Human exposure to environmental contaminants: direct probe TOF-MS reveals a multitude of chemicals indoors

Transcription

1 Human exposure to environmental contaminants: direct probe TF-MS reveals a multitude of chemicals indoors Jacob de Boer, Ana Ballesteros-Gómez, Sicco andsma, Pim Leonards

2 ominated Flame Retardants BDE-47 BDE-209 H CH 3 CH 3 TBBPA H HBCD

3 (B)FR Research ca. 20 years ongoing K. Norén, D. Meyronité, Chemosphere 40, Nature 394, (2 July 1998) Do flame retardants threaten ocean life? J. de Boer, P. Wester, H. Klamer, W. Lewis, J. Boon

4 DecaBDE in sewage sludge NL and UK NL UK

5 DecaBDE in River Sediments EB Elbe EM Ems SN Seine TH Thames H Humber TB Tees Bay DH Dubllin Harbour WS Western Scheldt LB Liverpool Bay RM River Mersey 5

6 Flame retardants production PBBs TCBTs PCTs PCBs PFRs NBFRs CPs HBCD, TBBP-A PBDEs

7 ABSTRACT: A number of volatile phosphoruscontaining flame retardant species has been identified as possible replacements for brominecontaining formulations used in textile backcoatings because of the need for vapor-phase activity.

8 8 Public, Clariant BL Flame Retardants Dr. Adrian Beard, BU Additives, Flame Retardants, Global Consumption of Flame Retardants (2010) 5600 mio. USD FR Market by Region Share in percent, mio. metric tons FR Market by Chemistry Share in percent, 2010 ther Asia 18% 25% North America Antimony xides 7% 7% thers 12% 12% 21% ominated China 14% 0% 1% 2% 2% Central and South America 19% rganophosphorus 10% Japan Africa Middle East Central and Eastern Europe 28% Western Europe Alumina- Trihydrate 34% 8% Chlorinated Estimated average growth 2010 to 2015 ca. 2.9% p.a. Source: SRI/IHS consulting 2011

9 Selection of PFRs TDCIPP Tris(1,3-dichloro-2-propyl) phosphate TNBP Tributyl phosphate TCEP Tris(2-chloroethyl) phosphate TCIPP Tris(chloropropyl) phosphate TEHP Tris(2-ethylhexyl) phosphate TPHP Triphenyl phosphate EHDPP 2-Ethylhexyl diphenyl phosphate TMPP (TCP) Tricresylphosphate

10 ENFIR: Safe P-Based Alternatives DP Ammoniumpolyphosphate Melamine polyphosphate P P n RDP BDP Aluminium diethylphosphinate 10

11 Chlorinated paraffins (CPs): Application Additives in metal cutting fluids Window sealants Flame retardants Leather treatment Plasticizers Rubber Additives in paint Additives in two-stroke engines

12 Short and Medium-Chain Chlorinated Paraffins Production : > 700,000 tons per year in China alone SCCPs now under Stockholm Convention on PPs 12

13 Liquid-nitrogen-cooled jet modulator (N 2 jets) Injector N 2 (g) N 2 (g) Detector Heater N 2 (l) Cold jets 2 nd dim. column Hot jets 1 st dim. column

14 P C A _ N C I _ c 1 0 _ 5 5 % C l _ # R T : A V : 6 S B : N L : E 3 T : { 0 ; 0 } - c C I F u l l [ ] m / z m / z P C A _ N C I _ c 1 0 _ 5 5 % C l _ # R T : A V : 1 5 S B : N L : E 3 T : { 0 ; 0 } - c C I F u l l [ ] m / z P C A _ N C I _ c 1 0 _ 5 5 % C l _ # R T : A V : 1 1 S B : N L : E 3 T : { 0 ; 0 } - c C I F u l l [ ] m / z C 10, 55% Cl, m/z ,5,6,9-C 10 Cl 4 1,2,5,6,9-C 10 Cl 5 4Cl GCxGC-ECNI-ToF-MS 1,2,5,6,9,10-C 10 Cl 6 7Cl 6Cl 5Cl 1,1,1,3,8,10,10,10-C 10 Cl 8 1,2-C 10 Cl 2 1,1,1,3-C 10Cl 4 1,2,9,10-C 10 Cl 4 1,1,1,3,9,10-C 10 Cl [M-Cl] C 10 H 16 Cl 6 [M-HCl] 2 nd dimension retention time (s) C 10, 55% Cl, m/z Relative Abundance 278 [M-Cl] [M-HCl] [M] 314 C 10 H 17 Cl 5 Relative Abundance Relative Abundance [M-2HCl] 276 6Cl [M-2HCl] [M-Cl] C 10 H 15 Cl 7 [M-HCl] C 10, 65% Cl, m/z Cl 7Cl 8Cl 9Cl Mass spectrum of peak Relative Abundance st dimension retention time (min) 14

15 2 nd dimension retention time (s) BB153 2H-28 6H-47 4H , ,66 6Me , F-27 40, me-tbbp-a 25, ,33 BB , BB , F BB BB ,79 3F ,123 22,37 6F F , H Me-49 97, F-69 6F F F H-99 4 F BB153 me-tbbp-a 131,158, TBBP-A 142 HBCD PBDEs: GCxGC BB , TBBP-A HBCD ,6F-199 2,4 F PCAs F st dimension retention time (min) 80

16 Interlaboratory study

17 FR levels at contaminated sites FR Sediment Fish Dust Refs. BDE ,750 andsma 2014 BDE ,350 Shoeib 2012 HBCD andsma, Shoeib, Cao 2014 DBDPE ,400 Kierkegaard 2004, Stapleton 2012 Dechlorane Plus Sverko 2007, Kang 2012 Total SCCP ,000 Marvin 2003, Parera, Jiang 2013 Total MCCP ,000 Hilger 2013, Reth, 2005 TIBP andsma 2014, Cao 2014 TCEP ,300 id TBEP ,000 id TPHP id EDHPP id Sediment, fish: Western Scheldt (NL), Great Lakes, Baltic, Spanish rivers Sediment, house, office, hotel dust: ng/g dw, fish: ng/g ww 17

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19 PFRs in cars and houses

20 V6 in Baby Products, House Dust, and Car Dust V6: 2,2-bis(chloromethyl)-propane-1,3-diyltetrakis(2-chloroethyl) bisphosphate a dimer of TCEP 24 to 60 mg/g of foam in baby products <5 to 1110 ng/g in house dust <5 to 6160 ng/g in car dust Fang et al. Environ. Sci. Technol., 2013, 47,

21 Fast ambient mass spectrometry methods for flame retardants Slider DIP ASSEMBLY Capillary grip Slider Track Capillary Pneumatic gas attachment Mount

22 Identification of novel flame retardants in plastics Intens. x Intens. x SMART FRMULA, BRUKER Lower formula Upper formula Measured m/z 6 Ion formula m/z error ppm MSigma Score C H N ? m/z DP-APCI(+)HRTF-MS spectra of a power board sample Match! Looking in databases CMPUND CRAWLER BRUKER

23 TTBP TAZ? Replacement for banned flame retardants: Possible for octabde mix in ABS DecaBDE in HIPS (EPA, 2014) Hexabromocyclododecane (HBCD) in HIPS (UNEP, 2011) Toxicity 2,4,6 tris(2,4,6 tribromophenoxy) 1,3,5 triazine TTBP TAZ toxicity is considered mainly low, but very high persistence and high bioaccumulation (EPA 2014)

24 Quantitation of TTBP TAZ in dust ( ng g 1 ), n=3 (total 5 samples) (160 ng g 1 ), n=1 (total 2 samples) ( ng g 1 ), n=3 (total 5 samples) A. Ballesteros Gómez et al. ES&T. 48 (2014), 4468

25 Development of fast ambient mass spectrometry methods for flame retardants in plastics (30 PFRS+BFRs) Standard method Direct probe method 12 h per sample 5 min per sample Ballesteros Gómez et al., Analytical and Bionalytical Chemistry 406 (2014)

26 Suitability of DIP APCI/APPI HRTF_MS for Screening of Flame Retardants and Plasticizers Many are highly non polar, e.g. PBDEs and only suitable for APCI and APPI but not for ESI ionization They are at high concentrations in samples of plastics, waste (>0.1% w/w) Avoid losses during extraction/ separation (e.g. thermolabile compounds) Avoid the need of extensive extraction steps in complex plastic matrices Fast screening for compliance of legislation Recycling purposes. WEEE. Directive 2002/96/EC European Court of Justice , C 14/06, 2008), limits of 0.1 % w/w by mass for pentabde and octabde in market products 26

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28 Biphenol-A in thermal paper S NH NH S? H H H S H

29 Reversible reaction between BPA and leuco dye R 2 N R 2 + H R 2 + N - R 2 + H CH H 1.13 µg BPA is transferred to the pad of a finger holding a cash receipt for 5 s if the fingers are somewhat dry

30 BPA alternatives in thermal paper H S H H S H H S H H S H H H H H H

31 How are all these compounds effecting ourselves? Inhibition voltage-gated calcium channels From: Marieke Meijer, PhD thesis, 2016, University Utrecht

32 Conclusions Indoor dust in hotels, homes, offices, cars and schools is a highly complex cocktail of many types of FRs and other chemicals SCCPs and MCCPs need much more attention in outdoor and indoor environment (Neuro)toxicity of many PFRs is of concern Direct Probe MS is a fast technique for screening materials and e waste Urgent need for studies on mixture effects

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