New Insight into Chlorinated Paraffin Pollution

Transcription

1 New Insight into Chlorinated Paraffin Pollution Bo Yuan Postdoctoral researcher Department of Environmental Science and Analytical Chemistry (ACES), Stockholm University, Stockholm, Sweden Uppsala; Nov 16, 2017

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3 New Insight into Chlorinated Paraffin Pollution

4 What are chlorinated paraffins

5 Chlorinated Paraffins Metal-working fluids Plasticizers Flame retardants Sealants Paints, etc. CP Chlorinated Paraffins

6 Chlorinated Paraffins C n H 2n+2 + mcl 2 C n H 2n+2-m Cl m + mhcl C 6 C 38 Paraffin Mixture Molecule chlorine Chlorinated paraffin mixture Congener group (450): C n Cl m Category Abbr. chain length range congener group amount Impurities/byproducts C 6 C 9 6 n 9 30 C n Cl m Short-chain SCCP 10 n C n Cl m Medium-chain MCCP 14 n C n Cl m Long-chain LCCP 18 n C n Cl m Environment Canada (2016)

7 Annual global production Glüge et al. / Science of the Total Environment (2016)

8 CP importation in Sweden tons/y In Sweden, CPs are only imported. The highest importation was 4800 tons in 1991 in Sweden. Since the early 1990s, the use of CPs in Sweden has decreased by 80%. N: Flux (ng/g dw) CP import data from KEMI.se with thanks to Markus Ifverberg (KEMI)

9 Why do we study CPs

10 SCCPs April, 2017 SCCPs were included in the Stockholm Convention on persistent organic pollutants (POPs). UNEP (2017)

11 Annual global production SCCPs 16% Other CPs 84% Glüge et al. / Science of the Total Environment (2016)

12 "The other" CPs MCCPs are persistent in sediments for as long as years. MCCPs and C 18 LCCPs showed bioaccumulation and biomagnification potentials. SCCPs and MCCPs are on the EU priority list of substances for further evaluation of their role in endocrine disruption. SCCPs, MCCPs and LCCPs are considered toxic to aquatic organisms such as invertebrates. Darnerud et al. / Archives of Toxicology (1982) Zeng et al. / Environmental Science & Technology (2017) Iozza et al. / Environmental Science & Technology (2008) Zeng et al. / Environmental Pollution (2017) Glüge et al. / Science of the Total Environment (2016) Environment Canada (2015)

13 Thermal degradation products Thermal degradation products include polychlorinated benzenes, toluenes, biphenyls and naphthalenes. Bergman et al. / Chemosphere (1984) Xin et al. / Chemosphere (2017)

14 Recent advances in techniques for CP analysis

15 GC-based analytical techniques Category Abbr. chain length range congener group amount GC GC analysis Impurities/byproducts C 6 C 9 6 n 9 30 C n Cl m 2 C n Cl m Short-chain SCCP 10 n C n Cl m 24 C n Cl m Medium-chain MCCP 14 n C n Cl m 24 C n Cl m Long-chain LCCP 18 n C n Cl m Total CP 450 C n Cl m 50 C n Cl m Environment Canada (2016) Xia et al. / Environmental Science & Technology (2016)

16 Recent development of APCI-QTOF-MS techniques Allows analysis of over 400 C n Cl m in technical products or environmental matrices Few matrix interferences

17 New insight - Baltic Sea Coastal Sediment Core - Indoor dust - Commercial products

18 Sediment core sampling site Sweden Baltic Sea Himmerfjärden sewage treatment plant serves about persons of the southern Stockholm's metropolitan area. STPs are sinks and sources of CPs Zeng et al. / Environ. Sci. Tech. (2011)

19 Chlorinated paraffins in a 50-year-old sediment section C8 C 8 C 36 CPs were observed in a sediment section representing the year C 24 was the dominant alkane-chain-length group, which is consistent with the reported alkane-chain-length distributions of several LCCP products (Zitko, V., Chlorinated paraffins. 1980) Yuan et al. / Organohalogen Compd. (2017)

20 Year of Deposition Historical profiles of alkane-chain lengths Himmerfjärden, a sewage treatment plant nearby ng/g d.w. C# C 8-9 SCCPs MCCPs LCCPs The environment and human beings may have been under exposure to CPs of various ingredients for decades SCCPs (10 ± 3%), MCCPs (50 ± 19%), and LCCPs (40 ± 20%) Mean percentage of SCCPs in the imported CP products was 10% (KEMI, ). Yuan et al. / Environmental Science & Technology (Just accepted)

21 Indoor dust Canada (6) The U.K. (4) Sweden (5) China (5) Australia (5) Wong et al. / Chemosphere (2017) 17 halogenated flame retardants (HFRs); 17 polybrominated biphenyl ethers (PBDEs); 13 organophosphate esters (OPEs); chlorinated paraffins (CPs)

22 AU UK CA SE CH SRM AU UK CA SE CH SRM AU UK CA SE CH SRM AU UK CA SE CH SRM Dust concentration (μg/g) Total concentrations of HFRs, BDEs, OPEs and CPs in dust HFRs PBDEs OPEs CPs Wong et al. / Chemosphere (2017) AU = Australia; UK = The United Kingdom; CA = Canada; SE = Sweden; CH = China; SRM = NIST2585

23 Australia C14 AU1 Canada CA5 China CH5 Sweden C18 SE5 The U.K. UK C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20

24 Commercial CP products CP42 CP52 CP70 CP42 CP52 CP70 Glüge et al. / Science of the Total Environment (2016)

25 Detector response Commercial CP products C9 SCCP MCCP LCCP Cereclor 60L (SCCP 60 %Cl, ICI, UK) Hüls52G (MCCP 52 %Cl, Hüls AG, Germany) Witchlor44 (LCCP 44 %Cl, Dynamit Nobel, Germany) Uniclor 40 (LCCP 40 %Cl, Neville Chemical, USA) CP-52 (?CP 52 %Cl, China) Cl # C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31

26 Highlights CPs with chain lengths shorter than 10 and LCCPs are "old" contaminants that have recently been detected. C 8 C 36 CPs appear to have persisted in the sediment for c.a. 50 years. Dominant flame retardant contaminants in indoor environnent. Highly impure commercial CP products.

27 Perspective

28 C8

29 Acknowledgements SLU och Naturvårdsverket APCI-QTOF-MS method developement Christian Bogdal (ETH Zurich), Urs Berger (UFZ), Matthew MacLeod, Tomas Alsberg, Cynthia A. de Wit Baltic Sea sediment study Volker Brüchert (IGV), Anna Sobek, Cynthia A. de Wit Indoor dust study Fiona Wong, Go Suzuki (NIES), Cynthia A. de Wit Commercial product study Anna Strid, Magnus Breitholtz, Åke Bergman (Swetox) Your attention