Supporting Information

Calibration and Application of Passive Sampling for Per- and Polyfluoroalkyl Substances in a Drinking Water Treatment Plant

Laura Gobeliusa, Caroline Perssona, Karin Wiberga, Lutz Ahrensa,*

a Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences

(SLU), Box 7050, SE-750 07 Uppsala, Sweden

*Corresponding Author: Lutz Ahrens, email: lutz.ahrens@slu.se; phone: +46 (0)70-2972245

This Document Contains 4 Figures, 27 Tables and 26 pages

S1

Sample preparation and analysis. The composite water samples from the DWTP were filtered using glass fiber filters (GFF; 1.2 μm, GE Healthcare Life Sciences, Whatman, UK), while the 100 mL grab samples from the laboratory uptake experiment were extracted directly. All water samples were spiked with 100 µL of IS mixture (20 pg µL-1 for individual IS). Prior to the solid phase extraction (SPE) of the water samples, the Oasis WAX cartridges (6 cm3, 150 mg, 20 µm, Waters Corporation, Ireland) were preconditioned with 4 mL of a 0.1% ammonium hydroxide in methanol solution, 4 mL of methanol and 4 mL Millipore water. After loading (with either 100 mL from the laboratory uptake experiment or 1 L from the DWTP), the flow rate was adjusted to ~1 drop s-1. Ultimately, the cartridge was washed with 4 mL 25 mM ammonium acetate buffer in Millipore water. Subsequently, cartridges were dried in a centrifuge for 2 min at 3000 rpm and the extracts were eluted with 4 mL of methanol and 8 mL of a 0.1% ammonium hydroxide solution in methanol into 15 mL PP-tubes.

Quality assurance and quality control. MDLs were calculated based on the mean blank concentration plus the standard deviation of the blank times three. If a compound was not detected in the blanks, the MDL was set to the lowest calibration point (i.e. 0.050 ng L-1). The MDL was 0.050 ng L-1 for both, POCIS-WAX and POCIS-HLB, since no PFASs were detected in the blanks, while the mean MDL of the water samples ranged from 0.050 ng L-1 to 0.19 ng L-1 based on 1 L water volume (Table S4). The mean relative standard deviation of ∑14PFASs for duplicate samples from the laboratory uptake experiment was 18% for POCIS-WAX and 21% for POCIS-HLB while the mean relative standard deviation of the POCIS-WAX in the DWTP was 25% (Tables S6-S7). The high relative standard deviation can be explained by the fact that the concentrations at the DWTP were close to the MDL, and therefore higher uncertainties are expected.

S2

Figure S1 Setup of the calibration study with the two tanks and passive samplers.

Figure S2 Individual PFASs concentrations [ng L-1] from the tankreservoir on day 28 of the calibration study.

S3

Figure S3 Scheme of the full-scale and pilot-scale drinking water treatment plant (DWTP) and sampling locations.

Figure S4 Bucket with passive samplers as deployed in the drinking water treatment plant.

S4

Table S1 Target analyte names, CAS-numbers, acronyms, supplier and purity for the calibration study (n = 14) and the DWTP study (n = 26) including mass-labelled standards and corresponding PFASs for quantification

Analyte CAS No Acronym Supplier (purity)

target analytes for calibration study (n = 10)

perfluorobutane sulfonic acid 375-73-5 or 59933-66-3

PFBS Sigma Aldrich (98%)

perfluorohexane sulfonic acid 355-46-4 PFHxS Sigma Aldrich (≥98%)

perfluorooctane sulfonic acid 1763-23-1 PFOS Sigma Aldrich (≥98%)

perfluorobutanoic acid 375-22-4 PFBA Sigma Aldrich (98%)

perfluoropentanoic acid 2706-90-3 PFPeA Sigma Aldrich (97%)

perfluorohexanoic acid 307-24-4 PFHxA Sigma Aldrich (≥97%)

perfluoroheptanoic acid 375-85-9 PFHpA Sigma Aldrich (99%)

perfluorooctanoic acid 335-67-1 PFOA Sigma Aldrich (96%)

perfluorononanoic acid 375-95-1 PFNA Sigma Aldrich (97%)

perfluorodecanoic acid 335-76-2 PFDA Sigma Aldrich (98%)

perfluoroundecanoic acid 2058-94-8 PFUnDA Sigma Aldrich (95%)

perfluorododecanoic acid 307-55-1 PFDoDA Sigma Aldrich (95%)

perfluorotetradecanoic acid 376-06-7 PFTeDA Sigma Aldrich (97%)

perfluorooctane sulfonamide 754-91-6 FOSA Sigma Aldrich (n.a.)

target analytes for DWTP study (n = 26)

perfluorobutane sulfonic acid 375-73-5 or 59933-66-3

PFBS Wellington Laboratories (>98%)

perfluorohexane sulfonic acid 355-46-4 PFHxS Wellington Laboratories (>98%)

perfluorooctane sulfonic acid 1763-23-1 PFOS Wellington Laboratories (>98%)

perfluorodecane sulfonic acid 335-77-3 PFDS Wellington Laboratories (>98%)

perfluorobutanoic acid 375-22-4 PFBA Wellington Laboratories (>98%)

perfluoropentanoic acid 2706-90-3 PFPeA Wellington Laboratories (>98%)

perfluorohexanoic acid 307-24-4 PFHxA Wellington Laboratories (>98%)

perfluoroheptanoic acid 375-85-9 PFHpA Wellington Laboratories (>98%)

perfluorooctanoic acid 335-67-1 PFOA Wellington Laboratories (>98%)

perfluorononanoic acid 375-95-1 PFNA Wellington Laboratories (>98%)

perfluorodecanoic acid 335-76-2 PFDA Wellington Laboratories (>98%)

perfluoroundecanoic acid 2058-94-8 PFUnDA Wellington Laboratories (>98%)

perfluorododecanoic acid 307-55-1 PFDoDA Wellington Laboratories (>98%)

perfluorotridecanoic acid 72629-94-8 PFTriDA Wellington Laboratories (>98%)

S5

perfluorotetradecanoic acid 376-06-7 PFTeDA Wellington Laboratories (>98%)

perfluorohexadecanoic acid 67905-19-5 PFHxDA Wellington Laboratories (>98%)

perfluorooctadecanoic acid 16517-11-6 PFOcDA Wellington Laboratories (>98%)

perfluorooctane sulfonamide 754-91-6 FOSA Wellington Laboratories (>98%)

N-methyl perfluorooctane sulfonamide 31506-32-8 MeFOSA Wellington Laboratories (>98%)

N-ethyl perfluorooctane sulfonamide 4151-50-2 EtFOSA Wellington Laboratories (>98%)

N-methyl perfluorooctane sulfonamidoethanol 24448-09-7 MeFOSE Wellington Laboratories (>98%)

N-ethyl perfluorooctane sulfonamidoethanol 1691-99-2 EtFOSE Wellington Laboratories (>98%)

perfluorooctanesulfonamidoacetic acid 2806-24-8 FOSAA Wellington Laboratories (>98%)

N-methylperfluorooctanesulfonamidoacetic acid

2355-31-9 MeFOSAA Wellington Laboratories (>98%)

N-ethylperfluorooctanesulfonamidoacetic acid 2991-50-6 EtFOSAA Wellington Laboratories (>98%)

6:2 fluorotelomersulfonate 425670-75-3 6:2 FTSA Apollo Scientific Ltd (n.a)

mass-labeled internal standards (IS) corresponding PFAS for quantification

perfluoro-(18O2)-hexane sulfonic acid PFHxS, PFBS,6:2 FTSA

18O2-PFHxS Wellington Laboratories (>98%)

perfluoro-(13C4)-octane sulfonic acid PFOS, PFDS 13C4-PFOS Wellington Laboratories (>98%)

perfluoro-(13C4)-butanoic acid PFBA 13C4-PFBA Wellington Laboratories (>98%)

perfluoro-(13C2)-hexanoic acid PFHxA, PFPeA

13C2-PFHxA Wellington Laboratories (>98%)

perfluoro-(13C4)-octanoic acid PFOA, PFHpA

13C4-PFOA Wellington Laboratories (>98%)

perfluoro-(13C5)-nonanoic acid PFNA 13C5-PFNA Wellington Laboratories (>98%)

perfluoro-(13C2)-decanoic acid PFDA 13C2-PFDA Wellington Laboratories (>98%)

perfluoro-(13C2)-undecanoic acid PFUnDA 13C2-PFUnDA Wellington Laboratories (>98%)

perfluoro-(13C2)-dodecanoic acid PFDoDA, PFTriDA, PFTeDA, PFHxDA, PFOcDA

13C2-PFDoDA Wellington Laboratories (>98%)

perfluoro-1-(13C8)octane sulfonamide FOSA 13C8-FOSA Wellington Laboratories (>98%)

N-methyl-d3-perfluorooctane sulfonamide MeFOSA D3-MeFOSA Wellington Laboratories (>98%)

N-ethyl-d5-perfluorooctane sulfonamide EtFOSA D5-EtFOSA Wellington Laboratories (>98%)

N-methyl-d7-perfluorooctane sulfonamido ethanol

MeFOSE D7-MeFOSE Wellington Laboratories (>98%)

N-ethyl-d9-perfluorooctane sulfonamido ethanol

EtFOSE D9-EtFOSE Wellington Laboratories (>98%)

N-methyl-d3-perfluorooctanesulfonamidoacetic acid

MeFOSAA, d3-MeFOSAA Wellington Laboratories (>98%)

S6

FOSAA

N-ethyl-d5-perfluorooctanesulfonamidoacetic acid

EtFOSAA d5-EtFOSAA Wellington Laboratories (>98%)

Mass labelled injection standard (InjS)

perfluoro-(13C8)-octanoic acid 13C8-PFOA Wellington Laboratories (>98%)

S7

Table S2 PFAS concentrations [ng L-1] in tankpassive sampler during the calibration study for the days 0, 2, 4, 7, 14, 21, and 28. Mean, Median and Standard Deviation (SD) indicate that individual PFAS concentrations were stable during the experiment

Day PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTeDA FOSA PFBS PFHxS PFOS0 461 518 515 511 510 517 461 402 340 117 406 575 449 3722 462 495 464 433 419 415 390 339 261 81 330 524 375 2674 493 522 482 449 426 421 405 299 197 46 295 581 365 2707 515 549 501 456 439 420 377 297 187 37 220 590 382 269

14 588 617 567 517 500 469 460 377 275 52 247 648 428 30821 652 678 629 594 589 552 522 389 255 52 250 764 504 35828 692 720 675 628 626 586 522 399 228 33 235 854 567 425

Mean 552 586 548 513 501 483 448 357 249 60 283 648 439 324Median 515 549 515 511 500 469 460 377 255 52 250 590 428 308

SD 93 87 79 75 81 70 60 46 52 29 66 119 75 62

S8

Table S3 Mean concentrations [ng absolut] and standard deviation (SD) for duplicate samples from the POCIS-HLB and POCIS-WAX during the four week calibration study in the laboratory

POCIS-HLBday PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTeDA FOSA PFBS PFHxS PFOS

0 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050

20.48 ± 0.10 41 ± 4.9 160 ± 8.0

290 ± 4.4

380 ± 11

380 ± 20

280 ± 6.5 210 ± 25 79 ± 17

0.66 ± 0.28 300 ± 29 204 ± 19 290 ± 14 130 ± 29

4 0 ± 0 24 ±4.0 120 ± 36 220 ± 66290 ± 98

290 ± 82

230 ± 56 160 ± 39 69 ± 15

3.5 ± 0.67 220 ± 67 160 ± 44 220 ± 63 120 ± 34

70.016 ± 0.023 29 ± 7.3 210 ± 16 420 ± 42

603 ± 69

670 ± 98

440 ± 38 320 ± 28 140 ± 15

3.5 ± 0.25 507 ± 52 370 ± 64 430 ± 25 360 ± 77

140.31 ± 0.44 58 ± 6.9 290 ± 55 505 ± 97

770 ± 150

830 ± 109

504 ± 59 360 ± 42 160 ± 20

5.2 ± 0.23 606 ± 99

480 ± 130 590 ± 83

490 ± 130

210.35 ± 0.012 38 ± 18 280 ± 150

550 ± 220

850 ± 370

910 ± 400

530 ± 165 390 ± 130 180 ± 72 6.4 ± 2.3

650 ± 330

530 ± 350

620 ± 230

604 ± 380

280.059 ± 0.083 25 ± 0.43 370 ± 22

870 ± 7.7

1400 ± 20

1600 ± 8.0

780 ± 3.1 560 ± 5.0 320 ± 1.2 12 ± 0.32

1050 ± 17 850 ± 22 970 ± 81

1200 ± 13

POCIS-WAXday PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTeDA FOSA PFBS PFHxS PFOS

0<0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050

285 ± 13

170 ± 23 260 ± 39

290 ± 42

330 ± 49

320 ± 49 240 ± 25 170 ± 26 58 ± 13 1.5 ± 0.26 230 ± 33 260 ± 25 250 ± 37 91 ± 20

481 ± 10

160 ± 21 240 ± 28

270 ± 16

309 ± 20

305 ± 23 230 ± 8 180 ± 16 74 ± 7 5.5 ± 2.5 220 ± 18 280 ± 28 240 ± 13 140 ± 14

7104 ± 48

201 ± 73

320 ± 131

370 ± 140

460 ± 190

460 ± 170 340 ± 98 230 ± 65 94 ± 29 2.4 ± 0.49

320 ± 130 430 ± 200

350 ± 130

250 ± 130

14130 ± 23

280 ± 51 480 ± 90

550 ± 74

730 ± 74

750 ± 37 460 ± 13 330 ± 11 150 ± 3 4.2 ± 0.84 490 ± 24 680 ± 47 630 ± 50 490 ± 16

21130 ± 15

300 ± 48

520 ± 110

580 ± 104

780 ± 190

790 ± 240 480 ± 88 360 ± 78 160 ± 38 5.6 ± 0.68

480 ± 130 620 ± 170

610 ± 150

450 ± 140

28130 ± 0

410 ± 35

830 ± 190

1000 ± 270

1400 ± 400

1400 ± 340 690 ± 99 520 ± 71 270 ± 31

8.4 ± 0.017

790 ± 180

1300 ± 190

970 ± 160

980 ± 170

S9

Table S4 Measured water parameters temperature, discharge, approximated flow rate, pH, UV transmission and total organic carbon (TOC) for all sampling sites at the DWTPa

Sampling location Temperature Discharge Flow rate vertical pH UV 254 TOC[oC] [mL s-1] [cm s-1] [5 cm; %T] [mg L-1]

RW 6.9b 7.6c NA 7.8b 1.22b 7.7b

SF 8.8c 36c 0.35 6.8b 0.42b 4.5b

GAC 1 (full scale) 8.4c 20c 0.20 6.6c 0.44d NADW 10c 14c 0.14 7.1c NA NAGAC 2 (pilot) 11c 16c 0.16 6.5c 0.30d NANF (pilot) 10c 36c 0.35 6.4c 0.11b 1.1b

GAC 3 (pilot) 9.7c 16c 0.16 6.5c 0.007d NAa NA = not availablebdata (mean) from DWTP autosampling (5 minute intervals) for dates 25/11/2014-09/12/2014; cmeasured on 25/11/2014; dmean values from DWTP autosampling (days 26/11/2014, 02/12/2014, 05/12/2014, 08/12/2014, 11/12/2014, 15/12/2014)

S10

Table S5 Blanks and method detection limits (MDL) for the water samples. No PFASs were detected in the blanks of POCIS-WAX and POCIS-HLB and the MDL was set to 0.05 ng L-1, which corresponds to the lowest calibration pointa

Aqueous sampleslaboratory

blanksn 12

MDL mean ± SDng L-

1 ng L-1

PFBA 0.72 <0.72 NAPFPeA 0.27 <0.27 NAPFHxA 0.45 <0.45 NAPFHpA 0.59 <0.59 NAPFOA 0.85 <0.85 NAPFNA 0.62 <0.62 NAPFDA 0.57 <0.57 NAPFUnDA 0.45 <0.45 NAPFDoDA 0.72 <0.72 NAPFTriDA 0.050 <0.050 NAPFTeDA 0.37 <0.37 NAPFHxDA 0.050 <0.050 NAPFOcDA 0.050 <0.050 NAPFBS 0.86 <0.86 NAPFHxS 0.64 <0.64 NAPFOS 0.44 <0.44 NAPFDS 0.050 <0.050 NA6:2 FTSA 0.050 <0.050 NAFOSA 0.14 <0.14 NAMeFOSA 0.050 <0.050 NAEtFOSA 0.050 <0.050 NAMeFOSE 0.050 <0.050 NAEtFOSE 0.050 <0.050 NAFOSAA 0.050 <0.050 NAMeFOSAA 0.050 <0.050 NAEtFOSAA 0.050 <0.050 NAa NA = not available

S11

Table S6 Recoveries from the calibration study and the DWTP deployment study given in means and standard deviation (SD) for aqueous samples, POCIS-WAX and POCIS-HLB

Aqueous samples POCIS-WAX POCIS-HLBlaboratory uptake

studylaboratory uptake

studyDWTP study

laboratory uptake study

DWTP study

n 8 12 14 12 7mean ± SD mean ± SD mean ± SD mean ± SD mean ± SD

13C4 PFBA 113 6 81 11 51 24 116 32 87 1913C2 PFHxA 78 3 56 13 74 12 66 16 72 1513C4 PFOA 84 4 59 12 96 12 63 15 107 913C5 PFNA 60 5 36 11 87 12 36 13 103 913C2 PFDA 58 6 58 6 80 10 60 8 100 813C2 PFUnDA 55 5 63 10 94 29 66 12 126 1113C2 PFDoDA 52 5 75 13 74 10 78 16 106 818O2 PFHxS 76 5 55 13 89 11 58 14 95 713C4 PFOS 68 7 45 15 85 10 44 18 90 1113C8-FOSA 71 9 44 13 88 11 42 14 98 7d3-MeFOSA 41 18 79 15 101 13 85 19 114 8d5-EtFOSA 37 17 90 10 106 12 100 11 121 8d7-MeFOSE 43 7 85 16 97 25 92 20 118 8d9-EtFOSE 41 5 84 12 101 13 99 14 123 12d3-MeFOSAA 82 7 48 18 96 12 49 23 142 15d5-EtFOSAA 65 5 65 14 101 11 73 22 159 19

S12

Table S7 The 26 targeted PFASs including their acronyms, molecular formulas, structural formulas, molecular weight (MW), water solubility (Sw), acid dissociation constant (pKa) values, the octanol-water partition coefficient (log Kow) and the soil organic carbon-water partitioning coefficient (log Koc) (see also Gobelius et al., 2017) (NA = not available)

Substance Acronym Molecularformular

MW[g mol-1]

Sw[mg L-1] pKa

Log Kow[L kg-1]

Log Koc[L kgoc

-1]PFCAs (perfluoroalkyl carboxylates)perfluorobutanoicacid

PFBA C3F7CO2H 214 563a 0.05b

0.4c2.91d

2.82a1.88i

perfluoro-pentanoic acid

PFPeA C4F9CO2-H 264 113000a -0.10b 3.69d

3.43a1.37i

perfluorohexanoicacid

PFHxA C5F11CO2-H 314 15700c

21700a-0.17b

-0.16c4.50d

4.06a1.6j

perfluoro-heptanoic acid

PFHpA C6F13CO2-H 364 118.0e

4180a-0.20b 5.36d

4.67a2.9l

perfluorooctanoicacid

PFOA C7F15CO2-H 414 4340e

3400c-0.21b,c 6.26d

5.30a3.5l

2.11k

perfluorononanoicacid

PFNA C8F17CO2-H 464 131a -0.21b 7.23d

5.92a4.0l

2.5m

perfluorodecanoicacid

PFDA C9F19CO2-H 514 260e

25a-0.22b 8.26d

6.50a4.6l

2.92k

perfluoro-undecanoic acid

PFUnDA C10F21CO2-H 564 92.3e

4.13a-0.22b 2.32e

7.15a5.1l

3.47k

perfluorodo-decanoic acid

PFDoDA C11F23CO2-H 614 7.05 *

10-1a-0.22b 7.77a NA

perfluorotri-decanoic acid

PFTriDA C12F25CO2-H 664 1.71 *

10-1a-0.22b 8.25a NA

perfluorotetra-decanoic acid

PFTeDA C13F27CO2-H 714 2.71 *

10-2a-0.22b 8.90a NA

perfluorohexa-decanoic acid

PFHxDA C15F31CO2-H 814 NA -0.22b NA NA

perfluoroocta-decanoic acid

PFOcDA C17F35CO2-H 914 NA -0.22a NA NA

PFSAs (perfluoroalkyl sulfonates)perfluorobutane-sulfonic acid

PFBS C4F9SO3-H 300 510e

46200c0.14b,c 3.90a 1.5j

perfluorohexane-sulfonic acid

PFHxS C6F13SO3-H 400 1400c 0.14b,c 0.97e

5.17a3.7l

perfluorooctane-sulfonic acid

PFOS C8F17SO3-H 500 570c,e 0.14b

-3.27c4.67d

7.66a4.8l

2.68k

perfluorodecane-sulfonic acid

PFDS C10F21SO3-H 600 NA 0.14b 7.66a 3.66k

FOSAs (methyl- and ethylperfluorooctanesulfonamides)perfluorooctane-sulphonamide

FOSA C8F17SO2

NH2

499 1850000a 6.56b 2.56e 4.5l

N-methyl-d3-perfluorooctanesulfonamide

MeFOSA C8F17SO2

NHCH3

513 0.81e

263000a7.69b 6.07a NA

N-ethyl-d5-perfluorooctanesulfonamide

EtFOSA C8F17SO2

NHCH2CH3

527 306a 7.91b 6.71a NA

S13

FOSEs (methyl- and ethylperfluorooctanesulfonamidoethanols)

N-methyl-d7-perfluorooctane sulfonamido ethanol

MeFOSE C8F17SO2N(CH2)2CH3OH

557 0.81e 14.4b NA NA

N-ethyl-d9-perfluorooctane sulfonamido ethanol

EtFOSE C8F17SO2

N(CH2)3OH556 NA 14.4b NA NA

FOSAAs (methyl- and ethylperfluorooctanesulfonamidoacetic acids)perfluorooctane-sulfonamidoaceticacid

FOSAA C8F17SO2NHCH3CO2

557 NA NA NA NA

N-methyl-d3-perfluorooctanesulfonamidoacetic acid

MeFOSAA C8F17SO2NCH3CH2CO2

558 NA -3.27f NA 3.35k

N-ethyl-d5-perfluorooctanesulfonamidoacetic acid

EtFOSAA C8F17SO2N(CH2)2CH3

CO2

584 NA NA NA 3.49k

FTSAs (fluorotelomer sulfonates)6:2 fluorotelomer-sulfonic acid

6:2 FTSA C8H4F13SO3H 428 10-25g 1.31h 4.44h NA

aWang et al., 2011bAhrens et al., 2012cDu et al., 2014

dRayne and Forest, 2009eRahman et al., 2014fBrooke et al., 2004

gWang et al., 2011hConcawe, 2016

iGuelfo and Higgins, 2013jErika Schedin, 2013kHiggins and Luthy, 2006lAhrens et al., 2010

Table S2 Pearson correlation of sampling rates from POCIS-WAX and POCIS-HLB with organic carbon-water partitioning coefficient (Koc), molecular weight (MW), water solubility (Sw), and octanol-water partitioning coefficient

Koc vs Rs MW vs Rs Sw vs Rs Log Kow vs Rsadsorbent WAX HLB WAX HLB WAX HLB WAX HLB

Pearson coefficient 0.60 0.70 0.16 0.31 0.60 0.68 -0.20 -0.14p-value 0.022 0.0057 0.59 0.29 0.022 0.0072 0.50 0.64

S14

Table S9 Results [ng L-1] from the DWTP deployment study for the POCIS-WAX, including standard deviation (SD) for the duplicates, showing the measured PFCAs. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

PFBA PFPeAPFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTriDA PFTeDA PFHxDA PFOcDA

MDL (ng L-1) 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050RW 1.3 ±

0.32< 0.050 3.4 ±

1.20.59 ± 0.48

1.2 ± 0.72

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

SF 0.76 ± 0.040

< 0.050 2.6 ± 0.042

0.29 ± 0.10

0.73 ± 0.13

< 0.050 0.11 ± 0.0048

< 0.050 0.066 ± 0.093

< 0.050 < 0.050 < 0.050 < 0.050

GAC 1 (full)

1.8 ± 0.61

< 0.050 3.3 ± 0.22

0.74 ± 0.14

1.5 ± 0.32

< 0.050 0.72 ± 0.15

< 0.050 0.24 ± 0.12

< 0.050 0.25 ± 0.35

< 0.050 < 0.050

DW 0.24 ± 0.12

< 0.050 3.05 ± 0.16

0.63 ± 0.16

2.1 ± 0.16

< 0.050 0.78 ± 0.49

< 0.050 0.15 ± 0.032

< 0.050 < 0.050 < 0.050 < 0.050

GAC 2 (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

NF (pilot)

1.1 ± 0.089

< 0.050 2.6 ± 0.27

0.43 ± 0.28

0.74 ± 0.21

< 0.050 < 0.050 < 0.050 0.062 ± 0.088

< 0.050 < 0.050 < 0.050 < 0.050

GAC 3 (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

S15

Table S10 Results [ng L-1] from the DWTP deployment study for the POCIS-WAX, including standard deviation (SD) for the duplicates, showing the measured PFSAs. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

PFBS PFHxS PFOS PFDSMDL (ng L-1) 0.050 0.050 0.050 0.050RW 4.1 ± 1.2 1.8 ± 0.59 0.63 ± 0.15 < 0.050SF 3.7 ± 0.51 1.3 ± 0.28 0.38 ± 0.0076 < 0.050GAC 1 (full) 4.3 ± 0.23 1.8 ± 0.17 0.56 ± 0.033 < 0.050DW 3.9 ± 0.023 2.1 ± 0.0053 0.72 ± 0.10 < 0.050GAC 2 (pilot) < 0.050 < 0.050 < 0.050 < 0.050NF (pilot) 5.4 ± 0.61 1.9 ± 0.27 0.56 ± 0.24 < 0.050GAC 3 (pilot) < 0.050 < 0.050 < 0.050 < 0.050

Table S31 Results [ng L-1] from the DWTP deployment study for the POCIS-WAX, including standard deviation (SD) for the duplicates, showing the measured PFAS precursors and the sum of all detected PFASs, ∑26PFAS. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

 6:2 FTSA FOSA MeFOSA EtFOSA MeFOSE EtFOSE FOSAA MeFOSAA EtFOSAA ∑26PFASMDL(ng L-1) 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050RW < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 13SF < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 9.8GAC 1 (full)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 15

DW < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 14GAC 2 (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 -

NF(pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 13

GAC 3 (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 -

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Table S42 Results [ng L-1] from the DWTP deployment study for the POCIS-HLB, showing the measured PFCAs. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTriDA PFTeDA PFHxDA PFOcDAMDL(ng L-1) 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050RW < 0.050 < 0.050 1.6 < 0.050 0.27 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050SF < 0.050 < 0.050 2.0 0.11 0.19 < 0.050 0.53 0.16 0.31 < 0.050 < 0.050 < 0.050 < 0.050GAC 1 (full)

< 0.050 < 0.050 3.1 < 0.050 0.13 < 0.050 0.55 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

DW < 0.050 < 0.050 1.5 0.12 1.27 < 0.050 0.43 < 0.050 0.12 < 0.050 < 0.050 < 0.050 < 0.050GAC 2 (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

NF (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 1.18 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

GAC 3 (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

Table S53 Results [ng L-1] from the DWTP deployment study for the POCIS-HLB, showing the measured PFSAs. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

PFBS PFHxS PFOS  PFDSMDL (ng L-1) 0.050 0.050 0.050 0.050RW 1.5 1.7 0.38 < 0.050SF 1.4 1.1 0.29 < 0.050GAC 1 (full) 2.0 1.0 0.27 < 0.050DW 0.95 2.1 0.61 < 0.050GAC 2 (pilot) < 0.050 < 0.050 < 0.050 < 0.050NF (pilot) < 0.050 < 0.050 < 0.050 < 0.050GAC 3 (pilot) < 0.050 < 0.050 < 0.050 < 0.050

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Table S64 Results [ng L-1] from the DWTP deployment study for the POCIS-HLB, showing the measured PFAS precursors and the sum of all detected PFASs, ∑26PFAS. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

6:2 FTSA FOSA MeFOSA EtFOSA MeFOSE EtFOSE FOSAA MeFOSAA EtFOSAA ∑26PFASMDL(ng L-1) 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050RW < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 5.5SF < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 6.1GAC 1 (full)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 7.0

DW < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 7.1GAC 2 (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 -

NF (pilot) < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 -GAC 3 (pilot)

< 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 -

S18

Table S75 Results [ng L-1] from the DWTP deployment study for the 1 L composite water samples, showing the measured PFCAs. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

PFBA PFPeAPFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTriDA PFTeDA PFHxDA PFOcDA

MDL(ng L-1) 0.72 0.27 0.45 0.59 0.85 0.62 0.57 0.45 0.72 0.050 0.37 0.050 0.050RW 2.3 < 0.27 0.84 < 0.59 < 0.85 < 0.62 < 0.57 < 0.45 < 0.72 < 0.050 < 0.37 < 0.050 < 0.050SF 1.7 < 0.27 0.83 < 0.59 < 0.85 < 0.62 < 0.57 < 0.45 < 0.72 < 0.050 < 0.37 < 0.050 < 0.050GAC 1 (full) 1.7 < 0.27 < 0.45 < 0.59 < 0.85 < 0.62 < 0.57 < 0.45 < 0.72 < 0.050 < 0.37 < 0.050 < 0.050DW 2.3 < 0.27 0.98 < 0.59 < 0.85 < 0.62 < 0.57 < 0.45 < 0.72 < 0.050 < 0.37 < 0.050 < 0.050GAC 2 (pilot) < 0.72 < 0.27 < 0.45 < 0.59 < 0.85 < 0.62 < 0.57 < 0.45 < 0.72 < 0.050 < 0.37 < 0.050 < 0.050NF (pilot) 0.75 < 0.27 < 0.45 < 0.59 < 0.85 < 0.62 < 0.57 < 0.45 < 0.72 < 0.050 < 0.37 < 0.050 < 0.050GAC 3 (pilot) 0.74 < 0.27 < 0.45 < 0.59 < 0.85 < 0.62 < 0.57 < 0.45 < 0.72 < 0.050 < 0.37 < 0.050 < 0.050

Table S86 Results [ng L-1] from the DWTP deployment study for the 1 L composite water samples, showing the measured PFSAs. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

PFBS PFHxS PFOS  PFDSMDL (ng L-1) 0.86 0.64 0.44 0.050RW 2.9 1.1 1.2 < 0.050SF 2.3 0.66 1.3 < 0.050GAC 1 (full) 2.9 < 0.64 1.8 < 0.050DW 2.4 0.67 1.8 < 0.050GAC 2 (pilot) < 0.86 < 0.64 < 0.44 < 0.050NF (pilot) 2.5 < 0.64 0.99 < 0.050GAC 3 (pilot) 3.1 < 0.64 0.92 < 0.050

S19

Table S97 Results [ng L-1] from the DWTP deployment study for the 1 L composite water samples, showing the measured PFAS precursors and the sum of all detected PFASs, ∑26PFAS. The abbreviations stand for RW = raw water at the DWTP intake, SF = sand filtrate from the full-scale DWTP, GAC 1 (full) = GAC filtrate from the full-scale DWTP, DW = finished drinking water from the full-scale DWTP, GAC 2 = GAC filtrate from the pilot DWTP, NF = nanofiltrate from the pilot DWTP, GAC 3 = GAC filtrate from the pilot DWTP after the nano-filtration

6:2 FTSA FOSA MeFOSA EtFOSA MeFOSE EtFOSE FOSAA MeFOSAA EtFOSAA ∑26PFASMDL(ng L-1) 0.050 0.14 0.050 0.050 0.050 0.050 0.050 0.050 0.050RW < 0.050 < 0.14 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 8.5SF < 0.050 < 0.14 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 7.4GAC 1 (full) < 0.050 < 0.14 0.39 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 7.9DW < 0.050 0.24 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 8.7GAC 2 (pilot) < 0.050 < 0.14 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 -NF (pilot) < 0.050 < 0.14 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 4.8GAC 3 (pilot) < 0.050 < 0.14 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 4.8

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Table S108 Removal efficiency [%] for detected PFCAs, PFSAs and PFAS precursors of the full-scale and the pilot DWTP based on the concentrations measured by the POCIS-WAX after the different treatment steps sand filtration (SF), GAC filtration (GAC 1; filter in the full-scale plant), drinking water (DW) from the full-scale DWTP, GAC filtration (GAC 2; filter in the pilot plant), nano-filtration (NF) in the pilot DWTP, GAC filter (GAC 3) in the pilot DWTP after the nano-filtration. Negative values indicate an increase of the compound after treatmenta

PFBA PFHxA PFHpA PFOA PFBS PFHxS PFOSSF 40 26 52 40 10 31 39GAC 1 (full) -43 4 -25 -27 -5 2 12DW 81 11 -6 -69 4 -15 -13Full-scale 78 41 21 -56 8 18 38GAC 2 (pilot) 100 100 100 100 100 100 100NFP (pilot) 15 24 27 40 -33 -3 11GAC 3 (pilot) 100 100 100 100 100 100 100a NA = not available

Table S19 Removal efficiency [%] for detected PFCAs, PFSAs and PFAS precursors of the full-scale and the pilot DWTP based on the concentrations measured by the POCIS-HLB after the different treatment steps sand filtration (SF), GAC filtration (GAC 1; filter in the full-scale plant), drinking water (DW) from the full-scale DWTP, GAC filtration (GAC 2; filter in the pilot plant), nano-filtration (NF) in the pilot DWTP, GAC filter (GAC 3) in the pilot DWTP after the nano-filtration. Negative values indicate an increase of the compound after treatmenta

PFHxA

PFOA

PFTeDA

PFBS

PFHxS

PFOS

SF -22 30 -10 9.4 31 23GAC 1 (full) -89 50 100 -30 39 29

DW 11-

374 100 39 -29 -62Full-scale -100

-295 190 18 41 -10

GAC 2 (pilot) 100 100 100 100 100 100NFP (pilot) 100

-339 100 100 100 100

GAC 3 (pilot) 100 100 100 100 100 100aNA = not available

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Table S20 Removal efficiency [%] for detected PFCAs, PFSAs and PFAS precursors of the full-scale and the pilot DWTP based on the concentrations measured by the composite grab water samples after the different treatment steps sand filtration (SF), GAC filtration (GAC 1; filter in the full-scale plant), drinking water (DW) from the full-scale DWTP, GAC filtration (GAC 2; filter in the pilot plant), nano-filtration (NF) in the pilot DWTP, GAC filter (GAC 3) in the pilot DWTP after the nano-filtration. Negative values indicate an increase of the compound after treatmenta

PFBA

PFHxA

PFHpA

PFDoDA

PFTeDA

PFBS

PFHxS

PFOS

SF 27 0.85 -481 0.22 -10 21 38 -6.2GAC 1 (full) 26 53 -125 43 100 -1.2 55 -55

DW

-0.9

6 -17 -285 59 100 16 37 -52Full-scale 52 37 -892 103 190 36 130

-114

GAC 2 (pilot) 100 100 100 100 100 100 100 100NFP (pilot) 68 91 100 100 100 12 60 16GAC 3 (pilot) 68 100 100 100 100 -8.3 100 22aNA = not available

S22

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