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Home My WebLink AboutDEQ-CFW_00082291MMM Supporting information includes analytical method description, 8tohles, and 5 figures. MeiSun 1,c',8|ba» Mark Strvnarl, Az�drevvLind�rmn�,N�i�hac|Dichardoon�Ben KearnS4 Admn Pickett5, Chris and DcddFLU. /Department ofCivil and Environmental Engineering University ofNorth Carolina aLCharlotte North Carolina 28223,USA 2Department of Civil, Construction, and Environmental Engineering North Carolina State University Raleigh, North Carolina 27695, USA »Nbhona| Exposure Research Laboratory U.S. Protection Agency Research Triangle Park, North Carolina 27711, USA 4Cape Fear Public Utility Authority Wilmington, North Carolina 28403, USA oTovvnofPiMeboro Pittsboro, North Carolina 27312, USA o Fayetteville Public Works Commission North Carolina 283O1,USA *Corresponding Author Email: msun8(0uncc.edu; Phone: 704-687-1723 Page I of 12 OEQ-CFVV_00082291 Analytical standards: PFASs studied inthis research are listed bnTable S1. For legacy PFASs, native and isotopically labeled standards were purchased from Wellington Laboratories (Guelph, Ontario, Canada). Native PPPrOPzAwas purchased from Thermo Fisher Scientific (Waltham, M/\). Noanalytical standards were available for other PB8CAs. PFAS quantification: PPAS concentrations in samples frorn DWTPs and adsorption tests were determined hyliquid chromatography tandem mass spectrometry (L{-Mg/w&S)using alarge- volume 0.9mDcirect'ection method. An AgilentllOOSeries LC pump and PESciesAPI 3OOOLC-MS/M5system equipped vvidha4.6rnms5OnnnHPLC cokomun/|{inchcsCl@5pn lOO` 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-p.m 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 perfhzorodecomoic acid,i and 1OnvfL.for other legacy PB/\Ss and PPPr(}Pz/\. The ()Lvvao defined as the first point of the standard curve, for which the regression equation yielded a calculated value within ±3O% error. For P98CAsvvithouL analytical standards, chromatographic peak areas are reported. PP/\S concentrations along the treatment train of[XyVTPCwere analyzed using aWaters /\ronitvuhra performance Unnk1 chromaLog7onh interfaced with aWaters C)uattroPremier XB triple quadrupole mass spectrometer (Waters, Milford, LMA, USA) after solid phase extraction. Method details are described elsewhere.' The ()Lfor all PF/\Sy with analytical standards was O.2nF/L,and peak areas were recorded for pFBC/\awithout standards. Page 2 of 12 Table SI. Perfluoroalkyl substances (PFASs) detected in the Cape Fear River (CFR) watershed Perfluorocarboxylic acids (PFCAs) ................................................................................................................................................................................................. ........................................... .............................................. .................................................. ........................................................... .......................................................... Perfluorobutanoic acid (PFBA) 214.0 C4HF702 375-22-4 3 4 Perfluoropentanoic acid (PFPeA) 264.0 C5HF902 2706-90-3 4 5 ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ Perfluorohexanoic acid (PFHxA) ------------------------------------------- 314.1 ---------------------------------------------- ------------------------------------------------- C6HF1102 ----------------------------------------------------------- 307-24-4 --------------------------------------------------------- 5 6 Perfluoroheptanoic acid (PFHpA) 364.1 C7HF1302 375-85-9 6 7 ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ Perfluorooctanoic acid (PFOA) ------------------------------------------- 414.1 ----------------------------------------------- -------------------------------------------------- C8HF1502 ----------------------------------------------------------- 335-67-1 --------------------------------------------------------- 7 8 Perfluorononanoic acid (PFNA) 464.1 C9HF1702 375-95-1 8 9 ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ Perfluorodecanoic acid (PFDA) -------------------------------------------- 514.1 ---------------------------------------------- ------------------------------------------------- C1oHF1902 ----------------------------------------------------------- 335-76-2 --------------------------------------------------------- 9 10 .......................................................... Perfluorosulfonic ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- ------------------------------------------- .............................................................................................................................................................. acids (PFSAs) ---------------------------------------------- -------------------------------------------------- ----------------------------------------------------------- .......................................................... --------------------------------------------------------- Perfluorobutane sulfonic acid (PFBS) 300.1 C4HF9SO3 375-73-5 4 5 Perfluorohexane sulfonic acid (PFHxS) 400.1 .............. .................................................. C6HF13SO3 ........................................................... 355-46-4 ......................................................... 6 7 ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ Perfluorooctane sulfonic acid (PFOS) ------------------------------------------- 500.1 ---------------------------------------------- ------------------------------------------------- C8HF17SO3 : ----------------------------------------------------------- 1763-23-1 --------------------------------------------------------- 8 9 ................................................................................................................................................................................................. ........................................... Perfluoroalkyl ether carboxylic acids with ................................................ .............................................................................................................. .......................................................... one ether group (mono -ether PFECAs) ......................................................... Perfluoro-2-methoxyacetic acid (PFMOAA) 180.0 C3HF503 674-13-5 2 4 Perfluoro-3-i-nethoxypropanoic acid (PFMOPrA) 230.0 C4HF703 377-73-1 3 5 ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- Perfluoro-4-methoxybutanoic acid (PFMOBA) ------------------------------------------- 280.0 ----------------------------------------------- -------------------------------------------------- C5HF903 ----------------------------------------------------------- 863090-89-5 --------------------------------------------------------- 4 6 Perfluoro-2-propoxypropanoic acid (PFPrOPrA) 330.1 C6HF1103 13252-13-6 : 5 7 ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- ------------------------------------------- ----------------------------------------------- --------------------------------------------------- ------------------------------------------------------------ : --------------------------------------------------------- Perfluoroalkyl ether carboxylic acids with multiple ether group (multi -ether PFECAs) ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ ------------------------------------------ ---------------------------------------------- ------------------------------------------------- ----------------------------------------------------------- --------------------------------------------------------- Perfluoro(3,5-dioxahexanoic) acid (PF02HxA) 246.0 C4HF704 39492-88-1 3 6 ................................................................................................................................................................................................. Perfluoro(3,5,7-trioxaoctanoic) acid (PF030A) ........................................... 312.0 ............................................... .................................................. C5HF905 ...................................................... 39492-89-2 4 8 Per fluoro(3,5,7,9-tetraoxadecanoic) acid (PF04DA) ............................................................................................................................................................................................................................................. 378.1 C6HF1106 ............................................... .................................................. 39492-90-5 ........................................................... 5 ......................................................... 10 Page 3 of 12 DEQ-CFW-00082293 Table S2. Operational conditions of DWTP C on sampling day (August 18,2014) Raw water ozone dose 3.1 mg/L Raw water total organic carbon concentration 6.0 mg,,,L Aluminum sulfate coagulant dose 43 mg/L Coagulation pH 5.70 Settled water ozone dose 1.3 mg,,,L Settled water total organic carbon concentration 1.90 mg,,"L Empty bed contact time in biological activated carbon filters 9.4 minutes for granular activated carbon layer 2.3 minutes for sand layer Meditun pressure UV dose 25MJ/CM2 Free chlorine dose 1.26 mg/L asC12 Free chlorine contact time 17.2 hours Table S3. Water quality characteristics of surface water used in adsorption tests Table S4. LC gradient method for PFAS analysis Mobile phase A: 2 mM ammonium acetate in ultrapure water with 5% methanol Mobile phase B: 2 mM ammonium acetate in acetonitrile with 5% ultrapure water Page 4 of 12 DEQ-CFW-00082294 Tab|cS5. MStransitions for PFAS Analysis Page 5 of 12 Page 5 of 12 Tab|eS6. Maximum, minimum, mean and median concentrations (np/i)ofPPASoa1th,cc drinking water intakes. °Concentrations less than quantitation limits were considered as zero to calculate means and PFASs. �Other PFECAs were present inwater samples from community Cbut could not be quantifiedand were therefore not included in Page 6 of 12 F 0 Cluff xe OH PFMOAA F F F 0 F F F OH F PFMODA F F 0 F F 0 0-----/, +� "b /H, , F F PFO2HxA F / F F \ \ 0 / /r- F F 0 F F F F F PF04DA 0 F f 0- F OH F PFmOprA PFPrOPrA rI*UiUA Figure SI. Molecular structures of PFECAs evaluated in this study Page 7 of 12 DEQ-CFW-00082297 N Rhvr mnui.Wy A N DIAUP Deep Mver Flow direction . ..... .......... Community B DWTP North Carolina Cape Fear Ili �,er WA ........... so I : ............. Wi 7 ................. ... NY . ............ ........ ...... ........ ta fu ON . ..... rTk co KS Mo .......... VA ......... ............. TU Az nN OR . ...... ......... AR AL 0,k . . . ........ . TX . . ......... . . ............... -� for PA C u.',, `., 3 100 km comn-lunity C DVV-TP Figure S2. Sampling sites in the Cape Fear River watershed, North Carolina. The scale is for the Cape Fear River watershed map. Page 8 of 12 DEQ-CFW-00082298 1200 1000 0) c u c 0 600 cu c c(Da 400 c 0 N# 0 Q�Q�pQ�PQ�g Q��e Q��yQ��PQ�pPQ��Pp�®PQ�g pE, Q� ma 150 0 ®PP��PP�®P� ��P�p p�P�k4�p� Page 9 of 12 DEQ-CFW 00082299 im C 0 CU 2000 a) 0 a Q�Q�OQ(PQ�Qj Q�QO Q��-�,��'QF'`4�®Q`Q�,�Q`Q�,oQ`��Qj ��,�-{.�Q�Q54�®Px��®� 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 75t', and 25thpercentile, respectively; the middle line represents the median; upper and lower bars represent the 901hand 10thpercentile, respectively; and dots represent outliers (>90thor <10ffi percentile). Page 10 of 12 DEQ-CFW-00082300 2,5E+07 2,0E+07 S 1, 5 E+07 LOE+07 5,OE+06 2500 2000 1500 19 1000 Vl. 500 . ........... . ............ ............. 0 611`15/13 711" -; 0 113 %1`13/13 1 OIQ 21/ 13 12/ 12/13 '00 4,E�07 M e a n #1 om, 400 PFASs 300 �P is 2,E�07 2,0c LE4-07 100 '0 0 ----------------------------------------------- ..... 0 6/1,5,'13 760."13 911"13/13 Q/ 2 8 3 12VIV13 07 Community C 5,&�-07 al Mean flow 4,E 7 PM ks- -g, I07 21-�-07 1,E+07 O,E,00 ......................................... ... 6 1/13 7/11/13 7/31/13 8/301,113 91'1"/29/13 6000 5000 4000 C 3000 V� 2000 1000 0 Fig -Lire 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 DEQ-CFW-00082301 ----------------------------------------------------------------------------------------------------------------------------- a 80% 60% ....................... ......... 40% 20nX 0% -20% ----------------- ----------------------------------------------------- --- ---------------- - -- -------------------------------- 0 20 40 60 so 10G. 120 140 firne (min) -4!-PFBA --?A,-PFPeA -.--.-,,,PFHXA -*-PFHpA -XI PFOA PF NA --(>-PFDA PRS -*-PFOS C 60% 40% 20- -20% ----------------- ----------------- ----------------- ---------------------------------------------------------- ----------------- 0 20 40 60 so 100 120 140 firne (min) -4-PFSA -�-PFPeA -.-.-,,-PFHXA -*-PFHpA -\- PFOA PF N.'A -<)-PFDA --O-PFBS --.:,.-PFHS -*-PFOS loc.% or e 4M,, 2055 -20% A ................. ................. T ---------------- T ---------------- T ---------------- T ----------------- ----------------- 1 : 0 20 40 60 80 1 or, 120 140 time (min) --,t,-PFBA --*-PFPeA PFHY.A --X-PFP.[)A PFOA PFNA -<)-PFDA -*-PFBS Mix" --.A-PFOS —111 SaX. 6M. 4(YX E 2, OIX 0% -20% 0 80% 6 W/c. 4 WX 101 2 u 0% -20% 0 1-11. 801% 6M. E 0% -20% 0 20 40 60 80 100 120 140 tittle (min) -,�!-PFMOPrA -8-PFMOSA PFPrOPrA --,'�-PF02HxA -0-PF030A PF04DA 20 40 60 so loc) 120 140 time (min) -*-PFtVI0PrA -0-PFMOBA PFPrOPrA ,>-PF02HxA -G-PFO.30A PF04DA 20 40 60 80 1.00 120 140 time (min) -4-PFNIOPrA -0-PFMOBA PFPrOPrA �—PF02HxA -0-PF030A PF04DIA 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. Tcchnol. 2007,41, (15), 5271-5276. Page 12 of 12 DEQ-CFW-00082302