EU Water Framework Directive Precautionary Principle

Transcription

1 Levels and spatial distribution of emerging contaminants in the Iberian rivers Mira Petrovic 1,2, Marina Gorga 3, Victoria Osorio 3, Sandra Perez 3, Damia Barcelo 1,3,4 1 ICRA, Girona, Spain 2 ICREA, Barcelona, Spain 3 IDAEA-CSIC, Barcelona, Spain 4 King Saud University, Riyadh, Kingdom of Saudi Arabia EU Water Framework Directive Precautionary Principle Dynamic list update every 4 years Upcoming Priorities Emerging Contaminants (Future Candidates for Monitoring) Substances that are not part of routine monitoring programmes but have been shown to occur in the environment and may be candidate for future regulations, depending on research on their (eco)toxicity, potential health effects, public perception and on monitoring data regarding their occurrence in the various environmental compartments

2 Emerging contaminats: Facts The issue of emerging contaminants is closely tied to analytical capabilities. Increased sensitivity in mass spectrometry (more efficient ionisation techniques and better detectors) has allowed detection of virtually any new and potentially harmful contaminant at a very low level. Consequently, a number of new or previously ignored and/or unrecognized contaminants have bean brought under scrutiny. Widely expanded use of industrial chemicals in domestic and commercial applications multiple pathways to sanitary sewer Potential impacts to organisms at low concentrations lack of data Endocrine disruption Persistence in the environment Bioaccumulation Synergistic effects Possible toxicity Potential generational effects WWTPs seen as a point source although sources are actually diffuse Emerging Substances of Concern Algal and cyanobacterial toxins Brominated flame retardants Disinfection by-products Gasoline additives Hormones and other endocrine disrupting compounds Organometallics Organophosphate flame retardants and plasticisers Perfluorinated compounds Pharmaceuticals and personal care products Polar pesticides and their degradation/transformation products Surfactants and their metabolites

3 River basins SCARCE project Ebro Llobregat Júcar Guadalquivir River basins SCARCE project Ebro Llobregat - To determine the presence of priority and emerging contaminants in Mediterranen river ecosystems in the Iberian Peninsula Júcar - To asses the effect of chemical and environmental stressors on biodiversity pattern Guadalquivir

4 Strategy of the field work in SCARCE WP4 1 st layer General extensive monitoring Wide spatial coverage (4 river basins; main river + tributaries; reference sites + contaminated sites; different contamination and hydrological gradients) Wide range of contaminants (priority and emerging) Analysis of biodiversity pattern based on existing data for invertebrates (calculation of biological indices) + detailed characterization at 4-5 sites per river basin Three hydrological regimes (low, medium, high flow) Levels and spatial distribution of pharmaceuticals and endocrine disruptors and related compounds in the Iberian rivers

5 (90 compounds classified by therapeutic groups) Pharmaceuticals Analgesics and antiinflamatories Naproxen Ketoprofen Ibuprofen Indomethacine Salycylic acid Acetaminophen Diclofenac 4-OH-Diclofenac Phenazone Propyphenazone Piroxicam Tenoxicam Meloxicam Nimesulide Oxycodone Codeine Hydrocodone Histamine H1 and H2 receptor antagonists Loratadine Desloratadine Ranitidine Famotidine Cimetidine B-blockers Atenolol Sotalol Metoprolol Propranolol Nadolol Antihypertensive Amlodipine Antiplatelet agent Clopidogrel Treatment of prostatic hyperplasia Salmeterol Anticoagulant Warfarin Acridone Antibiotics Cefalexin Erithromycin Azithromycin Clarithromycin Tetracyclin Ofloxacin Ciprofloxacin Sulfamethoxazole Trimethoprim Metronidazole Metronidazole OH Amoxicillin Lipid regulators Bezafibrate Gemfibrozil Pravastatin Fluvastatin Diuretic Hydrochlrothiazide Furosemide Psychiatric drugs Fluoxetine Norfluoxetine Paroxetine Diazepam Lorazepam Alprazolam Carbamazepine 2 OH Carbamazepina 10,11 epoxycarbamazepine Sertraline Citalopram Venlafaxine Olanzapine Trazodone To treat hypertension Enalapril Enalaprilat Irbesartan Losartan Valsartan Torasemide Diltiazem Anti-diabetic Metformin Glibenclamide Antipsychotic Risperidone X-ray contrast agents Iopromide Iohexol Diatrizoate Veterinary pharmaceuticals Albendazol Thiabendazole Triclabendazole Levamisol Oxyclozanide Dexamethasone Dimetridazole Ronidazole Xylazine Carazolol Azaperona Azaperol Pharmaceuticals WATER SEDIMENT

6 Llobregat Pharmaceuticals - Llobregat WATER

7 Pharmaceuticals - Llobregat SEDIMENT Sorption of pharmaceuticals is governed by several processes, such as hydrophobic partitioning, ion exchange, complexation and hydrogen bonding. In case of polar and ionic pharmaceuticals the sorption properties cannot be evaluated from the log Kow and normalization to organic carbon content does not give a straightforward relationship. Generally, it was observed that compounds with basic characteristics (pka > 7) show higher tendency to bound to suspended solids. High values of pka indicate that these compounds are positively charged at ph conditions of river water and other interactions (cationic interactions, complexation, hydrogen bonding) can affect the fate of these compounds. Pharmaceuticals - Ebro

8 Pharmaceuticals - Ebro Endocrine disruptors and related compounds Estradiol (E2) Estriol (E3) Estrone (E1) Natural and synthetic estrogens and conjugates Alkylphenolic compounds Antiseptics Bactericides Flame Retardants Anticorrosives Plasticizer Ethinyl estradiol (EE2) Diethylstilbestrol (DES) Estrone 3-sulfate (E1-3S) Estriol 3-sulfate (E3-3S) Estrone 3-glucuronide (E1-3G) Estriol 16-glucuronide (E3-16G) Estradiol 17-glucuronide (E2-17G) Octylphenol (OP), Nonylphenol (NP) Octylphenol monoethoxylate (OP1EO) Nonylphenol monoethoxylate (NP1EO) Octylphenol diethoxylate (OP2EO) Nonylphenol diethoxylate (NP2EO) Octylphenol monocarboxylate(op1ec) Nonylphenol monocarboxylate (NP1EC) Metilparaben, Etilparaben, Propilparaben, Benzilparaben Triclosan, Triclorocaraban Tris(cloroisopropil) phosphate (TCCP) Tris(2-cloroetil) phosphate (TCEP) Tris(butoxietil) phosphate (TBEP) 1H-Benzotriazole (BT), Tolytriazol (TT) Bisphenol A (BPA)

9 Endocrine disruptors and related compounds Endocrine disruptors and related compounds

10 Ebro Ebro

11 Llobregat Llobregat

12 Júcar Júcar

13 Guadalquivir Guadalquivir

14 Endocrine disruptors and related compounds Ebro Llobregat Júcar Guadalquivir Endocrine disruptors and related compounds Ebro Llobregat Júcar Guadalquivir

15 Conclusiones and future work -A wide range of pharmacueticals and EDCs and related compounds found in water and sediment of four Iberian rivers - Generally Llobregat followed by Ebro show the highest concentrations of studied contaminants - Concentrations directly related to the vicinity of point sources of contamination (WWTP) and flow rates (dillution factors) - Future work will focus on establishing correlations between chemical stressors and biodiversity Acknowledgements This work has been supported by: Spanish Ministry of Science and Innovation: Project Cemagua CGL /HID and SCARCE Consolider-Ingenio 2010 Waters Corporation is gratefully acknowledged for providing the UPLC columns and SPE cartridges Applied Biosystems is gratefully acknowledged for the equipment and technical support of the 4000 Q-Trap system We would like to thanks the collaboration with Thermo Fisher Scientific