Novel fluoroalkylated surfactants in soils following firefighting foam deployment during the Lac-Mégantic railway accident

Transcription

1 Supporting Information Novel fluoroalkylated surfactants in soils following firefighting foam deployment during the Lac-Mégantic railway accident Sandra Mejia-Avendaño a, Gabriel Munoz a,b, Sung Vo Duy b, Mélanie Desrosiers c, Paul Benoit d, Sébastien Sauvé b, Jinxia Liu a, * a Department of Civil Engineering, McGill University, Montreal, Quebec, H3A 0C3, Canada b Department of Chemistry, Université de Montréal, Montreal, Quebec, H3C 3J7, Canada c Centre d expertise en analyse environnementale du Québec (CEAEQ), ministère du Développement Durable, de l Environnement, et de la Lutte contre les changements climatiques, Quebec City, Quebec, G1P 3W8, Canada. d Direction générale de l analyse et de l expertise régionales - Estrie et Montérégie, ministère du Développement durable, de l Environnement, et de la Lutte contre les changements climatiques, Longueuil, Québec, J4K 2T5, Canada. *Corresponding author. Tel: ; fax: address: jinxia.liu@mcgill.ca 48 pages 13 tables 7 figures SI-1

2 Table of Contents Nomenclature of compounds with authentic standards... 4 Soil sampling... 6 Background soil... 6 Soil collected in Soil collected in Soil sampled from biopiles in Aqueous Film Forming Foams used during the 2013 firefighting at Lac-Mégantic... 9 Hydrocarbons in soil...10 Sample preparation...11 Analytical methods...12 Details on calibration curve...15 Investigated families of PFASs...16 Quantification of PFASs with and without standards...18 Levels of PFASs in the background soil...22 PFASs concentrations - Quantitative analytes...23 Trends of PFASs concentration profiles...30 Short-chain versus long-chain PFASs...31 List of detected PFASs in Full Scan MS mode...32 MS-MS spectra of qualitatively identified PFASs...35 References...48 SI-2

3 List of Tables Table SI- 1. Nomenclature table of compounds with authentic standards... 4 Table SI- 2. AFFF used during emergency measures... 9 Table SI- 3. Petroleum hydrocarbon (C10-C50) and moisture content in analyzed samples Table SI- 4. Quantitative analytical method...12 Table SI- 5. Monitored transitions for quantitative analytical method...13 Table SI- 6. Qualitative analytical method...14 Table SI- 7. LOD, LOQ and linearity range for each analyte (ng/ml) Table SI- 8. Investigated families of PFASs Table SI- 9. Semiquantitative and indicative analytes and corresponding reference analytes...20 Table SI- 10. Background PFASs concentrations in a clean soil...22 Table SI- 11. Concentrations of quantitative PFASs in soils...23 Table SI- 12. Summary of the statistics of the correlation of several pairs of key components..30 Table SI- 13. Detected PFASs in full scan MS mode...32 List of Figures Figure SI- 1. Location of Lac-Mégantic... 6 Figure SI- 2. Location of background soil collection Figure SI- 3. Zoom map of the sampled stations (Picture corresponding to July 10, 2013)... 7 Figure SI- 4. Map of the location of the sampling area Figure SI- 5. Map showing the location of the sampling points in July Figure SI- 6. Fraction of the long-chain PFASs relative to the total PFASs that were estimated using a semi-quantification approach Figure SI- 7. MS-MS spectra of identified PFASs...35 SI-3

4 Nomenclature of compounds with authentic standards Table SI- 1. Nomenclature table of compounds with authentic standards Acronym Name Formula PFAA Perfluoroalkyl acid F(CF2)nCOOH F(CF2)nSO3 - PFCA Perfluoroalkyl carboxylic acid F(CF2)nCOOH PFBA Perfluorobutanoic acid F(CF2)3COOH PFPeA Perfluoropentanoic acid F(CF2)4COOH PFHxA Perfluorohexanoic acid F(CF2)5COOH PFHpA Perfluoroheptanoic acid F(CF2)6COOH PFOA Perfluorooctanoic acid F(CF2)7COOH PFNA Perfluorononanoic acid F(CF2)8COOH PFDA Perfluorodecanoic acid F(CF2)9COOH PFUdA Perfluoroundecanoic acid F(CF2)10COOH PFDoA Perfluorodecanoic acid F(CF2)11COOH PFTrDA Perfluorotridecanoic acid F(CF2)12COOH PFTeDA Perfluorotetradecanoic acid F(CF2)13COOH PFSA Perfluoroalkyl sulfonic acid F(CF2)nSO3 - PFBS Perfluorobutane sulfonate F(CF2)4SO3 - PFHxS Perfluorohexane sulfonate F(CF2)6SO3 - PFHpS Perfluoroheptane sulfonate F(CF2)7SO3 - PFOS Perfluorooctane sulfonate F(CF2)8SO3 - PFDS Perfluorodecane sulfonate F(CF2)10SO3 - EtFOSA Ethyl perfluorooctane sulfonamide F(CF2)8SO2NHCH2CH3 FOSAA Perfluorooctane sulfonamidoacetic acid F(CF2)8SO2NHCH2COOH FOSA Perfluorooctane sulfonamide F(CF2)8SO2NH2 n:2 FTSA n:2 Fluorotelomer sulfonate F(CF2)nCH2CH2SO3-4:2 FTSA 4:2 Fluorotelomer sulfonate F(CF2)4CH2CH2SO3-6:2 FTSA 6:2 Fluorotelomer sulfonate F(CF2)6CH2CH2SO3-8:2 FTSA 8:2 Fluorotelomer sulfonate F(CF2)8CH2CH2SO3 - n:2 FTUA n:2 Fluorotelomer unsaturated acid F(CF2)n-1CF=CHCOOH 6:2 FTUA 6:2 Fluorotelomer unsaturated acid F(CF2)5CF=CHCOOH 8:2 FTUA 8:2 Fluorotelomer unsaturated acid F(CF2)7CF=CHCOOH n:3 FTCA n:3 Fluorotelomer carboxylic acid F(CF2)nCH2CH2COOH 5:3 FTCA 5:3 Fluorotelomer carboxylic acid F(CF2)5CH2CH2COOH 7:3 FTCA 7:3 Fluorotelomer carboxylic acid F(CF2)7CH2CH2COOH PFOSAm Perfluorooctanesulfonamide amine F(CF2)8SO2NHCH2CH2CH2N(CH3)2 PFOSAmS Perfluoroctanesulfonamide ammonium salt F(CF2)8SO2NHCH2CH2CH2N + (CH3)3 PFOAAmS Perfluorooctaneamide ammonium salt F(CF2)7CONHCH2CH2CH2N + (CH3)3 PFOSNO Perfluoroctanesulfonamide amine oxide F(CF2)8SO2NH(CH2)3NO(CH3)2 PFOANO Perfluorooctaneamide amine oxide F(CF2)7CONH(CH2)3NO(CH3)2 PFOSB Perfluoroctanesulfonamide betaine F(CF2)8SO2NH(CH2)3N + (CH3)2CH2COOH PFOAB Perfluorooctaneamide betaine F(CF2)7CONH(CH2)3N + (CH3)2CH2COOH 6:2FTAB 6:2 Fluorotelomer sulfonamide betaine F(CF2)6CH2CH2SO2NH(CH2)3N + (CH3)2CH2COOH 6:2FTNO 6:2 Fluorotelomer sulfonamide amine oxide F(CF2)6CH2CH2SO2NH(CH2)3NO(CH3)2 SI-4

5 Table SI-1 (Continued) Acronym Name Formula MPFBA Perfluoro-n-[1,2,3,4-13 C4]butanoic acid F( 13 CF2)3 13 COOH MPFHxA Perfluoro-n-[1,2-13 C2]hexanoic acid F(CF2)4 13 CF2 13 COOH MPFOA Perfluoro-n-[1,2,3,4-13 C4]octanoic acid F(CF2)4( 13 CF2)3 13 COOH MPFNA Perfluoro-n-[1,2,3,4,5-13 C5]nonanoic acid F(CF2)4( 13 CF2)4 13 COOH MPFDA Perfluoro-n-[1,2-13 C2]decanoic acid F(CF2)8 13 CF2 13 COOH MPFUdA Perfluoro-n-[1,2-13 C2]undecanoic acid F(CF2)9 13 CF2 13 COOH MPFDoA Perfluoro-n-[1,2-13 C2]dodecanoic acid F(CF2)10 13 CF2 13 COOH MPFHxS Perfluoro-1-hexane[ 18 O2]sulfonate F(CF2)6SO 16 O2 - MPFOS Perfluoro-1-[1,2,3,4-13 C4]octanesulfonate F(CF2)4( 13 CF2)4SO3 - d-etfosa-m Ethyl-d5-perfluorooctanesulfonamide F(CF2)8SO2NHCD2CD3 M6:2 FTUA 2H-perfluoro-[1,2-13 C2]-2-octenoic acid F(CF2)5CF= 13 CH 13 COOH M8:2 FTUA 2H-perfluoro-[1,2-13 C2]-1-decenoic acid F(CF2)7CF= 13 CH 13 COOH M6:2 FTSA 1H,1H,2H,2H-perfluoro-1-[1,2-13 C2]-octane sulfonate F(CF2)6 13 CH2 13 CH2SO3 - M8:2 FTSA 1H,1H,2H,2H-perfluoro-1-[1,2-13 C2]-decane sulfonate F(CF2)8 13 CH2 13 CH2SO3 - SI-5

6 Soil sampling The following map shows the location of Lac-Mégantic, Québec (Canada). Figure SI- 1. Location of Lac-Mégantic Four sets of samples were used for the study: background soil, soil collected in 2013, soil collected in 2015 and soil sampled from treatment biopiles. Details are given below. Background soil This soil was used to investigate the background PFASs levels before the accident, as well as to optimize the extraction method. It was sampled next to Chaudière River, approximately 5km away of the derailment site in Lac-Mégantic (Québec, Canada), on the east shore of the river - opposite side to the river than that of the accident. Figure SI- 2. Location of background soil collection. SI-6

7 Soil collected in 2013 Soil samples were collected on October 17 th, 2013 from 12 points close to the shore of Chaudière River. The location of the sampling stations is shown in the following aerial view. Figure SI- 3. Zoom map of the sampled stations (Picture corresponding to July 10, 2013). For reference, the following photograph, taken 7 days after the accident, shows the location of the sampling stations and also the site of the derailment (on the top-left corner) Figure SI- 4. Map of the location of the sampling area. SI-7

8 Soil collected in 2015 After the accident on July, 2013, the most heavily contaminated soil was excavated for offsite treatment. The remediation process is ongoing and some remaining soil was not excavated until Soil was sampled on July 15, Figure SI- 5 shows the location of the corresponding sampling points. Figure SI- 5. Map showing the location of the sampling points in July Soil sampled from biopiles in 2015 The contaminated soil resulting from the derailment was excavated for offsite treatment in biopiles by LVM, with the objective of remediating the high content of petroleum hydrocarbons in soil. Three biopiles constructed between 2013 and 2014 were sampled on July 15, SI-8

9 Aqueous Film Forming Foams used during the 2013 firefighting at Lac- Mégantic Golder Associés, Table SI- 2. AFFF used during emergency measures Brand name Product name Composition (according to MSDS) Ansul Ansulite ARC 3x6 Diethylene glycol butyl ether (3 7 %) Other (>60%) Chemguard Angus Fire Chemguard AR- AFFF C363 Niagara 1/3 AR- AFFF Ansul SILV-EX Plus Lauryl alcohol (1 2.5 %) Propylene glycol ( %) Other (>90%) Williams Fire Thunderstorm FC- 601A AR-AFFF Unifoam Unifoam A4P 3/6 Foam National Foam Universal Plus 3% / 6% AR-AFFF Diethylene glycol butyl ether (4 7 %) Proprietary hydrocarbon surfactants mixture (% not provided) Proprietary fluorosurfactant mixture (% not provided) Polysaccharide gum (1 2 %) Water (70 80 %) Sodium Chloride (5 10 %) 2-methylpentane-2,4-diol (1 7 %) 1,3,5-tris(2-hydroxyethyl)-hexahydro-1,3,5-triazine ( %) Iron (II) chloride (< 0.2 %) Water ( balance ) Diethylene glycol butyl ether (4 13 %) Proprietary hydrocarbon surfactants mixture (% not provided) Proprietary fluorosurfactant mixture (% not provided) Polysaccharide gum (1 2 %) Water ( balance ) Diethylene glycol butyl ether (3 7 %) Perfluoroalkylated polymer (< 2%) Dipropylene glycol methyl ether (2-5%) Proprietary mixture of synthetic detergents (4 10 %) Fluoroalkyl surfactant (0.5 2 %) Polysaccharide (0.5 2 %) Water (78 93 %) SI-9

10 Hydrocarbons in soil The concentration of petroleum hydrocarbon (C10-C50) in soil was investigated according to CEAEQ reference method. 2 Table SI- 3. Petroleum hydrocarbon (C10-C50) and moisture content in analyzed samples. Moisture C10-C50 Soil content (%) (mg/kg) LM <100 LM LM <100 LM <100 LM <100 LM <100 LM LM (10 cm) LM (20 cm) LM (30 cm) LM RC RC RC RC RC RC RC RC RC RC RC <100 RC BP BP BP2rep BP5 12 <100 BP5rep Class A 300 Class B 700 Class C 3500 SI-10

11 Sample preparation The extraction method is detailed elsewhere. 3 Approximately 2 grams of soil were placed in a 15mL polypropylene centrifuge tube, 2.5 ml of MeOH with 0.1%NH 4OH were added to each tube and the tubes were sonicated for 30 min and shaken in a rotational shaker for 60 min. They were centrifuged for 15 min at 4000g and the supernatant was pipetted out. The extraction was repeated two more times in the same fashion. The combined extracts were concentrated under a gentle stream of nitrogen at C to a volume of 2mL. The concentrated extracts were mixed with 50±5mg of ENVICarb for cleanup, vortexed for 30s and centrifuged at 20,000g for 20 min. The supernatant was pipetted out and stored at -20 C until analysis. Before analysis, the samples were spiked with a mix of all the internal standards for a final concentration of 2ng/mL each. SI-11

12 Analytical methods Details on the analytical methods are described in tables SI-3 to SI-5. Table SI- 4. Quantitative analytical method Instrument Ionization Acquisition mode Analytical column Delay column Column Temperature 40 C Mobile Phases Shimadzu Nexera UHPLC coupled to an AB Sciex 5500 QTrap mass spectrometer Positive and negative electrospray Multiple reaction monitoring (MRM) Agilent Zorbax SB-C8, 3.5 μm, 100 x 2.1 mm Kinetex EVO C18, 5 μm, 50 x 3.1 mm A: 0.15% acetic acid in LC-MS water B: 0.15% acetic acid in acetonitrile Gradient Profile Time (min) Percentage B Time (min) Stop 11.5 Injection Volume Calibration Quantified compounds 5 μl Linear calibration curve, 1/x weighted Analyte PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUdA PFDoA PFTrDA PFTeDA PFHxDA PFBS PFHxS PFHpS PFOS PFDS 4:2FTSA RT (min) Analyte 6:2FTSA 8:2FTSA 6:2FTUA 8:2FTUA 5:3FTCA 7:3FTCA EtFOSA FOSAA FOSA PFOSAm PFOSAmS PFOAAmS PFOSNO PFOANO PFOSB PFOAB 6:2 FTAB 6:2 FTNO RT (min) SI-12

13 Table SI- 5. Monitored transitions for quantitative analytical method Compound Ionization mode Quantifying transition Qualifying transition Internal standard IS transition PFBA MRM 213 > 169 MPFBA 217 > 172 PFPeA MRM 263 > 219 MPFHxA 315 > 270 PFHxA MRM 313 > > 119 MPFHxA 315 > 270 PFHpA MRM 363 > > 169 MPFOA 417 > 372 PFOA MRM 413 > > 169 MPFOA 417 > 372 PFNA MRM 463 > > 219 MPFNA 468 > 423 PFDA MRM 513 > > 169 MPFDA 515 > 470 PFUdA MRM 563 > > 169 MPFUdA 565 > 520 PFDoA MRM 613 > > 219 MPFDoA 615 > 570 PFTrDA MRM 663 > > 219 MPFDoA 615 > 570 PFTeDA MRM 713 > > 219 MPFDoA 615 > 570 PFHxDA MRM 813 > > 169 MPFDoA 615 > 570 PFBS MRM 299 > > 99 MPFHxS 403 > 103 PFHxS MRM 399 > > 99 MPFHxS 403 > 103 PFHpS MRM 499 > > 99 MPFOS 503 > 80 PFOS MRM 549 > > 99 MPFOS 503 > 80 PFDS MRM 599 > > 99 MPFOS 503 > 80 EtFOSA MRM 526 > > 219 d-etfosa-m 531 > 169 FOSAA MRM 556 > > 80 d-etfosa-m 531 > 169 FOSA MRM 498 > > 64 d-etfosa-m 531 > 169 4:2 FTSA MRM 327 > > 307 M6:2 FTSA 429 > 81 6:2 FTSA MRM 427 > > 407 M6:2 FTSA 429 > 81 8:2 FTSA MRM 527 > > 507 M8:2 FTSA 529 > 81 6:2 FTUA MRM 357 > > 143 M6:2 FTUA 359 > 294 8:2 FTUA MRM 457 > > 243 M8:2 FTUA 459 > 394 5:3 FTCA MRM 341 > > 217 MPFOA 417 > 372 7:3 FTCA MRM 441 > > 317 MPFDA 515 > 470 PFOSAm MRM 583 > > 219 MPFOS 503 > 80 PFOSAmS +MRM 599 > > 476 MPFOS 503 > 80 PFOAAmS +MRM 513 > > 426 MPFOA 417 > 372 PFOSNO MRM 599 > > 169 MPFOS 503 > 80 PFOANO MRM 513 > > 169 MPFOA 417 > 372 PFOSB MRM 641 > > 483 MPFOS 503 > 80 PFOAB MRM 555 > > 378 MPFOA 417 > 372 6:2 FTAB +MRM 569 > > 120 M6:2 FTSA 429 > 81 6:2 FTNO +MRM 527 > > 120 M6:2 FTSA 429 > 81 SI-13

14 Table SI- 6. Qualitative analytical method Instrument Ionization Dionex UHPLC system coupled to a Q-Exactive Orbitrap mass spectrometer Positive and negative heated electrospray Acquisition mode Full scan MS mode (R: 70,000 at m/z = 200) t-ms 2 mode Analytical Column Column Temperature 40 C Mobile Phases Thermo C18 Hypersil Gold column, 1.9 μm, 100 x 2.1mm A: 0.1% formic acid in LCMS water B: 0.1% formic acid in acetonitrile Gradient Profile: Time (min) Percentage B Flow Rate (ml/min) (Stop) Injection Volume 5 μl (Full scan) 10 μl (t-ms 2 ) SI-14

15 Details on calibration curve Details on the calibration of each analyte can be found in Table SI-7. The limit of detection (LOD) is defined as the lowest concentration at which S/N>3; the limit of quantitation (LOQ) is the lowest concentration at which 80%<Accuracy<120%. The concentration expressed in ng/ml is aproximately equivalent to ng/g (dry soil), since 2g of soil were extracted and the final volume of extract brought to 2mL. Table SI- 7. LOD, LOQ and linearity range for each analyte (ng/ml). Analyte LOD LOQ Linearity range PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUdA PFDoA PFTrDA PFTeDA PFBS PFHxS PFHpS PFOS PFDS EtFOSA FOSAA FOSA :2 FTSA :2 FTSA :2 FTSA :2 FTUA :2 FTUA :3 FTCA :3 FTCA PFOSNO PFOANO PFOSB PFOAB :2 FTAB :2 FTNO PFOSAm PFOSAmS PFOAAmS SI-15

16 Investigated families of PFASs The structures investigated in a qualitative manner have been previously reported 4-8. All the following structures were scouted qualitatively with high resolution mass spectrometry. Table SI- 8. Investigated families of PFASs. Acronym Name Structure Reference Perfluoroalkyl carboxylic acid Backe et al PFCA PFSA FASA Perfluoroalkyl sulfonic acid Perfluoroalkyl sulfonamide Place and Field 2012 Backe et al EtFASA Ethyl-perfluoroalkyl sulfonamide FASAA Perfluoroalkyl sulfonamidoacetic acid n:3 FTCA n:3 fluorotelomer carboxylic acid n:2 FTSA n:2 fluorotelomer sulfonic acid Backe et al n:2 FTUA n:2 fluorotelomer unsaturated acid PFAAAm Perfluoroalkylamido amine PFASAm Perfluoroalkylsulfonamido amine Place and Field 2012 Backe et al D Agostino and Mabury 2013 PFAAAmS Perfluoroalkyl-amido ammonium salt D Agostino and Mabury 2013 PFASAmS Perfluorotalkylsulfonamido ammonium salt SI-16

17 PFAANO Perfluoroalkyl-amido amine oxide D Agostino and Mabury 2013 PFASNO PFAAB PFASB n:2 FTNO n:2 FTAB Perfluorotalkylsulfinamido amine oxide Perfluoroalkyl-amido betaine Perfluoroalkylsulfonamido betaine n:2 fluorotelomer sulfonamde alkyl amine oxide n:2 fluorotelomer sulfonamide alkyl betaine n:2 fluorotelomer sulfonamide D Agostino and Mabury 2013 Backe et al D Agostino and Mabury 2013 Backe et al D Agostino and Mabury 2013 Place and Field 2012 Backe et al D Agostino and Mabury 2013 Munoz et al n:2 FTA n:3 FTB n:1:2 FTB n:2 FTSAS n:2 FTSASsulfoxide n:2 FTSHA n:2 FTSHAsulfoxide n:2:1 FTSC n:2 fluorotelomer sulfonamide amine n:3 fluorotelomer betaine n:1:2 fluorotelomer betaine n:2 fluorotelomermercaptoalkylamido sulfonate n:2 fluorotelomermercaptoalkylamido sulfonate-sulfoxide n:2 fluorotelomerthiohydroxyl ammonium n:2 fluorotelomerthiohydroxyl ammonium-sulfoxide n:2:1 fluorotelomermercaptoalkyl carboxylate Place and Field 2012 Backe et al D Agostino and Mabury 2013 Place and Field 2012 Backe et al D Agostino and Mabury 2013 Place and Field 2012 Backe et al D Agostino and Mabury 2013 Place and Field 2012 Backe et al D Agostino and Mabury 2013 Place and Field 2012 Backe et al D Agostino and Mabury 2013 D Agostino and Mabury 2013 D Agostino and Mabury 2013 SI-17

18 n:2:2 FTSC n:2 FTSAB n:2 FTSAAC n:2 FTSAA n:2:2 fluorotelomermercaptoalkyl carboxylate n:2 fluorotelomerthioalkylamido betaine n:2 fluorotelomerthioalkylamido amine carboxylate Fluorotelomer thioalkylamido amine D Agostino and Mabury 2013 D Agostino and Mabury 2013 Place and Field D Agostino and Mabury 2013 n:2 FTSoAAmS PFAAiPrE PFASAC Fluorotelomer sulfinyl alkylamido ammonium D Agostino and Mabury 2013 Perfluoroalkyl-amido amine isopropylester Backe et al Perfluoroalkylsulfonamido amino carboxylate Place and Field 2012 D Agostino and Mabury 2013 PFASBC Perfluoroalkylsulfonamido betaine carboxylate Place and Field 2012 D Agostino and Mabury 2013 PFACHS Perfluoroalkyl cyclohexane sulfonate Quantification of PFASs with and without standards The quantification of PFASs was classified in three different categories, depending on the quantitation performance: Quantitative (Qn), Semi-quantitative (Sq) and Indicative (Ql), explained below: o o Quantitative (Qn). Only those compound for which there are true standards (see Table SI-1) and that were analyzed in MRM mode are considered quantitative. Semi-quantitative (Sq). For families of compounds for which there is one true standard, the available compound is used to estimate the concentration of the rest of the congeners in the family with different chain lengths. This is accomplished in high resolution full scan MS mode, by assuming an equimolar response when compared to SI-18

19 o the standard and using the same internal standard for all the compounds in the family and the available native standard. Such is the case of n:2ftsa, n:2ftab and n:2ftno. For instance, 10:2-FTSA was semi-quantified based on the calibration curve of 8:2- FTSA and using M8:2-FTSA as internal standard. Indicative (Ql). For families of compounds for which there is not a true standard, the concentration is estimated by comparison with the calibration curve of a compound with a similar structure. As with the case of the semi-quantitation, an equimolar response is assumed, using the same internal standard as for the available analyte. Alhtough these results are only indicative, they can still be useful to to compare the order of magnitude of the analyte concentration between different types of samples. Table SI-8 shows a list of the proposed analytes with the reference standard used for estimation of the concentration. SI-19

20 Table SI- 9. Semiquantitative and indicative analytes and corresponding reference analytes. Analyte n Reference compound Internal standard n:2 FTSA 10, 12 8:2 FTSA M8:2 FTSA n:2 FTAB 8, 10, 12, 14 6:2 FTAB M6:2 FTSA n:2 FTNO 8, 10 6:2 FTNO M6:2 FTSA n:2 FTA 4, 6, 8, 10, 12 PFOSAm MPFOS n:3 FTB 5, 7, 9, 11, 13, 15 6:2FTAB M6:2FTS n:1:2 FTB 5, 7, 9, 11, 13, 15 6:2FTAB M6:2FTS n:2 FTSAS 6, 8, 10, 12, 14 8:2FTS M8:2FTS n:2 FTSAS-sulfoxide 6, 8, 10, 12 8:2FTS M8:2FTS n:2 FTSHA 4, 6, 8, 10, 12 PFOSAmS MPFOS SI-20

21 n:2 FTSHA-sulfoxide 4, 6, 8, 10 PFOSAmS MPFOS n:2 FTSAB 6, 8, 10, 12, 14 6:2FTAB M6:2FTS n:2 FTSAA 6, 8, 10, 12, 14 PFOSAm MPFOS n:2 FTSoAAmS 6, 8, 10 PFOSAmS MPFOS Compounds from Table SI-8 that were not detected in any of the samples have been omitted from Table SI-9. SI-21

22 Levels of PFASs in the background soil Clean soil collected from upstream Rivière Chaudière was extracted as described previously to establish the background levels of all quantifiable analytes in soil. Background concentrations in soil are presented in Table SI-10. Table SI- 10. Background PFASs concentrations in a clean soil Background concentration in soil ± SD (n=3) ng/g (dw) PFBA ± PFPeA ± PFHxA ± PFHpA ± PFOA ± PFNA ± PFDA ± PFUdA ± PFDoA ± PFTrDA ± PFTeDA ± PFBS ± PFHxS ± PFHpS ± PFOS ± PFDS ± EtFOSA <LOD FOSA ± FOSAA ± :2 FTSA <LOD 6:2 FTSA <LOD 8:2 FTSA ± :2 FTUA ± :2 FTUA ± :3 FTCA ± :3 FTCA <LOD PFOSAm <LOD PFOSAmS <LOD PFOAAmS <LOD PFOSNO <LOD PFOANO <LOD PFOSB ± PFOAB <LOD 6:2 FTAB <LOD 6:2 FTNO <LOD SI-22

23 PFASs concentrations - Quantitative analytes Table SI- 11. Concentrations of quantitative PFASs in soils (ng/g) LM LM LM LM PFBA 1.06 ± ± ± ± PFPeA 3.06 ± ± ± ± 0.09 PFHxA 1.11 ± ± ± ± PFHpA ± ± ± ± PFOA ± ± ± ± PFNA ± ± ± ± PFDA ± ± <LOD <LOD PFUdA ± ± <LOD <LOD PFDoA <LOD <LOD <LOD <LOD PFTrDA <LOD <LOD ± <LOD PFTeDA <LOD <LOD <LOD <LOD PFBS 1.25 ± 0.88 <LOD <LOD <LOD PFHxS ± ± <LOD <LOD PFHpS <LOD <LOD <LOD <LOD PFOS ± ± ± ± PFDS ± ± <LOD <LOD 4:2 FTSA ± ± ± ± :2 FTSA ± ± <LOD <LOD 8:2 FTSA ± <LOD <LOD <LOD EtFOSA <LOD ± <LOD ± FOSA ± ± ± ± FOSAA <LOD <LOD ± ± :3 FTCA ± ± ± ± :3 FTCA ± ± ± ± :2 FTUA ± ± ± ± :2 FTUA ± ± ± ± :2 FTAB 3.16 ± ± ± ± 0.66 PFOSB <LOD <LOD <LOD <LOD 6:2 FTNO <LOD <LOD <LOD <LOD PFOSNO <LOD <LOD <LOD <LOD PFOANO <LOD <LOD <LOD <LOD PFOSAm <LOD <LOD <LOD <LOD PFOSAmS <LOD <LOD ± <LOD ΣPFCA 6.58 ± ± ± ± 0.16 ΣPFSA 1.11 ± ± ± ± ΣPFAA 7.69 ± ± ± ± 0.17 ΣPFASs 12.4 ± ± ± ± 1.18 TPH < <100 <100 SI-23

24 LM LM LM LM (10) PFBA 2.42 ± ± ± ± PFPeA 13.0 ± ± ± ± 0.09 PFHxA 7.22 ± ± ± ± 0.23 PFHpA 3.31 ± ± ± ± 0.09 PFOA 1.42 ± ± ± ± 0.04 PFNA ± ± ± ± PFDA ± ± ± ± PFUdA ± <LOD <LOD ± PFDoA ± <LOD <LOD ± PFTrDA ± <LOD <LOD ± PFTeDA ± <LOD <LOD ± PFBS <LOD <LOD <LOD ± PFHxS ± ± <LOD ± PFHpS <LOD <LOD <LOD ± PFOS ± ± ± ± PFDS <LOD ± ± ± :2 FTSA ± ± ± ± :2 FTSA ± ± ± ± :2 FTSA ± ± ± ± 0.24 EtFOSA ± ± ± ± FOSA ± ± ± ± FOSAA ± <LOD <LOD ± :3 FTCA 1.09 ± ± ± ± :3 FTCA ± ± ± ± :2 FTUA ± <LOD ± ± :2 FTUA ± ± ± ± :2 FTAB 3.17 ± ± ± ± 1.3 PFOSB <LOD <LOD <LOD <LOD 6:2 FTNO <LOD <LOD <LOD <LOD PFOSNO <LOD ± <LOD <LOD PFOANO <LOD <LOD <LOD ± PFOSAm <LOD <LOD <LOD <LOD PFOSAmS <LOD <LOD <LOD <LOD ΣPFCA 28.3 ± ± ± ± 0.4 ΣPFSA ± ± ± ± ΣPFAA 28.4 ± ± ± ± 0.5 ΣPFASs 35.9 ± ± ± ± 2.9 TPH <100 < SI-24

25 LM (20) LM (30) LM BP1 PFBA 1.60 ± ± ± ± 2.5 PFPeA 5.27 ± ± ± ± 28 PFHxA 3.47 ± ± ± ± 21 PFHpA 1.94 ± ± ± ± 3.0 PFOA 2.97 ± ± ± ± 1.93 PFNA ± ± ± ± 0.34 PFDA ± ± ± ± 0.33 PFUdA ± <LOD ± ± PFDoA ± <LOD <LOD ± PFTrDA <LOD ± ± ± PFTeDA <LOD <LOD <LOD ± PFBS <LOD ± ± ± PFHxS ± ± ± ± PFHpS ± ± ± ± PFOS ± ± ± ± PFDS ± ± ± ± :2 FTSA ± ± ± ± :2 FTSA 1.11 ± ± ± ± :2 FTSA ± ± ± ± 9.1 EtFOSA ± ± ± ± FOSA ± ± ± ± FOSAA <LOD ± <LOD <LOD 5:3 FTCA 1.23 ± ± ± ± :3 FTCA ± ± ± ± :2 FTUA ± ± ± ± :2 FTUA ± ± ± ± :2 FTAB 8.18 ± ± ± ± 33 PFOSB <LOD <LOD <LOD <LOD 6:2 FTNO <LOD <LOD <LOD ± PFOSNO <LOD ± <LOD <LOD PFOANO ± <LOD <LOD ± PFOSAm <LOD <LOD <LOD <LOD PFOSAmS <LOD <LOD <LOD <LOD ΣPFCA 16.2 ± ± ± ± 55 ΣPFSA ± ± ± ± ΣPFAA 16.6 ± ± ± ± 55 ΣPFASs 29.3 ± ± ± ± 128 TPH SI-25

26 BP2 BP22 BP5 BP52 PFBA 6.74 ± ± ± ± PFPeA 48.9 ± ± ± ± 0.27 PFHxA 20.3 ± ± ± ± PFHpA 8.29 ± ± ± ± PFOA 4.27 ± ± ± ± PFNA ± ± ± ± PFDA ± ± ± ± PFUdA ± <LOD ± <LOD PFDoA <LOD <LOD ± <LOD PFTrDA <LOD <LOD ± <LOD PFTeDA <LOD <LOD ± <LOD PFBS ± <LOD ± <LOD PFHxS ± ± ± ± PFHpS <LOD <LOD ± <LOD PFOS ± ± ± ± PFDS ± ± ± ± :2 FTSA ± ± ± ± :2 FTSA 1.37 ± ± ± ± :2 FTSA ± ± ± ± EtFOSA <LOD ± <LOD ± FOSA ± ± ± ± FOSAA <LOD <LOD <LOD <LOD 5:3 FTCA ± ± ± ± :3 FTCA ± ± ± ± :2 FTUA ± ± ± <LOD 8:2 FTUA ± ± ± ± :2 FTAB 13.0 ± ± ± ± 0.66 PFOSB <LOD <LOD <LOD <LOD 6:2 FTNO <LOD <LOD ± <LOD PFOSNO <LOD <LOD <LOD <LOD PFOANO ± <LOD <LOD <LOD PFOSAm <LOD <LOD <LOD <LOD PFOSAmS <LOD <LOD <LOD <LOD ΣPFCA 89.2 ± ± ± ± 0.49 ΣPFSA ± ± ± ± ΣPFAA 89.4 ± ± ± ± 0.50 ΣPFASs 106 ± ± ± ± 0.76 TPH < SI-26

27 RC RC RC RC PFBA 3.22 ± ± ± ± 0.03 PFPeA 21.6 ± ± ± ± 0.38 PFHxA 25.9 ± ± ± ± 0.16 PFHpA 3.45 ± ± ± ± 0.03 PFOA 3.45 ± ± ± ± 0.03 PFNA ± ± ± ± PFDA ± ± ± ± PFUdA ± ± ± ± PFDoA ± ± ± <LOD PFTrDA <LOD ± ± ± PFTeDA ± ± ± <LOD PFBS ± ± ± <LOD PFHxS ± ± ± ± PFHpS ± ± ± <LOD PFOS ± ± ± ± PFDS ± ± ± ± :2 FTSA ± ± ± ± :2 FTSA 40.6 ± ± ± ± :2 FTSA 9.58 ± ± ± ± 0.06 EtFOSA <LOD <LOD <LOD <LOD FOSA ± ± ± ± FOSAA <LOD <LOD <LOD <LOD 5:3 FTCA 2.25 ± ± ± ± :3 FTCA ± ± ± ± :2 FTUA ± ± ± ± :2 FTUA ± ± ± ± :2 FTAB 149 ± ± ± ± 2.8 PFOSB <LOD <LOD <LOD <LOD 6:2 FTNO <LOD <LOD <LOD <LOD PFOSNO <LOD <LOD <LOD <LOD PFOANO <LOD <LOD <LOD <LOD PFOSAm <LOD <LOD <LOD <LOD PFOSAmS <LOD <LOD <LOD ± ΣPFCA 58.9 ± ± ± ± 0.6 ΣPFSA ± ± ± ± ΣPFAA 59.3 ± ± ± ± 0.6 ΣPFASs 261 ± ± ± ± 3.4 TPH SI-27

28 RC RC RC RC PFBA 3.04 ± ± ± ± 0.14 PFPeA 4.86 ± ± ± ± 0.5 PFHxA 18.2 ± ± ± ± 0.33 PFHpA 10.8 ± ± ± ± 0.17 PFOA 21.6 ± ± ± ± 0.11 PFNA 16.1 ± ± ± ± PFDA 24.5 ± ± ± ± PFUdA 7.94 ± ± ± ± PFDoA 13.9 ± ± ± 0.9 <LOD PFTrDA 3.14 ± ± ± ± PFTeDA 7.17 ± ± ± 0.64 <LOD PFBS 2.37 ± ± ± 1.72 <LOD PFHxS ± ± ± ± PFHpS ± ± ± <LOD PFOS ± ± ± ± PFDS ± ± ± ± :2 FTSA ± ± ± ± :2 FTSA 1302 ± ± ± ± 19 8:2 FTSA 304 ± ± ± ± 12 EtFOSA <LOD ± ± <LOD FOSA ± ± ± ± FOSAA ± ± ± <LOD 5:3 FTCA 5.38 ± ± ± ± :3 FTCA 8.96 ± ± ± ± :2 FTUA 3.01 ± ± ± ± :2 FTUA 2.38 ± ± ± ± :2 FTAB 1828 ± ± ± ± 5.8 PFOSB ± ± ± <LOD 6:2 FTNO <LOD <LOD <LOD <LOD PFOSNO <LOD <LOD ± <LOD PFOANO ± ± ± 2.79 <LOD PFOSAm 4.57 ± ± ± 0.49 <LOD PFOSAmS <LOD <LOD <LOD <LOD ΣPFCA 131 ± ± ± ± 1.3 ΣPFSA 12.9 ± ± ± ± ΣPFAA 144 ± ± ± ± 1.2 ΣPFASs 3606 ± ± ± ± 31 TPH SI-28

29 RC RC RC RC PFBA ± ± ± ± 0.7 PFPeA 1.73 ± ± ± ± 2.2 PFHxA 4.10 ± ± ± ± 1.7 PFHpA 1.02 ± ± ± ± 0.6 PFOA 2.06 ± ± ± ± 0.46 PFNA 1.14 ± ± ± ± 0.33 PFDA 6.00 ± ± ± ± 0.04 PFUdA 2.36 ± ± <LOD ± PFDoA 4.20 ± ± 0.09 <LOD ± PFTrDA ± ± <LOD ± PFTeDA 2.05 ± ± <LOD ± PFBS ± ± <LOD ± PFHxS ± ± <LOD ± PFHpS 1.62 ± ± <LOD ± PFOS 1.88 ± ± ± ± PFDS 12.2 ± ± <LOD ± :2 FTSA ± ± ± ± :2 FTSA 106 ± ± ± ± 5.2 8:2 FTSA 65.3 ± ± ± ± 1.7 EtFOSA <LOD ± <LOD <LOD FOSA ± ± ± ± FOSAA <LOD <LOD <LOD <LOD 5:3 FTCA 1.75 ± ± ± ± 3.1 7:3 FTCA ± ± ± ± :2 FTUA ± ± ± ± :2 FTUA ± ± ± ± :2 FTAB 142 ± ± ± ± 155 PFOSB ± ± <LOD <LOD 6:2 FTNO ± ± 0.08 <LOD <LOD PFOSNO <LOD ± <LOD <LOD PFOANO <LOD <LOD <LOD <LOD PFOSAm ± ± <LOD <LOD PFOSAmS ± ± <LOD <LOD ΣPFCA 25.9 ± ± ± ± 5 ΣPFSA 12.4 ± ± ± ± 0.24 ΣPFAA 38.3 ± ± ± ± 6 ΣPFASs 356 ± ± ± ± 144 TPH < SI-29

30 Trends of PFASs concentration profiles Table SI- 12. Summary of the statistics of the correlation of several pairs of key components. Independent Dependent Sample type Slope Tau p-value TPH ΣPFASs E E-04 Biopile E-03 ΣPFASs ΣPFCAs E E-07 Biopile E-06 ΣPFASs ΣFTSAs E E-09 Biopile E-06 ΣPFASs 6:2 FTAB E E-07 Biopile E-05 ΣFTSAs ΣPFCAs E E-04 Biopile E-06 SI-30

31 Short-chain versus long-chain PFASs 1.0 RC RC RC RC RC RC RC RC RC RC RC RC BP1 BP2 BP22 BP5 BP52 LM LM LM LM LM LM LM LM (10) LM (20) LM (30) LM Fraction of long chain PFAS, estimation Figure SI- 6. Fraction of the long-chain PFASs relative to the total PFASs that were estimated using a semi-quantification approach. SI-31

32 List of detected PFASs in Full Scan MS mode The list of all detected PFASs in full scan MS mode is presented in the following table, along with theoretical and observed m/z, error and retention time. Table SI- 13. Detected PFASs in full scan MS mode Acronym M +, [M+H] + or [M-H] - Theoretical m/z Observed m/z Error (ppm) Retention time min) MPFBA [ 13 C4F7O2] MPFHxA [ 13 C2C4F1102] MPFOA [ 13 C4C4F15O2] MPFNA [ 13 C5C4F17O2] MPFDA [ 13 C2C8F19O2] MPFUdA [ 13 C2C9F21O2] MPFDoA [ 13 C2C10F23O2] MPFHxS [C6F13S 18 O2O] MPFOS [ 13 C4C4F17SO3] d-etfosa-m [ 13 C2C6F13H4SO3] M6:2 FTUA [ 13 C2C8F17H4SO3] M8:2 FTUA [ 13 C2C6F12HO2] M6:2 FTSA [ 13 C2C8F16HO2] M8:2 FTSA [C10F17D5NSO2] PFBA [C4F7O2] PFPeA [C5F9O2] PFHxA [C6F11O2] PFHpA [C7F13O2] PFOA [C8F15O2] PFNA [C9F17O2] PFDA [C10F19O2] PFUdA [C11F21O2] PFDoA [C12F23O2] PFTrDA [C13F25O2] PFTeDA [C14F27O2] PFBS [C4F9SO3] PFHxS [C6F13SO3] PFHpS [C7F15SO3] PFOS [C8F17SO3] PFDS [C10F21SO3] EtFOSA [C10F17H5NSO2] FOSAA [C10F17H3NSO4] FOSA [C8F17HNSO2] :2 FTSA [C6F9H4SO3] :2 FTSA [C8F13H4SO3] :2 FTSA [C10F17H4SO3] :2 FTUA [C8F12HO2] :2 FTUA [C10F16HO2] :3 FTCA [C8F11H4O2] :3 FTCA [C10F15 H4 O2] PFOSAm [C13F17H14N2SO2] PFOSAmS C14F17H16N2SO SI-32

33 Acronym M +, [M+H] + or [M-H] - Theoretical m/z Observed m/z Error (ppm) Retention time min) PFOSNO [C13F17H14N2SO3] PFOANO [C13F15H14N2O2] PFOSB [C15F17H16N2SO4] :2FTAB [C15F13H20N2SO4] :2FTNO [C13F13H18N2SO3] :2 FTSA a [C12F21H4SO3] :2 FTSA [C14F25H4SO3] :2 FTAB b [C17F17H20N2SO4] :2 FTAB [C19F21H20N2SO4] :2 FTAB [C21F25H20N2SO4] :2 FTAB [C23F29H20N2SO4] :2 FTNO c [C 15F 17H 18N 2SO 3] :2 FTNO [C17F21H18N2SO3] :2 FTA [C11F9H18N2SO2] :2 FTA d [C13F13H18N2SO2] :2 FTA [C15F17H18N2SO2] :2 FTA [C17F21H18N2SO2] :2 FTA [C19F25H18N2SO2] :3 FTB [C12F11H15NO2] :3 FTB e [C14F15H15NO2] :3 FTB [C16F19H15NO2] :3 FTB [C18F23H15NO2] :3 FTB [C20F27H15NO2] :3 FTB [C22F31H15NO2] :1:2 FTB [C12F12H14NO2] :1:2 FTB f [C14F16H14NO2] :1:2 FTB [C16F20H14NO2] :1:2 FTB [C18F24H14NO2] :1:2 FTB [C20F28H14NO2] :1:2 FTB [C22F32H14NO2] :2 FTSAS g [C15F13H17NS2O4] :2 FTSAS [C17F17H17NS2O4] :2 FTSAS [C19F21H17NS2O4] :2 FTSAS [C21F25H17NS2O4] :2 FTSAS [C23F29H17NS2O4] :2 FTSAS sulfoxide [C16F13H22N2SO2] :2 FTSAS sulfoxide h [C18F17H22N2SO2] :2 FTSAS sulfoxide [C20F21H22N2SO2] :2 FTSAS sulfoxide [C22F25H22N2SO2] :2 FTSHA C12F9H19NSO :2 FTSHA i C14F13H19NSO :2 FTSHA C16F17H19NSO :2 FTSHA C18F21H19NSO :2 FTSHA C20F25H19NSO :2 FTSHA sulfoxide C12F9H19NSO :2 FTSHA sulfoxide C14F13H19NSO :2 FTSHA sulfoxide j C16F17H19NSO :2 FTSHA sulfoxide C18F21H19NSO :2 FTSAB k [C17F13H22N2SO3] :2 FTSAB [C19F17H22N2SO3] :2 FTSAB [C21F21H22N2SO3] SI-33

34 Acronym M +, [M+H] + or [M-H] - Theoretical m/z Observed m/z Error (ppm) Retention time min) 12:2 FTSAB [C23F25H22N2SO3] :2 FTSAB [C25F29H22N2SO3] :2 FTSAA l [C15F13H20N2SO] :2 FTSAA [C17F17H20N2SO] :2 FTSAA [C19F21H20N2SO] :2 FTSAA [C21F25H20N2SO] :2 FTSAA [C23F29H20N2SO] :2 FTSoAAmS C16F13H22N2SO :2 FTSoAAmS m C18F17H22N2SO :2 FTSoAAmS C20F21H22N2SO a b c d e f g h i j k l m MS-MS spectrum in Figure SI-7a MS-MS spectrum in Figure SI-7b MS-MS spectrum in Figure SI-7c MS-MS spectrum in Figure SI-7d MS-MS spectrum in Figure SI-7e MS-MS spectrum in Figure SI-7f MS-MS spectrum in Figure SI-7g MS-MS spectrum in Figure SI-7h MS-MS spectrum in Figure SI-7i MS-MS spectrum in Figure SI-7j MS-MS spectrum in Figure SI-7k MS-MS spectrum in Figure SI-7l MS-MS spectrum in Figure SI-7m SI-34

35 MS-MS spectra of qualitatively identified PFASs Figure SI- 7a. MS-MS spectrum of 10:2 FTSA

36 Figure SI- 7b. MS-MS spectrum of 8:2 FTAB SI-36

37 Figure SI- 7c. MS-MS spectrum of 8:2 FTNO SI-37

38 Figure SI- 7d. MS-MS spectrum of 6:2 FTA SI-38

39 Figure SI- 7e. MS-MS spectrum of 7:3 FTB SI-39

40 Figure SI- 7f. MS-MS spectrum of 7:1:2 FTB SI-40

41 Figure SI- 7g. MS-MS spectrum of 6:2 FTSAS SI-41

42 Figure SI- 7h. MS-MS spectrum of 8:2 FTSAS-sulfoxide SI-42

43 Figure SI- 7i. MS-MS spectrum of 6:2 FTSHA SI-43

44 Figure SI- 7j. MS-MS spectrum of 8:2 FTSHA-sulfoxide SI-44

45 Figure SI- 7k. MS-MS spectra of 6:2 FTSAB

46 Figure SI- 7l. MS-MS spectrum of 6:2 FTSAA

47 Figure SI- 7m. MS-MS spectrum of 8:2 FTSoAAmS SI-47

48 References 1. Golder Associés, Rapport de caractérisation de la Rivière Chaudière. In Rapport présenté au Ministère Développement Durable, de l Environnement, de la Faune et des Parcs, Direction régionale du Centre de contrôle environnemental de la Capitale-Nationale et de la Chaudière-Appalaches, 2014; p 75p. 2. CEAEQ, Détermination des hydrocarbures pétroliers (C10 à C50) : dosage par chromatographie en phase gazeuse couplée à un étecteur à ionisation de flamme. In MA HYD Rev. 3, Ministère du Développement durable, de l;environnement, et Lutte contre les changements climatiques du Québec, Centre d'expertise en analyse environnementale du Québec.: 2016; p Mejia-Avendaño, S.; Munoz, G.; Sauvé, S.; Liu, J., Assessment of the influence of soil characteristics and hydrocarbon fuel co-contamination on the solvent extraction of per- and polyfluoroalkyl substances. Analytical Chemistry 2017, 89, (4), Backe, W. J.; Day, T. C.; Field, J. A., Zwitterionic, Cationic, and Anionic Fluorinated Chemicals in Aqueous Film Forming Foam Formulations and Groundwater from U.S. Military Bases by Nonaqueous Large-Volume Injection HPLC-MS/MS. Environmental Science & Technology 2013, 47, (10), Place, B. J.; Field, J. A., Identification of Novel Fluorochemicals in Aqueous Film- Forming Foams Used by the US Military. Environmental Science & Technology 2012, 46, (13), Munoz, G.; Vo Duy, S.; Labadie, P.; Botta, F.; Budzinski, H.; Lestremau, F.; Liu, J.; Sauvé, S., Analysis of zwitterionic, cationic, and anionic poly- and perfluoroalkyl surfactants in sediments by liquid chromatography polarity-switching electrospray ionization coupled to high resolution mass spectrometry. Talanta 2016, 152, D Agostino, L. A.; Mabury, S. A., Identification of Novel Fluorinated Surfactants in Aqueous Film Forming Foams and Commercial Surfactant Concentrates. Environmental Science & Technology 2013, 48, (1), Munoz, G.; Desrosiers, M.; Duy, S. V.; Labadie, P.; Budzinski, H.; Liu, J.; Sauvé, S., Environmental Occurrence of Perfluoroalkyl Acids and Novel Fluorotelomer Surfactants in the Freshwater Fish Catostomus commersonii and Sediments Following Firefighting Foam Deployment at the Lac-Mégantic Railway Accident. Environmental Science & Technology 2017, 51, (3),