New Brominated Flame Retardants (BFR) in the Nordic and Arctic Environments

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1 New ominated Flame Retardants (BFR) in the Nordic and Arctic Environments Martin Schlabach NILU, Norway

2 Background Flame retardants: Compounds used to reduce flammability of materials ominated flame retardants (BFR): PBDE, HBCD, TBBPA, and other new BFRs High focus on PBDE use, fate, and effects Ban of PentaBDE and Octa BDE Expect increase of other BFRs

3 Selection procedure Review: Emerging New ominated Flame Retardants in Flame Retardant Products and the Environment Current State of Knowledge and Monitoring Requirements SFT TA-2462/2008 Summarise/estimate: Properties, production volumes, effects Special focus on persistency and long range transport potential (LRTP) Priority list (14 compounds)based on production volume, LRTP, and Bioaccumulation

4 Several screening studies in 2009 Environmental screening of selected new brominated flame retardants and selected polyfluorinated compounds KLIF, Oslo TA- 2625/2010 Screening of decabromodiphenyl ethane (dbdpe) in lake sediment, marine sediment and peregrine falcon (Falco peregrinus) eggs. Ricklund, N., A. et al. (2009). ITM, Stockholm New brominated flame retardants in Arctic biota. Sagerup et al. KLIF, Oslo TA-2630/2010 Results from the Swedish National Screening Programme 2009: Subreport 2. Dechlorane Plus. Kaj et al. IVL report in prep. Arctic mammal screening on new brominated flame retardants, Bert van Bavel, Örebro university ominated Flame Retardants (BFR) in the Nordic Environment. Remberger et al. TemaNorden report 2011:528

5 Compounds selected for NMR study Compound name Abbreviation CAS # Phenolic BFRs 2,4-Dibromophenol 24DBP ,4,6-Tribromophenol 246TBP Pentabromophenol PBP Tetrabromobisphenol-A TBBPA BFR ethers and esters 2,4,6-Tribromophenyl allyl ether ATE ,3-Dibromopropyl- 2,4,6- tribromophenyl ether DPTE ,2-Bis (2,4,6-tribromophenoxy) ethane BTBPE omoallyl-2,4,6-tribromophenyl ether BATE - 2,4,6-Tribromoanisol TBA Bis (2-ethylhexyl) tetrabromophthalate BEHTBP Ethylhexyl- 2,3,4,5-tetrabromobenzoate EHTeBB Other flame retardants Dechlorane Plus DP Hexabromobenzene HBB Pentabromotoluene PBT Pentabromoethylbenzene PBEB Decabromodiphenylethane DBDPE ,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane TBECH Reference compounds Standard PBDEs

6 Typical chemical structures 246-TBP OH HBB TBECH O BEHTBP O O O O BTBPE O DBDPE

7 Sampling National responsibility Emission samples: Sludge, waste water Environmental samples: Air, moss, needles, sediment, biota Spatial distribution: Some sample types from all Nordic countries and the Arctic

8 Analysis Different Nordic laboratories Extraction (Derivatisation of Phenolic compounds) Dedicated clean-up GC/LRMS, GC/HRMS, LC/MS Different detection limits

9 Measurement uncertainties Study design: Selection of compounds Selection of sample type, sites, time & frequency Sampling Transport & storage Chemical analysis Data treatment Quantitation of uncertainty extremly difficult: Estimated analytical uncertainty at least ± %

10 Results - Detection frequency NMR Norway Main land Arctic Matrix Air Sediment Sludge Biota Air Moss/ needles Sediment Sludge Wastewater Biota Biota Number of samples Phenolic BFRs % % % % % % % % % % % 24DBP TBP PBP TBBPA BFR esters & ethers ATE DPTE BTBPE BATE TBA BEHTBP EHTeBB TBBPA-AE TBBPA-DPBPE TBPA

11 Results - Detection frequency NMR Norway Main land Arctic Matrix Air Sediment Sludge Biota Air Moss/ needles Sediment Sludge Wastewater Biota Biota Number of samples % % % % % % % % % % % Others flame retardants DP HBB PBT PBEB DBDPE TBECH, sum BTBPI Reference BFR BDE BDE BDE-71/ BDE BDE BDE BDE BDE BDE BDE BDE BDE BDE BDE BDE BDE

12 Råö, Nov. Råö. Jan. Lille Valby Copenhagen Oslo, Alna 1 Oslo, Alna 2 Oslo, Alna 3 Stockholm, Jan. Stockholm, Nov. pg/m3 Air NMR BFR ethers/esters Background air Urban air DPTE BTBPE BEHTBP EHTeBB 1 ATE SE SE DK - DK NO NO NO SE SE

13 Råö, Nov. Råö. Jan. Lille Valby - Copenhagen Oslo, Alna 1 Oslo, Alna 2 Oslo, Alna 3 Stockholm, Jan. Stockholm, Nov. - Oslo, SFT 1 Oslo, SFT 2 Oslo, SFT 3 pg/m3 Air NMR Other FRs Background air Urban air Indoor air HBB PBT PBEB DBDPE TBECH, sum 10 0 SE SE DK - DK NO NO NO SE SE - NO NO NO

14 Air Råö/Pallas PBDE Hansson K. et al. (2006), IVL U1967

15 Roskilde (Bjergmarken) Silkeborg (Søholt) Torshavn ( Hospital LSH) Torshavn (Sjersanvikin) Espoo (Suomenoja) Helsinki (Viikki) Kalteva (Hyvinkää) Klettagarðar untreated Klettagarðar Odorit treated Ålesund (Åse) WWTP 1 Ålesund (Åse) WWTP 2 Lidingö (Käppala) Stockholm (Henriksdal) ng/g d.w Sludge NMR Other FRs ng/g DP PBT DBDPE TBECH DK DK FO FO FI FI FI IS IS NO NO SE SE

16 Sewage/seepage water Norway

17 Fornæs Roskilde Marina Klaksvik Skalafjord Torshavn Helsinki Pori (Gr 1) Waldemarsudde (Gr 2) Biskopsudde (Gr 3) Torsbyfjärden ng/g d.w. Sediment NMR Phenolic BFRs DBP 246TBP PBP DK DK FO FO FO FI FI FI NO SE SE SE

18 Fornæs Roskilde Marina Klaksvik Skalafjord Torshavn Helsinki Pori (Gr 1) Waldemarsudde (Gr 2) Biskopsudde (Gr 3) Torsbyfjärden ng/g d.w. Sediment NMR Other FRs DPsyn/anti HBB PBT PBEB DBDPE 0.0 DK DK FO FO FO FI FI FI NO SE SE SE

19 Koltur Skuyoy Stora Karlsö 1 Stora Karlsö 2 Mylingsgrunnutin - IS O1 - Myrarnar Helsinki Riddarfjärden Stora Essingen IS O2 - ng/g f. w. Biota NMR Phenolic BFRs Egg Fish, liver Fish, muscle Mussel 24DBP 246TBP 0 FOFOSESE - FONONONO IS - FO FI FI FI FI FI FI SESE IS - NONO

20 Koltur Skuyoy Stora Karlsö 1 Stora Karlsö 2 Mylingsgrunnutin - IS O1 - Myrarnar Helsinki Riddarfjärden Stora Essingen IS O2 - ng/g f. w. Biota NMR BFR ethers/esters ng/g Egg Fish, liver Fish, muscle Mussel DPTE BTBPE 0.1 BEHTBP EHTeBB FOFOSESE - FONONONO IS - FO FI FI FI FI FI FISESE IS - NONO

21 Koltur Skuyoy Stora Karlsö 1 Stora Karlsö 2 Mylingsgrunnutin - IS O1 - Myrarnar Helsinki Riddarfjärden Stora Essingen IS O2 - ng/g f. w. Biota NMR HBB/PBT Egg Fish, liver Fish, muscle Mussel HBB PBT 0.00 FOFOSE SE - FONONONO IS - FO FI FI FI FI FI FI SE SE IS - NONO

22 Koltur Skuyoy Stora Karlsö 1 Stora Karlsö 2 Mylingsgrunnutin - IS O1 - Myrarnar Helsinki Riddarfjärden Stora Essingen IS O2 - ng/g f. w. Biota NMR DBDPE/TBECH Egg Fish, liver 1.6 ng/g Fish, muscle Mussel 0.40 DBDPE TBECH FOFOSESE - FONONONO IS - FO FI FI FI FI FI FI SESE IS - NONO

23 Biota Arctic EHTeBB/BEHTBP

24 Summary results Selected compounds regularly found in environmental and emission samples: Phenolic BFRs BFR esters & ethers Others flame retardants 24DBP DPTE DP 246TBP BTBPE HBB (TBA) PBT BEHTBP PBEB EHTeBB DBDPE TBECH, sum

25 Summary results NMR Biota (ng/g f.w.) a Sediment (ng/g d.w.) b Sludge (ng/g d.w.) c Matrix Phenolic BFRs 24DBP < < < TBP < < < BFR esters & ethers BTBPE < < < TBA BEHTBP < < < EHTeBB < < < Other BFRs DP syn+anti HBB < < PBT < < PBEB < < < DBDPE < < < TBECH, sum Reference compounds pentabde d

26 Conclusion Waste reclamation Important point source Present in air samples Long range atmospheric transport Widespread in biota Bioaccumulation Real effect data are scarce Ecotox. relevance unclear

27 Conclusion Bioaccumulation Negative effects on higher organisms cannot be excluded Some compounds in same concentration as PBDE oader monitoring and more effect studies are recommended Selection based on production volume and fate modelling is working

28 Acknowledgement Thanks to Audience for attention NORMAN for arranging this workshop NMR for this project My colleagues for good collaboration

Workshop. New brominated flame retardants as emerging contaminants in the environment: sources, occurrence, pathways and measurement methods

Workshop. New brominated flame retardants as emerging contaminants in the environment: sources, occurrence, pathways and measurement methods Workshop New brominated flame retardants as emerging contaminants in the environment: sources, occurrence, pathways and measurement methods www.norman-network.net NORMAN Association N W604002510 New brominated