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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.

SLIDE 1

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

11th World Wide Workshop for Young environmental scientists France – Arcueil Thursday 9 June 2011

SLIDE 2

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 2

Bisphenol A (BPA)

C H3 CH3 O H OH

1 2 6 3 5 4

R (O-CH2-CH2)n-OH

Alkylphenols (APs) R = 9 Nonyl- 80 % R = 8 Octyl- 20 % 4-4’- dihydroxy-2,2- diphenylpropane Uses : monomer in the manufacture of polycarbonate plastics (water bottles, baby bottles); epoxy resins (food contact lacquers : cans, tin cans ). World annual consumption : 450 000 t/year

(Vanderberg 2007)

Uses: non-ionic surfactants, detergents, industrial wetting agents or emulsifiers. n could range from 1 to 50 units, ex : NP1 EO World annual consumption : 500 000 t/year

(Ying 2002)

Alkylphenols and bisphenol A

SLIDE 3

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 3

Studied compounds

Structures Nomenclatures Names

H19C9 O-CH2-CH2 O-CH2-CH2-OH

NP2EO Nonylphenol die thoxylate

H19C9 O-CH 2-CH2-OH

NP1EO Nonylphenol monoethoxylate

H19C9 OH

NP Nonylphenol

H19C9 O CH2 C O OH

NP1EC Nonylphenol acetic acid

H17C8 O-CH2-CH2 O-CH2-CH2-OH

OP2EO Octylphenol diethoxylate

H17C8 O-CH2-CH2-OH

OP1EO Octylphenol monoethoxylate

C H3 C H3 CH3 C H3 CH3 OH

OP Octylphenol

C H3 CH3 O H OH

BPA Bisphenol A

SLIDE 4

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 4

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

SLIDE 5

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 5

Combined sewerage systems

Dry weather periods

Wastewater Wastewater treatment plants Seine River

Wet weather periods

Wastewater Stormwater Wastewater treatment plants Combined sewer

verflows (CSO)

Seine River Combined sewage

SLIDE 6

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 6

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

SLIDE 7

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 7

Clichy

utfall

Paris

10 km Seine Marne

Seine

Clichy outfall

Triel-sur-Seine

Sampling : 250 ml every 5 min Total duration : 3h

Source : DDP SIAAP

SLIDE 8

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 8

Sampling campaigns

69 % 26 % 5 % 2005-2010

20 40 60 80 < 150 150 < x < 400 x > 400

discharged volumes (103 m3) %

Sampling campaigns Discharged volumes (m3) Conductivities (µS.cm-1) % wastewater 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

144,000 346 27

08/11/2010 08/11/2010

42,000 451 39

09/11/2010 09/11/2010

286,000 374 30

duration of CSO (hh:mm)

5,000 10,000 15,000 20,000 25,000 30,000 0:00 1:12 2:24 3:36 4:48 6:00 7:12

Discharged volumes (m3/5min)

SLIDE 9

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 9

Analytical procedure

Combined water Filtration

GF/D (2.7 µm) GF/F (0.45 µm) OASIS HLB (200 mg/ 6ml)

Extraction (SPE) Particulate Dissolved Extraction

Microwave : Multiwave 3000

Purification

SPE cartridge OASIS HLB

Freeze dry

Alpha 1-2 LDplus

UPLC-MS-MS

Internal standard (BPA-d16, 4-n-NP, 4-n-NP1 EO)

Calliper: AutoTrace SPE Anton Paar: Multiwave 3000 Waters : UPLC-MS-MS

SLIDE 10

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 10

Results: Total concentrations

53 47 ng.l-1 Huge concentrations of BPA: 917 – 2,098 ng.l-1; WWTP effluents : 47 ng.l-1 Literature (wastewater): 226 – 12,000 ng.l-1

1,000 2,000 3,000 4,000 5,000 6,000 7,000

06/06 12/07 14/07 08/09 24/09 26/09 08/11 09/11 WWTP effluents Seine River Concentrations (ng.l-1) BPA OP OP1 EO OP2 EO NP NP1 EC NP1 EO NP2 EO

Mean concentration : 1,410 ng.l-1 ± 437 ng.l-1 ± 31 %

SLIDE 11

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 11

Results: Total concentrations

CSOs: low NP1 EC : 207 – 572 ng.l-1 ; WWTP effluents : 1,454 ng.l-1 Mean concentration : 2,260 ng.l-1 ± 740 ng.l-1 ± 33 % 1 801 374 ng.l-1 Mean concentration CSO ≈ WWTP effluent concentration

1,000 2,000 3,000 4,000 5,000 6,000 7,000

06/06 12/07 14/07 08/09 24/09 26/09 08/11 09/11 WWTP effluents Seine River Concentrations (ng.l-1) BPA OP OP1 EO OP2 EO NP NP1 EC NP1 EO NP2 EO

SLIDE 12

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 12

CSO loads vs. daily loads Σ WWTP ( 5 WWTPs 8 million inhabitant equivalent)

Loads of BPA: Small 2 times higher than WWTP loads Medium 4 times higher than WWTP High 13 times higher than WWTP CSOs could be important sources of BPA within receiving waters at the scale of the event

Σ APs

Loads of APs: Small – medium – high : < 50 % of WWTP loads CSOs do not appear as important sources

f APs within receiving waters at the scale
f the event

CSO loads vs. WWTP loads

CSO loads = sum of loads of all CSO outfalls of the Greater Paris

0% 10% 20% 30% 40% 50% CSO loads/ WWTP loads 0% 250% 500% 750% 1000% 1250% 1500% x < 300 300 < x < 1,000 1,000 < x CSO loads/ WWTP loads Discharged volumes (103 m3) Discharged volumes (m3) x < 300 300 < x < 1,000 1,000 < x

BPA

SLIDE 13

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 13

CSO loads vs. Seine River loads

CSO loads vs. daily exported loads by the Seine River (dry weather)

Loads of BPA: Small Exported loads are 20 % higher Medium Exported loads are 40 % higher High Exported loads can double CSOs may play a key role for exported loads of BPA by the Seine River during wet weather periods Loads of APs: Small – medium – high : ≤ 20 % of exported loads by the Seine River CSOs do not play an important role for exported loads of APs by the Seine River during wet weather periods

0% 5% 10% 15% 20% 25% CSO loads/ Exported loads 0% 20% 40% 60% 80% 100% 120% 140% CSO loads/ Exported loads x < 300 300 < x < 1,000 1,000 < x x < 300 300 < x < 1,000 1,000 < x Discharged Volumes (103 m3) Discharged volumes (m3)

Σ APs BPA

SLIDE 14

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 14

First assessment of annual loads

Σ Paris outfalls Σ WWTP effluents Seine River % Σ Paris outfalls % Σ WWTP effluents Volume (m3.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 OP1EO 0.9

OP2EO

0.2 33 29 0.8 115.4 4-NP 9.8 251 777 1.3 32.3 NP1EC 4.0 923 1,007 0.4 91.7 NP1EO 4.4 344 469 1.0 76.6 NP2EO 2.9 501 449 0.5 106.8 Sum APEOs 22.8 2,080 2,831 0.8 73.5

At the scale of a year CSOs are not relevant sources of BPA and APs within Seine River

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

Loads : kg/year

SLIDE 15

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 15

Conclusions and outlooks

Conclusions : At the scale of an event: CSOs could play a key role for BPA loads but not for APs High concentrations of BPA (1,410 ng.l-1) within CSO Concentrations of APs in CSOs similar to WWTP effluents Outlooks : Improve our estimation of CSO loads and exported loads by modeling (PROSE) Evaluate the proportion of contamination owed to wastewater or runoff for each event At the scale of a year: CSOs are not relevant sources of BPA and APs within Seine River Improve our understanding of the influence of CSO on exported loads (particulate loads)

SLIDE 16

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

SLIDE 17

09/ 06/ 2011 WWW-YES-2011 – Cladière et al. 17

Distribution dissolved / particulate

0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% BPA OP OP1 EO OP2 EO NP NP1 EC NP1 EO NP2 EO

BPA 92 % in dissolved phase NP, NPEO highly present in particulate phase (mean 39%), except NP1EC (4%)

Particulate Dissolved

SLIDE 18

H19C9 O(CH2-CH2-O) OH O O OH H19C9

NP2EO NPnEO

O OH H19C9

NP1EO fast slow terminal oxidation of the polyethoxy chain

H19C9 O(CH2-CH2-O) COOH

NPnEC

O O COOH H19C9

NP2EC

O COOH H19C9

NP1EC

OH H19C9

unknown mechanisms Lente Ipso-substitution,

under aerobic conditions

C H3 OH C H3 C H3 C H3

OH OH

Mineralization 4-NP Very slow

Simplified NPnEO biodegradation

(Giger et al 2009)

n n

Discharge of endocrine disrupting chemicals by combined sewer overflows into receiving waters : case-study of the Paris conurbation

; C. Lorgeoux ; B. Tassin

Bisphenol A (BPA)

Alkylphenols (APs) R = 9 Nonyl- 80 % R = 8 Octyl- 20 % 4-4’- dihydroxy-2,2- diphenylpropane Uses : monomer in the manufacture of polycarbonate plastics (water bottles, baby bottles); epoxy resins (food contact lacquers : cans, tin cans ). World annual consumption : 450 000 t/year

Uses: non-ionic surfactants, detergents, industrial wetting agents or emulsifiers. n could range from 1 to 50 units, ex : NP1 EO World annual consumption : 500 000 t/year

Alkylphenols and bisphenol A

Studied compounds

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

Combined sewerage systems

Dry weather periods

Wet weather periods

Objectives

Evaluate the concentrations of APs and BPA in CSO Comparison of loads discharge at the scale of an event

Comparison of loads discharge at the scale of a year

Clichy

Paris

Clichy outfall

Sampling : 250 ml every 5 min Total duration : 3h

Sampling campaigns

Analytical procedure

Combined water Filtration

Extraction (SPE) Particulate Dissolved Extraction

Purification

Freeze dry

UPLC-MS-MS

Results: Total concentrations

53 47 ng.l-1 Huge concentrations of BPA: 917 – 2,098 ng.l-1; WWTP effluents : 47 ng.l-1 Literature (wastewater): 226 – 12,000 ng.l-1

Mean concentration : 1,410 ng.l-1 ± 437 ng.l-1 ± 31 %

Results: Total concentrations

CSOs: low NP1 EC : 207 – 572 ng.l-1 ; WWTP effluents : 1,454 ng.l-1 Mean concentration : 2,260 ng.l-1 ± 740 ng.l-1 ± 33 % 1 801 374 ng.l-1 Mean concentration CSO ≈ WWTP effluent concentration

CSO loads vs. daily loads Σ WWTP ( 5 WWTPs 8 million inhabitant equivalent)

CSO loads vs. WWTP loads

CSO loads = sum of loads of all CSO outfalls of the Greater Paris

CSO loads vs. Seine River loads

CSO loads vs. daily exported loads by the Seine River (dry weather)

First assessment of annual loads

Conclusions and outlooks

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

Distribution dissolved / particulate

Simplified NPnEO biodegradation

Anaerobic biodegradation pathway aerobic biodegradation pathway