Analysis and risk assessment of pharmaceuticals in the drinking water chain

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1 Analysis and risk assessment f pharmaceuticals in the drinking water chain Crine J. Hutman, Jan Kresbergen, Bart Pieterse, Albert de la Mar, Jan Peter van der Hek Cntents Intrductin Drinking water prductin in the Netherlands Why are pharmaceuticals relevant fr dw cmpanies? A multicmpnent snapsht f pharmaceuticals and pesticides in the river Meuse basin Human health risk assessment f pharmaceuticals in water 1

2 Drinking water prductin in the Netherlands A shrt histry: Histrically mainly grund water: pumps, wells 1853: first drinking water supply: fresh grund water extracted frm the dunes. Cnsumptin frm 10 (1850) t L p.p.p.d. >1950: infiltratin f surface water frm rivers Drinking water prductin in the Netherlands Prductin 1.1 billin cubic meters /y Micrbilgically safe withut chlrinatin grundwater riverbank filtrated grund water surface water dune infiltrated surface water 37% 15% natural dune water DW Prductin (10E6 m^3 in 2010) 2

3 Why are pharmaceuticals relevant fr dw cmpanies? Surces: DW prductin philsphy Aim: impeccable drinking water: chemically and micrbilgically safe DW is a natural prduct; simple treatment shuld be sufficient Sustainable prtectin f surface water surces: preventin > remval > transfrmatin / degradatin Drinking water: Safety f cnsumers if there might be a health risk (precautinary principle) Legislatin: Drinking Water Act: 1 ug/l anthrpgenic cntaminants Public Perceptin: cnsumer wrries abut hrmnes, pharmaceuticals etc. in dw Envirnment: switch t bttled water withut micrbilgical need => higher carbn ftprint Careful mnitring f surces and prduced drinking water Research n treatment techniques, txiclgy, risk assessment Thughtful cmmunicatin with custmers abut DW quality Why are pharmaceuticals relevant fr dw cmpanies? Surces: DW prductin philsphy Aim: impeccable drinking water: chemically and micrbilgically safe DW is a natural prduct; simple treatment shuld be sufficient Sustainable prtectin f surface water surces: preventin > remval > transfrmatin / degradatin Drinking water: Safety f cnsumers if there might be a health risk (precautinary principle) Legislatin: Drinking Water Act: 1 ug/l anthrpgenic cntaminants Public Perceptin: cnsumer wrries abut hrmnes, pharmaceuticals etc. in dw Envirnment: switch t bttled water withut micrbilgical need => higher carbn ftprint, Careful mnitring f surces and prduced drinking water Research n treatment techniques, txiclgy, risk assessment Thughtful cmmunicatin with custmers abut DW quality Use f target analyses, screening, biassays and cmbinatins theref. 3

4 Example f biassays: Estrgenic and gluccrticid acticity Estrgenic activity detected at all 4 surface water lcatins, gluccrticid at 3 f them. => Sme samples analysed fr causative cmpunds with UPLC-tQ-MS methd fr sterid hrmnes Successful identificatin f sterids frm varius classes: estrgenic (17α-E2), andrgenic (andrstenedine), prgestagenic(prgesterne, cyprterne-ac) and gluccrticid sterids. In agreement with CALUX results n sterids detected in drinking water samples. Cntents Intrductin Drinking water prductin in the Netherlands Why are pharmaceuticals relevant fr dw cmpanies? A multicmpnent snapsht f pharmaceuticals and pesticides in the river Meuse basin Human health risk assessment f pharmaceuticals in water 4

5 A multicmpnent snapsht f pharmaceuticals and pesticides in the river Meuse basin (Hutman et al., Env. Txiclgy & Chemistry 2013, 2013 (11): ) Aims: A. Snapsht f pharmaceuticals and pesticides in the river Meuse B. Crrelatin between lcatins and cntaminatin patterns? Can multi-cmpnent methds help t answer these questins? 9 Multi-cmpnent snapsht river Meuse - sampling Lcatins: 1. Belgian brder (Eijsden) (3x) 2. Geleen (industry) 3. Meuse Rsteren 4. Meuse Mk 5. Meuse Maasdriel 6. River Dmmel Eindhven (STP effluent) 7. River Dmmel Den Bsch (diluted) 8. River Aa Veghel (STP effluent) 9. Channel Suth William 10. Meuse after entrance Dmmel Aa and CSW 11. Enclsed Meuse 12. Meuse Keizersveer (3x) 16 lcatins Belgian brder => Nrth Sea 1 wk Lc. 11: dw intake site, histrical mnitring data Main stream Feeding rivers 13. Biesbsch 14. River Waal Werkendam 15. Meuse after entrance Waal 16. Sluices Haringvliet 10 5

6 Multi-cmpnent snapsht river Meuse - analyses General WQ parameters Multicmpnent methds fr pharmaceuticals and pesticides Lcatins: 1. Belgian brder (Eijsden) (3x) 2. Geleen (industry) 3. Meuse Rsteren 4. Meuse Mk 5. Meuse Maasdriel 6. River Dmmel Eindhven (STP effluent) 7. River Dmmel Den Bsch (diluted) 8. River Aa Veghel (STP effluent) 9. Channel Suth William 10. Meuse after entrance Dmmel Aa and CSW 11. Enclsed Meuse 12. Meuse Keizersveer (3x) 13. Biesbsch 14. River Waal Werkendam 15. Meuse after entrance Waal 16. Sluices Haringvliet 11 A. Snapsht f pharmaceuticals: histrical data Representatives f all therapeutic classes Range f cnc.: (<) 0.1 ng/l 1 ug/l) Cnfrm cnsumptin vlumes: antidiabetic(metfrmin) stimulants (caffeine) beta blckers 6

7 A. Snapsht f pharmaceuticals Seasnal patterns: carbamazepine, sulfamethxazle, caffeine, ibuprfen degradatin winter < summer Tempral trend: carbamazepine agrees with cnsumpin B. Crrelatin between lcatins and cntaminatin patterns- Pharmaceuticals Individual cncentratins lw, but in ttal up t 2 µg/l. Meuse diffusely cntaminated with pharmaceuticals f all kinds: 90% f analysed pharmaceuticals detected. 7

8 B. Crrelatin between lcatins and cntaminatin patterns- Pesticides Cncentratins between <10 ng/l t 2 µg/l; in ttal up t 2,8 µg/l. 14% f analysed pesticides detected (higher LOD than pharmaceuticals). Mst prminently present: AMPA (metablite f glyphsate) and herbicides. B. Crrelatin between lcatins and cntaminatin patterns- Pesticides Cncentratins between <10 ng/l t 2 µg/l; in ttal up t 2,8 µg/l. 14% f analysed pesticides detected (higher LOD than pharmaceuticals). Mst prminently present: AMPA (metablite f glyphsate) and herbicides. Cntaminatin patterns intercrrelated and max fur-fld difference => difficult t relate t lcatins at first sight 8

9 B. Crrelatin between lcatins and cntaminatin patterns Use multivariate statistics Principal cmpnent analysis (PCA): Clustering f lcatins accrding t cntaminatin pattern B. Crrelatin between lcatins and cntaminatin patterns Factr ladings 9

10 B. Crrelatin between lcatins and cntaminatin patterns - Factr ladings 1. Cluster f lcatins clse t Belgian brder 2. Cluster f lcatins in western part f river basin clser t Nrth Sea 3. Cluster f feeding rivers receiving STP effluent B. Crrelatin between lcatins and cntaminatin patterns - Factr ladings PC 2: water cmpsitin first part f river basin 1. Cluster f lcatins clse t Belgian brder 3. Cluster f feeding rivers receiving STP effluent 2. Cluster f lcatins in western part f river basin clser t Nrth Sea PC 1: less influence by STP effluent 10

11 B. Crrelatin between lcatins and cntaminatin patterns - Factr scres Factr scres: which cmpunds are fund at which type f lcatins B. Crrelatin between lcatins and cntaminatin patterns - Factr scres 1. Nitrate, pesticides glyphsate, AMPA, diurne Leaching frm sandy sil treated with manure Intensive chicken and pig farming 3. NH4 +, TOC, urea: markers fr STP Pharmaceuticals with lw remval rates in STP 2. HCO3 -, ph crrelated via carbnate equilibrium ph and Cl - high in delta area (influence Nrth Sea) 11

12 Cntents Intrductin Drinking water prductin in the Netherlands Why are pharmaceuticals relevant fr dw cmpanies? A multi-cmpnent snapsht f pharmaceuticals and pesticides in the river Meuse basin Human health risk assessment f pharmaceuticals in water T cnclude Water qualıty mnıtrıng requıres bıassays, screenıng, target analyses and cmbınatıns theref. Legıslatın: smetımes target analyses serve lıtteral ınterpretatın whereas bıassays serve purpse! Cllectıng data ıs nly half the wrk => ınterpretatın & rısk assessment Risk assessment Pharmaceuticals present at ng/l cncentratins in dw. Nevertheless: dw cmplies with Drinking Water Acts and ethical limits. RA: risk f adverse health effects f life-lng expsure can be cnsidered negligibly lw. Applicatin f mixture txicity cnfirms this picture fr cmbined expsure. Inclusin f mixtures in RA methdlgy research deserves mre attentin t supprt RA in applied fields. Thanks fr yur attentin! 12

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