Angélique Goffin, Sabrina Guérin, Vincent Rocher, Gilles Varrault

Transcription

1 Excitation-emission matrix Fluorescence spectroscopy to assess quality and quantity of dissolved organic matter in the Seine River from the upstream to the downstream of the Paris agglomeration during a hydrological year Angélique Goffin, Sabrina Guérin, Vincent Rocher, Gilles Varrault

2 Organic matter influence Drinking water treatment plant - Organic matter quality - Disinfection by-products Ground water - Organic matter quality Biochemistry of aquatic environment - Spatial and temporal change of organic matter origin/quality Water Receiving environment - Eutrophication - Organic and metallic pollutants biodisponibility Wastewater treatment plant - Membrane Fooling - Foaming events - Organic matter quality 1

3 Organic matter influence Drinking water treatment plant - Organic matter quality - Disinfection by-products Ground water - Organic matter quality Biochemistry of aquatic environment - Spatial and temporal change of organic matter origin/quality Water Receiving environment - Eutrophication - Organic and metallic pollutants biodisponibility Wastewater treatment plant - Membrane Fooling - Foaming events - Organic matter quality 1

4 Excitation Wavelength What is 3D EEM-Fluorescence Spectrosocopy? Fluorescence intensity (A.U) Emission Wavelength 3D Excitation-Emission matrix (EEM) fluorescence spectra of wastewater influent 2

5 Excitation Wavelength What is 3D EEM-Fluorescence Spectrosocopy? Fluorescence intensity (A.U) 3D EEM Fluorescence spectroscopy: Fluorophore number Relative concentration (intensity) Fluorophores type (λex/λem) Emission Wavelength 3D Excitation-Emission matrix (EEM) fluorescence spectra of wastewater influent Parameters : Spectrofluorimeter FP-83, JASCO (Japan) Excitation nm (5 nm) Emission 25-6 nm (2 nm) 2

6 Data interpretation by Coble (1996), Parlanti et al., (2) β λ Ex nm λ Em nm Autochthonous production γ λ Ex nm λ Em 3 32 nm Protein-like (Tyrosine) γ δ β α α' 3D Excitation-Emission matrix fluorescence spectra of wastewater after data treatment (R.U) δ λ Ex nm λ Em nm Protein-like (Tryptophan) α λ Ex nm λ Em nm Humic-like substances α' λ Ex nm λ Em nm Humic-like substances 3

7 D après Coble (1996), Parlanti et al., (2) β λ Ex nm λ Em nm Autochthonous production γ λ Ex nm λ Em 3 32 nm Protein-like (Tyrosine) γ δ Humic-acid (Stevenson 1982) β α α' 3D Excitation-Emission matrix fluorescence spectra of wastewater after data treatment (R.U) δ λ Ex nm λ Em nm Protein-like (Tryptophan) α λ Ex nm λ Em nm Humic-like substances α' λ Ex nm λ Em nm Humic-like substances 3

8 Parallel factor analysis (PARAFAC) Parallel factor analysis = Multivariate data analysis (Bro, 1997) Measuring data i sample j emission wavelength k excitation wavelength Modeled Data Components concentrations Emission propriety Excitation propriety Residues Unexplained data (Residual fluorescence, interferences.) Data validation by split half analysis Residues < 5% on EEM after deconvolution (Murphy et al., 213) 4

9 The Seine River catchment in France 75, km 2 16 million inhabitants 28% French population = Anthropogenic impacts? Dynamic of organic matter through the time? 5

10 Seine Grésillons WWTP (3, m 3.day -1 ) Seine Aval WWTP (1,7, m 3.day -1 ) Sampling points Seine Centre WWTP (24, m 3.day -1 ) North Legend Wastewater treatment plant Sampling points Discontinuous urban fabric Continuous urban fabric 7 Paris Industrial or commercial units Artificial, non agricultural vegetated areas Mixed forest Arable land/agricultural land Marne Aval WWTP (75, m 3.day -1 ) 2 3 Seine Amont WWTP (6, m 3.day -1 ) Sampling point map and land use of Parisian conurbation One year of sampling July June 216: Weekly sampling on 13 spots (n = 373) 3D EEM fluorescence spectroscopy + UV-Vis spectroscopy 254 nm (Filtration.7µm, GF/F) Global parameters: SS, COD, soluble COD, BOD 5, soluble BOD 5, TOC, DOC, NH 4+, NO 3-, NO 2-6

11 PARAFAC model C1 C9 C5 C8 Bibliothèque de spectres C3 C6 3D fluorescence spectrum (n=373) C1 C7 C2 C4 7

12 PARAFAC model Protein-like component C1 C9 C5 C8 Bibliothèque de spectres Recent Humic-like component C3 C6 3D fluorescence spectrum (n=373) Humic-like component C1 C7 C2 C4

13 Upstream vs downstream Seine Grésillons WWTP (3, m 3.day -1 ) Seine Aval WWTP (1,7, m 3.day -1 ) Seine Centre WWTP (24, m 3.day -1 ) Legend Paris Sampling point map of upstream-downstream Parisian conurbation 2 Wastewater treatment plant Sampling points 1 - Champigny sur marne 2 - Chennevières sur marne 3 - Choisy 4 - Ivry 5 - Alfortville 6 - Confluence Alfortville-Ivry 7 - Suresnes 8 - Argenteuil 9 - Sartrouville 1 - Conflans Oise 11 - Conflans Seine 12 - Poissy 13 -Triel sur Seine Marne Aval WWTP (75, m 3.day -1 ) Seine Amont WWTP (6, m 3.day -1 ) 8

14 Fluorescence intensity (R.U) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ) Focus on upstream of Parisian conurbation (Choisy) debits C1 C2 C3 C4 C5 C6 C7 C8 C9 Flow C1 COD DOC 1, ,8 12 1,6 8,4 6 4,2 2 Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River For Upstream of Paris between July 215 and June 216 DOM fluorescence intensity change with the Seine River flow Fluorescence spectroscopy can be used to follow quantity of fluorescence material 9

15 Fluorescence intensity (R.U) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ) Focus on upstream of Parisian conurbation (Choisy) debits C1 C2 C3 C4 C5 C6 C7 C8 C9 Flow C1 COD DOC 1,2 18 1,8,6,4,2 A Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River For Upstream of Paris between July 215 and June 216 Low flow period June-November 215 9

16 Fluorescence intensity (R.U) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ) Focus on upstream of Parisian conurbation (Choisy) debits C1 C2 C3 C4 C5 C6 C7 C8 C9 Flow C1 COD DOC 1,2 18 1,8,6,4,2 A B Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River For Upstream of Paris between July 215 and June 216 Low flow period June-November 215 Exceptional high flow (Paris flood) June 216 => 1 years occurrence event 9

17 June 216 Last week Paris under water: Following a 1-year occurrence flood event Alma Bridge 8.62 m 6.1 m Bridge of Arcola 1

18 Fluorescence intensity (R.U) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ) Fluorescence intensity (R.U) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ) Focus on upstream of Parisian conurbation (Choisy) A Low flow (June-November 215) B High flow (May-June 216), , ,15 1 8,1 6, ,2 1,8,6,4, Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River, upstream of Parisian conurbation Low flow : - Acid fulvic-like (C1) - Biological humic-like substances (C3) - Protein-like (C5 + C1) High flow : - Acid fulvic-like (C1) - Biological Humic-like substances (C3) + Humic-like substances (C2) EEM Fluorescence Spectroscopy is able to following change of DOM quality 11

19 Fluorescence intensity (R.U) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ) Downstream of Parisian conurbation (Conflans-Sainte-Honorine) debits C1 C2 C3 C4 C5 C6 C7 C8 C9 Flow C1 COD DOC,8 18,7 16,6 14,5 12 1,4 8,3 6,2 4,1 2 Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River at Conflans-Sainte-Honorine (Downstream) from July 215 to June 216 Variations of fluorescence intensity in the Seine River impacted by flow variation, but. 13

20 Fluorescence intensity (R.U) One year of DOM fluorescence monitoring : Downstream of Parisian conurbation (Conflans-Sainte-Honorine) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ) debits C1 C2 C3 C4 C5 C6 C7 C8 C9 Flow C1 COD DOC,8 18,7 16,6 14,5 12 1,4 8,3 6,2 4,1 2 Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River at Conflans-Sainte-Honorine (Downstream) from July 215 to June

21 Fluorescence intensity (R.U) One year of DOM fluorescence monitoring : Downstream of Parisian conurbation (Conflans-Sainte-Honorine) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ),8,7,6,5,4,3,2,1 debits C1 C2 C3 Flow C8 COD DOC Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River at Conflans-Sainte-Honorine (Downstream) from September 215 to March 216 From 7/1/15 to 6/1/16 MOD Biological humic like (C3) + protein-like (C8) From 6/1/16 to 16/3/16 : - Acid fulvic-like (C1) - Biological Humic-like substances (C3) + Humic-like substances (C2) 14

22 Fluorescence intensity (R.U) One year of DOM fluorescence monitoring : Downstream of Parisian conurbation (Conflans-Sainte-Honorine) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ),8,7,6,5,4,3,2,1 debits C1 C2 C3 Flow C8 COD DOC Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River at Conflans-Sainte-Honorine (Downstream) from September 215 to March 216 From 7/1/15 to 6/1/16 MOD Biological humic like (C3) + protein-like (C8) From 6/1/16 to 16/3/16 : - Acid fulvic-like (C1) - Biological Humic-like substances (C3) + Humic-like substances (C2) Maintenance of WWTP = Impact of WWTP effluent End of WWTP malfunctioning + flow increase 14

23 Fluorescence intensity (R.U) One year of DOM fluorescence monitoring : Downstream of Parisian conurbation (Conflans-Sainte-Honorine) Seine River flow measured at Austerlitz (m 3 /s) [DOC] (mgc.l -1 ),8,7,6,5,4,3,2,1 debits C1 C2 C3 Flow C8 COD DOC Chronic of fluorescence intensity, DOC concentration and measured flow in the Seine River at Conflans-Sainte-Honorine (Downstream) from September 215 to March 216 From 7/1/15 to 6/1/16 MOD Biological humic like (C3) + protein-like (C8) From 6/1/16 to 16/3/16 : - Acid fulvic-like (C1) - Biological Humic-like substances (C3) + Humic-like substances (C2) 3D EEM Fluorescence spectroscopy highlight WWTP impact on receiving water 14

24 [DOC] observed (mgc.l -1 ) DOC prediction (all sampling sites): Absorbance 254 nm vs Fluorescence [DOC] observed (mgc.l -1 ) [DOC] (mgc.l -1 ) predicted by Abs 254 nm r 2 =,79 p<,1 [DOC] (mgc.l -1 ) predicted by C4 (Humic-like fluorescence) r 2 =,718 p<, [DOC] predicted (mgc.l -1 ) Correlation between [DOC] predicted with simple linear regression and [DOC] observed values in all sampling sites (Seine-Oise-Marne Rivers) 2 n= 373 n= [DOC] predited (mgc.l -1 ) Correlation between [DOC] predicted with simple linear regression and [DOC] observed values in all sampling sites (Seine-Oise-Marne Rivers) Good [DOC] prediction with Absorbance 254 nm Fluorescence of Humic-like component is also correlated with [DOC] 15

25 [DOC] observed (mgc.l -1 ) DOC prediction (all sampling sites) [DOC] (mgc.l -1 ) by fluorescence (C8, C1) and Abs 254 nm r 2 =,86 r 2 ajusted =,858 p<, n= [DOC] predicted (mgc.l -1 ) Correlation between [DOC] predicted with multiple linear regression and [DOC] observed values in all sampling sites (Seine-Oise-Marne Rivers) Amelioration of [DOC] prediction by Abs 254 nm with Protein-like fluorescence (C1 tyrosine + C8 tryptophan) 16

26 Conclusions Fine approach of DOM fluorescence by EEM-Fluorescence Spectroscopy => 1 PARAFAC components 3D EEM-Fluorescence Spectroscopy allow to follow spatio-temporal variation of DOM quality/quantity in the Seine River - Fluorescence intensity variations from downstream to upstream + Seasonal variations - Highlight of protein-like component «effluent WWTP finger-print» Better prediction of DOC by EEM-Fluorescence Spectroscopy combined with Uv-visible Spectroscopy at 254 nm. EEM-Fluorescence Spectroscopy = great application potential: DOM treatability potential (Drinking Water treatments) Information on receiving water biochemistry 17

27 Thanks for your attention Excitation-emission matrix Fluorescence spectroscopy to assess quality and quantity of dissolved organic matter in the Seine River from the upstream to the downstream of the Paris agglomeration during a hydrological year Angélique Goffin: goffin.angel@gmail.com Acknowledgments: French ministery Elise Alibert & SIAAP Laboratory. 19

28 [DOC] (mgc.l -1 ) Seine River flow measured at Austerlitz (m 3.s -1 ) DOC variation in the Seine River Choisy Sartrouville Conflans Triel débits Chronic of DOC concentration and measured flow in the Seine River For upstream (dotted line) and downstream (full line) of Paris between July 215 and June 216 1