Source control measures to minimize contamination of rivers and streams

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1 Source control measures to minimize contamination of rivers and streams Adriano Joss Neptune Workshop April 2009 Koblenz, Germany

2 Contents Pharmaceuticals: relevant micropollutant load Measures at the source complement centralized treatment Consumer s and producer s choice Source separation On site treatment 2

3 Pharmaceutical: Relevant micropollutant load 5 ngee2/l: young generation missing in entire lake experiment (Kidd et al, 2005, PNAS) 1 ng EE2/L: lack of males and no reproduction in fathead minnows (Joanne Parrott, NWRI, Burlington, Canada) hatching success [%] ** no males and no spawning at 3.2 to 32 ng EE2/L 0 Control Solvent control EE2 [ng/l] 3

4 Pharmaceutical: Relevant micropollutant load Single persistent pharmaceuticals trespass PNEC in surface water Diclofenac Carbamazepin < 0.01 PNEC < 0.1 PNEC < 1 PNEC < 10 PNEC 10 PNEC no Q 95% available Discharge to lake Ort et al., Env.Sci.Tech.,

5 Urban water cycle 5 Drinking water treatment Tab Pharmaceutical industry Households, hospitals Sewer Wastewater treatment Surface and groundwater

6 Measurable concentr. acceptable? Measures at the source: Efficiency gain? 6 Drinking water treatment Urban water cycle Pharmaceutical industry Consider water cycle Households, hospitals Compound choice Source separation 5% - 20% losses Wastewater treatment Good water quality status?

7 Source control: Develop and choose degradable compounds Degradation experiment with activated sludge from a typical wastewater treatment plant Ibuprofen Diclofenac Soluble concentration [µg/l] Time [d] Soluble Soluble concentration [µg/l] [µg/l] Time [d] Blank (CAS) CAS CAS+SS Blank (MBR) MBR MBR+SS Example Ibuprofen and diclofenac: analgesics with comparable mode of action Ibuprofen: >95% degradation during wastewater treatment Diclofenac: 25% degradation Diclofenac has killed 90% of vulture population in regions of India 7

8 Compound labelling: Scope Supply patients and doctors with environmental information on pharmaceuticals Initiate public discussion Testing acceptability of new products Voluntary basis, testing feasibility of new legislative tools Successful label: Influencing consumer behaviour by 5% 15% 8

9 Compound labelling: Swedish model (PBT) Persistence - ability to resist degradation in the aquatic environment Bioaccumulation - accumulation in adipose tissue of aquatic organisms Toxicity the potential to poison aquatic organisms Property assessed Method/Cut off value Score Persistence Mineralization Easy biodegradable >60% in 28 d 0 Not biodegradable 60% in 28 d 3 Bioaccumulation Log P OW Potential to bioaccumulation 3 3 Not potential to bioaccumulation <3 0 Eco-toxicity LC/EC/IC 50 (fish, daphnia, algae) Low >100 mg L -1 0 Moderate mg L -1 1 High 1-10 mg L -1 2 Very high <1 mg L -1 3 Label exists since

10 Compound classification scheme: Considering removability Not considered in the Swedish model Drinking water relevance: public acceptance of impurities Removability with state-of-the-art treatment Extended classification scheme Persistence Bioaccumulation PBT, Swedish model Toxicity Removability with activated carbon Removability by ozonation Removability by flocculation Ternes and Joss, IWA-Publishing,

11 Aspirin 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Urine separation Analgesics Antibiotic Feces Urine Paracetamol Propoxyphene Tramadol Amoxicillin Azithromycin Ciprofloxacin Clarithromycin Erythromycin Metronidazole Mupirocin Sulfamethoxazole Tetracycline Trimethoprim Metformin Troglitazone Gabapentin Phenytoin Valproate Allopurinol Cimetidine Ranitidine Ibuprofen Nabumetone Naproxen Atenolol Metoprolol Verapamil Pseudoephedrine Hydrochlorothiazide Triamterene Carisoprodol Bupropion Nefazodone Setraline Lienert et al., Env.Sci.Tech., Excretion Antidiabetic Antiepileptic Antigout Antihistamine Antiphlogistic Beta-blocker Anti-arrhythmic Sympathicomimetic Diuretic Muscle relaxant Antidepressant Urine contains 2/3 of the pharmaceuticals Micropollutant removal not sufficient to justify household urine separation

12 Source separation for iodinated constrast media Persistent compounds, costly removal Drinking water: >100 ng/l (public acceptability?) Chlorination: formation of carcinogenics? Oxidative degradation: only side chains Low sorption to activated carbon: high dosing & costs Low reactivity with O 3 : high dosing & costs I R R I I R Load caused by 1 person of Excretion in urine, 90% within 24h (e.g. iopromide) Options for source control Urine collection + anaerobic digestion (dehalogenation) Urine collection + incineration Substitute with CO 2 as contrast agent (not always indicated) 12

13 Source separation feasible for iodinated constrast media? R I I What do you prefer? R R I Toxicology covers all relevant aspects of human toxicology? In the bag? Not sure Yes Or in the tab? 13

14 On site treatment: Hospital wastewater Hospital wastewater Sewer WWTP influent PNEC Optimal treatment before dilution WWTP effluent Ciprofloxacin Receiving Norfloxacin river (Glatt) Concentration [µg L -1 ] Alder et al

15 Consumption at the cantonal hospital in Baden (2007) Predicted concentration in wastewater (from consumption, excretion rate, 315 m 3 /day wastewater) Concentration (μg/l) 0 Iopamidol (XCM) Iopromide (XCM) Ioxitalamic acid (XCM) Amoxicillin (antibiotic) Iomeprol (XCM) 4-Methylaminoantipyrin (analgesic) Piperacillin (antibiotic) Gadoteric acid (XCM) Isoflurane (anesthetic) Cefuroxim (antibiotic) Paracetamol (analgesic) Ceftazidim (antibiotic) Clavulanic acid (antibiotic) Ciprofloxacin (antibiotic) Flucloxacillin (antibiotic) Metformin (antidiabetic) Diatrizoate (XCM) Tazobactam (antibiotic) Thiopental (anesthetic) Salicylic acid (analgesic) McArdell et al., Neptune & Micropoll project,

16 Hospital wastewater on site treatment Amount of pharmaceuticals in hospital wastewater: X-ray contrast media: 50% of the hospital consumption Cytostatics: % of the hospital consumption refined modeling of mass flows under way Costs: efficiency gain? screen PAC ozonisation recirculation hospital recirculation to river or WWTP aeration membran bioreactor ozone biofilter 16 Moser et al., Neptune & Micropoll project, 2009

17 Case Study Hospital Winterthur: cost-benefit annual costs (millions EUR per year) EUR / mio./a 97 +/- 2% 60 +/- 15% upgrade WWTP Hard EUR / mio./a 100 % pharmaceutical residues 20 +/- 5% 14 +/- 5% separate treatment for hospital waste water annual costs ratio of captured pharmaceutical residues ratio of eliminated pharmaceutical residues Hunziker Betatech AG 0 ratio of captured and eliminated pharmaceutical residues (%) 17

18 Conclusion Measures at the source complement centralized treatment Efficiency gain Elimination before loss from sewer Compound labelling Is useful also for pharmaceuticals Initiates public discussion Classification scheme: include PBT and removability Urine separation Suitable for specific therapies (e.g. X-ray imagery) On average only 2/3 of the pharmaceuticals removed On site treatment Currently being tested 18

19 Thank you and the EU for financing Poseidon and NEPTUNE, 6 th Framework Programme This study was part of the EU Neptune project (Contract No , SUSTDEV II.3.2), which was financially supported by grants obtained from the EU Commission within the Energy, Global Change and Ecosystems Program of the Sixth Framework (FP Global-4) 19