Pharmaceuticals in waste water

Transcription

1 Pharmaceuticals in waste water Assoc. Prof. Stuart Khan RACI PHARMACEUTICAL SCIECE GRUP (SW) 21 ovember, 2017 Stuart Khan:

2 Sydney Water Act (1994) Pollution reduction targets Aluminium Ammonia (insofar as it is a toxicant) Arsenic Barium Benzidene Boron Cadmium Chloride Chromium Cobalt Copper Cyanide Dichlorobenzidine Diphenylhydrazine Selenium Silver Sulphate Surfactants Tin Trihalomethanes Total residual chlorine, including available chloramines Zinc Halogenated aliphatic compounds, including chlorinated alkanes and alkenes Iron Lead Manganese Mercury Molybdenum Monocyclic aromatic compounds, including chlorinated benzenes, chlorinated phenols and phenolic compounds ickel itrate and nitrite (insofar as they are toxicants) Pesticides, including organochlorines and organophosphates Polyaromatic hydrocarbons, including chlorinated naphthylenes, polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs)

3 Fall of the Berlin Wall (1989)

4 Clofibric acid in groundwater Survey of herbicides in groundwater after collapse of Berlin Wall Serendipitous identification of Mecoprop isomer: Stan, Heberer & Linkerhagner (1994) ccurrence of clofibric acid in the aquatic system - Is the use in human medical care the source of the contamination of surface, ground and drinking water? Vom Wasser, 83, Thomas Heberer

5 Clofibric acid is a drug metabolite CH 3 Cl Cl H 3 C H 3 C CH 3 Clofibrate CH 3 Etofibrate metabolism Cl CH H 3 C CH 3 Clofibric acid Cl H 3 C CH 3 Etophylline Clofibrate CH 3 CH 3

6 River bank filtration

7 Sewage effluents are hormonally active (1994) John Sumpter Brunel University, London

8 Widespread sexual disruption in wild fish (1998) Prof Susan Jobling Brunel University, London

9 USGS Reconnaissance Survey (2002) 139 stream sites across USA 95 hormones, pharmaceuticals and other organics surveyed 82 detected Kolpin, et al. (2002) Environ. Sci. Technol., 36(6),

10 Synthetic steroidal hormones Me H C CH Me H C CH H Me Ethinyloestradiol Mestranol Me H C CH Et H C CH orethisterone Levonorgestrel

11 on-steroidal anti-inflammatory (SAI) agents CH 2 CH Cl CH 3 CH H Cl Diclofenac C Ketoprofen CH 3. CH 3 CH CH 3 CH 3 CH 3 CH aproxen Ibuprofen

12 Population crash first noted in late 1990s. Banned from veterinary use in 2006 (India, epal and Pakistan). Diclofenac

13 Cytotoxics and cytostatics (antineoplastic agents) Cl Cl H P Cl Cl P H Ifosfamide Cyclophosphamide C 2 H H 2 H C 2 H H 2 Me Methotrexate

14 Antibiotics H CH 3 2 H F C 2 H Ciprofloxacin Metronidazole H 3 C H S H 2 H S CH 3 CH 3 C 2 H Sulfamethoxazole Penicillin G

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16 Antibiotics: An indirect threat? Jury et al (2011)

17 Mass balance PPCPs during wastewater treatment Caffeine 0.0% 0.1% Triclosan 2.9% 25.4% Gemfibrozil 44.9% 52.3% 56.0% 99.8% 18.6% Amitriptyline 0.0% Carbamazepine 15.7% Diclofenac 31.7% 8.0% 35.8% 55.7% 68.3% MBR effluent 76.3% 8.5% Trinh et al (2011) Sorption to biomass Biodegradation/transformation

18 Diurnal variations in antibiotics loads Le Minh et al (2011)

19 Diurnal variations in antibiotics loads Sulfamethoxazole Trimethoprim Concentration (ng/l) Effluent Influent 10 MQL = 10 ng/l Percentile (%) Concentration (ng/l) Effluent Influent 10 MQL = 3ng/L Percentile (%) Sulfamethoxazole + 4 -acetyl metabolite Sulfapyridine Concentration (ng/l) Effluent Influent Concentration (ng/l) Effluent MQL = 10 ng/l Influent Percentile (%) Percentile (%) Le Minh et al (2011)

20 Where did sulfapyridine come from? Veterinary-use antibiotic, not registered in Australia for human use. Human metabolism sulfasalazine sulfapyridine Le Minh et al (2011)

21 Long term monitoring of PPCPs in WWTP effluents

22 The Cooks River (Sydney) Cooks River Sydney CBD umber of samples detected (out of 49) Standard deviation (ng/l) rganics Mean conc. Max conc. (ng/l) (ng/l) Caffeine 45 7,9E+02 5,0E+03 1,3E+03 DEET 41 8,3E+01 3,4E+02 8,9E+01 Bisphenol A 38 1,5E+03 1,1E+04 2,6E+03 Triclosan 38 3,1E+01 2,6E+02 5,6E+01 Paracetamol 38 1,2E+03 7,4E+03 1,9E+03 TCEP 34 2,0E+02 3,9E+03 9,7E+02 Salicilic acid 32 1,8E+02 1,0E+03 1,2E+02 Ibuprofen 27 4,4E+01 2,3E+02 5,4E+01 Primidone 25 1,2E+03 4,9E+03 1,5E+03 Carbamazepine 23 1,2E+01 4,5E+01 1,1E+01 aproxen 19 4,0E+01 6,6E+02 1,5E+02 Polyparaben 18 1,7E+01 1,8E+02 4,0E+01 Diclofenac 13 1,3E+01 5,2E+01 1,7E+01 t-octyphenol 12 2,7E+01 1,3E+02 3,1E+01 Gemfibrozil 8 1,5E+01 6,0E+01 1,9E+01 Atrazine 8 1,2E+02 3,6E+02 1,1E+02 Laou et al (2011)

23 ADWG on pharmaceuticals

24 Australian guidelines for water recycling ~200 trace organic chemicals, including: Disinfection byproducts Pesticides Fragrances Pharmaceuticals Fire retardants Dioxins and PCBs Guideline values: Many in ng/l range A few <1 ng/l

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27 Synthetic wastewater treatment Hashim,. H., ghiem, L. D., Stuetz, R. M. and Khan, S. J. (2011) Enantiospecific fate of ibuprofen, ketoprofen and naproxen in a laboratory-scale membrane bioreactor. Water Res., 45(18),

28 EU ERA Guidelines (2006)

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30 EU Water Framework Directive Directive 2000/60/EC Adopted European Commission in 2000 to protect water quality & ecological attributes of rivers, lakes, groundwater and beaches Focus on control of chemical substances, which when released to water bodies may lead to detrimental ecological impacts. 2008/105/EC introduced priority chemical substances. 2013/39/EU introduced a watch list of substances for which Union-wide monitoring data are to be gathered for the purpose of supporting future prioritisation exercises. May contain up to 10 substances, which are to include Diclofenac, 17- beta-estradiol (E2) and 17-alpha-ethinylestradiol (EE2)). The watch list is to be updated every 2 years.

31 Assessment of candidate substances for the Watch List.

32 EU WFD First watch list (2015) (BHT) antioxidant, food additive. Sunscreen (absorbs UV-B) Erythromycin, clarithromycin, azithromycin

33 Dr ora Hashim Dr Lili Wang Dr Trang Trinh Dr hat Le Minh Dr James McDonald Dr Heather Coleman Assoc Prof. Frederic Leusch Acknowledgements