SUPPORTING INFORMATION

Transcription

1 SUPPORTING INFORMATION Spatio-temporal dynamics of poly- and perfluoroalkyl substances (PFASs) and transfer to periphytic biofilm in an urban river: casestudy on the River Seine Gabriel Munoz a, Lise C. Fechner b,c, Emmanuel Geneste a, Patrick Pardon a, Hélène Budzinski d and Pierre Labadie d * a : University of Bordeaux, EPOC, UMR 5805, LPTC Research Group, 351 Cours de la Libération, F Talence, France b : Irstea Antony, Unité de Recherche Hydrosystèmes et Bioprocédés (HBAN), 1 rue Pierre- Gilles de Gennes, CS 10030, F Antony Cedex, France c : AgroParisTech, F Paris, France d : CNRS, EPOC, UMR 5805, LPTC Research Group, 351 Cours de la Libération, F Talence, France *Corresponding author. Contact: pierre.labadie@u-bordeaux.fr

2 TABLE OF CONTENTS Location of the sampling sites...s-3 Characteristics of water samples..s-4 Characteristics of biofilm samples. S-5 PFAS detection frequency and concentration range..s-6 Grain-size distribution in sediment samples S-7 PFAS levels and profiles in sediment samples...s-8 PFAS levels and profiles in biofilm samples....s-9 Correlations......S-10 S-2

3 Location of the sampling sites Fig.S1. Location of the three sampling sites along the Seine river. Paris downtown is shown in purple and the Paris urban area in pink. Arrows indicate river flow directions. S-3

4 Characteristics of water samples Table S1. Physico-chemical characteristics of water samples collected along the River Seine (mean and standard deviation (SD, n = 3 4)); N/A: not available. Conductivity (µs cm -1 ) Ca 2+ (mg/l) Mg 2+ (mg L -1 ) K + (mg L -1 ) Na + (mg L -1 ) ph T ( C) Site Campaign Period Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Marnay 1 Sept Bougival 1 Sept Triel 1 Sept Marnay 2 March 2012 N/A N/A N/A 10.9 N/A Bougival 2 March 2012 N/A N/A N/A 11.7 N/A Triel 2 March 2012 N/A N/A N/A 11.7 N/A Marnay 3 July N/A Bougival 3 July N/A Triel 3 July N/A Marnay 4 Nov Bougival 4 Nov Triel 4 Nov S-4

5 Characteristics of biofilm samples Table S2. Characteristics of biofilm samples collected along the River Seine (mean and standard deviation (SD), n=1 4); N/A: not available. Dry weight* (µg cm -2 ) Organic Carbon (%) Organic Nitrogen (%) Organic C/N ratio Heterotrophic activity* (nm MUF -1 h -1 cm -² ) Chlorophyll a* (mg cm -2 ) Autotrophic index* Site Campaign Period Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Marnay 1 Sept N/A 0.9 N/A 10.7 N/A N/A Bougival 1 Sept N/A 1.0 N/A 7.9 N/A N/A Triel 1 Sept N/A 1.2 N/A 7.1 N/A N/A Marnay 2 March N/A 0.7 N/A 8.5 N/A N/A Bougival 2 March N/A 0.9 N/A 7.4 N/A N/A Triel 2 March N/A 1.5 N/A 6.3 N/A N/A Marnay 3 July N/A 0.7 N/A 7.9 N/A N/A Bougival 3 July N/A 1.1 N/A 7.0 N/A N/A Triel 3 July N/A 1.6 N/A 5.6 N/A N/A Marnay 4 Nov N/A 0.5 N/A 8.8 N/A N/A N/A N/A N/A Bougival 4 Nov N/A 0.4 N/A 8.1 N/A N/A N/A N/A N/A *: data taken from Faburé, J., Dufour, M., Autret, A., Uher, E., Fechner, L.C., Impact of an urban multi-metal contamination gradient: Metal bioaccumulation and tolerance of river biofilms collected in different seasons. Aquat. Toxicol. 159, S-5

6 PFAS detection frequency and concentration range Table S3. Detection frequency and concentration ranges determined in water (dissolved phase), sediment and biofilm samples. Detection Frequency (%) Water Sediment Biofilm Concentration Range (ng L -1 ) Detection Frequency (%) Concentration Range (ng g -1 dw) Detection Frequency (%) Concentration Range (ng g -1 dw) PFPeA PFHxA PFHpA PFOA nd PFNA 97 nd nd nd 1.5 PFDA 94 nd nd PFUnA 39 nd nd nd 1.1 PFDoA 18 nd nd nd 3.8 PFTrDA 0-33 nd nd 0.76 PFTeDA 6 nd nd nd 1.1 PFBS 70 nd PFHxS nd PFHpS nd Br-PFOS nd nd 0.82 L-PFOS PFDS 3 nd nd nd 0.19 FOSA 76 nd nd nd 0.32 MeFOSA 15 nd EtFOSA :2 FTSA 97 nd nd nd 1.1 PFASs S-6

7 Grain-size distribution in sediment samples Fig.S2. Grain size distribution in sediment samples collected along the River Seine. S-7

8 PFAS levels and profiles in sediment samples Table S4. Total PFAS levels (mean ± SD) in sediment samples collected along the River Seine. Sampling site PFASs ng g -1 dry weight PFASs ng g -1 organic carbon Marnay 1.1 ± ± 9.6 Bougival 2.6 ± ± 32.7 Triel 0.8 ± ± 33.2 MARNAY BOUGIVAL TRIEL Fig.S3. PFAS molecular pattern in sediment samples collected along the River Seine. S-8

9 PFAS levels and profiles in biofilm samples Fig.S4. Total PFAS level in biofilm samples (ng g -1 dry weight); results are expressed as the mean value and error bars represent the standard deviation (n = 3 4). MARNAY BOUGIVAL TRIEL Fig.S5. PFAS molecular pattern in biofilm collected in the River Seine (3 4 samples analyzed per site). S-9

10 Correlations (1/4) Table S5. Spearman Rank Order correlation coefficients between PFASs in the River Seine (dissolved phase) at MARNAY (n=12). Significant coefficients (p<0.05) are indicated in bold. PFHxA PFBS PFHpA PFOA PFHxS PFNA PFHpS PFDA Br-PFOS L-PFOS FOSA 6:2-FTSA River flow rate PFPeA PFHxA PFBS PFHpA PFOA PFHxS PFNA PFHpS PFDA R-PFOS L-PFOS FOSA :2-FTSA 0.48 S-10

11 Correlations (2/4) Table S6. Spearman Rank Order correlation coefficients between PFASs in the River Seine (dissolved phase) at BOUGIVAL (n=12). Significant coefficients (p<0.05) are indicated in bold. PFHxA PFBS PFHpA PFOA PFHxS PFNA PFHpS PFDA Br-PFOS L-PFOS FOSA 6:2-FTSA River flow rate PFPeA PFHxA PFBS PFHpA PFOA PFHxS PFNA PFHpS PFDA R-PFOS L-PFOS FOSA :2-FTSA S-11

12 Correlations (3/4) Table S7. Spearman Rank Order correlation coefficients between PFASs in the River Seine (dissolved phase) at TRIEL (n=12). Significant coefficients (p<0.05) are indicated in bold. PFHxA PFBS PFHpA PFOA PFHxS PFNA PFHpS PFDA Br-PFOS L-PFOS FOSA 6:2-FTSA River flow rate PFPeA PFHxA PFBS PFHpA PFOA PFHxS PFNA PFHpS PFDA R-PFOS L-PFOS FOSA :2-FTSA S-12

13 Correlations (4/4) Table S8. Spearman Rank Order Correlation coefficients between river flow rate and major cations in the River Seine (n=12); significant coefficients (p<0.05) are indicated in bold. Marnay Ca 2+ Mg 2+ K + Na + flow rate Ca Mg K Bougival Ca 2+ Mg 2+ K + Na + flow rate Ca Mg K Triel Ca 2+ Mg 2+ K + Na + flow rate Ca Mg K Table S9. Pearson Product Moment Correlation coefficients between BCF and biogeochemical parameters or biofilm characteristics. Significant coefficients (p<0.05) are indicated in bold. BCF PFOA BCF PFHxS BCF PFOS Temperature Dissolved Ca Dissolved Mg Dissolved K Dissolved Na ph Dissolved PFAS concentration Biofilm dry weight (µg cm -2 ) Biofilm organic nitrogen content (%) Biofilm organic carbon content (%) Biofilm organic C/N ratio Heterotrophic activity (nm MUF/h/cm²) Autotrophic index Chlorophyll a (mg cm -2 ) S-13