11 th World Wide Workshop for Young environmental scientists France – Arcueil Thursday 9 June 2011 Discharge of endocrine disrupting chemicals by combined sewer overflows into receiving waters : case-study of the Paris conurbation M. Cladière ; J. Gasperi ; C. Lorgeoux ; B. Tassin 1
Alkylphenols and bisphenol A Bisphenol A 4-4’- dihydroxy-2,2- diphenylpropane (BPA) Uses : monomer in the manufacture of polycarbonate H 3 C CH 3 plastics (water bottles, baby bottles); epoxy resins (food contact lacquers : cans, tin cans ). World annual consumption : 450 000 t/year ( Vanderberg 2007 ) H O OH Alkylphenols (APs) Uses: non-ionic surfactants, detergents, industrial 5 6 wetting agents or emulsifiers. R 4 1 (O-CH 2 -CH 2 ) n -OH 3 2 n could range from 1 to 50 units, ex : NP 1 EO R = 9 R = 8 Nonyl- Octyl- World annual consumption : 500 000 t/year ( Ying 2002 ) 80 % 20 % 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 2
Studied compounds Structures Nomenclatures Names H 19 C 9 O-CH 2 -CH 2 O-CH 2 -CH 2 -OH NP 2 EO Nonylphenol die thoxylate H 19 C 9 O-CH 2 -CH 2 -OH NP 1 EO Nonylphenol monoethoxylate H 19 C 9 OH NP Nonylphenol O H 19 C 9 OH NP 1 EC Nonylphenol acetic acid CH 2 C O H 17 C 8 O-CH 2 -CH 2 O-CH 2 -CH 2 -OH OP 2 EO Octylphenol diethoxylate H 17 C 8 O-CH 2 -CH 2 -OH OP 1 EO Octylphenol monoethoxylate CH 3 H 3 C CH 3 H 3 C OP Octylphenol OH H 3 C H 3 C CH 3 BPA Bisphenol A H O OH 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 3
Interest of studying BPA and APs? Compounds ubiquitous in environment ( Uguz et al. 2003 ) Toxicity � NP, OP and BPA have estrogenic effects on wildlife Endocrine disrupting chemicals (EDC) ( Correa-Reyes et al. 2007 ) Disruptions on wildlife: Deformity (gills, liver, kidneys) Rosy barb ( Battcharaya et al. 2008 ) Reproductive toxicity : male mice ( El-dakdoki and Helal 2007 ) Embryo development: Daphnia magna ( Zhang et al. 2002 ) Rosy Barb Daphnia magna 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 4
Combined sewerage systems Wet weather periods Dry weather periods Wastewater Stormwater Wastewater Combined sewage Wastewater Combined sewer Wastewater treatment plants treatment plants overflows (CSO) Seine River Seine River 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 5
Objectives Evaluate the concentrations of APs and BPA in CSO Comparison of loads discharge at the scale of an event Against daily wastewater treatment plant loads Against daily exported loads by the Seine River Comparison of loads discharge at the scale of a year Against annual wastewater treatment plant loads Against annual exported loads by the Seine River 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 6
Clichy outfall Sampling : 250 ml every 5 min Total duration : 3h N Seine Clichy outfall Triel-sur-Seine Paris Marne Seine 10 km Source : DDP SIAAP 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 7
Sampling campaigns Discharged volumes Conductivities Sampling campaigns % wastewater (m 3 ) (µS.cm -1 ) 16/06/2010 16/06/2010 34,000 449 39 12/07/2010 12/07/2010 580,000 284 20 14/07/2010 14/07/2010 1,000,000 201 11 08/09/2010 08/09/2010 38,000 380 31 24/06/2010 24/06/2010 279,000 260 18 26/06/2010 26/06/2010 30,000 144,000 346 27 08/11/2010 08/11/2010 42,000 451 39 Discharged volumes (m 3 /5min) 09/11/2010 09/11/2010 286,000 374 30 25,000 80 69 % 2005-2010 60 20,000 % 40 26 % 20 5 % 0 15,000 < 150 150 < x < 400 x > 400 discharged volumes (10 3 m 3 ) 10,000 5,000 0 0:00 1:12 2:24 3:36 4:48 6:00 7:12 duration of CSO (hh:mm) 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 8
Analytical procedure Combined water Filtration GF/D (2.7 µm) GF/F (0.45 µm) Dissolved Particulate Anton Paar : Multiwave 3000 Calliper : AutoTrace SPE Freeze dry Extraction (SPE) Alpha 1-2 LDplus OASIS HLB (200 mg/ 6ml) Extraction Microwave : Multiwave 3000 Purification SPE cartridge OASIS HLB UPLC-MS-MS Internal standard (BPA-d16, 4-n-NP, 4-n-NP 1 EO) Waters : UPLC-MS-MS 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 9
Results: Total concentrations Huge concentrations of BPA: 917 – 2,098 ng.l -1 ; WWTP effluents : 47 ng.l -1 Literature (wastewater): 226 – 12,000 ng.l -1 7,000 BPA OP OP 1 EO OP 2 EO NP NP 1 EC NP 1 EO NP 2 EO 6,000 Mean concentration : 1,410 ng.l -1 Concentrations (ng.l -1 ) ± 437 ng.l -1 5,000 ± 31 % 4,000 3,000 2,000 47 53 ng.l -1 1,000 0 06/06 12/07 14/07 08/09 24/09 26/09 08/11 09/11 WWTP Seine effluents River 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 10
Results: Total concentrations Mean concentration CSO ≈ WWTP effluent concentration CSOs: low NP 1 EC : 207 – 572 ng.l -1 ; WWTP effluents : 1,454 ng.l -1 7,000 BPA OP OP 1 EO OP 2 EO NP NP 1 EC NP 1 EO NP 2 EO Mean concentration : 2,260 ng.l -1 6,000 ± 740 ng.l -1 Concentrations (ng.l -1 ) ± 33 % 5,000 4,000 1 801 374 ng.l -1 3,000 2,000 1,000 0 06/06 12/07 14/07 08/09 24/09 26/09 08/11 09/11 WWTP Seine effluents River 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 11
CSO loads vs. WWTP loads CSO loads vs. daily loads Σ WWTP ( 5 WWTP s � 8 million inhabitant equivalent) CSO loads = sum of loads of all CSO outfalls of the Greater Paris BPA Σ APs CSO loads/ WWTP loads 1500% 50% CSO loads/ WWTP loads 1250% 40% 1000% 30% 750% 20% 500% 250% 10% 0% 0% x < 300 300 < x < 1,000 1,000 < x x < 300 300 < x < 1,000 1,000 < x Discharged volumes (10 3 m 3 ) Discharged volumes (m 3 ) Loads of BPA: Loads of APs: Small � 2 times higher than WWTP loads Small – medium – high : < 50 % of WWTP loads Medium � 4 times higher than WWTP High � 13 times higher than WWTP CSOs do not appear as important sources CSOs could be important sources of BPA of APs within receiving waters at the scale within receiving waters at the scale of the of the event event 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 12
CSO loads vs. Seine River loads CSO loads vs. daily exported loads by the Seine River (dry weather) BPA Σ APs CSO loads/ Exported loads CSO loads/ Exported loads 140% 25% 120% 20% 100% 15% 80% 60% 10% 40% 5% 20% 0% 0% x < 300 300 < x < 1,000 1,000 < x x < 300 300 < x < 1,000 1,000 < x Discharged Volumes (10 3 m 3 ) Discharged volumes (m 3 ) Loads of BPA: Loads of APs: Small � Exported loads are 20 % higher Small – medium – high : ≤ 20 % of exported loads by the Seine River Medium � Exported loads are 40 % higher High � Exported loads can double CSOs do not play an important role for CSOs may play a key role for exported exported loads of APs by the Seine River loads of BPA by the Seine River during wet during wet weather periods weather periods 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 13
First assessment of annual loads CSO annual loads � estimation thanks to total volumes discharged from 2005 to 2010 WWTP annual loads � estimation thanks to 5 monthly sampling campaigns: 2010-2011 Seine River loads � estimation thanks to 10 monthly sampling campaigns: 2010 Σ WWTP % % Σ Paris outfalls Seine River effluents Σ Paris outfalls Σ WWTP effluents Volume (m 3 .y -1 ) 14,443,482 772,705,000 9,486,374,400 0.2 8.1 BPA 17.3 33 468 3.7 7.1 4-t-OP 0.9 28 101 0.9 27.6 OP 1 EO 0.9 - - - - OP 2 EO 0.2 33 29 0.8 115.4 4-NP 9.8 251 777 1.3 32.3 NP 1 EC 4.0 923 1,007 0.4 91.7 NP 1 EO 4.4 344 469 1.0 76.6 NP 2 EO 2.9 501 449 0.5 106.8 Sum APEOs 22.8 2,080 2,831 0.8 73.5 Loads : kg/year At the scale of a year � CSOs are not relevant sources of BPA and APs within Seine River 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 14
Conclusions and outlooks Conclusions : High concentrations of BPA (1,410 ng.l -1 ) within CSO Concentrations of APs in CSOs similar to WWTP effluents At the scale of an event: CSOs could play a key role for BPA loads but not for APs At the scale of a year: CSOs are not relevant sources of BPA and APs within Seine River Outlooks : Improve our estimation of CSO loads and exported loads by modeling (PROSE) Improve our understanding of the influence of CSO on exported loads (particulate loads) Evaluate the proportion of contamination owed to wastewater or runoff for each event 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 15
Thank you for your attention Acknowledgement: SIAAP and Paris Municipality: Providing sampling site, and volumes discharged from 2005 to 2010 LEESU: Florent Leroy, Mohamed Saad and Alexandre Segor for their technical assistances Source : DDP SIAAP 16
Distribution dissolved / particulate BPA � 92 % in dissolved phase NP, NPEO � highly present in particulate phase (mean 39%), except NP 1 EC (4%) 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% BPA OP OP 1 EO OP 2 EO NP NP 1 EC NP 1 EO NP 2 EO Particulate Dissolved 09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 17
Simplified NPnEO biodegradation terminal oxidation of the H 19 C 9 H 19 C 9 polyethoxy chain NP n EO NP n EC n n O(CH 2 -CH 2 -O) OH O(CH 2 -CH 2 -O) COOH fast Anaerobic O O OH biodegradation pathway O O COOH NP 2 EO NP 2 EC H 19 C 9 H 19 C 9 slow aerobic O O COOH OH NP 1 EO NP 1 EC biodegradation pathway H 19 C 9 H 19 C 9 Very slow unknown mechanisms OH 4-NP H 19 C 9 Ipso -substitution, only under Lente aerobic conditions OH H 3 C H 3 C OH (Giger et al 2009) + Mineralization H 3 C H 3 C OH
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