Supporting information

Transcription

1 Supporting information PFOA and PFOS Are Generated from Zwitterionic and Cationic Precursor Compounds During Water Disinfection with Chlorine or Ozone Feng Xiao*,, Ryan A. Hanson, Svetlana A. Golovko, Mikhail Y. Golovko, William A. Arnold Department of Civil Engineering, University of North Dakota, 24 Centennial Drive Stop 85, Grand Forks, North Dakota 5822, United States Department of Biomedical Sciences, University of North Dakota, Columbia Road North Stop 97, Grand Forks, ND 5822, United States Department of Civil, Environmental, and Geo-Engineering, University of Minnesota, 5 Pillsbury Drive Southeast, Minneapolis, Minnesota 55455, United States *corresponding author contact information: Phone: ; fax: ; addresses: Feng.Xiao@engr.UND.edu; fxiaoee@gmail.com S

2 Contents Surface water treatment details UPLC QToF-MS method Table Sa. Formulas and confirmed or proposed structures of identified degradation products of PFOAB and during chlorination (NaOCl) and ozonation (O ) by high-resolution mass spectrometry Table Sb. Formulas and confirmed or proposed structures of identified degradation products of PFOAAmS and PFOSAmS during chlorination (NaOCl) and ozonation (O ) by high-resolution mass spectrometry... 6 Figure S. Removal of four zwitterionic and cationic PFASs at various concentrations by coagulation/flocculation using alum Figure S2. Degradation of and PFOSAmS during chlorination in pretreated surface water (after coagulation/flocculation and paper filtration) Figure S. Degradation of a mixture of PFOAB, PFOAAmS,, and PFOSAmS during chlorination in buffered DI water at ph of ~7.4 at relatively low (<.2 μmol/l) and high ( μmol/l) concentrations Figure S4. Degradation of /PFOSAmS and corresponding generation of PFOS from a -d reaction between /PFOSAmS and chlorine in buffered DI water Figure S5. Degradation of PFOAB/PFOAAmS and corresponding generation of PFOA from a -d reaction between PFOAB/PFOAAmS and chlorine in buffered DI water Figure S6. Degradation of a mixture of four precursor compounds (PFOAB, PFOAAmS,, and PFOSAmS) during ozonation in pre-treated surface water and generation of PFOA and PFOS in this process.... Figure S7a. Compounds # ( 484.) and #4 (PFOA; ) generated during the reaction between chlorine and PFOAB... Figure S7b. MS E (upper figure) and MS (bottom figure) spectra of compound # ( 484. at UPLC retention time (RT) of 4.88 min) identified as a result of the reaction between PFOAB and chlorine.... Figure S8a. Compounds # ( 484.), #2 ( ), # ( 485.7), and #4 (PFOA; ) generated during the reaction between PFOAB and ozone.... Figure S8b. MS E (upper figure) and MS (bottom figure) spectra of compound # ( 484. at UPLC RT of 4.8 min) identified as a result of the reaction between PFOAB and ozone Figure S8c. MS E (upper figure) and MS (bottom figure) spectra of compound #2 ( at UPLC RT of 4.77 min) identified as a result of the reaction between PFOAB and ozone Figure S8d. MS E (upper figure) and MS (bottom figure) spectra of compound # ( at UPLC RT of 4.72 min) identified as a result of the reaction between PFOAB and ozone.... Figure S9a. Compounds # ( 484.), #2 ( ), and #4 (PFOA; ) generated during the reaction between PFOAAmS and ozone.... Figure S9b. MS E (upper figure) and MS (bottom figure) spectra of compound # ( Figure Sa. Compounds #7 ( ), #8 ( at 5.7 min), #9 (PFOSA; ), and # (PFOS; 498.9) generated during the reaction between and chlorine Figure Sb. MS E (upper figure) and MS (bottom figure) spectra of compound #7 ( at UPLC RT of 8 min) identified as a result of the reaction between and chlorine S2

3 Figure Sc. MS E (upper figure) and MS (bottom figure) spectra of compound #8 ( at UPLC RT of 5.69 min) identified as a result of the reaction between and chlorine Figure Sd. MS E (upper figure) and MS (bottom figure) spectra of compound #9 (PFOSA; at UPLC RT of 5.52 min) identified as a result of the reaction between and chlorine Figure Sa. Compounds #4 (PFOA; ), #5 ( 57.5), #6 ( 58.98), #7 ( ), #8 ( ), #9 (PFOSA; ), and # (PFOS; 498.9) identified as a result of the reaction between and ozone Figure Sb. MS E (upper figure) and MS (bottom figure) spectra of compound #6 ( at UPLC RT of 5.87 min) identified as a result of the reaction between and ozone Figure Sc. MS E (upper figure) and MS (bottom figure) spectra of compound #7 ( at UPLC RT of 8 min) identified as a result of the reaction between and ozone Figure Sd. MS E (upper figure) and MS (bottom figure) spectra of compound #8 ( at UPLC RT of 5.6 min) identified as a result of the reaction between and ozone Figure Se. MS E (upper figure) and MS (bottom figure) spectra of compound #9 (PFOSA; at UPLC RT of 5.52 min) identified as a result of the reaction between and ozone Figure S2a. Compounds #7 ( ), #8 ( ), #9 (PFOSA; ), and # (PFOS; 498.9) generated during the reaction between PFOSAmS and chlorine Figure S2b. MS E (upper figure) and MS (bottom figure) spectra of compound #7 ( at UPLC RT of 8 min) identified as a result of the reaction between PFOSAmS and chlorine... 2 Figure S2c. MS E (upper figure) and MS (bottom figure) spectra of compound #8 ( at UPLC RT of 4.92 min) identified as a result of the reaction between PFOSAmS and chlorine... 2 Figure S2d. MS E (upper figure) and MS (bottom figure) spectra of compound #9 (PFOSA; at UPLC RT of 5.52 min) identified as a result of the reaction between PFOSAmS and chlorine Figure S. Compounds #4 (PFOA), #9 (PFOSA; ), and # (PFOS) generated during the reaction between PFOSAmS and ozone Figure S4a. UPLC chromatogram of a standard of PFOSA Figure S4b. MS E (upper figure) and MS (bottom figure) spectra of a standard of PFOSA at UPLC RT of min Figure S5. Degradation of ((a) and (b)) and PFOSAmS ((c) and (d)) during ozonation in presence of 5 mmol/l tertiary butanol References of Supporting Information... 2 S

4 Surface water treatment details. Coagulation and flocculation of FA/FS-spiked surface river water were performed in a jar tester with six square, 2-L jars and with alum as the coagulant. After a known volume of alum stock solution ( g/l) was added to the solution in the jar, the stirrer immediately mixed the solution at 5 rpm for min coagulation and then at 4 rpm for 2 min flocculation, followed by -min settling. Aliquots of solution were taken before coagulation and after settling and microfiltered (.45 μm) to HPLC vials for further analysis. The supernatant after settling was filtered through a Whatman filter paper and the filtrate was treated by breakpoint chlorination with sodium hypochlorite (NaOCl) (Acros Organics) or conventional ozonation. Chlorination of FA/FS in the pretreated surface water or buffered distilled (DI) water (with - mol/l sodium bicarbonate; ph: ) was conducted in a series of 6-mL amber glass tubes (test tubes) corresponding to different chlorination time. The water was dosed with NaOCl at a free chlorine dose of 5. mg/l after the breakpoint. After a certain chlorination time, samples were taken from a test tube and a control tube, quenched with sodium thiosulfate at a 5: molar ratio to the initial chlorine dose and microfiltered (.45 μm) to HPLC vials for further analysis. A second set of tubes with the same concentrations of FA/FS in the pretreated surface water or buffered DI water were also prepared as controls to assess the possible loss of FA/FS due to hydrolysis and adsorption (without disinfectants). We did not observe the generation of PFOA and PFOS in the control tubes in as long as three days. The concentrations of a FA and FS in the control tubes varied by that was generally within the range of sampling and analytical variability; no significant concentration decline of a FA and FS was observed in the control tubes. The residual free chlorine was measured by the conventional DPD method by means of a Hach (Loveland, CO) chlorine test kit including a colorimeter. The residual free chlorine was mg/l after.5. h, which declined to mg/l after 2 h. Ozonation experiments were also performed by bubbling ozone gas through an air stone diffuser for up to 9 min. Ozone was generated by an ozone generator (model: Z-7G, capacity: 7 g O /h; A2Z Ozone Inc., Louisville, KY) with oxygen as the source. Dissolved ozone concentrations in the buffered DI water were measured spectrophotometrically (254 nm; ε = 295 M cm ) 2 by a UV-visible spectrophotometer (Evolution TM 2, Thermo Scientific) and by the indigo method using a Hach Ozone test kit and a Hach DR 2 spectrophotometer (Hach Inc., Loveland, CO) in the pretreated surface water. Samples were taken at different ozonation time, quenched with sodium thiosulfate at a 5: molar ratio to the initial ozone dose, and microfiltered (.45 μm) to HPLC vials for further analysis. In initial experiments, chlorination or ozonation (with a higher ozone dose of 7.6 mg/l) was conducted in pretreated water with all the four FAs and FSs; this was to provide a baseline for subsequent degradation experiments with an individual FA/FS. Certain ozonation experiments were conducted in the presence of a strong OH scavenger (5 mmol/l tertiary butanol,4 (99.5 extra pure, Acros Organics)) in order to study the generation of PFOA/PFOS by direct ozonation. Six procedural blanks were prepared with buffered DI water and were treated via the same coagulation/flocculation, sedimentation, filtration, and disinfection processes without spiking any PFASs. FA and FS compounds were not found in the six procedure blanks; PFOS and PFOA were detected in one of the procedural blanks with concentrations lower than LOQs (see below for values). UPLC QToF-MS method. The analysis was carried out on a Waters Acquity ultrahigh pressure liquid chromatography (UPLC) system coupled with a Waters hybrid QToF-MS (Synapt G2-S, Waters Corporation, Milford, MA, USA) available in the Department of Biomedical Sciences of University of North Dakota. Chromatography was performed using a Waters Acquity UPLC BEH Shield RP8 column ( 2. mm; Å;.7 μm) with a Waters Acquity UPLC BEH Shield RP8 VanGuard pre-column (5 2. mm; Å;.7 μm). The mobile phase consisted of eluent A (2 mm ammonium formate in Optima TM water; LC/MS grade) and eluent B (2 mm ammonium formate in Optima TM methanol; LC/MS grade). The elution started at 2 B for.5 min and then was linearly increased to 85 B in 5 min, further increased to 98 B in. min and kept isocratic S4

5 for.5 min. At 7. min, the A/B ratio changed back to the initial value of 8/2 over. min to re-equilibrate the column for another. min. Analytes were eluted using a Waters Acquity UPLC pump with a wellplate autosampler at 8 C. The flow rate was maintained at.45 ml/min, and the column temperature was 55 C. Mass spectrometry analysis was performed using the Synapt G2-S QToF-MS with an ESI source operated in either a negative or positive ion mode (ESI - or ESI + ). MS operating conditions were as follows: cone voltage, 2 V; capillary voltage,.8 kv; source temperature, C; desolvation temperature, 5 C; cone gas flow rate, L/h; and desolvation gas flow,, L/h. The analyzer was operated with an extended dynamic range at, resolution (fwhm at 554) with an acquisition time of.s. The Synapt G2-S ToF MS E mode was used to collect data with the T-wave element alternated between a low energy of 2V (MS) and high energy (MS E ) states in which the transfer T-wave element voltage ranged from 25 V. 5 Leucine enkephalin (4 pg/μl) was infused at a rate of μl/min for mass correction. MassLynx V4. software (Waters) was used for instrument control, acquisition, and mass analysis. The structural information of the degradation products was obtained by the state-of-the-art MS E function that allows the simultaneous acquisition of both MS and MS/MS fragmentation during a single chromatographic run. 6 Quantification of all target PFASs (four FA and FS compounds, PFOS, and PFOA) were made based on their values and UPLC retention times relative to a six point external calibration standard series. The limit of quantification (LOQ) was determined based on an averaged peak signal-to-noise ratio of : that was obtained with six replicate analyses of an individual PFAS. The LOQs was ~.5 μmol/l for PFOA and PFOS measured under the ESI - mode and ranged from.9.2 μmol/l for FAs and FSs measured under the ESI + mode. Most of the measured concentrations of PFASs were greater than corresponding LOQs. However, nine points were assigned as half of LOQ as the concentrations were lower than corresponding LOQs. Table Sa. Formulas and confirmed or proposed structures of identified degradation products of PFOAB and during chlorination (NaOCl) and ozonation (O ) by high-resolution mass spectrometry. PFOAB (ESI + /4.8) (ESI + /5.27) Level of confidence C5H6F5N2O + ( ) C5H6F7N2O4S + ( ) NaOCl O NaOCl O Level of confidence # (ESI - /4.82) # (ESI - /4.82) #4 (ESI - /; PFOA) CH5F5NO - ( 484.5) CH5F5NO - ( 484.5) #2 (ESI - /) C8F5O2 - ( ) #5 (ESI + /5.2) CHF5NO - ( ) # (ESI + /) C2H2F7N2O2S + ( 57.4) #6 (ESI + /5.8) C2H2F5N2O + ( ) C2H7F7NO4S + ( 58.98) S5

6 #4 (ESI - /; PFOA) C8F5O2 - ( ) #4 (ESI - /; PFOA) C8F5O2 - ( ) #7 (ESI - /) CH5F7NO4S - ( ) #8 (ESI - /5.7) #7 (ESI - /) CH5F7NO4S - ( ) #8 (ESI - /5.7) CHF7NO4S - ( ) #9 (ESI - /5.) CHF7NO4S - ( ) #9 (ESI - /5.) C8HF7NO2S - ( ) # (ESI - /4.97; PFOS) C8HF7NO2S - ( ) # (ESI - /4.97; PFOS) C8F7OS - C8F7OS - ( ) ( ) Note: ESI + /4.8 indicates this compound was identified under positive (+) ESI mode and the UPLC retention time was 4.8 min. The levels of confidence were assigned based on the recommendations of Schymanski and co-workers (level : confirmed structures; level : tentative/unconfirmed structures). 7 Table Sb. Formulas and confirmed or proposed structures of identified degradation products of PFOAAmS and PFOSAmS during chlorination (NaOCl) and ozonation (O ) by high-resolution mass spectrometry. PFOAAmS (ESI + /) Level of confidence PFOSAmS (ESI + /5.9) C4H6F5N2O + ( 5.8) C4H6F7N2O2S + ( ) NaOCl O NaOCl O Level of confidence # (ESI - /4.82) CH5F5NO - ( 484.5) #2 (ESI - /) #7 (ESI - /) #4 (ESI - /; PFOA) C8F5O2 - ( ) #4 (ESI - /; PFOA) CHF5NO - ( ) #4 (ESI - /; PFOA) CH5F7NO4S - ( ) #8 (ESI - /5.7) S6

7 C8F5O2 - ( ) C8F5O2 - ( ) CHF7NO4S - ( ) #9 (ESI - /5.) C8HF7NO2S - ( ) # (ESI - /4.97; PFOS) # (ESI - /4.97; PFOS) C8F7OS - C8F7OS - ( ) ( ) Note: ESI + / indicates this compound was identified under positive (+) ESI mode and the UPLC retention time was min. The levels of confidence were assigned based on the recommendations of Schymanski and co-workers (level : confirmed structures; level : tentative/unconfirmed structures). 7 Aquous concentration ( mol/l) (a) PFOAB PFOAAmS Aquous concentration ( mol/l) (b) PFOAB PFOAAmS PFOAB PFOAAmS PFOSAmS Alum (mg/l) Alum (mg/l) Alum (mg/l) Figure S. Removal of four zwitterionic and cationic PFASs at various concentrations by coagulation/flocculation using alum. The dashed lines in (a) are a guide for the eye. The results show that cationic PFASs (PFOAAmS and PFOSAmS) are not readily removed by coagulation/flocculation. Conventional coagulation at an alum dose of 4 mg/l can remove ~2 of PFOAB (a zwitterionic PFAS). A typical alum dose of 4 mg/l was selected to coagulate water for degradation experiments. Note that the removal of anionic PFASs (PFOS and PFOA) during alum coagulation/flocculation was less than 25 in a previous study. 8 S7

8 Concentration of PFOAB/PFOAAmS ( mol/l). (a) PFOAB PFOAAmS PFOA Hours of chlorination Concentration of PFOA ( mol/l) Concentration of /PFOSAmS ( mol/l) (b) PFOS PFOSAmS Hours of chlorination Concentration of PFOS ( mol/l) Figure S2. Degradation of and PFOSAmS during chlorination in pretreated surface water (after coagulation/flocculation and paper filtration). The initial free chlorine dose after the breakpoint was 5. mg/l, which dropped to ~.2 mg/l after 24 h of chlorination. Concentration of PFOAB/PFOAAmS ( mol/l).. E- E-4 (a) PFOAB PFOAAmS k =.5 h - ; t /2 =.5 h k =.76 h - ; t /2 = 9. h PFOA k =.8 h - ; t /2 = 8.7 h k =.87 h - ; t /2 = 7.9 h Hours of chlorination Concentration of PFOA ( mol/l) Concentration of /PFOSAmS ( mol/l.. E- (b) PFOSAmS PFOS E Hours of chlorination Concentration of PFOS ( mol/l) Figure S. Degradation of a mixture of PFOAB, PFOAAmS,, and PFOSAmS during chlorination in buffered DI water at ph of ~7.4 at relatively low (<.2 μmol/l) and high ( μmol/l) concentrations. The initial free chlorine dose after the breakpoint was 5. mg/l, which dropped to mg/l after 2 h of chlorination. The open and half-open symbols represent high and low initial concentrations of precursor compounds, respectively. The dashed lines represent the best linear fits (R 2 =.8.96) assuming a pseudo first-order degradation within 5 hours. A fitting with a higher R 2 was obtained at low initial concentrations of PFOAB or PFOAAmS. At a higher initial concentration of PFOAB or PFOAAmS or longer chlorination time (e.g., > 5 hours), the assumption of a first-order reaction may become less valid due to the significant change of chlorine concentration relative to the concentration of PFOAB/PFOAAmS. S8

9 Before chlorination.2.2 After chlorination Concentration ( mol/l) Concentration ( mol/l) PFOSAmS. PFOS from PFOS from PFOSAmS Figure S4. Degradation of /PFOSAmS and corresponding generation of PFOS from a -d reaction between /PFOSAmS and chlorine in buffered DI water. The dose of free chlorine is 5. mg/l and.9 4. mg/l after d. Before chlorination After chlorination Concentration ( mol/l) x -4 Concentration ( mol/l) PFOAB PFOAAmS. PFOA from PFOAB PFOA from PFOAAmS Figure S5. Degradation of PFOAB/PFOAAmS and corresponding generation of PFOA from a -d reaction between PFOAB/PFOAAmS and chlorine in buffered DI water. The dose of free chlorine is 5. mg/l and mg/l after d. S9

10 Concentration ( mol/l) Concentration ( mol/l) PFOA PFOS PFOAB PFOAAmS PFOSAmS Ozonation (min) Figure S6. Degradation of a mixture of four precursor compounds (PFOAB, PFOAAmS,, and PFOSAmS) during ozonation in pre-treated surface water and generation of PFOA and PFOS in this process. The input ozone dose was 7.6 mg/l. The solid lines in (a) are a guide for the eye. k = k Abiotic degradation products of PFOAB. PFOAB d Cl2 9_26_27_neg Da 4.9e PFOAB d Cl2 9_26_27_neg Da e PFOAB d Cl2 9_26_27_neg Da e Figure S7a. Compounds # ( 484.) and #4 (PFOA; ) generated during the reaction between chlorine and PFOAB PFOAB d Cl2 9_26_27_neg e PFOAB d Cl2 9_26_27_pos : TOF MS ES Da PFOAB d Cl2 9_26_27_pos : TOF MS ES Da ; PFOAB d Cl2 9_26_27_pos : TOF MS ES Da S

11 PFOAB d Cl2 9_26_27_neg 62 (4.88) e PFOAB d Cl2 9_26_27_neg 6 (4.82) e PFOAB O 9_26_27_neg Da.85e PFOAB O 9_26_27_neg Da ; Figure S7b. MS E (upper figure) and MS.25 (bottom figure) spectra of compound # 6.75 ( at PFOAB O 9_26_27_neg Da UPLC retention time (RT) of 4.88 min) identified as a result of the reaction between PFOAB and.e4 chlorine. PFOAB O 9_26_27_neg The MS response of compound # is not strong. See Figure S8b for MS spectra of this compound Da e6 at a relatively high MS response PFOAB O 9_26_27_neg PFOAB O 9_26_27_pos 5.2 : TOF MS.2Da ES e Da e PFOAB O.7 9_26_27_neg ; Da PFOAB O 9_26_27_neg Da e PFOAB O 9_26_27_neg : TOF MS ES- PFOAB O 9_26_27_pos 9.7 : TOF MS.2Da ES e Da PFOAB O 9_26_27_neg Da e e PFOAB O 9_26_27_neg Da PFOAB O O 9_26_27_neg _26_27_pos : TOF : TOF MS MS ES+ ES ; Da Da.66e e PFOAB O _26_27_neg ;.72.7; Da e PFOAB O 9_26_27_neg Da e PFOAB O O 9_26_27_neg 9_26_27_pos : TOF : TOF MS MS ES+ ES Da e e PFOAB O 9_26_27_neg Da e PFOAB O 9_26_27_neg e6 Figure S8a..5 Compounds # ( ),..5 #2 ( ), # ( ), and 7. #4 (PFOA; 7.5 PFOAB O.25 9_26_27_pos : 7.75 TOF MS ES+ PFOAB O 9_26_27_neg ) generated during the reaction between PFOAB and 4.8 ozone..44; ; e7.66e6 S

12 PFOAB O 9_26_27_neg 6 (4.8) e PFOAB O 9_26_27_neg 6 (4.82) e Figure S8b. MS E (upper figure) and MS (bottom figure) spectra of compound # ( 484. at UPLC RT of 4.8 min) identified as a result of the reaction between PFOAB and ozone. PFOAB O 9_26_27_neg 599 (4.7) e ; ; PFOAB O 9_26_27_neg 6 (4.77) e Figure S8c. MS E (upper figure) and MS (bottom figure) spectra of compound #2 ( at UPLC RT of 4.77 min) identified as a result of the reaction between PFOAB and ozone S2

13 PFOAB O 9_26_27_pos 59 (4.72) : TOF MS ES+ 2.e PFOAB O 9_26_27_pos 594 (4.76) : TOF MS ES e5 PFOAAmS O 9_26_27_neg Da ; PFOAAmS O 9_26_27_neg Da e PFOAAmS O 9_26_27_neg ; Da Figure S8d. MS E (upper figure) 9.7and MS (bottom figure) spectra 25.4 of compound # ( at UPLC RT of 4.72 min) identified as a result of the reaction between PFOAB and ozone PFOAAmS O 9_26_27_neg Da e ; Abiotic degradation products of PFOAAmS PFOAAmS O 9_26_27_neg Da e.64e ; PFOAAmS O 9_26_27_neg Da e6.5e PFOAAmS O 9_26_27_neg Da e PFOAAmS O 9_26_27_neg Da e 2.28e4 Figure S9a. Compounds # ( 484.), #2 ( ), and #4 (PFOA; ) generated during the reaction between PFOAAmS and ozone PFOAAmS O 9_26_27_neg Da e6.64e PFOAAmS O 9_26_27_neg e S

14 PFOAAmS O 9_26_27_neg 62 (4.86). 4.49e PFOAAmS O 9_26_27_neg 6 (4.82) : TOF MS ES e4 d Cl2 9_26_27_neg Da e d Cl2 9_26_27_neg Da e ; d Cl2 9_26_27_neg Figure S9b. MS E Da e5 (upper figure) and MS (bottom figure) spectra of compound # ( 484. at UPLC RT of 4.86 min) identified as a result of the reaction between PFOAAmS and chlorine. The MS response of compound # is not strong. See Figure S8b for MS spectra of this compound 5.8 at a relatively high MS response. Abiotic degradation products of d d Cl2 Cl2 9_26_27_neg 9_26_27_neg : : TOF TOF MS MS ES- ES Da Da e 4.9e d Cl2 9_26_27_neg Da e.57e e d Cl2 9_26_27_neg Da e5 6.26e.78e d Cl2 9_26_27_neg Da e5 2.5e5 4.9e d Cl2 9_26_27_neg Da e e5.57e d Cl2 9_26_27_neg Da e e S

15 Figure Sa. Compounds #7 ( ), #8 ( at 5.7 min), #9 (PFOSA; ), and # (PFOS; 498.9) generated during the reaction between and chlorine. d Cl2 9_26_27_neg 672 (8) e ; d Cl2 9_26_27_neg 672 (4) e4 d Cl2 9_26_27_neg 627 (4.96) e ; d Cl2 9_26_27_neg 644 (5.65) e d Cl2 9_26_27_neg 627 (4.96) : TOF MS ES e d Cl2 9_26_27_neg (5.69) : TOF MS ES e Figure Sb. MS E (upper figure) and MS (bottom figure) spectra of compound ; #7 ( at UPLC RT of 8 min) identified as a result of the reaction between and chlorine. d Cl2 9_26_27_neg 644 (5.65) e d Cl2 9_26_27_neg 628 (4.99) e d Cl2 9_26_27_neg (5.69) e d Cl2 9_26_27_neg (5.6) e d Cl _26_27_neg 628 (4.99) : TOF MS ES e d Cl2 9_26_27_neg 656 (5.58) e d Cl2 9_26_27_neg (5.6) : TOF MS ES e Figure Sc. MS E 25. (upper figure) and MS (bottom figure) spectra of compound #8 ( at UPLC RT of 5.69 min) identified as a result of the reaction between and chlorine d Cl2 9_26_27_neg 656 (5.58) e S5

16 d Cl2 9_26_27_neg 72 (5.52) e box_ 2 MM_9_9_27_neg Da e ; d Cl2 9_26_27_neg 72 (5.57) e O_O2 9_26_27_neg Da e MM_9_9_27_neg Da 25..8e O_O2 9_26_27_pos : TOF MS ES Da O_O2 9_26_27_neg : TOF MS ES e Da e5 2 MM_9_9_27_neg : TOF MS ES e Figure Sd. MS E (upper figure) and MS (bottom figure) spectra of compound #9 (PFOSA; ; ; O_O2 9_26_27_neg at UPLC RT of 5.52 min) identified as a result of the reaction between and chlorine. : TOF MS 22.7 ES Da e6 O_O2 9_26_27_pos : TOF MS ES Da O_O2 9_26_27_neg Da e O_O2 9_26_27_neg : TOF 7.95 MS ES Da e5.84e O_O2 9_26_27_neg O_O2 9_26_27_pos : TOF MS ES Da.e e O_O2 9_26_27_neg Da e e4.5e O_O2 O_O2 9_26_27_neg 9_26_27_pos : : TOF MS ES+ ES Da e5.84e5.55e6.7e O_O2 9_26_27_neg Da e4 9.64e4.84e O_O2 9_26_27_pos : TOF MS ES e O_O2 9_26_27_neg Da Da e6.e6 5.5e ; O_O2 9_26_27_neg O_O2 9_26_27_neg Da Da e e O_O2 9_26_27_neg O_O2 9_26_27_neg Da e e ; S

17 O_O2 9_26_27_neg ; Da O_O2 O_O2 9_26_27_neg 9_26_27_neg : : TOF TOF MS MS ES- ES Da e4.55e O_O2 9_26_27_neg Da e O_O2 9_26_27_neg e6 Figure Sa. Compounds #4 (PFOA; ), #5 ( 57.5), #6 ( 58.98), #7 ( ), #8 ( ), #9 (PFOSA; ), and # (PFOS; 498.9) 5.45 identified as a result of the reaction between and ozone O_O2 9_26_27_neg Da Da 9.64e4 O_O2 9_26_27_neg 685 (5.87) O_O2 9_26_27_neg ; e4.e O_O2 9_26_27_neg 686 (5.9) e ; ; Figure Sb. MS E (upper figure) and MS (bottom figure) spectra of compound #6 ( at UPLC RT of 5.87 min) identified as a result of the reaction between and ozone. S7

18 O_O2 9_26_27_neg 672 (8) e O_O2 9_26_27_neg 672 (4) e ; ; Figure Sc. MS E (upper figure) and MS (bottom figure) spectra of compound #7 ( at UPLC RT of 8 min) identified as a result of the reaction between and ozone. O_O2 9_26_27_neg 656 (5.6) e ; O_O2 9_26_27_neg 657 (5.65) e Figure Sd. MS E (upper figure) and MS (bottom figure) spectra of compound #8 ( at UPLC RT of 5.6 min) identified as a result of the reaction between and ozone. S8

19 O_O2 9_26_27_neg 72 (5.52) e PFOSAmS d Cl2 9_26_27_neg Da O_O2 9_26_27_neg 7 (5.525) e ; PFOSAmS d Cl2 9_26_27_neg Da PFOSAmS d Cl2 9_26_27_neg Da e PFOSAmS d Cl2 9_26_27_neg Da e Figure Se. MS E (upper figure) and MS (bottom figure) spectra of compound #9 (PFOSA; ; at UPLC RT of 5.52 min) identified as a result of the reaction between and ozone PFOSAmS d Cl2 9_26_27_neg Da e Abiotic 9.7 degradation products of PFOSAmS ; PFOSAmS PFOSAmS d d Cl2 Cl2 9_26_27_neg 9_26_27_neg : : TOF TOF MS MS ES- ES Da e e ; PFOSAmS PFOSAmS d d Cl2 Cl2 9_26_27_neg 9_26_27_neg : : TOF TOF MS MS ES- ES Da..79e e e PFOSAmS d Cl2 9_26_27_neg Da e5.42e 2.29e PFOSAmS d Cl2 9_26_27_neg Da e4 2.29e5 5.76e PFOSAmS d Cl2 9_26_27_neg Da e6.66e e5 Figure S2a. Compounds #7 ( ), #8 ( ), #9 (PFOSA; ), 25.4and # (PFOS; 498.9) generated during the reaction between PFOSAmS and chlorine PFOSAmS d Cl2 9_26_27_neg Da e e PFOSAmS d Cl2 9_26_27_neg S9.79e6