Supporting Information Calibration and Application of Passive Sampling for Per- and Polyfluoroalkyl Substances in a Drinking Water Treatment Plant Laura Gobelius a , Caroline Persson a , Karin Wiberg a , Lutz Ahrens a,* 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: [email protected]; phone: +46 (0)70-2972245 S1
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ars.els-cdn.com · Web viewdmean values from DWTP autosampling (days 26/11/2014, 02/12/2014, 05/12/2014, 08/12/2014, 11/12/2014, 15/12/2014) Table S5 Blanks and method detection limits
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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
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
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
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
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
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)
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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
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
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)
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
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
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
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
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
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
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
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
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
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
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
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
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
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