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-33400 Talence, France b : Irstea Antony, Unité de Recherche Hydrosystèmes et Bioprocédés (HBAN), 1 rue Pierre- Gilles de Gennes, CS 10030, F-92761 Antony Cedex, France c : AgroParisTech, F-75005 Paris, France d : CNRS, EPOC, UMR 5805, LPTC Research Group, 351 Cours de la Libération, F-33400 Talence, France *Corresponding author. Contact: pierre.labadie@u-bordeaux.fr
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
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
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. 2011 371.3 14.5 68.1 4.8 4.3 0.3 1.6 0.1 7.9 0.6 7.8 0.5 18.2 0.8 Bougival 1 Sept. 2011 521.7 20.7 86.6 1.3 8.0 0.2 5.0 0.5 18.4 0.6 7.6 0.4 20.7 0.8 Triel 1 Sept. 2011 582.0 39.3 93.8 1.6 9.5 0.2 6.5 0.8 23.1 0.6 7.6 0.1 20.8 0.5 Marnay 2 March 2012 N/A N/A 100.4 14.3 4.3 0.4 4.7 0.3 10.5 0.7 7.5 N/A 10.9 N/A Bougival 2 March 2012 N/A N/A 114.1 3.9 7.2 0.2 5.6 0.3 16.4 0.8 7.9 N/A 11.7 N/A Triel 2 March 2012 N/A N/A 119.9 3.7 8.3 0.3 8.3 0.8 20.1 0.8 7.8 N/A 11.7 N/A Marnay 3 July 2012 527.0 N/A 138.2 5.8 4.3 0.2 1.6 0.5 6.1 1.0 7.9 0.2 17.5 1.1 Bougival 3 July 2012 547.0 N/A 138.8 7.6 4.9 0.4 6.0 0.8 15.4 2.4 7.8 0.2 20.5 1.3 Triel 3 July 2012 574.0 N/A 143.4 7.8 4.5 0.3 7.1 0.7 19.5 1.8 7.7 0.2 20.7 1.1 Marnay 4 Nov. 2012 532.3 7.9 122.2 11.9 2.6 1.5 1.8 0.3 7.0 1.5 8.0 0.3 7.1 1.5 Bougival 4 Nov. 2012 551.5 31.3 123.0 14.6 4.0 2.4 3.1 0.4 12.1 2.6 7.8 0.4 7.9 1.9 Triel 4 Nov. 2012 581.3 44.3 120.6 13.0 4.2 2.2 4.0 1.2 14.5 3.3 7.9 0.1 7.5 1.3 S-4
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. 2011 1226 12 9.1 N/A 0.9 N/A 10.7 N/A 5.1 0.1 9.5 0.4 233 N/A Bougival 1 Sept. 2011 2151 24 8.1 N/A 1.0 N/A 7.9 N/A 14 1.8 19.8 0.3 245 N/A Triel 1 Sept. 2011 1886 13 8.8 N/A 1.2 N/A 7.1 N/A 14.1 1.4 29.8 1.3 164 N/A Marnay 2 March 2012 4331 92 5.6 N/A 0.7 N/A 8.5 N/A 8.9 0.9 23.6 5 240 N/A Bougival 2 March 2012 1030 25 6.8 N/A 0.9 N/A 7.4 N/A 8.1 1.8 25.2 10.8 83 N/A Triel 2 March 2012 1986 46 9.6 N/A 1.5 N/A 6.3 N/A 15 0.6 10.6 0.6 424 N/A Marnay 3 July 2012 1213 197 5.2 N/A 0.7 N/A 7.9 N/A 30.9 2.3 9.9 0.7 264 N/A Bougival 3 July 2012 1067 32 7.7 N/A 1.1 N/A 7.0 N/A 17.7 3.6 10.2 0.2 399 N/A Triel 3 July 2012 1096 78 9.1 N/A 1.6 N/A 5.6 N/A 17.7 2.6 25 1 184 N/A Marnay 4 Nov. 2012 281 4 4.1 N/A 0.5 N/A 8.8 N/A 0.9 0.1 N/A N/A N/A N/A Bougival 4 Nov. 2012 796 13 3.1 N/A 0.4 N/A 8.1 N/A 1.3 0.2 N/A N/A N/A N/A *: data taken from Faburé, J., Dufour, M., Autret, A., Uher, E., Fechner, L.C., 2015. Impact of an urban multi-metal contamination gradient: Metal bioaccumulation and tolerance of river biofilms collected in different seasons. Aquat. Toxicol. 159, 276-289. S-5
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 100 0.075 6.4 0-0 - PFHxA 100 0.17 7.7 0-0 - PFHpA 100 0.074 2.8 0-0 - PFOA 100 0.16 5.9 89 nd 0.17 100 0.11 1.0 PFNA 97 nd 2.0 22 nd 0.017 73 nd 1.5 PFDA 94 nd 1.5 89 nd 0.27 100 0.10 1.6 PFUnA 39 nd 0.20 67 nd 0.21 82 nd 1.1 PFDoA 18 nd 0.15 78 nd 0.94 82 nd 3.8 PFTrDA 0-33 nd 0.21 64 nd 0.76 PFTeDA 6 nd 0.021 44 nd 0.40 45 nd 1.1 PFBS 70 nd 3.1 0-0 - PFHxS 100 0.28 7.8 67 nd 0.23 100 0.032 0.25 PFHpS 100 0.016 0.90 0-36 nd 0.087 Br-PFOS 100 0.33 14 33 nd 0.10 64 nd 0.82 L-PFOS 100 0.25 16 100 0.081 2.1 100 2.7 21 PFDS 3 nd 0.050 11 nd 0.10 45 nd 0.19 FOSA 76 nd 0.22 89 nd 0.18 73 nd 0.32 MeFOSA 15 nd 0.025 0-0 - EtFOSA 0-0 - 0-6:2 FTSA 97 nd 41 78 nd 0.51 73 nd 1.1 PFASs 1.8 105 0.18 5.1 4.3 32 S-6
Grain-size distribution in sediment samples Fig.S2. Grain size distribution in sediment samples collected along the River Seine. S-7
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 ± 0.3 27.8 ± 9.6 Bougival 2.6 ± 2.2 39.3 ± 32.7 Triel 0.8 ± 0.6 29.6 ± 33.2 MARNAY BOUGIVAL TRIEL Fig.S3. PFAS molecular pattern in sediment samples collected along the River Seine. S-8
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
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 0.70-0.32 0.77 0.67 0.60 0.30 0.66 0.78 0.46 0.50 0.55-0.30-0.56 PFHxA -0.28 0.91 0.98 0.57 0.83 0.86 0.80 0.49 0.51 0.82-0.60-0.58 PFBS -0.46-0.18 0.39-0.16 0.11-0.23 0.13 0.12-0.53 0.27 0.47 PFHpA 0.86 0.45 0.72 0.71 0.89 0.46 0.54 0.89-0.65-0.80 PFOA 0.57 0.79 0.83 0.72 0.46 0.49 0.72-0.56-0.52 PFHxS 0.37 0.86 0.60 0.66 0.63 0.27-0.29-0.23 PFNA 0.69 0.65 0.50 0.53 0.83-0.64-0.56 PFHpS 0.81 0.69 0.65 0.66-0.42-0.38 PFDA 0.65 0.68 0.86-0.56-0.72 R-PFOS 0.97 0.41-0.44-0.50 L-PFOS 0.42-0.49-0.61 FOSA -0.57-0.73 6:2-FTSA 0.48 S-10
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 0.86 0.87 0.89 0.79 0.69 0.89 0.83 0.69 0.88 0.87 0.69-0.05-0.60 PFHxA 0.81 0.96 0.89 0.95 0.90 0.94 0.82 0.97 0.93 0.86 0.20-0.83 PFBS 0.79 0.71 0.71 0.80 0.73 0.55 0.83 0.78 0.65-0.01-0.69 PFHpA 0.96 0.90 0.94 0.95 0.81 0.96 0.94 0.89 0.16-0.84 PFOA 0.91 0.90 0.96 0.85 0.94 0.94 0.92 0.18-0.86 PFHxS 0.81 0.92 0.77 0.92 0.86 0.92 0.33-0.93 PFNA 0.94 0.94 0.94 0.96 0.82-0.05-0.73 PFHpS 0.91 0.94 0.94 0.85 0.23-0.78 PFDA 0.85 0.90 0.71 0.18-0.56 R-PFOS 0.98 0.90 0.10-0.83 L-PFOS 0.86 0.02-0.76 FOSA 0.20-0.93 6:2-FTSA -0.26 S-11
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 0.98 0.65 0.99 0.94 0.77 0.87 0.76 0.94 0.85 0.94 0.72 0.63-0.86 PFHxA 0.64 0.97 0.94 0.80 0.83 0.76 0.88 0.86 0.93 0.78 0.64-0.92 PFBS 0.65 0.62 0.69 0.50 0.63 0.53 0.63 0.70 0.28 0.86-0.65 PFHpA 0.93 0.78 0.86 0.76 0.93 0.86 0.95 0.72 0.64-0.87 PFOA 0.79 0.89 0.79 0.89 0.85 0.96 0.79 0.67-0.86 PFHxS 0.47 0.96 0.61 0.98 0.89 0.63 0.89-0.72 PFNA 0.41 0.94 0.58 0.78 0.68 0.35-0.83 PFHpS 0.59 0.96 0.90 0.61 0.88-0.65 PFDA 0.70 0.84 0.72 0.46-0.79 R-PFOS 0.94 0.72 0.83-0.77 L-PFOS 0.72 0.78-0.83 FOSA 0.36-0.80 6:2-FTSA - 0.62 S-12
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 0.88-0.58-0.77-0.006 Ca 2+ -0.43 0.56 0.16 Mg 2+ -0.27 0.37 K + 0.10 Bougival Ca 2+ Mg 2+ K + Na + flow rate 0.84-0.92-0.78-0.86 Ca 2+ -0.88-0.75-0.56 Mg 2+ 0.78 0.79 K + 0.71 Triel Ca 2+ Mg 2+ K + Na + flow rate 0.72-0.92-0.92-0.93 Ca 2+ -0.88-0.66-0.67 Mg 2+ 0.81 0.89 K + 0.94 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 -0.19-0.15-0.44 Dissolved Ca 2+ -0.37-0.40-0.17 Dissolved Mg 2+ -0.58-0.56-0.67 Dissolved K + -0.68-0.71-0.76 Dissolved Na + -0.79-0.69-0.85 ph -0.03 0.16 0.32 Dissolved PFAS concentration -0.68-0.64-0.73 Biofilm dry weight (µg cm -2 ) 0.24-0.13-0.08 Biofilm organic nitrogen content (%) -0.48-0.41-0.58 Biofilm organic carbon content (%) -0.20-0.11-0.40 Biofilm organic C/N ratio 0.78 0.79 0.71 Heterotrophic activity (nm MUF/h/cm²) -0.16-0.35-0.29 Autotrophic index -0.03-0.06 0.06 Chlorophyll a (mg cm -2 ) -0.34-0.34-0.46 S-13