E/SE-Asia E-waste recycling with primitive techniques resulted in polluted megasites containing large pollution reservoirs: heavy metals,POPs (PBDEs, PCBs), unintentional POPs(Dioxins,PAHs) E-waste recycling ashes at river bank in China E-waste mountains E/SE-Asia

  14. 15 Primitive E-Waste management practice in Africa

  15. Use and human exposure of POP-PBDEs 16 • PBDE human milk levels from 3rd WHO study for the different regions. • Largest use of POP-PBDE in North America with specific flammability standards for e.g. furniture and transport. Malisch R (2003) results 3rd WHO human milk survey

  16. PBDEs/BFRs Toxicity profiling Endocrine substances Hierarchical ClusteringHamers et al., 2006

  17. 18 E-waste recycling site: Taizhou Control site: Lin’an city, Hangzhou Global comparison of PBDEs in human milk Lin’an city Lin’an city Taizhou region Tsydenova, Tanabe et al., Env. Poll. 2006

  18. Total Toxicity of Contaminant Mixtures at E-Waste Treatment ? 19 PBDEs, PBB, HBCDD, other BFRs, PhosphorFR, Phthalates, PCBs etc. PCDD/Fs; PBDD/Fs, PXDD/Fs, OHPBDE, PAHs; X-PAHs, Heavy Metals Total TOXICITY? Associated Risks? A range of POPs, UPOPs, heavy metals and other toxic contaminants make these areas complex polluted site. Photos by CIES, 2004

  19. 20 PBDE/BFR Contamination in Recycled Plastic? • What is the flow of PBDE/BFR in recycled materials? What articles are contaminated? What are risks to human and the environment? PBDE/BFRs in video tapes (5/5) (Hirai et al, BFR 2007.) PBDE in children toys South China (Chen et al, ES&T 43, 4200, 2009)  The recycling flow of PBDE/BFR containing plastic seems largely uncontrolled. Hence further allowance of recycling of PBDE containing articles (currently) increases the environmental and health risks in an uncontrolled manner!

  20. EMPA study on RoHS Substances in European WEEE polymers including PBDEs 21 • Turkey RoHS ? RoHS substances in WEEE polymers Wäger et al. (2010) RoHS Substances in Mixed Plastics from WEEE. EMPA 10/2010.

  21. Material flow c-PentaBDE containing articles ?

  22. 23 Assessment of Possible Health and Environmental Impact:Recycling of Polyurethane Foam & Human Exposure (US) POP-PBDE levels in workers recycling Polyurethane Foam PBDE in serum lipid (ng/g) PUR Foam recyclers Carpet installers Control (Spouse) Source: Stapleton et al. ES&T 42, 3453 (2008)

  23. 24 Assessment of Possible Health and EnvironmentalImpacts of Recycling Articles containing POP-PBDEs Recycling of PBDE containing PUR foam to carpet padding in the US:

  24. Life-Cycle PBDEs/HBB (BFRs) 25 Aquatic Recycled Products Emission Sources Environmental Transport Exposure Routes Thermal (e.g. incineration, metal industry, recycling accidential fires) BFR Production (e.g. PentaBDE, OctaBDE, DecaBDE, HBB, HBCDD, HBBz & 70 other BFRs) Intergenerational Atmosphere Inhalation Food ingestion Plants Reservoirs (landfills, contaminated sites, stockpilessludges, soils, sediments) Occupational Land BFR Use (e.g. Plastic, Electronics, car, house insulation, textiles, furniture) Accidental Animals/ Cattle SSl Indoor (dust, air) Products (e.g. Electronics, furniture, cars, plain, train, textiles, mattresses etc.) Fish & Shellfish 

  25. 26 New POPs in the product life cycle stages – Management material flows in the end-of-life • Recycling flows (WEEE; EOL Vehicles) are impacted by PBDEs. • Sewage Sludge is a sink for POPs/pollutants (but also phosphorous)

  26. Time Trend of POP-PBDE in Europe 27 Time trend POP-BDEs in Swiss Sewage Sludge (2002 versus 1993) BDE-49 to BDE-183approx.- 50 % Kohler et al, SEA Meeting 2003 - March 6th, 2003 - EPFL, Lausanne

  27. Time Trend of POP-PBDE in Europe 28 Time trend DecaBDEs in Swiss Sewage Sludge (2002 versus 1993) DecaBDE+ 560 % Kohler et al, SEA Meeting 2003 - March 6th, 2003 - EPFL, Lausanne

  28. 29 Material/Substance Flow Analysis (RiskCycle): Production/Use - Waste Managem. - Environment System boundary Chemicals Exports Incine-ration Production Recycl Imports Trade Sewage Landfill Use Goods Waste Water Treatm. Atmosphere Soil Hydrosphere

  29. Time Trend of POP-PBDE in Europe 30 Time trend of some POPs in Human milk Sweden. Source: Natural Research Defense Council

  30. Classes of 610 Priority Pollutants 31 • Chlorinated, brominated and fluorinated persistent toxic substances need to be assessed systematically. (Strempel et al., Environ. Sci. Technol. 46 (2012), DOI: 10.1021/es3002713) Source: Muir, Presentation Dioxin 2010, San Antonio, September 2010.

  31. Tesekkür Ederim Questions ? http://www.pops.int ssc@pops.int

  32. EMPA study on RoHS Substances in European WEEE polymers including PBDEs • RoHS substances in WEEE polymers • Turkey RoHS ? Wäger et al (2010) RoHS Substances in Mixed Plastics from WEEE. EMPA 10/2010.

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