Non-PBDE halogenated and non-halogenated flame retardants as global emerging contaminants

Transcription

1 Non-PBDE halogenated and non-halogenated flame retardants as global emerging contaminants Axel Möller, Zhiyong Xie, Renate Sturm, Hendrik Wolschke, Jürgen Gandraß, Ralf Ebinghaus Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research Institute for Coastal Research Department for Environmental Chemistry Geesthacht, Germany Sampling and Analysis of Emerging Contaminants in the Aquatic Environment: Current and Future Challenges slo,

2 PBDEs Polybrominated diphenyl ethers (PBDEs) used for several decades as FRs harmful for the environment and humans Persistent, bioaccumulative, toxic (PBT) long-range atmospheric transport (LRAT) ubiquitous in various compartments n n,m = 1-5 m ngoing worldwide banishment since early 2000s PBDEs 2004/2006 PentaBDE, ctabde (>0.1 %) 2008: DecaBDE in E&E 2009: Penta- and ctabde: PPs DecaBDE in other products no production, but import Axel Möller

3 what s next? PBDEs replacement by Non-PBDE BFRs Dechloranes rganophosphorus FRs old alternatives Dechlorane Plus chlorinated new alternatives other Dechloranes non-halogenated Axel Möller

4 Alternative BFRs HBB CH 3 H 3 C H CH 3 H 3 C PBBz PBT PBEB CH 3 BTBPE CH 3 EHTBB CH 3 H 3 C TBPH, BEHTBP + dozens of other new and old brominated FRs DPTE Axel Möller

5 Dechloranes syndp Dechlorane Plus (605) antidp Dechlorane 602 Dechlorane 603 Dechlorane 604 Axel Möller

6 rganophosphorus FRs Chlorinated Ps Flame retardants TCEP TCPP TDCP Alkylated Ps TnBP, TiBP plasticizer, hydraulic fluids, TEHP plasticizer, TBEP Flame retardant, plasticizer, Arylated P TPhP Flame retardant, plasticizers, + dozens of other (non)- halogenated PFRs Axel Möller

7 Production and properties 1. Production Little data on alternative BFRs and DP BFRs and DP in U.S. and Asia PFRs worldwide incl. Western Europe Production since several decades 2. PBT properties BFRs and DP: modelled P and B + bioaccumulation studies T mostly unknown, some effects observed PFRs: P high for chlorinated Ps, B? - but observed in biota T various known effects (carcinogenic, skin irritation, ) 3. LRAT BFRs and DP: modelled LRAT potential, occurence in Arctic biota PFRs: Atmospheric half life <1d, but occurence in snow, Antarctic aerosols ARCADIS 2010 Axel Möller

8 Global distribution of alternative FRs Heincke (+Prandtl) März, Mai, Juli 2010 Polarstern ARK-XXIV, 2009 Ny Alesund Büsum Snow dragon CHINARE Air Polarstern ANT-XXVII 2010/11 Polarstern ANT-XXV 2008/09 Snow dragon CHINARE /11 Seawater Axel Möller

9 BFRs Atlantic cean air and seawater Atmosphere Seawater HBB DPTE Axel Möller Xie et al., ES&T 2011

10 BFRs and DP Pacific cean air PBT > BDE-209 > HBB = PBBz = DPTE > BDE-47 Möller et al., ES&T 2011 Axel Möller

11 BFRs and DP Indian cean air again HBB Möller et al., ES&T 2012 Axel Möller

12 PFRs Pacific and Indian cean air global occurence, particle-bound concentrations up to 2 ng/m³ dominated by TCPP and TCEP but also non-halogentated PFRs! concentrations 1-3 magnitudes higher than typical PBDE concentrations marginal seas, open oceans and polar regions Axel Möller Möller et al., ES&T 2012

13 PFRs - North Sea + estuaries surface water River Station ΣP TCPP TCEP TDCP TEP TiBP TBEP TPhP TPP Elbe E E E n.d Rhine R R R R R R Scheldt S North Sea verall P discharge into the North Sea: ~50 tons/year Bollmann et al., Water Research 2012 Axel Möller

14 Conclusions several alternative BFRs, DP, and PFRs are present in the global marine atmosphere (and seawater) traditional alternative BFRs HBB, PBT, and DPTE in concentrations similar to or higher than PBDEs PFRs, especially TCPP and TCEP, 1-3 magnitudes higher than PBDEs BFRs and PFRs undergo gaseous (e.g., HBB, DPTE, PBT) and/or particle-bound (PFRs, DP) long-range atmospheric transport from source regions (Asia!) the oceans toward the Polar Regions PFRs are heaviliy emitted into surface waters and the (coastal) marine environment (sources: WWTPs ) there will be several more (non)-halogenated non PBDEs! over Axel Möller

15 Acknowledgements Many thanks to The captains and the crews of R/V Polarstern, R/V Xuelong, R/V Heincke, R/V Ludwig Prandtl Chinese Arctic and Antarctic Administration, State ceanic Administration of China and you for your attention! Axel Möller

16 Sampling and analysis air and water when sampling and analyzing PBDEs, (most) alternative BFRs and Dechloranes come for free! various methods for sampling and analysis of PFRs have been reported since decades! Air-sampling: High-vol (GFF + PUF/XAD-2) or PAS Water sampling: High-Vol (GFF + PAD-2/3) Extraction: Soxhlet, ASE, Analysis: GC-MS techniques, mostly ECNCI only bromine! HR or MS/MS techniques for comprehensive studies on BFRs Air-sampling: High-vol (GFF + PUF/XAD-2) or PAS Water sampling: Low volumes Extraction: SPE, LLE, Soxhlet, ASE, Analysis: GC-MS, GC-NPD, LC-MS/MS Axel Möller

17 BFRs and DP over the global oceans Year BDE-47 BDE-209 ΣPBDEs HBB PBT DPTE DP Atlantic cean [1] n.a n.a. n.a. n.a. n.a. Atlantic cean [2, 3] n.a Atlantic cean (North Sea) [4] n.d n.d n.d Pacific cean [5] n.d Pacific cean [6] < n.a. n.a. n.a. n.a. Pacific cean (East Asian Seas) [5] Pacific cean (East Asian Seas) [6] 2003 < < n.a. n.a. n.a. n.a. Pacific cean (East and South China n.a n.a. n.a. n.a. n.a. Seas) [1] Pacific cean (East Indian 2010/ n.d Archipelago and Philippine Sea) [7] Indian cean [1] n.a n.a. n.a. n.a. n.a. Indian cean [8] 2004/05 < < n.a. n.a. n.a. n.a. Indian cean [5] 2010/11 n.d n.d.-6.5 n.d n.d.-2.8 n.d Arctic cean [5] n.d Arctic cean [6] 2003 < < < n.a. n.a. n.a. n.a. Arctic cean (Greenland Sea) [3, 9] n.d n.d Southern cean [2, 3] n.a Southern cean [7] 2010/ n.d n.d. n.d [1] Li et al., AE 2012 [2] Xie et al., ES&T 2011 [3] Möller et al., ES&T 2010 [4] Möller et al., AE 2011 [5] Möller et al., ES&T 2011 [6] Wang et al., ES&T 2005 [7] Möller et al., ES&T under revision [8] Wurl et al., AE 2006 [9] Möller et al., EP 2011 Axel Möller