ROOT UPTAKE AND TRANSLOCATION OF PERFLUORINATED ALKYL ACIDS BY THREE HYDROPONICALLY GROWN CROPS

Transcription

1 Supporting Information for ROOT UPTAKE AND TRANSLOCATION OF PERFLUORINATED ALKYL ACIDS BY THREE HYDROPONICALLY GROWN CROPS Felizeter S 1, McLachlan MS 2 De Voogt P 1,3 1 Universiteit van Amsterdam, Institute for Biodiversity and Ecosystem Dynamics, Amsterdam, The Netherlands 2 Department of Applied Environmental Science, Stockholm University, Sweden 3 KWR Watercycle Research Institute, Nieuwegein, The Netherlands

2 Contents Table S1: List of chemicals used, their purity and suppliers Table S2: Chemical composition of the Hoaglands nutrient solution and the composition of the stock solutions used to achieve the final concentrations Table S3: Dates of the seed sowing, the start and the end of the experiments, as well as dates when the nutrient solutions were exchanged Description of the instrumental method Table S4: List of the analytes, their abbreviations and molecular formula, the 13Clabelled internal standards used, and the mass transitions used in the MS/MS analysis of the analytes Table S5: Concentrations of a repeated extraction of a cabbage leaf sample from the 500 ng L -1 nominal spiking concentration Table S6: Recoveries (in %) of internal mass-labeled standards Table S7: Ionization enhancement and/or suppression for the internal standards added to purified extracts Figure S1: Stem/root concentration factor Figure S2: Twig concentration factor (TCF) Figure S3: Twig/stem concentration factor Figure S4: Leaf/twig concentration factor Table S9: Mass distribution of PFAAs in different tissues of cabbage plants Table S10: Mass distribution of PFAAs in different tissues of zucchini plants Table S11: PFAA concentrations (mean ± standard deviation) in samples from the cabbage experiment Table S12: PFAA concentrations (mean ± standard deviation) in samples from the zucchini experiment Table S13: PFAA concentrations (mean ± standard deviation) in samples from the tomato experiment Figure S5: Edible part/leaf concentration factor Table S14: Overview of various hydrophobicity parameters References S1

3 Table S1: List of chemicals used, their purity and suppliers. Chemical Purity Supplier Wellington Laboratories, Ontario, MPFAC-Mix (internal standard) Canada Wellington Laboratories, Ontario, MPFAS-Mix (internal standard) Canada Wellington Laboratories, Ontario, M5PFPeA (internal standard) Canada Wellington Laboratories, Ontario, M4PFHpA (internal standard) Canada Wellington Laboratories, Ontario, PFAC-Mix (calibration standard) Canada Wellington Laboratories, Ontario, PFAS/FOSA-Mix (calibration standard) Canada PFBA 98% Sigma Aldrich, Zwijndrecht, Netherlands PFPeA 97% Sigma Aldrich, Zwijndrecht, Netherlands PFHxA 97% Sigma Aldrich, Zwijndrecht, Netherlands PFHpA 99% Sigma Aldrich, Zwijndrecht, Netherlands PFOA 96% Sigma Aldrich, Zwijndrecht, Netherlands PFNA 97% Sigma Aldrich, Zwijndrecht, Netherlands PFDA 98% Sigma Aldrich, Zwijndrecht, Netherlands PFUnA 95% Sigma Aldrich, Zwijndrecht, Netherlands PFDoA 95% Sigma Aldrich, Zwijndrecht, Netherlands PFTrA 97% Sigma Aldrich, Zwijndrecht, Netherlands PFTeA 97% Sigma Aldrich, Zwijndrecht, Netherlands K-PFBS 98% Sigma Aldrich, Zwijndrecht, Netherlands K-PFHxS 98% Sigma Aldrich, Zwijndrecht, Netherlands K-PFOS 98% Sigma Aldrich, Zwijndrecht, Netherlands Sodium carbonate 99% Sigma Aldrich, Zwijndrecht, Netherlands J.T. Baker Chemicals, deventer, Sodium hydroxide 98,8% Netherlands Sodium hydrogencarbonate 99,5% Merck, Darmstadt, Germany Sodium sulfate 99% Merck, Darmstadt, Germany Tetrabutylammoniumhydrogensulfate (TBA) 99% Merck, Darmstadt, Germany Ammonium hydroxide Sigma Aldrich, Zwijndrecht, Netherlands Ammonium acetate 99,999% Sigma Aldrich, Zwijndrecht, Netherlands Methanol ULC/MSgrade Biosolve, Valkenswaard, Netherlands Water ULC/MSgrade Biosolve, Valkenswaard, Netherlands tert-butyl methyl ether (MTBE) HPLC-grade Biosolve, Valkenswaard, Netherlands S2

4 Table S2: Chemical composition of the Hoaglands nutrient solution and the composition of the stock solutions used to achieve the final concentrations. Conc. Stock final conc. in nutrient ml Stock Component Solution solution Solution per 1 L g/l ppm KNO N 210 Ca(NO 3 ) 2 x 4H 2 O K 235 NH 4 NO Ca 200 MgSO 4 x 7H 2 O Mg 48 KH 2 PO S 64 (ph to 6.0 with 3M KOH) P 31 Iron (Fe-EDTA sodium salt) Fe 1,12 Minors: 1 H 3 BO B 0.5 MnCl 2 x 4H 2 O 1.81 Mn 0.5 ZnSO 4 x 7H 2 O 0.22 Zn 0.05 CuSO Cu 0.02 H 3 MoO 4 x H 2 O 0.09 Mo 0.01 S3

5 Table S3: Dates of the seed sowing, the start and the end of the experiments, as well as dates when the nutrient solutions were exchanged. Date of sowing Start of exposure Dates of exchange of spiked nutrient solution Harvest End of experiment Tomato * * to to * * Cabbage * to to * * * Zucchini to * at this date not all the plants received new nutrient solution Not all the plants grew equally fast or had ripe fruits at the same time. For tomato the fruits from the lowest branch were used for the paper. However, the experiment continued until all tomato plants had ripe fruits from all branches (low, medium and high). Cabbage plants were harvested when the cabbage heads started to crack open and no further growth could be expected. Zucchini fruits were harvested when they reached supermarket sizes. The experiment continued until at least 1 zucchini fruit of supermarket size was harvested from all plants. S4

6 Description of the instrumental method. The analytical methodology was according to the methods described by Eschauzier et al. (2010) [1]. The measurements were conducted in the scheduled MRM-mode (see Table S4). Briefly, instrumental settings included: Ion Transfer Voltage: V Interface Temperature: 450 C Curtain gas: 10 L min -1 Collision gas: 6 L min -1 Collision Energy: -10 V for PFPeA to PFOA, -15 V for PFBA, -25 V for PFNA to PFTeA and -70 V for the PFSAs The concentrations of calibration standards ranged from ng ml -1 (Calibration level 1) to 200 ng ml -1 (Calibration level 12). Peaks consisted of at least 24 scans and the smoothing width was 9 points. For separation on the column a gradient elution with two mobile phases, A (40:60 methanol:water) and B (95:5 methanol:water; both with 2 mm ammonium acetate) was used. The system was equilibrated for 8 minutes with the initial mobile phase composition of 60 %A at a flow of 0.2 ml/min prior to sample injection. After injection the mobile phase composition changed linearly to 100% B at 10 minutes. This was held isocratic until 20 minutes. Afterwards the solvent composition was returned to initial condition within 2 minutes. S5

7 Table S4: List of the analytes, their abbreviations and molecular formula, the 13C-labelled internal standards used, and the mass transitions used in the MS/MS analysis of the analytes. Due to the lack of available mass-labelled standards for PFTrA, PFTeA and PFBS, these chemicals were corrected with the closest available standard, which could lead to under- or overestimated results due to different responses or extraction efficiencies. Abbreviation Compound Transition 1 Transition 2 PFBA Perfluoro-n-butanoic acid PFPeA Perfluoro-n-pentanoic acid PFHxA Perfluoro-n-hexanoic acid PFHpA Perfluoro-n-heptanoic acid PFOA Perfluoro-n-octanoic acid PFNA Perfluoro-n-nonanoic acid PFDA Perfluoro-n-decanoic acid PFUnA Perfluoro-n-undecanoic acid PFDoA Perfluoro-n-dodecanoic acid PFTrA Perfluoro-n-tridecanoic acid PFTeA Perfluoro-n-tetradecanoic acid PFBS Perfluorobutane sulfonate PFHxS Perlfuorohexane sulfonate PFOS Perfluorooctane sulfonate C 4 PFBA Perfluoro-n-[1,2,3,4-13 C 4 ]butanoic acid C 5 PFPeA Perfluoro-n-[1,2,3,4,5-13 C 5 ]pentanoic acid C 2 PFHxA Perfluoro-n-[1,2-13 C 2 ]hexanoic acid C 4 PFHpA Perfluoro-n-[1,2,3,4-13 C 4 ]heptanoic acid C 8 PFOA Perfluoro-n-[1,2,3,4,5,6,7,8-13 C 8 ]octanoic acid C 9 PFNA Perfluoro-n-[1,2,3,4,5,6,7,8,9-13 C 9 ]nonanoic acid C 6 PFDA Perfluoro-n-[1,2,3,4,5,6-13 C 6 ]decanoic acid C 7 PFUnA Perfluoro-n-[1,2,3,4,5,6,7-13 C 7 ]undecanoic acid C 2 PFDoA Perfluoro-n-[1,2-13 C 2 ]dodecanoic acid O 2 PFHxS Perfluoro-1-hexane[ 18 O 2 ]sulfonate C 8 PFOS Perfluoro-1-[1,2,3,4,5,6,7,8-13 C 8 ]octanesulfonate Quantification by internal Molecular Formula Standard 13 C 4 PFBA CF 3 (CF 2 ) 2 COOH 13 C 5 PFPeA CF 3 (CF 2 ) 3 COOH 13 C 2 PFHxA CF 3 (CF 2 ) 4 COOH 13 C 4 PFHpA CF 3 (CF 2 ) 5 COOH 13 C 8 PFOA CF 3 (CF 2 ) 6 COOH 13 C 9 PFNA CF 3 (CF 2 ) 7 COOH 13 C 6 PFDA CF 3 (CF 2 ) 8 COOH 13 C 7 PFUnA CF 3 (CF 2 ) 9 COOH 13 C 2 PFDoA CF 3 (CF 2 ) 10 COOH 13 C 2 PFDoA CF 3 (CF 2 ) 11 COOH 13 C 2 PFDoA CF 3 (CF 2 ) 12 COOH 18 O 2 PFHxS CF 3 (CF 2 ) 3 SO 3 18 O 2 PFHxS CF 3 (CF 2 ) 5 SO 3 13 C 8 PFOS CF 3 (CF 2 ) 7 SO 3 S6

8 Table S5: Concentrations of a repeated extraction of a cabbage leaf sample from the 500 ng L -1 nominal spiking concentration. All values in ng g -1 fresh weight. PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFTrA PFTeA PFBS PFHxS Br-PFOS L-PFOS Sample Sample Sample Sample Sample Average Standard deviation % StDev 5% 3% 9% 6% 5% 10% 10% 7% 7% 10% 9% 2% 6% 7% 5% S7

9 Table S6: Recoveries (in %) of internal mass-labeled standards. They were determined by comparing the standard signal in the sample to the signal in matrix solutions which had been spiked with the same quantity of internal standard immediately prior to analysis. Mass labeled standards for PFPeA and PFHpA were not available at the time tomato roots and fruits were extracted. The bold entries are the mean recoveries (in %), while the non-bold entries are the respective standard deviations (in % of the mean). 13 C 4 PFBA 13 C 5 PFPeA 13 C 2 PFHxA 13 C 4 PFHpA 13 C 8 PFOA 13 C 9 PFNA 13 C 6 PFDA 13 C 7 PFUnA 13 C 2 PFDoA 18 O 2 PFHxS Cabbage Roots Stem Leaf Head Zucchini Roots Stem Twig Leaf Fruit Tomato Roots 77 n.a. 105 n.a Fruit 50 n.a. 102 n.a Stem Twig Leaf C 8 PFOS S8

10 Table S7: Ionization enhancement and/or suppression for the internal standards added to purified extracts. Matrix effects are expressed as a percentage in relation to the signal area response of a solvent-based, matrix free, internal standard solution (100% = no matrix effect). Cabbage 13 C 4 PFBA 13 C 5 PFPeA 13 C 2 PFHxA 13 C 4 PFHpA 13 C 8 PFOA 13 C 9 PFNA 13 C 6 PFDA 13 C 7 PFUnA 13 C 2 PFDoA 18 O 2 PFHxS Root Stem Leaf Head Zucchini Root Stem Twig Leaf Fruit Tomato Root Stem Twig Leaf Fruit C 8 PFOS S9

11 Table S8: Limits of Quantification (LoQ) in ng g -1 fresh weight. PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFTrA PFTeA PFBS PFHxS Br-PFOS L-PFOS Cabbage Root Stem Leaf Head Zucchini Root Stem Twig Leaf Fruit Tomato Root Stem Twig Leaf Fruit S10

12 10 1 Cabbage Zucchini Tomato Figure S1: Stem/root concentration factor, calculated by dividing the PFAA concentration in the stem by the PFAA concentration in the root (both on a fresh weight basis). Logarithmic scale. The factor shown is the average of all plants with quantifiable concentrations (see tables S11-13). Error bars denote standard error Zucchini Tomato Figure S2: Twig concentration factor (TCF), calculated by dividing the fresh weight based PFAA concentration in the twig by the PFAA concentration in the nutrient solution. The factor shown is the average of all plants with quantifiable concentrations (see tables S11-13). Error bars denote standard error. S11

13 Zucchini Tomato Figure S3: Twig/stem concentration factor, calculated by dividing the PFAA concentration in the twig by the PFAA concentration in the stem (both on a fresh weight basis). The factor shown is the average of all plants with quantifiable concentrations (see tables S11-13). Error bars denote standard error Cabbage Zucchini Tomato Figure S4: Leaf/twig concentration factor (for cabbage leaf/stem), calculated by dividing the PFAA concentration in the leaves by the PFAA concentration in the twig (stem) (all on a fresh weight basis). The factor shown is the average of all plants with quantifiable concentrations (see tables S11-13). Error bars denote standard error. S12

14 Table S9: Mass distribution of PFAAs in different tissues of cabbage plants, expressed as a percent of the total amount of PFAA found in the plant. Percent distributions were calculated for each plant. Values shown are the averages. Roots Stem Head Leaf PFBA 6% 4% 22% 67% PFPeA 10% 3% 33% 53% PFHxA 19% 3% 17% 62% PFHpA 24% 1% 1% 74% PFOA 39% 1% 1% 59% PFNA 63% 1% 0% 35% PFDA 79% 2% 0% 19% PFUnA 91% 2% 0% 6% PFDoA 97% 2% 0% 2% PFTrA 99% 0% 0% 0% PFTeA 100% 0% 0% 0% PFBS 20% 1% 1% 78% PFHxS 38% 1% 1% 61% Br-PFOS 64% 2% 0% 34% L-PFOS 82% 1% 0% 16% Table S10: Mass distribution of PFAAs in different tissues of zucchini plants, expressed as percent of the total amount of PFAA found in the plant. Percent distributions were calculated for each plant. Values shown are the averages. Roots Stem Twig Leaf Fruit PFBA 7% 2% 8% 72% 11% PFPeA 11% 4% 6% 57% 22% PFHxA 17% 24% 6% 38% 15% PFHpA 33% 24% 4% 32% 7% PFOA 50% 19% 6% 24% 2% PFNA 66% 13% 4% 16% 2% PFDA 81% 7% 3% 8% 1% PFUnA 93% 3% 2% 2% 0% PFDoA 98% 1% 1% 0% 0% PFTrA 100% 0% 0% 0% 0% PFTeA 100% 0% 0% 0% 0% PFBS 32% 4% 3% 56% 5% PFHxS 53% 11% 3% 32% 2% Br-PFOS 77% 7% 2% 14% 1% L-PFOS 85% 4% 2% 9% 0% S13

15 Table S11: PFAA concentrations (mean ± standard deviation) in samples from the cabbage experiment expressed in ng/l (water) and ng/g fresh weight (plant tissues). The nominal concentrations in the nutrient solution are given in the left hand column. The concentrations in the plant tissues were corrected for the concentrations in the control plants (data not shown). PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA Water ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 14.3 Root 10 <0.026 ± 0.13 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 6.25 Stem 10 <0.026 ± ± <0.026 ± <0.026 ± ± <0.026 ± <0.026 ± <0.026 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 4.02 Leaf ± ± ± ± ± ± ± <0.021 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 1.40 Head ± ± ± <0.021 ± <0.021 ± <0.021 ± <0.021 ± <0.021 ± ± ± ± ± ± <0.021 ± <0.021 ± <0.021 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± S14

16 Table S11: Continued PFDoA PFTrA PFTeA PFBS PFHxS Br-PFOS L-PFOS Water ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 18.2 Root ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 33.3 Stem 10 <0.026 ± <0.026 ± <0.026 ± <0.002 ± <0.002 ± <0.005 ± <0.018 ± ± <0.026 ± <0.026 ± ± ± ± ± ± ± 0.12 <0.026 ± 0.31 ± ± ± ± ± ± 0.12 <0.026 ± 0.90 ± ± ± ± 0.84 Leaf 10 <0.021 ± <0.021 ± <0.021 ± 0.21 ± ± ± <0.014 ± 100 <0.021 ± <0.021 ± <0.021 ± 1.96 ± ± ± ± ± 0.17 <0.021 ± <0.021 ± 10.1 ± ± ± ± ± 0.27 <0.021 ± <0.021 ± 21.4 ± ± ± ± 2.18 Head 10 <0.021 ± <0.021 ± <0.021 ± <0.001 ± <0.001 ± <0.004 ± <0.014 ± 100 <0.021 ± <0.021 ± <0.021 ± ± ± <0.004 ± <0.014 ± 500 <0.021 ± <0.021 ± <0.021 ± 0.30 ± ± ± ± <0.021 ± <0.021 ± <0.021 ± 0.88 ± ± ± ± S15

17 Table S12: PFAA concentrations (mean ± standard deviation) in samples from the zucchini experiment expressed in ng/l (water) and ng/g fresh weight (plant tissues). The nominal concentrations in the nutrient solution are given in the left hand column. The concentrations in the plant tissues were corrected for the concentrations in the control plants (data not shown). PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA Water ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 1.75 Root 10 <0.021 ± 0.10 ± 0.14 ± 0.16 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± Stem 10 <0.021 ± <0.021 ± 0.14 ± ± 0.13 ± ± ± ± <0.021 ± <0.021 ± 1.19 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 2.03 Twig 10 <0.019 ± <0.019 ± <0.019 ± <0.019 ± <0.019 ± <0.019 ± <0.019 ± <0.019 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.89 Leaf ± ± ± ± ± ± ± 0.05 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 3.57 Fruit 10 <0.013 ± <0.013 ± <0.013 ± <0.013 ± <0.013 ± <0.013 ± <0.013 ± <0.013 ± ± ± ± ± ± ± 0.01 <0.013 ± <0.013 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± S16

18 Table S12: Continued PFDoA PFTrA PFTeA PFBS PFHxS Br-PFOS L-PFOS Water ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 12.7 Root ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 7.50 Stem 10 <0.021 ± <0.021 ± <0.021 ± <0.001 ± ± ± ± ± <0.021 ± <0.021 ± 0.34 ± ± ± ± ± ± ± 1.38 ± ± ± ± ± ± ± 2.69 ± ± ± ± 0.94 Twig 10 <0.019 ± <0.019 ± <0.019 ± <0.001 ± <0.001 ± <0.004 ± <0.014 ± ± <0.019 ± <0.019 ± 0.15 ± ± ± ± ± ± 0.03 <0.019 ± 0.93 ± ± ± ± ± ± 0.04 <0.019 ± 1.48 ± ± ± ± 0.18 Leaf 10 <0.030 ± <0.030 ± <0.030 ± 0.47 ± ± ± 0.10 ± ± <0.030 ± <0.030 ± 4.81 ± ± ± ± ± ± <0.030 ± 22.8 ± ± ± ± ± ± <0.030 ± 41.1 ± ± ± ± 6.51 Fruit 10 <0.013 ± <0.013 ± <0.013 ± <0.001 ± <0.001 ± <0.002 ± <0.009 ± 100 <0.013 ± <0.013 ± <0.013 ± 0.07 ± 0.04 <0.001 ± ± <0.009 ± 500 <0.013 ± <0.013 ± <0.013 ± 0.36 ± ± ± ± <0.013 ± <0.013 ± <0.013 ± 0.74 ± ± ± ± S17

19 Table S13: PFAA concentrations (mean ± standard deviation) in samples from the tomato experiment expressed in ng/l (water) and ng/g fresh weight (plant tissues). The nominal concentrations in the nutrient solution are given in the left hand column. The concentrations in the plant tissues were corrected for the concentrations in the control plants (data not shown). PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA Water ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 114 Root 10 <0.021 ± <0.021 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 69.9 Stem ± <0.033 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 11.3 Twig 10 <0.053 ± <0.053 ± ± ± ± 0.11 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 76.1 Leaf ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 151 Fruit 10 <0.013 ± <0.013 ± <0.013 ± <0.013 ± <0.013 ± <0.013 ± <0.013 ± ± ± ± ± ± <0.013 ± <0.013 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± S18

20 Table S13: Continued PFUnA PFDoA PFTrA PFTeA PFBS PFHxS Br-PFOS L-PFOS Water ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 240 Root ± ± ± ± 0.44 <0.001 ± 0.15 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 65.7 Stem ± ± <0.033 ± <0.033 ± ± ± ± ± ± ± ± <0.033 ± 0.56 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 43.9 Twig ± <0.053 ± <0.053 ± <0.053 ± 0.17 ± ± ± ± ± ± ± <0.053 ± 1.68 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 29.1 Leaf 10 <0.053 ± <0.053 ± <0.053 ± <0.053 ± 0.65 ± ± ± ± ± ± <0.053 ± <0.053 ± 6.96 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 130 Fruit 10 <0.013 ± <0.013 ± <0.013 ± <0.013 ± <0.001 ± <0.001 ± <0.002 ± <0.009 ± 100 <0.013 ± <0.013 ± <0.013 ± <0.013 ± ± <0.001 ± <0.002 ± <0.009 ± 1000 <0.013 ± <0.013 ± <0.013 ± <0.013 ± 0.27 ± ± <0.002 ± <0.009 ± ± <0.013 ± <0.013 ± <0.013 ± 2.73 ± ± ± ± 0.12 S19

21 1 0.1 Cabbage Zucchini Tomato Figure S5: Edible part/leaf concentration factor, calculated by dividing the PFAA concentration in the edible part by the PFAA concentration in the leaves. Logarithmic scale. The factor shown is the average of all plants with quantifiable concentrations (see tables S11-13). Error bars denote standard error. Table S14: Overview of various hydrophobicity parameters. Log k0 by de Voogt et al. [2], modelled log KOW by Arp et al. [3], Wang et al. [4] and Kelly et al. [5], log P 0 by Jing et al. [6] and log DOW values modelled with ACD/PhysChem Suite, taken from log k 0 Calculated log K OW log P 0' log D OW method HPLC COSMO-therm Sparc Voltammetry ph 5.5 ph7.4 ref de Voogt Arp Wang Arp Kelly Jing ACD/PhysChem Suite PFBA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFBS PFHxS PFOS S20

22 References 1. Eschauzier, C.; Haftka, J.; Stuyfzand, P. J.; De Voogt, P., Perfluorinated compounds in infiltrated river Rhine water and infiltrated rainwater in coastal dunes. Environmental Science and Technology 2010, 44, (19), de Voogt, P.; Zurano, L.; Serné, P.; Haftka, J. J. H., Experimental hydrophobicity parameters of perfluorinated alkylated substances from reversed-phase high-performance liquid chromatography. Environmental Chemistry 2012, 9, (6), Arp, H. P. H.; Niederer, C.; Goss, K. U., Predicting the partitioning behavior of various highly fluorinated compounds. Environmental Science & Technology 2006, 40, (23), Kelly, B. C.; Ikonomou, M. G.; Blair, J. D.; Surridge, B.; Hoover, D.; Grace, R.; Gobas, F., Perfluoroalkyl Contaminants in an Arctic Marine Food Web: Trophic Magnification and Wildlife Exposure. Environmental Science & Technology 2009, 43, (11), Wang, Z.; MacLeod, M.; Cousins, I. T.; Sheringer, M.; Hungerbuhler, K., Using COSMOtherm to Predict Physicochemical Properties of Poly-and Perfluorinated Alkyl Substances (PFAS). Environ. Chem. 2011, 8, Jing, P.; Rodgers, P. J.; Amemiya, S., High Lipophilicity of Perfluoroalkyl Carboxylate and Sulfonate: Implications for Their Membrane Permeability. J. Am.Chem. Soc. 2009, 131, (6), S21