Impact of pharmaceuticals discharges on the receiving environment: a two years monitoring results www.isa-lyon.fr TRACES Group Technology and Research in Analytical Chemistry for Environment, health and their interactions Laure Wiest, Alexandre Bergé, Robert Baudot and Emmanuelle Vulliet 1
The SIPIBEL Site In 2012, opening of a new hospital : the Alps-Léman Hospital Center (CHAL) WW discharged into the Arve river www.sipibel.org Bellecombe WWTP 2
The SIPIBEL Site www.sipibel.org A field observatory Seven sampling sites 130 parameters Research actions Pollutant flows Treatment Risk Sociology 3
The SIPIBEL Observatory www.sipibel.org 450 beds 30,000 habitants 4
The SIPIBEL Observatory www.sipibel.org Physico-chemistry 5-day biochemical oxygen demand (BOD 5 ), chemical oxygen demand (COD), conductivity, dissolved organic carbon (DOC), ph, total suspended solids (TSS), total phosphorus (TP), phosphates (PO 4 3- ), kjedahl nitrogen (TKN), ammonium (NH 4+ ), adsorbable organic halogen (AOX) Emerging compounds Pharmaceuticals Microbiology Bacterial resistance to antibiotics Bioassays Microalgae, microcrustacean Endocrine disruptor Data base SIPIBEL 40,000 data 5
Pharmaceuticals Selection MOLECULE CONSOMME DOSABLE / EAU DOSABLE / CHAL ORGANISMES 1 17-β-ETHINYLESTRADIOL-EE2 1 4 ACIDE SALICYLIQUE 1 1 5 AMIODARONE 1 2 6 AMITRIPTYLINE 1 1 7 ATÉNOLOL 1 1 9 AZTREONAM 1 10 BÉZAFIBRATE 1 11 CARBAMAZEPINE 1 1 13 CIPROFLOXACINE 1 1 16 DESLORATADINE 1 2 17 DEXTROPROPOXYPHENE 3 18 DICLOFENAC 1 1 19 ECONAZOLE 1 1 25 HEXETIDINE 2 27 IBUPROFENE 1 1 34 ITRACONAZOLE 1 35 KETOPROFEN 1 1 36 LÉVONORGESTREL 1 1 38 MEROPENEME 1 1 43 MIFEPRISTONE 1 1 44 MITOTANE 1 2 45 NICARDIPINE 1 1 46 NORÉTHINDRONE 1 48 NORGESTIMATE 2 49 OXAZÉPAM 1 1 51 PARACETAMOL 1 1 53 PROPRANOLOL 1 1 55 RITONAVIR 1 1 56 ROXITHROMYCINE 1 1 57 SULFAMETHOXAZOLE 1 1 58 TAMOXIFENE 1 1 59 TELITHROMYCINE 1 2 62 VANCOMYCINE 1 1 - A list of 62 compounds - Hospital consumption - Domestic consumtion - PBT Index - A list of 35 compounds - Analytical feasibility - A list of 15 compounds - Economical feasibility 6
Pharmaceuticals List Analgesic Paracetamol Salicylic Acid Anti-inflammatory Ketoprofen Diclofenac Ibuprofen Beta-blocker Atenolol Propranolol Anti-fungal: Econazole Hormone: Ethinylestradiol Anti-convulsant: Carbamazepine Antibiotic Sulfamethoxazole Ciprofloxacin Aztreonam Meropenem Vancomycin
Analytical Method Sensitivity Wastewater 0.1 ng/l 1 ng/l 10 ng/l 100 ng/l 1 µg/l 10 µg/l 100 µg/l 1 mg/l 10 mg/l Surface water 0.1 ng/l 1 ng/l 10 ng/l 100 ng/l 1 µg/l 10 µg/l 100 µg/l 1 mg/l 10 mg/l 8
Raw wastewater Domestic vs Hospital
Domestic Wastewater 10
Hospital Wastewater 11
Raw WW: Concentrations 50 Concentrations (µg/l) 40 30 20 Domestic Hospital 10 0 Ketoprofen Ciprofloxacin Sulfamethoxazole Vancomycin 12
Raw WW: Flows /40 7 6 5 4 3 2 1 0 Flow (g/day) Domestic 4800 m 3 /d Ketoprofen Ciprofloxacin Sulfamethoxazole Vancomycin Hospital 130 m 3 /d Domestic Hospital 13
Raw WW: Variability 14
Raw WW: Metabolites Diclofenac (DCF) DCF COH DCF lactam DCF CH 2 OH CPAB Oxindole DCF 4 OH DCF 5 OH DCF carboxylic acid DCF glucuronide Sulfamethoxazole (SMX) SMX N-acetylated SMX glucuronide SMX iso 15
Raw WW: Metabolites Diclofenac (DCF) DCF COH DCF lactam DCF CH 2 OH CPAB Oxindole DCF 4 OH DCF 5 OH DCF carboxylic acid DCF glucuronide Sulfamethoxazole (SMX) SMX N-acetylated SMX glucuronide SMX iso 16
Raw WW: Metabolites Diclofenac (DCF) DCF COH DCF lactam DCF CH 2 OH CPAB Oxindole DCF 4 OH DCF 5 OH DCF carboxylic acid DCF glucuronide Sulfamethoxazole (SMX) SMX N-acetylated SMX glucuronide SMX iso 17
Wastewater treatment
Treated Wastewater 19
Treated WW: Flows 2,5 Flow (g/day) 2 1,5 1 0,5 0 Urbain Hôpital 20
Removal efficiency 120 Removal (%) 100 80 60 40 20 Domestic Hospital 0 21
Removal efficiency: variability Domestic WW Treatment 100,0 80,0 60,0 40,0 20,0 0,0 Diclofenac Ibuprofen Diclofenac 22
Removal efficiency: variability Hospital WW Treatment 100,0 80,0 60,0 40,0 20,0 0,0 Diclofenac Ibuprofen Diclofenac 23
Surface water
Arve Upstream Detection Frequency (%) Propranolol Ibuprofen Paracetamol < 30 % 30 à 70 % > 70 % Sulfamethoxazole Salicylic acid Econazole Ciprofloxacin Carbamazepine Ketoprofen Diclofenac Atenolol Not detected: * Ethinylestradiol * Hospital antibiotics 5 10 50 Concentration (ng/l) 25
Arve Downstream 26
Arve: a ressource for Human consumption Groundwater surface France-Switzerland border SIPIBEL Observatory 27
Arve: a ressource for Human consumption Groundwater surface France-Switzerland border SIPIBEL Observatory 28
Conclusions And Perspectives. 29
Conclusions Large scale of time and space consolidated data Raw and treated Wastewater, Surface water and groundwater Two years monitoring Hospital vs Domestic Wastewaters Hospital > Domestic in terms of concentrations Hospital < Domestic in terms of flows Mean removal efficiencies >50 % except Diclofenac and Carbamazepine Surface water and groundwater contamination in the ng/l range 30
Perspectives - Evolution of the list of Pharmaceuticals - Activated sludge analysis - Statistical correlation between parameters - Perspectives of the SIPIBEL observatory - Survey of Pharmaceuticals until at least 2018 - New projects? 31
Acknowledgments TRACES Group: Robert BAUDOT Alexandre BERGE Maëva FIEU Emmanuelle VULLIET www.isa-lyon.fr www.sipibel.org GRAIE: Vivien LECOMTE Elodie BRELOT 32
Thank you! 33