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Supporting information Legacy and Emerging Perfluoroalkyl Substances Are Important Drinking Water Contaminants in the Cape Fear River Watershed of North Carolina Supporting information includes analytical method description, 6 tables, and 5 figures. Mei Sun12-*, Elisa Arevalo2, Mark Strynar3, Andrew Lindstrom3, Michael Richardson4, Ben Kearns4, Adam Pickett5, Chris Smith6, and Detlef R.U. Knappe2 1Department of Civil and Environmental Engineering University of North Carolina at Charlotte Charlotte, North Carolina 28223, USA 2 Department of Civil, Construction, and Environmental Engineering North Carolina State University Raleigh, North Carolina 27695, USA 3 National Exposure Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711, USA 4 Cape Fear Public Utility Authority Wilmington, North Carolina 28403, USA 5 Town of Pittsboro Pittsboro, North Carolina 27312, USA 6 Fayetteville Public Works Commission Fayetteville, North Carolina 28301, USA '`'Corresponding Author Email: msun8@uncc.edu; Phone: 704-687-1723 Page 1 of 12 Sierra Club v. EPA 18cv3472 NDCA Tier 10 ED 002061 00270552-00001 Analytical standards: PFASs studied in this research are listed in Table SI. For legacy PFASs, native and isotopically labeled standards were purchased from Wellington Laboratories (Guelph, Ontario, Canada). Native PFPrOPrA was purchased from Thermo Fisher Scientific (Waltham, MA). No analytical standards were available for other PFECAs. PFAS quantification: PFAS concentrations in samples from DWTPs and adsorption tests were determined by liquid chromatography tandem mass spectrometry (LC-MS/MS) using a largevolume (0.9 mL) direct injection method. An Agilent 1100 Series LC pump and PE Sciex API 3000 LC-MS/MS system equipped with a 4.6 mm x 50 mm HPLC column (Kinetex C18 5pm 100A, Phenomenex Inc.) was used for PFAS analysis. The eluent gradient is shown in Table S4 in SI. All samples, calibration standards, and quality control samples were spiked with isotopically labeled internal standards, filtered through 0.45-pm glass microfiber syringe filters, and analyzed in duplicate. The MS transitions for PFAS analytes and internal standards are shown in Table S5 in SI. The quantitation limit (QL) was 25 ng/L for PFOS and perfluorodecanoic acid, and 10 ng/L for other legacy PFASs and PFPrOPrA. The QL was defined as the first point of the standard curve, for which the regression equation yielded a calculated value within 30% error. For PFECAs without analytical standards, chromatographic peak areas are reported. PFAS concentrations along the treatment train of DWTP C were analyzed using a Waters Acquity ultra performance liquid chromatograph interfaced with a Waters Quattro Premier XE triple quadrupole mass spectrometer (Waters, Milford, MA, USA) after solid phase extraction. Method details are described elsewhere.1The QL for all PFASs with analytical standards was 0.2 ng/L, and peak areas were recorded for PFECAs without standards. Sierra Club v. EPA 18cv3472 NDCA Tier 10 Page 2 of 12 ED 002061 00270552-00002 Table SI. Perfluoroalkyl substances (PFASs) detected in the Cape Fear River (CFR) watershed Compound Molecular weight Formula Perfluorocarboxylic acids (PFCAs) CAS# # of perfluorinated carbons Perfluorobutanoic acid (PFBA) 214.0 C4HF7O2 375-22-4 3 Perfluoropentanoic ad d (PFPeA) 264.0 C5HF9O2 2706-90-3 4 Perfluorohexanoic acid (PFHxA) Perfluoroheptanoic acid (PFH pA) 314.1 C6HF11O2 307-24-4 5 364.1 C7HF13O2 375-85-9 6 Perfluorooctanoic acid (PFOA) 414.1 CsHFisCh 335-67-1 7 Perfluorononanoic acid (PFNA) 464.1 C9HF17O2 375-95-1 8 Perfluorodecanoic acid (PFDA) 514.1 C10HF19O2 335-76-2 9 Perfluorosulfonic acids (PFSAs) Perfluorobutane sulfonic acid (PFBS) 300.1 C4HF9SO.3 375-73-5 4 Perfluorohexane sulfonic a d d (PFHxS) 400.1 CeHFisSOs 355-46-4 6 Perfluorooctane sulfonic acid (PFOS) 500.1 C8HF17SO3 1763-23-1 8 Perfluoroalkyl ether carboxylic acids with one ether group (mono-ether PFECAs) Perfluoro-2-methoxyacetic add (PFMOAA) 180.0 GHFsOs 674-13-5 2 Perfluoro-3-methoxypropanoic acid (PFMOPrA) 230.0 C4 H F7O 3 377-73-1 3 Perfluoro-4-methoxybutanoic add (PFMOBA) 280.0 C5 HF9O3 863090-89-5 4 Perfluoro-2-propoxypropanoic acid (PFPrOPrA ) 330.1 CH FiiOs 13252-13-6 5 Perfluoroalkyl ether carboxylic acids with multiple ether group (multi-ether PFECAs) Perfluoro(3,5-dioxahexanoic) add (PF0 2 H xA ) 246.0 C4HF7O4 39492-88-1 3 Perfluoro(3,5,7-trioxaoctanoic) add (P F 030A ) 312.0 G H F9O5 39492-89-2 4 Perfluoro(3,5/7/9-tetraoxadecanoic) acid (PF04D A ) 378.1 1 CHFnOe 39492-90-5 5 Chain length (including all C, O and S) 4 5 6 7 8 9 10 5 7 9 4 5 6 7 6 8 10 Page 3 of 12 Sierra Club v. EPA 18cv3472 NDCA Tier 10 ED 002061 00270552-00003 Table S2. Operational conditions of DWTP C on sampling day (August 18, 2014) Parameter Raw water ozone dose Raw water total organic carbon concentration Aluminum sulfate coagulant dose Coagulation pH Settled water ozone dose Settled water total organic carbon concentration Empty bed contact time in biological activated carbon filters Medium pressure UV dose Free chlorine dose Free chlorine contact time Value 3.1 mg/L 6.0 mg/L 43 mg/L 5.70 1.3 mg/L 1.90 mg/L 9.4 minutes for granular activated carbon layer 2.3 minutes for sand layer 25 m j/cm2 1.26 mg/L as Cb 17.2 hours Table S3. Water quality characteristics of surface water used in adsorption tests N on-purgeable organic carbon (mg/L) 9.036 U ltraviolet absorbance at a w avelength of 254 nm 0.399 pH 7.53 A lk a lin ity (m g/L as C a C O ) 19 C onductivity (uS cm) 133.5 Table S4. LC gradient method for PFAS analysis Time (min) Mobile Phase A% (v/v) Mobile Phase B% Flow Rate (mL/min) 0 -2 95 5 0.9 2 -5 95 5 0.9 O G\ LO 5-10 9 5 - > 10 0.9 10 -1 0 .1 10 90 0.9 10.1 - 1 4 10 - > 9 5 90 --> 5 0.9 Mobile phase A: 2 mM ammonium acetate in ultrapure water with 5% methanol Mobile phase B: 2 m M ammonium acetate in acetonitrile with 5% ultrapure water Sierra Club v. EPA 18cv3472 NDCA Tier 10 Page 4 of 12 ED 002061 00270552-00004 Table S5. MS transitions for PFAS Analysis Legacy PFASs PFECAs Internai standards Compound PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFBS PFHxS PFOS PFMOAA PFMOPrA PFMOBA PFPrOPrA PF02HxA PF030A PF04DA Perfluoro-n-[l,2,3,4-13C4]butanoic acid (13C4-PFBA) Perfluoro-n-[l,2-13C2]hexanoic acid (13C2-PFHxA) Perfluoro-n-[ l /2,3,4-13C2]octanoic acid (13C4-PFOA) Perfluoro-n-[l/2-13C2]decanoic acid (13C2-PFDA) Sodium perfluoro-1 hexane[1802]sulfonate (1802-PFH xS) Sodium perfluoro-1-[1,2,3,4-'3C4] octane sulfonate (13C4-PFOS) MS/MS Transition 212.8 168.8 Internai standard 13C4-PFBA 262.9 218.8 13C2- PFHxA 313.6 --> 268.8 j 13C2- PFHxA 362.9 --> 318.8 ! 13C4- PFOA 413.0 368.8 13C4- PFOA 463.0 418.8 13C4- PFOA 513.1 68.8 13C2-PFDA 299.1 98.8 1802-PFHxS 399.1 98.8 1802-PFHxS 498.9 98.8 13C4-PFOS 180.0 85.0 N/A 229.1 184.9 N/A 279.0 234.8 N/A 329.0 --> 284.7 j 13C2-PFH xA 245.1 -> 85.0 i N/A 311. - 84.9 N/A 377.1 >85.0 N/A 217.0 -> 172 315.1 -> 269.8 417.0 -> 372.0 515.1 -> 469.8 Not applicable 403.1 -> 83.8 502.9 -> 79.9 Sierra Club v. EPA 18cv3472 NDCA Tier 10 Page 5 of 12 ED 002061 00270552-00005 Table S6. Maximum, minimum, m ean and median concentrations (ng/L) of PFASs at three drinking water intakes. * PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFBS PFHxS PFOS PFPrOPrA PFOA+PFOS I PFASs** max 99 191 318 324 137 38 35 80 193 346 <10 447 1502 Community A min median <10 26 14 44 <10 48 <10 39 <10 34 <10 <10 <25 <25 <10 <10 <10 10 <25 29 <10 <10 0 64 18 212 mean 33 62 78 67 46 <10 <25 <10 14 44 <10 90 355 max 38 38 42 85 32 <10 <25 11 14 43 10 59 189 Community B min median <10 12 <10 19 <10 <10 <10 <10 <10 <10 <10 <10 <25 <25 <10 <10 <10 <10 <25 <25 <10 <10 0 0 0 47 mean 12 19 11 11 <10 <10 <25 <10 <10 <25 <10 9 62 max 104 116 24 24 17 <10 <25 <10 14 40 4560 55 4696 Community C min median <10 12 <10 30 <10 <10 <10 <10 <10 <10 <10 <10 <25 <25 <10 <10 <10 <10 <25 <25 55 304 <10 <10 55 345 * Concentrations less than quantitation limits were considered as zero to calculate means and PFASs. mean 22 36 <10 <10 <10 <10 <25 <10 <10 <25 631 <10 710 ** Other PFECAs were present in water samples from community C but could not be quantified and were therefore not included in PFASs Sierra Club v. EPA 18cv3472 NDCA Tier 10 Page 6 of 12 ED 002061 00270552-00006 F, / OH PFMOAA / F / F PFMOBA y OH OH Y- PF02HxA FF FF W V ,o. / V. ,.OH / 'x -o-/ \ / Y Y \ / F FF FF PF04DA Figure SI. Molecular structures of PFECAs evaluated in this study Sierra Club v. EPA 18cv3472 NDCA Tier 10 Page 7 of 12 ED 002061 00270552-00007 Figure S2. Sampling sites in the Cape Fear River watershed, North Carolina. The scale is for the Cape Fear River watershed map. Sierra Club v. EPA 18cv3472 NDCA Tier 10 Page 8 of 12 ED 002061 00270552-00008 Concentration (ng/L) 1200 1000 800 600 400 200 - 0 - Concentration (ng/L) Sierra Club v. EPA 18cv3472 NDCA Tier 10 Page 9 of 12 ED 002061 00270552-00009 Figure S3. PFAS concentration distributions in the CFR watershed at three drinking water intakes. Concentrations less than quantitation limits were considered as zero. Upper and lower edges of a box represent the 75th and 25thpercentile, respectively; the middle line represents the m edian; upper and lower bars represent the 90thand 10thpercentile, respectively; and dots represent outliers (>90thor <10* percentile). Sierra Club v. EPA 18cv3472 NDCA Tier 10 Page 10 of 12 ED 002061 00270552-00010 2.56*0? 2.0E+0? 1.5 E+? l.E+O? 5 5.E+6 * * # * * & y " .l Cofnmunity ..*--pOSnfiOW-- A | PFSs ! AII * W i l * . A MV 2500 2000 1500 |f 1000 w 500 .E4-00 .................................................................................. 0 6/15/13 7/30/13 9/13/13 10/28/13 12/12/13 4,64-07 3.6407 * # Community 8 # Mean flow AAJ2 -4FfAasSsS 500 400 300 "Xd 2,5407 % S 1.6407 0,6400 6/15/13 7/30/13 -M 9/13/13 200 CL w 100 27 a- 0 10/28/13 12/12/13 6000 5000 V/ E 4000 g 3000 2000 4\i 1000 0 Figure S4. Total PFAS concentrations in the source water and stream flow at the three studied DWTPs. Stream flow data were acquired from US Geological Survey stream gage records Page 11 of 12 Sierra Club v. EPA 18cv3472 NDCA Tier 10 ED 002061 00270552-00011 100% a 1-30% 80% ,Oo'-- 60% ~j! PFNA -O P F D A --o --PFBS <>??Kx$ ~*~PF0S -20% H------------1------------i------------i------------1----------- :------------1------------1 0 20 40 60 80 100 120 140 ppm OPrA * tim e {min) PFM CBA PFPrOPrA ~0~ PF02H:<A O PF3A <> PF04DA 100% -i------------------------------------------------------------------------------------ ; I d 80% "! --#- PFNA ~ O P F D A ~o~PF3S %>WPFHS ~&~PF0S "20% H------------(----------- !----------- !----------- !----------- !----------- :----------- i 0 20 40 60 80 100 120 140 tim e {min) -s^PFM O PrA HBhPFMOBA PFPrOPrA PF02HxA O PF030A -O -P F 04D A PFNA ~0~PFDA ~o*~PFBS 'Ya -'PFHxS ~A-~PF$ TM*TMPFM0PrA 0^PFO2HxA tim e {min) High PFM OBA -O P F 030A PFPrOPrA PF04DA Figure S5. PFAS adsorption at powdered activated carbon doses of (a, b) 30 mg/L, (c, d) 60 mg/L and (e, f) 100 mg/L. Figures show average PFAS removal percentages of duplicate tests. Reference 1. Nakayama, S.; Strynar, M. J.; Helfant, L.; Egeghy, P.; Ye, X.; Lindstrom, A. B., Perfluorinated compounds in the Cape Fear drainage basin in North Carolina. Environ. Sci. Technol. 2007,41, (15), 5271-5276. Page 12 of 12 Sierra Club v. EPA 18cv3472 NDCA Tier 10 ED 002061 00270552-00012