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Presentation on Overall trends of the replacements of long chain per- and polyfluoroalkyl substances by Zhanyun Wang from ETH Zurich

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On 19 May 2016, Eeva Leinala of the OECD Environment Directorate and Zhanyun Wang from ETH Zurich presented background information, an overview of alternatives and some initial lessons learned about the replacements of Long- Chain Per- and Polyfluoroalkyl Substances.

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Presentation on Overall trends of the replacements of long chain per- and polyfluoroalkyl substances by Zhanyun Wang from ETH Zurich

  1. 1. Overall trends of the Replacements of Long- Chain Per- and Polyfluoroalkyl Substances (PFASs) © ETH Zürich | Safety and Environmental Engineering Group Zhanyun Wang A, Ian T. Cousins B, Martin Scheringer A,C, Konrad Hungerbuehler A   A Institute for Chemical and Bioengineering, ETH Zurich, Switzerland B Department of Environmental Science and Analytical Chemistry, Stockholm University, Sweden C RECETOX, Czech Republic zhanyun.wang@chem.ethz.ch
  2. 2. May 19, 2016 Outline §  Background information §  An overview of the replacements of long-chain PFASs §  Some initial lessons learned about the replacements §  Acknowledgement 2
  3. 3. May 19, 2016 3 Background information
  4. 4. May 19, 2016 §  Poly- and perfluorinated alkyl substances (PFASs), CF3(CF2)n-R, are a group of widely used chemicals since 1950s, including 4 OECD (2015) Working towards global emission inventory of PFASs What are PFAS?
  5. 5. May 19, 2016 What are long-chain PFASs? §  Perfluoroalkyl carboxylic acids (PFCAs) with 7 or more perfluorinated carbons (CnF2n+1COOH, n >= 7), e.g. perfluorooctanoic acid (PFOA); §  Perfluoroalkane sulfonic acids (PFSAs) with 6 or more perfluorinated carbons (CnF2n+1SO3H, n >= 6), e.g. perfluorohexane sulfonic acid (PFHxS) and perfluorooctane sulfonate (PFOS); and §  Precursors of long-chain PFCAs and PFSAs. 5
  6. 6. May 19, 2016 §  PFCAs and PFSAs are highly persistent (P).1,2 §  The long-chain PFCAs and PFSAs are bioaccumulative (B),and can cause various adverse effects (T) in humans and biota.1,2 §  PFCAs, PFSAs and precursors have been detected ubiquitously in the environment, biota, food items and humans.1,2 à Consequently, various risk reduction actions have been taken worldwide to restrict/eliminate long-chain PFASs.3 à In particular, there is an ongoing industrial transition from long- chain PFASs to replacement substances/technologies. 6 1. OECD (2013) Synthesis paper on PFCs; 2. Scheringer et al. (2014) Chemosphere, 114, 337-339; 3. OECD (2015) Risk reduction approaches Major concerns about long-chain PFASs
  7. 7. May 19, 2016 7 An overview of the replacements to long-chain PFASs
  8. 8. May 19, 2016 General trends §  Chemical substitution in most cases §  Fluorinated replacements -  Short-chain PFCAs, PFSAs and related chemicals -  Perfluoroether carboxylic and sulfonic acids (PFECAs and PFESAs) -  Perfluoroalkyl phosphonic and phosphinic acids (PFPAs and PFPiAs) -  Perfluoropolyethers (PFPEs) §  Non-fluorinated replacements -  Siloxanes, paraffin wax, etc. §  Functionality substitution in some cases §  Here we present five examples; for more details, see in UNEP (2012) UNEP/POPS/POPRC.8/INF/17/Rev.1, Wang et al. (2013) Environ Int, 60, 242 and Wang et al. (2016) Environ Int, 89, 234. 8
  9. 9. May 19, 2016 Example 1: fluoropolymer manufacturing §  Original substances: PFOA and its salts §  Fluorinated replacements §  Various PFECAs1,2 §  C4/C4 PFPiA(?)3 §  Non-fluorinated replacements §  Hydrophobins(?)4 9 1. Buck et al. (2011) Integr Environ Assess Manag 7(4), 513 2.Wang et al. (2013) Environ Int, 60, 242; 3.Wang et al. (2016) Environ Int, 89, 234; 4.Wang et al. (2015) Environ Int, 75, 172
  10. 10. May 19, 2016 Example 2: metal plating §  Original substances: PFOS and its salt §  Functionality substitution: §  Decorative chrome plating: using chromium(III) instead of chromium(VI) (the former concern);1 §  Hard chrome plating: closed reactors2 §  Fluorinated replacements: §  Short-chain PFASs; PFESAs (only in China)1,3 §  Non-fluorinated replacements: §  Alkylsulfonates2 (in decorative chrome plating) 10 1. UNEP (2012) UNEP/POPS/POPRC.8/INF/Rev.1 2. UNEP-POPS-POPRC9FU-SUBM-PFOS-Germany-2-20140221 3.Wang et al. (2013) Environ Int, 60, 242;
  11. 11. May 19, 2016 Example 3: textile sector §  Original substances: §  POSF- or long-chain FT-based side-chain fluorinated polymers §  Fluorinated replacements: §  PBSF/PHxSF-based side-chain fluorinated polymers1,2 §  6:2 FT-based side-chain fluorinated polymers1,2,4 §  3:1/5:1 FT-based side-chain fluorinated polymers2 §  Perfluoropolyethers (PFPEs, e.g. Fluorolink® from Solvay)2 §  Non-fluorinated replacements: §  Dendrimers, siloxanes and polysiloxanes, paraffin wax, etc. (only water-repellency, no oil-repellency)1,3,4 11 1. UNEP (2012) UNEP/POPS/POPRC.8/INF/Rev.1 2.Wang et al. (2013) Environ Int, 60, 242; 3. http://goo.gl/cd2PSK 4. Holmquist et al. (2016) Environ Int 91, 251
  12. 12. May 19, 2016 Example 4: fire-fighting foams §  Original substances: §  PFOS, its salts and POSF-based substances, or §  long-chain FT-based substances §  Fluorinated replacements: §  6:2 FT-based substances1,2 §  Non-fluorinated replacements: §  Available in some cases, with unknown structures1 12 1. UNEP (2012) UNEP/POPS/POPRC.8/INF/Rev.1 2.Wang et al. (2013) Environ Int, 60, 242;
  13. 13. May 19, 2016 Example 5: food contact materials §  Original substances: §  POSF or long-chain FT-based phosphate monoesters and diesters §  POSF or long-chain FT-based side-chain fluorinated polymers §  Functionality substitution: §  Use extra-dense paper to prevent grease leakage through the paper1 §  Fluorinated replacements: §  6:2 FT phosphate diesters (6:2 diPAPs)2,3 §  6:2 FT-based side-chain fluorinated polymers2,3 §  Perfluoropolyethers (e.g. Solvera® from Solvay)2,3 13 1. UNEP (2011) UNEP/POPS/POPRC.6/§2/SS.2/REV.1 2. UNEP (2012) UNEP/POPS/POPRC.8/INF/Rev.1 3.Wang et al. (2013) Environ Int, 60, 242;
  14. 14. May 19, 2016 14 Some initial lessons learned about the replacements
  15. 15. May 19, 2016 Lessons learned about the replacements 15 §  Long-chain PFASs are being replaced by a large variety of substances; there is a general lack of information (identity, production, use, releases, hazardous properties, etc.) on many of the replacements.1-5 §  Many fluorinated replacements are not only structurally similar to long-chain PFASs, but may also have similar hazardous properties (e.g. high persistence, same/similar modes-of-action, etc.).1,2,4 §  Some non-fluorinated replacements (e.g. siloxanes) might be PBT substances and are subject to risk assessment, too.2,6 §  Future studies and early actions on replacements are needed.7,8 1. UNEP (2012) UNEP/POPS/POPRC.8/INF/17/Rev.1; 2.Wang et al. (2013) Environ Int, 60, 242 3. UNEP (2014) UNEP/POPS/POPRC.10/INF/7/Rev.1; 4.Wang et al. (2015) Environ Int, 75, 172 5.Wang et al. (2016) Environ Int, 89, 234; 6. UNEP (2014) UNEP/POPS/POPRC.10/INF/8/Rev.1 7. Scheringer et al. (2014) Chemosphere, 114, 337-339; 8. Blum et al. (2015) Environ Health Perspect 5, A107
  16. 16. May 19, 2016 Acknowledgement §  Swiss Federal Office for the Environment (BAFU) for financial support Thank you for your attention! 16

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