Endocrine Disruptors in Water for Human Consumption

Transcription

1 Endocrine Disruptors in Water for Human Consumption The EU and GWRC journey on EDCs Genoa, 30 November 2011

2 Topics Old or new issue? Overview of the Activities by the European Union Activities by the Global Water Research Coalition Key messages on drinking water and public health 2

3 The EDC issue is not new In 1938, the drug DES (diethylstilbestrol) was designed to prevent miscarriages in women. In 1970/1980, it was shown that DES causes severe problems (inborn abnormalities, cancer, ). As early as 1946, the harmful effects of DDT on birds, beneficial insects, fish, and marine invertebrates were seen in the environment; next PCB, dioxins, Focus on risk and impact of individual chemicals 3

4 How the EDC issue became a hot topic The term endocrine disruptor was coined at the Wingspread Conference Centre in Wisconsin in 1991 One of the early papers on the phenomenon was The Stolen Future by Theo Colburn in 1993: Environmental chemicals disrupt the development of the endocrine system Evidence of ED impact on wildlife via diffuse pollution presented Actions by i.e. European Commission and US (EPA) 4

5 Actions by the European Union In 1996: International meeting (UK) on potential impact of ED on human health and wildlife => The Weybridge Report In 1998: Resolution by EU Parliament to improve legislation, reinforce research efforts and inform the public In 1999: Community Strategy for Endocrine Disruptors by EU Commission inline with the precautionary principal (similar to pesticides) 5

6 EU Community Strategy for ED Short-term actions (information gathering) Priority list of potential ED Monitoring in suspect chemicals in food an the environment Identification of vulnerable groups of people (i.e. children) International network for info exchange and coordination Medium-term actions (research) Development of test methods to assess ED European test strategy for assessing ED (link to USA/Japan) Understanding ED mechanisms impact on human health Identification of alternative chemicals Long-term actions (legislation) 6

7 EU Community Strategy for ED Short-term actions (information gathering) Medium-term actions (research) Long-term actions (legislation) Adaptation of toxicity tests for hazards assessment and assessing health risk to people and wildlife Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) will include chemicals with ED potential Review of existing legislation regarding testing/use/disposal of i.e. pesticides, biocides and consumer products on ED risks Other ED substances via i.e. Water Framework Directive, UNECE POPs protocol etc. 7

8 EU Community Strategy for ED Information via EU websites en.htm Recent reports State of the Art Assessment of ED (EU, February 2011 (draft)) Novel Screening and Testing methods and Endpoints for Evaluating ED (OECD, June 2011 (draft)) Regular progress reports on implementation since th report (SEC 1001 final - August 2011) 8

9 EU Community Strategy for ED 4 th progress report (SEC 1001 final - August 2011) List of priority substances available (database => website) Monitoring of ED via national programs and EU FP projects ongoing (i.e. COPHES - human bio monitoring framework) Lack of coordination of monitoring! Understanding the ED mechanism and development of ED test methods and strategies (CREDO, REPROTECT); new endpoints? Strong focus on role of food i.e. BIOCOP, NECTAR, OBELIX, PERFOOD (PFCs) Websites in the air 9

10 EU Community Strategy for ED 4 th progress report (SEC 1001 final - August 2011) Prevention A number of EDCs are added to the Reach List of Substance Subject to Authorisation (Annex XIV); other additions are in preparation by member states Substances with ED properties cannot be authorised under the Plant Protection Products Regulations (PPPR). Criteria are under discussion Review of the Regulations on Cosmetics by 2015 (at the latest) Restriction of use of Bisphenol A in infant feeding bottles (other materials: migration < 0.6 mg/kg food) New regulation for Biocides and Toys (2011) includes EDC 10

11 EU Community Strategy for ED 4 th progress report (SEC 1001 final - August 2011) Water Quality DW Directive: no specific values but precautionary principle is still in place Water Framework Directive and the linked Directive on Environmental Quality Standards (for Priority Substances) may include EDC List of Priority Substances of the EQS is under review; proposal by the Commission is expected by end

12 EU supported research ED research projects via EU Framework Program Program Ongoing Finished Total FP FP FP FP Total Water related projects Sandrine, Comprehed, Poseidon, Fire, Eurorisk, Eden, Comprendo (all finished by 2007) Techneau (DW, KWR), Neptune (WW, Eawag) 12

13 EDC activities by the GWRC 13

14 14

15 The GWRC Members Water RF (US) WERF (US) VERI (Veolia) (FR) CIRSEE (Suez) (FR) TZW (DE) PUB (SG) KWR (NL) STOWA (NL) UKWIR (GB) WQRA (AU) WSAA (AU) WRC (ZA) Coordination of water research programs at a (inter) national level Roots in the water sector Indirectly serving 500 mio consumers GWRC partners: - US Environmental Protection Agency - International Water Association 15 (IWA)

16 GWRC & Endocrine Disruptors Selected as the first research area for joint actions (Berlin 2001) Inventory of finished, ongoing and planned activities and projects by members of the GWRC (February 2002) Set of 23 projects identified Value of 15 mio Euro Paris meeting (March 2002) Joint effort on EDC in sludge and biosolids Development of AC methods (UKWIR => WRc) Survey occurrence (AC, Yes => Calux) Board meeting (May 2002) => ED Research Strategy workshop in Pretoria 16

17 GWRC & Endocrine Disruptors State of the Science workshop (Pretoria, October 2002) WRC-SA lead agent Eight members participating Exchange of knowledge Survey of occurrence data List of Target EDC Research agenda (knowledge gaps and research needs) 17

18 Pretoria conclusions ED occurrence in water Hormones, pesticides, alkyl phenols, phthalates, bisphenol A, PCB, heavy metals Surface water, groundwater, influent and effluent WWT: ng-ug/l Treated drinking water: << compared to other routes Limited health risk via treated drinking water, but Direct use of surface water can be a risk Developing countries (i.e. DDT, ) Environmental problem impact of WWT Validation of analytical methods needed => ws Karlsruhe (2003) 18

19 Workshop EDC Analytical Methods (TZW - Karlsruhe, 2003) Methods reviewed by Analytical Experts Surface water and DW: OK => round robins Method development needed for EDC in WWT: sludge/influent ( ) Inter-laboratory comparison of AC methods (2005) The Goal: Toolbox of analytical methods (chemical, bio assays) 19

20 EDC Analytical Methods Comparison of Analytical Chemical Methods (Suez/Veolia) 14 laboratories from 7 countries) WW influent and effluent, SW, GW, sludge (plus spikes) March October 2005 EDC Toolbox I (WERF) Estrogens Literature review => selection of promising bioassays (2005) Field trials ( ) EDC Toolbox II (WQRA) Additional endpoints Literature review => selection of promising bioassays (2011) Field test (2012) Occurrence and Fate in WWT Member activities (CIRSEE, Stowa, UKWIR, VERI, WERF, EU Neptune) 20

21 LC-MS/MS ESI-(SPE PLRP-s) LC-Coulometric detection (SPE C18) EDC Analytical Methods Comparison of Analytical Chemical Methods (Suez/Veolia) 14 laboratories from 7 countries Samples: WW influent and effluent, SW, GW, DW, sludge (plus spikes) α and β estradiol, estrone, ethinylestradiol Methods used: GC-MS, GC-MS-MS, LC-MS, LC-MS-MS, LC-CD LC-MS/MS ESI-(SPE HLB) LC-MS/MS ESI-(SPE C18/SPE Florisil) LC-MS/MS ESI -(SPE 18-Silicagel) LC-MS/MS ESI-(SPE Lichrolut EN/RP C18/Silicagel) GC-MS EI MSTFA (SPE RP-C18) LC-MS/MS ESI-(SPE C18/SPE Florisil) LC-MS TOF APPI-(SPE SDB1-LC clean-up Zorbax Cyano/LC Clean-up GPC PIGel50) GC-MS/MS EI sigma sil A(DVB Speeddisk/LC Clean-up C18) LC-MS/MS APPI+(SPE SDB/LC Clean-up Agilent PL Gel/SPE Aminopropyl) Sample stability OK Good results for GW, SW and effluent Limited data on sludge (3 labs) LC-MS (MS) >> GC-MS (MS), LC CD Combination of powerful purification + highly selective and sensitive detection Ethinylestradiol in ng/l - Sample E 3 6 <5 Laboratory number 21

22 GWRC Interlaboratory Test: Raw Data Raw Wastewater Raw WW Lab 1 Lab 2 Lab 3 Lab 4 Lab 5 Lab 6 Lab 7 Lab 8 Lab 9 Lab 10 Lab 11 -Estradiol Estradiol na na EthinylEstr < LQ - - < LQ 51.4? < LQ Estrone Results expressed in ng/l

23 GWRC Interlaboratory Test: Raw Data Estrone Lab 1 Lab 2 Lab 3 Lab 4 Lab 5 Lab 6 Lab 7 Lab 8 Lab 9 Lab 10 Lab 11 Raw WW Treated W < LQ < LQ 1.0 Spiked Treated W Surface W Ground W < LQ Sludge Results expressed in ng/l or ng/g

24 EDC Analytical Methods EDC Toolbox I (WERF) EDC Estrogens Toolbox I (WERF) Estrogens Literature review (24 bioassays) Bioassays tested Literature Selection of review promising => selection bioassays of promising bioassays (2005) Field trials ( ) Field trials ( ) Yeast estrogen screen (YES) WRC (South Africa) UTS (Australia) ER-CALUX KIWA (Netherlands) MELN Univ. Paris Sud 11 (France) T47D-KBluc WRC (South Africa) USEPA (USA) - limited E-Screen CRCWQT (Australia) Landcare (New Zealand) The team Simultaneous chemical analysis TZW (Germany) CRCWQT (Australia) 24

25 Field Interassay Δ Many nondetects in YES assay ER-CALUX detects activity in all samples Some interlab Δ All assays show similar trends

26 Field Good agreement b/w chemistry and most bioassays

27 Estrogenicity in water GW1 > GW2 GW1 shallow GW2 deep aquifer STP removal efficiency: STP1 = 89.7% STP2 = > 95.4% Sewage 1 industrial Sewage 2 domestic River 1 < River 2 Riv. 1 large Riv. 2 small / impact?

28 Assay comparison Assay Field EEq CoV MDL Field M/P Overall YES ½ ER-CALUX ¾ MELN ¼ KBluc (++) N/A +++ (++) (++½) E-Screen ¼

29 EDC Analytical Methods EDC Toolbox II (WQRA) Additional ED endpoints Literature review of relevant endpoints and promising bioassays (2011) Field test (2012) Stage 1 State of the Science on assessment of androgen, progestagen, glucocorticoid, interference with steroidogenesis, thyroid, retinoid (RXR/RAR) and Peroxisome ( PPAR) activity in water. Relevance of endpoints and available bioassays 29

30 EDC Analytical Methods EDC Toolbox II (WQRA) Workshop in Nieuwegein (2-3 October) Review of the literature review and the selection of the priority endpoints and promising bioassays Meta analysis inter-assays comparison, field test and survey of occurrence 30

31 EDC Toolbox II Action Plan for stage 2 Coding ( = done or to be addressed in this project = already done by another project? = under consideration) Lit review Meta analysis Interlab / Interassay Field validation Sampling / preservation / extraction Androgen Receptor Signaling Activity AR Steroidogenesis Stgn Progestogen Receptor Signaling Activity PR Glucocorticoid Receptor Signaling Activity Retinoid Receptor Signaling Activity Peroxisome Proliferator-Activated Receptor Signaling Activity GR??? RX R PPA R????? Thyroid Receptor Signaling Activity TR? Estrogen Receptor Signaling Activity ER (previous GWRC project) 1 31

32 GWRC Reports EDC Reports Occurrence of EDC in water systems Sources and biological methods Priority list of EDC Knowledge gaps and research needs Workshop Analytical Methods EDC in sewage sludge: analytical method development Comparison of analytical chemical methods for EDC in water and sludge Bioassays to detect Estrogenic activity in environmental waters Part 1. Review of bioassays Part 2. Field tests Review of Bioassays for different ED endpoints (EDC Toolbox II)

33 Safe to drink..? YES...! 33

34 Public Health and Drinking Water Yes, EDC can be detected in source waters Why? We know where to look for and have improved the monitoring techniques (chemical methods and bioassays) No, there is no known impact on public health If present, the ED concentrations in drinking water (< ng/l) are negligible compare to other routes of exposure But, the water sector invests in permanent vigilance! The water sector continues to invest in the further improvement of water treatment and analytical methods to control and safeguard the water quality today and in the future. (The aquatic environment is a different story) 34

35 QUESTIONS? 35