Pharmaceuticals and transformation products in the water cycle

Transcription

1 Pharmaceuticals and transformation products in the water cycle Thomas ter Laak, Pascal Kooij, Jan Hofman, Annemarie van Wezel and many others, KWR, Nieuwegein,

2 Pharmaceuticals in the water cycle Production Human consumption Vet. consumption Excretion, metabolism Excretion, metabolism Waste water Manure Degradation Degradation STP Degradation, sorption leakage Manure tank Effluent Sludge overflow Degradation Surface water / sediment Soil Sorption, degradation, hydrology Groundwater Drinking water 2

3 Pharmaceutical consumption human and veterinary pharmaceuticals differ Human Cardiovascular Anti-diabetic Analgesic / anti-inflammatory Antibiotic Hormone Neurological Diagnostic.. and many more Veterinary Antibiotic (~90%!) Anti-parasitic Tranquilizer Hormone 3

4 Content 1. (veterinary) pharmaceuticals in groundwater 2. pharmaceuticals in surface water 3. transformation products 4

5 Veterinary pharmaceuticals consumption of VPs Antibiotic class Aminoglycosides (Am)phenicols β-lactams (Fluoro)quinolones Macrolides Penicillins Sulfonamides and trimethoprim Tetracyclins Total consumption Veterinary consumption NL (%) 1 - a - a b tons (2009) Veterinary consumption Germany (%) a b tons 1 Kemper, N., Mevius, D.J., Wit, B., van Pelt, W., 2007 & 2009 a not given b included in β-lactams c excluding penicillins 5

6 Veterinary pharmaceuticals Environmental fate of VPs Large fractions are excreted (as conjugates) 1,2 Sorption to soil varies per type of antibiotic Half-lives in manure, and soil range from days to a year 3 Half lives in water ranging from hours to months 3 1 Chee-Sanford JC, et al J Environ Qual 38: Du L, Liu W Agronomy Sust. Develop 32: data obtained by literature survey 6

7 Veterinary pharmaceuticals Occurrence of VPs in the environment mg/kg level in manure (tetracyclins and sulfonamides) µg/l up to mg/kg level in soil up to µg/l level in rural surface water Limited data on groundwater, sub µg/l to ng/l range (sulfonamides, trimethoprim and lincomycin) 7

8 (veterinary) pharmaceuticals in groundwater Field study, no VPs observed in agricultural areas Location Pharmaceuticals observed Remarks N=13 N=6 N=0 N=0 N=0 N=0 4) 5) Carbamazepine (0.03 µg/l) 10,11-trans-diol-carbamazepine (0.06 µg/l) phenazon (0.12 µg/l) propyphanazon (0.03 µg/l) AMPH (0.03 µg/l) 4-formylaminoantipyrine (0.02 µg/l) Carbamazepine ( µg/l) 10,11-trans-diol-carbamazepine ( µg/l) phenazon (0.01 µg/l) AMPH ( µg/l) 4-formylaminoantipyrine ( µg/l) Sotalol (0.01 µg/l) Tramadol (0.02 µg/l) Salbutamol (0.01 µg/l) Niacin (0.02 µg/l) Sulfamethoxazool (0.03 µg/l) diatrizoic zuur (0.07 µg/l) Metformine (0.15 µg/l) Guanyl urea (0.22 µg/l) Historical sewage infiltration Artificial surface water infiltration ter Laak, T.L et al. Veterinary Pharmaceuticals in drinking water sources; a first inventory. KWR, Nieuwegein, Netherlands. 8

9 Pharmaceuticals in surface water sources Consumption in catchment Excretion by human Removal STP Compare consumption and monitoring data Calculation for Lobith (Rhine catchment) Calculation for Geleenbeek (Meuse catchment) 9

10 Observed and predicted loads in Rhine Consumption based predictions match measured loads Predicted load = Q cons f Excr f STP ter Laak et al (2010) Environment International 36,

11 Observed and predicted loads in stream Consumption based predictions match measured loads 1000 Geleenbeek metformine predicted load (g/d) metoprolol sotalol carbamazepine gemfibrozil naproxen diclofenac bezafibraat trimethoprim sulfamethoxazole ketoprofen measured load (g/d) ter Laak and Hofman, in prep 11

12 Consumption based predictions successful Meuse catchment (average) loads can be predicted rather accurately on international and regional scale concentrations are more difficult to predict because they vary orders of magnitude in time (and space) propyphenazone metronidazool lincomycin erytromycin A bezafibraat N4-acetyl sulfamethoxazool ketoprofen trimethoprim oxcarbamazepine clindamycin anhydro erythromycine A carbamazepine-1011-epoxide 2-hydroxy carbamazepine propranolol sulfamethoxazool alfa-hydroxy metoprolol 3-hydroxy carbamazepine 4-formylaminoantipyrine niacin naproxen atenolol diclofenac venlafaxine gemfibrozil o-desmethyltramadol paracetamol 4-acetaminophen sulfaat carbamazepine furosemide diatrizoic zuur tramadol metoprolol hydroxy ibuprofen sotalol 1011-trans-diol-carbamazepine metformine guanylurea µg/l ter Laak and Hofman, in prep 12

13 3) Transformation products TPs are a relevant fraction of concentrations N compounds Total conc. of selected pharmaceuticals + TPs in Limburg = 6 to 27 µg/l TPs 30-86% of total conc. Additional research on fate, occurrence and risks of TPs relevant SW (14) T SW (10) DW SW (10) Pharmaceutical TP RBF (5) DW RBF (5) propyphenazone metronidazool lincomycin erytromycin A bezafibraat N4-acetyl sulfamethoxazool ketoprofen trimethoprim oxcarbamazepine clindamycin anhydro erythromycine A carbamazepine-1011-epoxide 2-hydroxy carbamazepine propranolol sulfamethoxazool alfa-hydroxy metoprolol 3-hydroxy carbamazepine 4-formylaminoantipyrine niacin naproxen atenolol diclofenac venlafaxine gemfibrozil o-desmethyltramadol paracetamol 4-acetaminophen sulfaat carbamazepine furosemide diatrizoic zuur tramadol metoprolol hydroxy ibuprofen sotalol 1011-trans-diol-carbamazepine metformine guanylurea 1. Escher, B.I., Fenner, K., ES&T 45, µg/l

14 Conclusion Limited data on pharmaceuticals in groundwater Some human pharmaceuticals found in infiltrated (ground) water No VP found >LOD in groundwater due to sorption and degradation Loads in surface water can be predicted, prediction of concentrations is more difficult Transformation products have relevant concentrations compared to their parents What are the risks?? (this will hopefully be answered in coming presentations) 14

15 Acknowledgements Joint Research Programme of the Dutch Water utilities and everybody that was involved in the presented research