Effect of effluent dissolved organic matter on trace metals sorption by mineral particles in aquatic systems under strong urban pressure

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1 Effect of effluent dissolved organic matter on trace metals sorption by mineral particles in aquatic systems under strong urban pressure Gilles Varrault, Caroline Soares-Pereira, Adèle Bressy Leesu: Water Environment and Urban Systems research group (Paris-Est University, UPEC, ENPC, AgroParisTech)

2 Why studying effluent dissolved organic matter (Ef)? Part of from WWTP (%) Water flow (m3/s) Organic matter from WWTPs Present in anthropized aquatic environment 10 to 60% of the in the Seine River is from the WWTP depending on the flow (low-flow period) oct-10 nov-10 janv-11 févr-11 mars-11 avr-11 mai-11 juin-11 sept-11 0 Matar et al. (2015) Environ Sci Pollut Res 22:

3 Why studying effluent dissolved organic matter (Ef)? Organic matter from WWTPs Present in anthropized aquatic environment 10 to 60% of the in the Seine River is from the WWTP depending on the flow (low-flow period) Physico-chemical properties different from natural More hydrophilic 20 to 40% of hydrophilic before Paris 50 to 55% of hydrophilic after Paris from river Ef Pernet-Coudrier et al. (2011) Biogeochemistry 106:

4 Why studying effluent dissolved organic matter (Ef)? Organic matter from WWTPs Present in anthropized aquatic environment 10 to 60% of the in the Seine River is from the WWTP depending on the flow (low-flow period) Physico-chemical properties different from natural More hydrophilic 20 to 40% of hydrophilic before Paris 50 to 55% of hydrophilic after Paris More nitrogen and sulfur groups Lower molecular weight Pernet-Coudrier et al. (2011) Biogeochemistry 106:

5 Why studying effluent dissolved organic matter (Ef)? Strong influence on the speciation of the trace metals 80 to 90% of lead and mercury are binded to Ef after Paris conurbation in the Seine River Decrease of the free copper (-70%) after Paris conurbation Matar et al. (2015) Environ Sci Pollut Res 22:

6 Why studying effluent dissolved organic matter (Ef)? Strong influence on the speciation of the trace metals Strong influence on the biodisponibility of the trace metals Copper EC 50 on daphnia magnae with different Decrease of the copper biodisponibility and toxicity with Ef Matar et al. (2015) Environ Sci Pollut Res 22:

7 Influence of on the trace metals fate in aquatic systems Sorption/desorption onto suspended solids Dissolved fraction Particulate fraction Trace metals Particles Studies focused on natural and natural particles 3

8 Objectives 1. To characterize Ef sorption onto mineral particles Natural : Suwanee River Fulvic Acid (SRFA) Ef: from WWTPs 4

9 Objectives 1. To characterize Ef sorption onto mineral particles Natural : Suwanee River Fulvic Acid (SRFA) Ef: from WWTPs 2. To characterize metals sorption onto mineral particles with or without Natural : Suwanee River Fulvic Acid (SRFA) Ef: from WWTPs 4

10 Methodology Metals Particles Under stirring during 72 hours at 19 C (10mgC/L) - Without - SRFA - Ef from WWTP Adsorbant (0-500mg/L) - Montmorillonite - Goethite 5

11 Methodology Metals Particles (10mgC/L) - Without - SRFA - Ef from WWTP Adsorbant (0-500mg/L) - Montmorillonite - Goethite Filtration on GF/F 0.7 µm DOC analysis 1. To characterize sorption onto mineral particles 5

12 Methodology Metals Particles Metals Under stirring during 72 hours at 19 C (10mgC/L) - Without - SRFA - Ef from WWTP 7 metals (Cd, Co, Cu, Ni, Pb, V and Zn) 1 metalloid (As) Adsorbant (0-500mg/L) - Montmorillonite - Goethite 5

13 Methodology Metals Particles Metals Filtration on cellulose acetate ICP-AES analysis (10mgC/L) - Without - SRFA - Ef from WWTP Dissolved metals Adsorbant (0-500mg/L) - Montmorillonite - Goethite 5

14 Methodology Metals Particles Metals (10mgC/L) - Without - SRFA - Ef from WWTP Dissolved metals Adsorbant (0-500mg/L) - Montmorillonite - Goethite Filtration on Chelex 100 ICP-AES analysis Inert metals 2. To characterize metals sorption onto mineral particles with or without 5

15 Influence of on Cu and Zn sorption on montmorillonite Sorption with or without -60 à -65% -17% -65% Without SRFA Ef Without SRFA Ef Copper and zinc Less sorption with 1. Retention in dissolved fraction complexes -Cu or -Zn 2. Competition vs. Cu and Zn for surface sites 6

16 Influence of on Cu and Zn sorption on montmorillonite Sorption with SRFA or Ef -61% Without SRFA Ef Without SRFA Ef Copper No influence of the type of Zinc Influence of the type of => less sorption with Ef Fate of Cu and Zn Between 65 and 80% in the dissolved fraction What speciation? Free or complexed? 7

17 Influence of on Cu and Zn sorption on montmorillonite Speciation of Cu and Zn: comparison SRFA and Ef Labile Inert Particulate 20-25% 10% 35% Acides SRFAfulviques Ef Seine-Aval Acides fulviques SRFA Seine-Aval Ef Cu speciation is similar with SRFA and Ef Zn inert fraction is higher with Ef With Ef, retention of complexes -Zn in dissolved fraction 8

18 Influence of on metals sorption on goethite Sorption without or with SRFA 90% -34% 90% 50% 50% ( ) Cu and Ni (+) Cd and Zn +162% +39% +39% ine-aval Ef Without Eau synthétique Without Eau synthétique Acides Seine-Aval Acides fulviques SRFA Seine-Aval Ef fulviques SRFA Ef Without Eau synthétique Acides fulviques SRFA Seine-Aval Ef 9

19 Influence of on metals sorption on goethite Sorption with SRFA or Ef 8% -54% -48% -54% -77% -77 Less adsorption with Ef 6% -46% -76% -46% ine-aval f Without Eau synthétique Without Eau synthétique Acides Seine-Aval fulviques Acides SRFA Seine-Aval Ef fulviques SRFA Ef Without Eau synthétique Acides fulviques SRFA Seine-Aval Ef 10

20 Influence of on metals sorption on goethite Cu Increase of labile fraction with Ef Labile Inert Particulate Cd, Ni and Zn Less sorption due to the retention in dissolved fraction by complexation SRFA Ef SRFA Ef 11

21 Conclusion and outlook Ef strongly influence the dissolved/particulate partition of metals and in particular Ef maintain metals in dissolved fraction by: Complexation and/or Competition for surface sites Ef strongly influence the speciation of metals in dissolved fraction Increase of zinc labile fraction with Ef and montmorillonite by complexation Strong increase of copper labile fraction with Ef and goethite Complete sorption isotherms => to model the constants describing dissolved/particulate partition of metals Explain the mechanisms responsible of the speciation 12

22 Thank you for your attention Effect of effluent dissolved organic matter on trace metals sorption by mineral particles in aquatic systems under strong urban pressure Gilles Varrault, Caroline Soares-Pereira, Adèle Bressy Water Environment and Urban Systems research group (Paris-Est Créteil University, École des Ponts, AgroParisTech) Corresponding author:

23 Influence of on the trace metals fate in aquatic systems Sorption/desorption onto suspended solids Dissolved fraction Particulate fraction 1. Competition between and metals at the particules surface (Moon et al., 2003) Trace metals Particules 3

24 Influence of on the trace metals fate in aquatic systems Sorption/desorption onto suspended solids Dissolved fraction Particulate fraction 1. Competition between and metals at the particules surface (Moon et al., 2003) 2. Increase of the fixation ability (Saada et al., 2003) Trace metals Particules 3

25 Influence of on the trace metals fate in aquatic systems Sorption/desorption onto suspended solids Dissolved fraction Particulate fraction 1. Competition between and metals at the particules surface (Moon et al., 2003) 2. Increase of the fixation ability (Saada et al., 2003) 3. Retention in dissolved fraction Trace metals Particules 3

26 Influence of on the trace metals fate in aquatic systems Sorption/desorption onto suspended solids Dissolved fraction Particulate fraction 1. Competition between and metals at the particules surface (Moon et al., 2003) 2. Increase of the fixation ability (Saada et al., 2003) 3. Retention in dissolved fraction Trace metals Particules 4. Adsorption of metals on (Wu et al., 2011) 3

27 Influence of on the trace metals fate in aquatic systems Sorption/desorption onto suspended solids Dissolved fraction Particulate fraction 1. Competition between and metals at the particules surface (Moon et al., 2003) 2. Increase of the fixation ability (Saada et al., 2003) 3. Retention in dissolved fraction Trace metals Particules 4. Adsorption of metals on (Wu et al., 2011) 5. Pores obstruction (Newcombe et al., 2002 ; Li et al., 2003) 3

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