BROMINATED FLAME RETARDANTS (BFRs)

Transcription

1 BROMINATED FLAME RETARDANTS (BFRs) Jana Hajšlová, Radek Kazda, Jan Poustka Institute of Chemical Technology, Prague Department of Food Chemistry and Analysis The 1st Workshop - Persistent Toxic Substances Contamination of the European Region November, 2003, Brno

2 Basic information» characteristic» toxicology» occurrence in the environment EU projects concerned with BFRs and other endocrine disruptors Results results of pilot studies Czech republic» analytical method» PBDEs in breast milk» BFRs in fish

3 Reduce fire hazards, interfer with a combustion process Wide use in various products: plastics, textiles, foams Brominated flame retardants - BFRs: cheapest alternative - 40 % of total FRs production rate

4 FLAME RETARDANCY MECHANISMUS HEAT (INCREASE OF TEMPERATURE) decomposition of FRs (earlier than the matrix of a polymer) release of products preventing / slowing down the fire The ideal situation: retardant decomposes at temp. approximately 50 C below the host polymer brominated flame retardants (BFRs) in combination with many common poloymers meet this requirement 2 types of FR reactive additive

5 O (DeBDE - 75 %) Br Br Commercial technical mixtures containing PBDEs: BROMKAL 70, DE - 71, FR 1205 etc.) B r B r B r B r B r B r

6 BDE group Mol. weight (g/mol) Log K ow State Solubility in water (25 C) Boling point ( C) TetraBDEs liquid 0.07 mg/l not available PentaBDEs solid mg/l > 300 HexaBDEs liquid mg/l not available DecaBDE solid 0,02 0,03 mg/l 310

7 Major uses of additive BFRS DecaBDE - most widespread additive used in high resistence polystyrenes, thermoplastics, polyolefins, PVC, elastomers and textiles Other PBDEs - wire and cable insulations, electronic connectors, building materials (walls, roofs etc.), packaging materials HBCD - polystyren foams and textiles.

8 OH Br CH 3 Br OH Br CH 3 Br Major use of TBPA Epoxy resins - for printed circuit boards (in computers) Phenol resins

9 Table I: Production of BFRs in tons / year (2001) Continent PeBDE OcBDE DeBDE TBBPA HBCD Europe Asia America Total

10 1979 (USA) detected in soil, freshwater and sludge 80 s findings in other countries occurrence biota including as well as in human tissues proved

11 Dominating BDE 209 (94-96 %) The highest concentrations of BDE 47 (major component of technical mixtures) BDE 99, 100, 153 and 154 usually also detected in high concentrations BDE 209 not detected degradation not bioavailable

12 Typical levels of BFRs in the environment TYPE OF SAMPLE AREA PBDES YEAR Air USA (Chicago) pg/m Sweden 1-8 pg/m Sediments Netherlands (several rivers) ng/g dry sediment 1998 Baltic sea n.d. 6 ng/g dry sediment 2000 Pike Sweden ng/g lipids 1997 Bream Netherlands ng/g fish weight 2001 Carp USA ng/g fish weight 2000 Human fat tissue Sweden ng/g lipids 1997 Human liver tissue Sweden 6-14 ng/g lipids 1999 Hunam breast milk Germany ng/g lipids 1988 Finland ng/g lipids 2000

13 hydroxy brominated diphenyl ethers naturally present in the environment - produced by sponges Dysidea herbecea or Phylospongia falascens methoxy brominated diphenyl ethers found in wildlife - producted by Phylospongia foliascens ANTHROPOGENIC SOURCES leaching from landfills (additive) during incineration (.dioxins?)

14 Possible mechanism of PBDDs / PBDFs formation from DecaBDE

15 Lack of comprehensive information Studies with rodents are running memory loss (neurotoxicity) hepatotoxicity (TBBPA) reduction of body weight Suspected endocrine disruptors

16 Endocrine Disrupting Chemicals (International Programme on Chemical Safety): Exogenous substances that alter function(s) of the endocrine system and consequently cause adverse health effects in an intact organism, or its progeny, or (sub)population

17 17-β-estradiol Binding on receptor p,p - DDT

18 Classification of Endocrine Disrupting Chemicals Two classes : 4Natural hormones 4Man-made substances, which include synthetically produced hormones and man-made made chemicals

19 PCBs MeHg: Bisphenol A: Foods the main source of humans exposure contaminated fish may leak from plastics into food products Pesticides (DDE, DDT etc): Contaminat. fish fruits vegetables Dioxins and dioxin-like compounds: animal fat in meat dairy products fish Brominated flame retardants: can be found in fish

20 For women: EDC: potential health risks For men: 4Breast and reproductive organ tissue cancers Fibrocystic disease of the breast Polycystic ovarian syndrome Endometriosis, uterine fibroids and PID Declining sex ratio (fewer women) Poor semen quality (low sperm counts, low ejaculate volume, high number of abnormal sperm, low number of mobile sperm) Testicular cancer Malformed reproductive tissue (undescended testes, small penis size) Prostate disease and other recognised abnormalities of male reproductive tissues

21 FIRE (Flame retardant Integrated Risk assessment for Endocrine disruption) 5th FP EU multi- and interdisciplinary project QLRT The overall objective Improving risk assessment of brominated flame retardants (BFRs) for human health and wildlife. Role of Institute of Chemical Technology (i) Human exposure assessment (ii) Aquatic exposure assessment

22 FIRE outline Theme 1 Prescreening - QSAR modelling and chemical - In vitro prescreening BFRS Theme 2 Human hazard identification - In vivo rat toxicity studies -Toxicokinetics TBBPA Theme 4 Human exposure assessment - Human exposure assessment - In vitro tests of contribution BFRs to total activity Theme 6 Integrated risk assessment for humans and aquatic wildlife Theme 7 Dissemination Theme 3 Aquatic wildlife hazard identification - In vivo fish toxicity studies Theme 5 Aquatic wildlife exposure assessment - Aquatic ecosystem exposure assessment - Environmental transformation - Aquatic food web modelling

23 Example of analytical procedures used for analysis of BFRs Sample Extraction Clean-up Identifiaction and quantification Reference Fish, Sediments Soxhlet Hexane/acetone (Acetone) GPC, H 2 SO 4 GC/MS-NCI Sellstrom, 1998 Fish, Sediments Soxhlet Hexane/acetone Al 2 O 3, SiO 2 GC/MS-NCI De Boer, 2001 Human breast milk LLE Lipidex, HCOOH, acetonitrile, methanol SiO 2 column impregnated by H 2 SO 4 GC/MS-EI Meironyté, 1999

24 Extraction Fish - Soxhlet extraction Milk - LLE Clean - up GPC Cyklohexane:Ethylacetate (1:1) Identification Quantification GC/MS/EI NCI Removal of residual lipids H 2 SO 4

25 Fig.. 1: GC/MS of real sample (bream)) in EI and NCI mode Abundance PBDE 47 bde bde bde bde Time--> Abundance PBDE 47 bde bde 28 bde 100 bde 154 TBBPA bde bde 75 bde71 bde 99 T im e-->

26 Fig.. 2: GC/MS of milk sample NCI mode (concentration( in ng/g of lipids) - seriously contaminated sample Abundance MILK BDE 37 (IS) BDE 47 (11.13 ng/g) BDE 28 BDE 49 (0.18 ng/g) BDE 66 (0.13 ng/g) BDE 99 BDE 100 (3.21 ng/g) (1.54 ng/g) BDE 154 (0.22 ng/g) BDE 153 (1.14 ng/g) PBDE 183 (< 0.15 ng/g) Time-->

27 Case 1: ANALYSIS S OF PBDEs 25 pg injected E I 100 % PBDE ion: mass window: 0.05 Da 100 PBDE M O D E % mass: mass window: 0.05 Da PBDE % PBDE m/z % TIC Septum bleed % m/z Column: DB-XLB, 30 30m 0.25 mm 0.1 µm film; Injected volume: 1 µl; Injector temperature: 275 C; GC oven: 110 (1 45 C.min 1 1 to to C.min 1 to to300 C (5 (5min); Carrier gas flow: 1.0 ml/min; acquisition speed: 1 spectrum/s; total run time: min

28 PBDEs by GC HR-TOF-MS and GC LR-Q-MS N C I GCT TOF-MS 0.1 pg injected PBDE % 5.47 PBDE 28 PBDE PBDE 49 PBDE PBDE PBDE PBDE 85 PBDE m/z Mass window: 0.02 Da PBDE PBDE M O D E % m/z Quadrupole MS (HP 5973) 0.5 pg injected PBDE 28 PBDE 49 PBDE 47 PBDE 66 PBDE 100 PBDE 99 PBDE 85 PBDE 154 PBDE 153 m/z PBDE 183

29 Detection limits of BFRs 50 pooled samples (270 fish) from 6 different localities on two main Czech rivers (Elbe and Moldau) were analysed 4 fish species were collected: chub, bream, barbel and perch Congener LOD (ng/g lipids) HBCD 2.00

30 AQUATIC ECOSYSTEM sampling sites in the Czech republic

31 Congeners 47 detected in each sample BDE 99, 100, 153 and 154 determined in most samples BDE 47 major congener in all samples % of the total amount BDE 28, 49, 85 and 183 only in few fish samples

32 Fig.. 3: Mean levels of BFRs in muscle of chubs collected at sampling sites located at Elbe (Labe) and Moldau (Vltava) river; Czech Republic 2003 c (ng / g of lipids) BDE 47 Other PBDEs HBCD 0 Valy LABE VLTAVA

33 Fig.. 4: The pattern of PBDEs in various fish species (Elbe River, locality Valy, 2003) 80 % Chub Barbel Bream Perch 0 BDE 28 BDE 47 BDE 49 BDE 85 BDE 99 BDE 100 BDE 153 BDE 154

34 Detection limits of BFRs 103 samples of human milk analysed Samples were collected by University hospital, Olomouc, Czech Republic, / 2003 Congener LOD (ng( ng/g lipids) HBCD 0.50

35 Congeners 47 detected in each sample BDE 99, 100 and 153 determined in most samples HBCD not detected in any sample No correlation among PBDEs levels and age of mothers, content of lipids, smoking or fish consuming was found

36 Fig. 5: CONCENTRATION OF BDE 47 IN MOTHER S MILK (samples collected by University hospital, Olomouc, Czech republic, 2003) BDE 47 c (ng/g of lipids) No. of sample 70 85

37 Fig.. 6: Levels of BDE 47 versus age of mothers c (ng/g of lipids) Sample 70 BDE 47 Sample 85 Sample Age (years)

38 Fig.. 7: Pattern of PBDEs congeners in mother s milk BDE % BDE 100 6% BDE % BDE 99 14% BDE 66 2% Sample no. 35 BDE 49 2% (PBDEs = 2.75 ng/g of lipids) BDE 47 44% BDE 66 1% Sample no. 70 (PBDEs = 5.41 ng/g of lipids) BDE 100 5% BDE 99 12% BDE 49 2% BDE 153 3% BDE 183 5% BDE 47 72%

39 Table II: Comparison of levels of PBDEs in Czech Republic to other studies BDE 47 Other PBDEs Sweden, 1998 Canada, 2000 Finland, 2000 Japan, 2000 Czech republic, (n=39) 1.75 (n = 10) 0.85 (n = 11) 0.48 (n = 6) 0.86 (n = 103)

40 BFRs have been monitored in Czech Republic for about 3 years BFRs detected in all fish and breast milk samples BDE 47 major BFR in analysed samples, contributes with % to the total amount of BFRs HBCD detected in relatively high levels in fish, not detected in breast milk samples Further fish and milk samples will be analysed within the project FIRE