DEQ-CFW_00002928

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Smencedeldondogg Lf TTf �S pubs.acs.org/journal/esticu
Legacy and Emerging Perfluoroalkyl Substances Are Important
Drinking Water Contaminants in the Cape. Fear River Watershed of
North Carolina
Meier_ *'t'$19 Elisa Arevalo,* Mark Strynar,§ Andrew Lindstrom,' Michael Richardson,'' Ben Kearns,ll
Adam Picckett,1 Chris Smith," and Detlef R U. Knape$
tDepartment of Civil and Environmental Engineering, University of North Carolina at Charlotte, Charlotte, North Carolina 28223,
United States
*Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Raleigh, North Carolina
27695, United States
National Exposure Research Laboratory, U.S. Environmental Protection Agency Research, Triangle Park, North Carolina 27711,
United States
"Cape Fear Public Utility Authority, Wilmington, North Carolina 28403, United States
1Town of Pittsboro, Pittsboro, North Carolina 27312, United States
#Fayetteville Public Works Commission, Fayetteville, North Carolina 28301, United States
© Supporting Information
ABSTRACT: Long -chain per- and polyfluoroalkyl substances Point & A � Leg cy PFAS
(PFASs) are being replaced by short -chain PFASs and non -point b A
0
fluorinated alternatives. For ten legacy PFASs and seven sources • B a PFPrOPrA ("GenX")
recently discovered perfluoroalkyl ether carboxylic acids c
(PFECAs), we report (1) their occurrence in the Cape Fear o zoo aoo 600 soo
River (CFR) watershed, (2) their fate in water treatment F PFAS Concentration (ng/L)
processes, and (3) their adsorbability on powdered activated F •g
carbon (PAC). In the headwater region of the CFR basin, F_ F F F O
PFECAs were not detected in raw water of a drinking water I I I OH Fluorochemical
treatment plant (DWTP), but concentrations of legacy PFASs F F F Manufacturer C�
were high. The U.S. Environmental Protection Agency's PFPrOPrA ("GenX")
lifetime health advisory level (70 ng/L) for perfluorooctane-
sulfonic acid and perfluorooctanoic acid (PFOA) was exceeded on 57 of 127 sampling days. In raw water of a DWTP
downstream of a PFAS manufacturer, the mean concentration of perfluoro-2-propoxypropanoic acid (PFPrOPrA), a replacement
for PFOA, was 631 ng/L (n = 37). Six other PFECAs were detected, with three exhibiting chromatographic peak areas up to 15
times that of PFPrOPrA. At this DWTP, PFECA removal by coagulation, ozonation, biofiltration, and disinfection was negligible.
The adsorbability of PFASs on PAC increased with increasing chain length. Replacing one CF2 group with an ether oxygen
decreased the affinity of PFASs for PAC, while replacing additional CF2 groups did not lead to further affinity changes.
■ INTRODUCTION
Per- and polyfluoroalkyl substances (PFASs) are extensively
used in the production of plastics, water/stain repellents,
firefighting foams, and food -contact paper coatings. The
widespread occurrence of PFASs in drinking water sources is
closely related to the presence of sources such as industrial
sites, military fire training areas, civilian airports, and waste-
water treatment plants.' Until 2000, long -chain perfluoroalltyl
sulfonic acids [C„F2n+1S03H; n > 6 (PFAAs)] and perfluoro-
alkyl carboxylic acids [C„F2n+1COOH; n > 7 (PFCAs)] were
predominantly used.2 Accumulating evidence about the
ecological persistence and human health effects associated
with exposure to long -chain PFASs3'4 has led to an increased
level of regulatory attention. Recently, the U.S. Environmental
Protection Agency (USEPA) established a lifetime health
ACS Publications ® XXXX American Chemical Society A
advisory level (HAL) of 70 ng/L for the sum of
perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic
acid (PFOS) concentrations in drinking water.516 Over the past
decade, production of long -chain PFASs has declined in Europe
and North America, and manufacturers are moving toward
short -chain PFASs and fluorinated alternatives.-10 Some
fluorinated alternatives were recently identified,s'" but others
remain unknown12-14 because they are either proprietary or
manufacturing byproducts.
Received: October 13, 2016
Revised: November 8, 2016
Accepted: November 10, 2016
Published: November 10, 2016
DOI: 10.1021 /acs.estlett.6b00398
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One group of fluorinated alternatives, perfluoroalkyl ether
carboxylic acids (PFECAs), was recently discovered in the Cape
Fear River (CFR) downstream of a PFAS manufacturing
facility.' 1 Identified PFECAs included perfluoro-2-methoxy-
acetic acid (PFMOAA), perfluoro-3-methoxypropanoic acid
(PFMOPrA), perfluoro-4-methoxybutanoic acid (PFMOBA),
perfluoro-2-propoxypropanoic acid (PFPrOPrA), perfluoro-
(3,5-dioxahexanoic) acid (PF02HxA), perfluoro(3,5,7-trioxa-
octanoic) acid (PF030A), and perfluoro(3,5,7,9-tetraoxadeca-
noic) acid (PF04DA) (Table S1 and Figure S1). The
ammonium salt of PFPrOPrA is a known PFOA altemativels
that has been produced since 2010 with the trade name
"GenX". To the best of our knowledge, the only other
published PFECA occurrence data are for PFPrOPrA in Europe
and China,'s and no published data about the fate of PFECAs
during water treatment are available. Except for a few studies
(most by the manufacturer),16-20 little is known about the
toxicity, pharmacokinetic behavior, or environmental fate and
transport of PFECAs.
The strong C—F bond makes PFASs refractory to abiotic and
biotic degradation ,21 and most water treatment processes are
ineffective for legacy PFAS removal.22-27 Processes capable of
removin PFCAs and PFAAs include nanofiltration,28 reverse
osmosis, s ion exchange,28,29 and activated carbon adsorp-
tion,28,29 with activated carbon adsorption being the most
widely employed treatment option.
The objectives of this research were (i) to identify and
quantify the presence of legacy PFASs and emerging PFECAs
in drinking water sources, (2) to assess PFAS removal by
conventional and advanced processes in a full-scale drinking
water treatment plant (DWTP), and (3) to evaluate the
adsorbability of PFASs on powdered activated carbon (PAC).
■ MATERIALS AND METHODS
Water Samples. Source water of three DWTPs treating
surface water in the CFR watershed was sampled between June
14 and December 2, 2013 (Figure S2). Samples were collected
from the raw water tap at each DWTP daily as either 8 h
composites (DWTP A, 127 samples) or 24 h composites
(DWTP B, 73 samples; DWTP C, 34 samples). Samples were
collected in 250 mL HDPE bottles and picked up (DWTPs A
and B) or shipped overnight (DWTP C) on a weekly basis. All
samples were stored at room temperature until they were
analyzed (within 1 week of receipt). PFAS losses during storage
were negligible on the basis of results of a 70 day holding study
at room temperature. On August 18, 2014, grab samples were
collected at DWTP C after each unit process in the treatment
train [raw water ozonation, coagulation/flocculation/sedimen-
tation, settled water ozonation, biological activated carbon
(BAC) filtration, and disinfection by medium -pressure UV
lamps and free chlorine]. Operational conditions of DWTP C
on the sampling day are listed in Table S2. Samples were
collected in 1 L HDPE bottles and stored at room temperature
until they were analyzed. On the same day, grab samples of
CFR water were collected in six 20 L HDPE carboys at William
0. Huske Lock and Dam downstream of a PFAS manufacturing
site and stored at 4 °C until use in PAC adsorption experiments
(background water matrix characteristics listed in Table S3).
Adsorption Experiments. Adsorption of PFASs by PAC
was studied in batch reactors (amber glass bottles, 0.45 L of
CFR water). PFECA adsorption was studied at ambient
concentrations (-1000 ng/L PFPrOPrA, chromatographic
peak areas of other PFECAs being approximately 10-800%
of the PFPrOPrA area). Legacy PFASs were present at low
concentrations (<40 ng/L) and spiked into CFR water at
—1000 ng/L each. Data from spiked and nonspiked experi-
ments showed that the added legacy PFASs and methanol (1
ppm,) from the primary stock solution did not affect native
PFECA removal. A thermally activated, wood -based PAC
(PicaHydro MP23, PICA USA, Columbus, OH; mean diameter
of 12 µm, BET surface area of 1460 m2/Q)30 proven to be
effective for PFAS removal in a prior studY2 was used at doses
of 30, 60, and 100 mg/L. These doses represent the upper
feasible end for drinking water treatment. Samples were taken
prior to and periodically after PAC addition for PFAS analysis.
PFAS losses in PAC -free blanks were negligible.
PFAS Analysis. Information about analytical standards and
liquid chromatography —tandem mass spectrometry (LC —MS/
MS) methods for PFAS quantification is provided in the
Supporting Information.
■ RESULTS AND DISCUSSION
Occurrence of PFASs in Drinking Water Sources. Mean
PFAS concentrations in source water of three DWTPs treating
surface water from the CFR watershed are shown in Figure 1.
PFBA ■ PFPeA ■ PFHxA ■ PFHPA ■ PFOA ■ PFNA
■ PFDA ■ PFBS ■ PFHxS ■ PFOS ■ PFRONA
Community A
n=127
Community B
n-73
Community C
n=3A
0 200 400 600 800
Average concentration in drinking watersource (ng/L)
Figure 1. Occurrence of PFASs at drinking water intakes in the CFR
watershed. Concentrations represent averages of samples collected
between June and December 2013. Individual samples with
concentrations below the quantitation limits (QLS) were considered
as 0 when calculating averages, and average concentrations below the
QLs were not plotted.
In communities A and B, only legacy PFASs were detected
(mean YPFAS of 355 ng/L in community A and 62 ng/L in
community B). Detailed concentration data are shown in Table
S6 and Figure S3. In community A, PFCAs with four to eight
total carbons, perfluorohexanesulfonic acid (PFHxS), and
PFOS were detected at mean concentrations above the
quantitation limits (QLs). During the 127 day sampling
campaign, the sum concentration of PFOA and PFOS exceeded
the USEPA HAL of 70 ng/L on 57 days. The mean sum
concentration of PFOA and PFOS over the entire study period
was 90 ng/L, with approximately equal contributions from
PFOS (44 ng/L) and PFOA (46 ng/L). Maximum PFOS and
PFDA concentrations were 346 and 137 ng/L, respectively.
Similar PFOS and PFOA concentrations were observed in the
same area in 2006,31 suggesting that PFAS source(s) upstream
of community A have continued negative impacts on drinking
water quality. Also, our data show that legacy PFASs remain as
surface water contaminants of concern even though their
production was recently phased out in the United States. It is
important to note, however, that among the PFCAs that were
measured in both 2006 and 2013 (PFHxA to PFDA), the
PFCA speciation shifted from long -chain (-80-85%
C„F2n+1COOH; n = 7-9) in 2006 to short -chain (76%
C„F2„+1COOH; n = 5-6) in 2013. In contrast, the PFSA
speciation was dominated by PFOS in both 2006 and 2013.
DOI: 10.1021 /acs.estlett.6600398
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Relating total PFAS concentration to average daily streamflow
(Figure S4) illustrated a general trend of low PFAS
concentrations at high flow, and high concentrations at low
flow, consistent with the hypothesis of one or more upstream
point sources.
In community B, perfluorobutanoic acid (PFBA) and
perfluoropentanoic acid (PFPeA) were most frequently
detected with mean concentrations of 12 and 19 ng/L,
respectively. Mean PFOA and PFOS concentrations were
below the QLs, and the maximum sum concentration of PFOA
and PFOS was 59 ng/L. Lower PFAS concentrations in
community B relative to community A can be explained by the
absence of substantive PFAS sources between the two
communities, dilution by tributaries, and the buffering effect
of Jordan Lake, a large reservoir located between communities
A and B.
In community C (downstream of a PFAS manufacturing
site), only mean concentrations of PFBA and PFPeA were
above the QLs. The relatively low concentrations of legacy
PFASs in the finished drinking water of community C are
consistent with results from the USEPA's third unregulated
contaminant monitoring rule for this DWTP. ;2 However, high
concentrations of PFPrOPrA were detected (up to —4500 ng/
L). The average PFPrOPrA concentration (631 ng/L) was
approximately 8 times the average summed PFCA and PFSA
concentrations (79 ng/L). Other PFECAs had not yet been
identified at the time of analysis. Similar to communities A and
B, the highest PFAS concentrations for community C were also
observed at low flow (Figure S4). Stream flow data were used
in conjunction with PFPrOPrA concentration data to
determine PFPrOPrA mass fluxes at the intake of DWTP C.
Daily PFPrOPrA mass fluxes ranged from 0.6 to 24 kg/day with
a mean of 5.9 kg/day.
Fate of PFASs in Conventional and Advanced Water
Treatment Processes. To investigate whether PFASs can be
removed from impacted source water, samples from DWTP C
were collected at the intake and after each treatment step.
Results in Figure 2 suggest conventional and advanced
treatment processes (coagulation/flocculation/sedimentation,
raw and settled water ozonation, BAC filtration, and
disinfection by medium -pressure UV lamps and free chlorine)
did not remove legacy PFASs, consistent with previous
studies.22-26 The data further illustrate that no measurable
PFECA removal occurred in this DWTP. Concentrations of
some PFCAs, PFSAs, PFMOPrA, PFPrOPrA, and PFMOAA
may have increased after ozonation, possibly because of the
oxidation of precursor compounds.25 Disinfection with
medium -pressure UV lamps and free chlorine (located between
the BAC effluent and the finished water) may have decreased
concentrations of PFMOAA, PFMOPrA, PFMOBA, and
PFPrOPrA, but only to a limited extent. Small concentration
changes between treatment processes may also be related to
temporal changes in source water PFAS concentrations that
occurred in the time frame corresponding to the hydraulic
residence time of the DWTP.
Results in Figure 2 further illustrate that the PFAS signature
of the August 2014 samples was similar to the mean PFAS
signature observed during the 2013 sampling campaigns shown
in Figure 1; i.e., PFPrOPrA concentrations (400-500 ng/L)
greatly exceeded legacy PFAS concentrations. Moreover, three
PFECAs (PFMOAA, PF02HxA, and PF030A) exhibited peak
areas 2-113 times greater than that of PFPrOPrA (Figure 2b).
(a) Raw water
Pre -ozone effluent
Settled water
Settled -ozone effluent
BAC effluent
Finished water
0 100 200 300 400 500 600 700 800
Concentration of traditional PFASs
at a NTP in Community C (ng/L)
■ PFPrOPrA PFBA ■ PFPeA ■ PFHxA ■ PFHpA ■ PFOA
• PFNA ■ PFDA ■ PFBS ■ PFHS ■ PFOS �—
(b) Raw water
Pre -ozone effluent
Settled water
Settled -ozone effluent
BAC effluent
Finished water
a
a
■
0 -90,000 100,000 150,000 200,000 250,000 300,000
Peak area counts of emerging PFASs
at a wrP in Community C
■ PFPrOPrA a PFMOAA PFMOPrA ■ PFMOBA
PF02HxA ■ PF030A PF07DA
Figure 2. Fate of (a) legacy PFASs and PFPrOPrA and (b) PFECAs
through a full-scale water treatment plant. Because authentic standards
were not available for PFECAs other than PFPrOPrA, chromato-
graphic peak area counts are shown in panel b. PFPrOPrA data are
shown in both panels and highlighted with dashed ovals for reference.
Compounds with concentrations below the QLs were not plotted.
The existence of high levels of emerging PFASs suggests a need
for their incorporation into routine monitoring.
Adsorption of PFASs by PAC. PAC can effectively remove
long -chain PFCAs and PFSAs, but its effectiveness decreases
with decreasing PEAS chain length.24,25,29 It is unclear,
however, how the presence of ether group(s) in PFECAs
impacts adsorbability. After a contact time of 1 h, a PAC dose
of 100 mg/L achieved >80% removal of legacy PFCAs with
total carbon chain lengths of >7. At the same PAC dose,
removals were 95% for PF04DA and 54% for PF030A, but
<40% for other PFECAs. Detailed removal percentage data as a
function of PAC contact time are shown in Figure S5. There
was no meaningful removal of PFMOBA or PFMOPrA, and the
variability shown in Figure S5 is most likely associated with
analytical variability. PFMOAA could not be quantified by the
analytical method used for these experiments; however, on the
basis of the observations that PFAS adsorption decreases with
decreasing carbon chain length and that PFECAs with one or
two more carbon atoms than PFMOAA (i.e., PFMOPrA and
PFMOBA) exhibited negligible removal (Figure 3), it is
expected that PFMOAA adsorption is also negligible under
the tested conditions.
To compare the affinity of different PFASs for PAC, PEAS
removal percentages were plotted as a function of PFAS chain
length [the sum of carbon (including branched), ether oxygen,
and sulfur atoms] (Figure 3b). The adsorbability of both legacy
and emerging PFASs increased with increasing chain length.
PFSAs were more readily removed than PFCAs of matching
chain length, a result that agrees with those of previous
DOI: 10.1021 /acs.estlett.6b00398
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1001;
>e 80%
60%
0
40%
20%
0%
-20%
(a) ■ 30 mg/L
■ 60 mg/L
■ 100 mg/L
fb u X ¢fl, Q
Oc
Q \ a ¢ �v
Q• Qf
x O
0 C O
N O O
a
PFCAs
Mono -ether PFECAs
Multi -ether PFECAs PFSAs
g� 100%
4 80%
a 60%
n £ 40%
20%
0
£ e 0%
it
-20%
(b)
a
3 5 7 9 11
Chain length
--w-PFCAs - -Mono-ether PFECAs --o-Multi-ether PFECAs - PFSAs
Figure 3. PFAS adsorption on PAC (a) at carbon doses of 30, 60, and 100 mg/L and (b) as a function of PFAS chain length. The PAC contact time
in CPR water was 1 h. Legacy PFASs were spiked at —1000 ng/L, and the emerging PFASs were at ambient concentrations. Figures show average
PFAS removal percentages, and error bars show one standard deviation of replicate experiments.
studies.zazs,zv PFECAs exhibited adsorbabilities lower than
those of PFCAs of the same chain length (e.g., PFMOBA <
PFHxA), suggesting that the replacement of a CFZ group with
an ether oxygen atom decreases the affinity of PFASs for PAC.
However, the replacement of additional CFZ groups with ether
groups resulted in small or negligible affinity changes among
the studied PFECAs (e.g., PFMOBA — PFO2HxA, PFPrOPrA
PF03OA). Alternatively, if only the number of perfluorinated
carbons were considered as a basis of comparing adsorbability,
the interpretation would be different. In that case, with the
same number of perfluorinated carbons, PFCAs have an affinity
for PAC higher than that of mono ether PFECAs (e.g., PFPeA >
PFMOBA) but an affinity lower than that of multi -ether
PFECAs (e.g., PFPeA < PF030A).
To the best of our knowledge, this is the first paper reporting
the behavior of recently identified PFECAs in water treatment
processes. We show that PFECAs dominated the PFAS
signature in a drinking water source downstream of a
fluorochemical manufacturer and that PFECA removal by
many conventional and advanced treatment processes was
negligible. Our adsorption data further show that PFPrOPrA
("GenX") is less adsorbable than PFOA, which it is replacing.
Thus, PFPrOPrA presents a greater drinking water treatment
challenge than PFOA does. The detection of potentially high
levels of PFECAs, the continued presence of high levels of
legacy PFASs, and the difficulty of effectively removing legacy
PFASs and PFECAs with many water treatment processes
suggest the need for broader discharge control and contaminant
monitoring.
■ ASSOCIATED CONTENT
© Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.estlett.6b00398.
Six tables, five figures, information about PFASs,
analytical methods, and detailed results (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: [e-mail]. Phone: [phone].
ORCID 0
Mei Sun: 0000-0001-5854-9862
Notes
The views expressed in this article are those of the authors and
do not necessarily represent the views or policies of the
USEPA.
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research was supported by the National Science
Foundation (Grant 1550222), the Water Research Foundation
(Project 4344), and the North Carolina Urban Water
Consortium.
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(25) Rahman, M. F.; Peldszus, S.; Anderson, W. B. Behaviour and
fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in
drinking water treatment: A review. Water Res. 2014, 50, 318-340.
(26) Appleman, T. D.; Higgins, C. P.; Quinones, 0.; Vanderford, B.
J.; Kolstad, C.; Zeigler-Holady, J. C.; Dickenson, E. R. V. Treatment of
poly- and perfluoroalkyl substances in U.S. full-scale water treatment
systems. Water Res. 2014, 51, 246-255.
(27) Merino, N.; Qu, Y.; Deeb, R. A.; Hawley, E. L.; Hoffmann, M.
R; Mahendra, S. Degradation and removal methods for perfluoroalkyl
and polyfluoroalkyl substances in water. Environ. Eng. Sci. 2016, 33 (9),
615-649.
(28) Appleman, T. D.; Dickenson, E. R. V.; Bellona, C.; Higgins, C.
P. Nanofiltration and granular activated carbon treatment of
perfluoroalkyl acids. J. Hazard. Mater. 2013, 260, 740-746,
(29) Dudley, L. A.; Arevalo, E. C.; Knappe, D. R. U. Removal of
p4uoroalkyl substances by PAC adsorption and anion exchange; Water
Research Foundation: Denver, 2015.
(30) Dunn, S. E.; Knappe, D. R U. Disinfection by-product precursor
and micropollutant removal by powdered activated carbon; Water
Research Foundation: Denver, 2013.
(31) 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.
(32) Unregulated contaminant monitoring rule 3 (UCMR 3). http://
water.epa.gov/lawsregs/rulesregs/sdwa/ucmr/ucmr3/; U.S. Environ-
mental Protection Agency: Washington, DC (accessed July 29, 2016).
DOI: 10.1021 /acs.estle".W0398
Environ. Sci. Technol. Lett. XXXX, XXX, XXX—XXX
DEQ-CFW 00002932

all
",- 1 /1" t/, ` - 0(
DEQ-CFW-00002933

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 Sun',', ", Elisa Areval02, Mark Strynar3, Andrew Lindstrom', Michael Richardson4, Ben
Kearns4, Adam Pickett', Chris Smith6, and Detlef R.U. Knappe2
' Department 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: [e-mail]; Phone: [phone]
Page 1 of 12
DEQ-CFW 00002934

Analytical standards: PFASs studied in this research are listed in Table S1. 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 large -
volume (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 5µm
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-µm 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.' The QL for all PFASs with analytical standards was
0.2 ng/L, and peak areas were recorded for PFECAs without standards.
Page 2 of 12
DEQ-CFW 00002935

Table S1. Perfluoroalkyl substances (PFASs) detected in the Cape Fear River (CFR) watershed
Molecular - Of Chain length
Conipound weight Forniula CAS:perfluorinated (including all
carbons C, • and S)
Perfluorocarboxylic acids (PFCAs)
Perfluorobutanoic acid (PFBA)
214.0
C4HF702
375-22-4
3
4
Perfluoropentanoic acid (PFPeA)
264.0
C5HF9O2
2706-90-3
4
5
Perfluorohexanoic acid (PFHxA)
314.1
C6HF11O2
307-24-4
5
6
Perfluoroheptanoic acid (PFHpA)
364.1
C7HF13O2
375-85-9
6
7
Perfluorooctanoic acid (PFOA)
414.1
C8HF15O2
335-67-1
7
8
Perfluorononanoic acid (PFNA)
464.1
C9HF17O2
375-95-1
8
9
Perfluorodeanoic acid (PFDA)
514.1
CloHF19O2
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-methoxypropanoic acid (PFMOPrA)
230.0
C4HF703
377-73-1
3
5
Perfluoro-4-methoxybutanoic acid (PFMOBA)
280.0
C5HF9O3
863090-89-5
4
6
Perfluoro-2-propoxypropanoic acid (PFPrOPrA)
330.1
C6HF11O3
13252-13-6
5
7
Perfluoroalkyl ether carboxylic acids with multiple ether group (multi -ether PFECAs)
Perfluoro(3,5-dioxahexanoic) acid (PFO2HxA)
246.0
C4HF704
39492-88-1
3
6
Perfluoro(3,5,7-trioxaoctanoic) acid (PFO3OA)
312.0
C5HF9O5
39492-89-2
4
8
Perfluoro(3,5,7,9-tetraoxadecanoic) acid (PFO4DA)
378.1
C6HF11O6
39492-90-5
5
10
Page 3 of 12

Table S2.Operational conditions of DWTP C on sampling day (August 18, 2014)
Parameter
Raw water ozone dose
Value
3.1 m /L
Raw water total organic carbon concentration
6.0 m /L
Aluminum sulfate coagulant dose
43 m /L
Coagulation pH
5.70
Settled water ozone dose
1.3 m /L
Settled water total organic carbon concentration
1.90 m
Empty bed contact time in
biological activated carbon filters
9.4 minutes for granular activated
carbon layer
2.3 minutes for sand layer
Medium pressure UV dose
25 mJ/cm2
Free chlorine dose
1.26 m /L as C12
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
Time (min)
1
Mobile Phase A"o (v/v)
'5
Mobile Phase B%
Flow Rate (inL/min)
1•
95
5
1•
1
• 1
91
1 •
1
91
1 •
1
1 •
91
1 •
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 00002937

Table S5. MS transitions for PFAS Analysis
Coinpound
Transition
PFBA
212.8 168.8
13C4-PFBA
PFPeA
262.9 218.8
13C2- PFHxA
PFHxA
313.6 268.8
13C2- PFHxA
PFHpA
362.9 -> 318.8
13C4- PFOA
PFOA
413.0 368.8
13C4- PFOA
Legacy PFASs
PFNA
463.0 418.8
13C4- PFOA
PFDA
513.1 68.8
13C2-PFDA
PFBS
299.1 -> 98.8
1802-PFHxS
PFHxS
399.1 -> 98.8
1802-PFHxS
PFOS
498.9 -> 98.8
13C4-PFOS
PFMOAA
180.0 -> 85.0
N/A
PFMOPrA
229.1 184.9
N/A
PFMOBA
279.0 -> 234.8
N/A
PFPrOPrA
329.0 284.7
13C2- PFHxA
PFECAs
PFO2HxA
245.1 -> 85.0
N/A
PFO3OA
311. -> 84.9
N/A
PFO4DA
377.1 -> 85.0
N/A
Perfluoro-n-[1,2,3,4-13C4]butanoic acid
(13C4-PFBA)
217.0 -> 172
Perfluoro-n-[1,2-13C2]hexanoic acid
(13C2-PFHxA)
315.1 -► 269.8
Perfluoro-n-[1,2,3,4-13C2]octanoic acid (13C4-PFOA)
417.0 � 372.0
Internal standards
Not applicable
pp
Perfluoro-n-[1,2-13C2]decanoic acid
(13C2-PFDA)
515.1 469.8
Sodium perfluoro-l-
hexane[1 02]sulfonate (1802-PFHxS)
403.1 83.8
Sodium perfluoro-l-[1,2,3,4-13C4]octane
sulfonate (13C4-PFOS)
502.9 79.9
Page 5 of 12
DEQ-CFW 00002938

Table S6. Maximum,
minimum, mean and median concentrations
(ng/L) of PFASs at three drinking
water intakes. *
Community
A
Community
B
Community
PFBA
max
99
min
<10
median
26
mean
33
max
38
min
<10
median
12
mean
12
max
104
min median
<10
12
mean
22
PFPeA
191
14
44
62
38
<10
19
19
116
<10
30
36
PFHxA
318
<10
48
78
42
<10
<10
11
24
<10
<10
<10
PFHpA
324
<10
39
67
85
<10
<10
11
24
<10
<10
<10
PFOA
137
<10
34
46
32
<10
<10
<10
17
<10
<10
<10
PFNA
38
<10
<10
<10
<10
<10
<10
<10
<10
<10
<10
<10
PFDA
35
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
PFBS
80
<10
<10
<10
11
<10
<10
<10
<10
<10
<10
<10
PFHxS
193
<10
10
14
14
<10
<10
<10
14
<10
<10
<10
PFOS
346
<25
29
44
43
<25
<25
<25
40
<25
<25
<25
PFPrOPrA
<10
<10
<10
<10
10
<10
<10
<10
4560
55
304
631
PFOA+PFOS
447
0
64
90
59
0
0
9
55
<10
<10
<10
F, PFASs**
1502
18
212
355
189
0
47
62
4696
55
345
710
* Concentrations less than quantitation limits were considered as zero to calculate means and E PFASs.
** Other PFECAs were present in water samples from community C but could not be quantified and were therefore not included in
Y, PFASs
Page 6 of 12

F O
O
F
F OH
F F
PFMOAA
F F F O
O
F
F F F OH
F
F
PFMOBA
F
F F F O
O--<O
F OH
F
F
PF02HxA
F F O
O
F
F F -< OH
F
F
F F F F F
F O O
OH
O O
F F F F F
PF04DA O
PFMOPrA
PFPrOPrA
rrU3OA
Figure S1. Molecular structures of PFECAs evaluated in this study
Page 7 of 12
DEQ-CFW 00002940

--k,
Haw
River
Cape Fear River watershed
Z Commt" A i N
DWTP
S
Deep River
Flow direction
Community B DWTP
North Carolina `" -� f `_ Cape Fear River
�y PFAS <
Cape Fear river basin manufacturing
plant
ND
MN
ID fD YN MI
�r NY
� U1
M. INON ►A r t
face water sampling site
-t. for PAC test
Community C
DWTP !
% NV UT CO Kf MO MN DE --I
KY PI"l
CA OK TN 1 NC AZ NM AR
Mt LA AL
OA
\ Tx
100 km ~'
ME
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 00002941

1200
1000
800
rn
c
c
0 600
ca
L
c
400
0
U
200
0
FP�pPtPPP� PFPe PF� PF�PPPFpPPF�PPFpPPF� PF���PFp PFP�xPFpG
P � PPpP
200
150
0
FP,pP`P PPS PFPe PF� PF�11 ,, p& PF�PPFpP PF� PFe*5 Po PFP� kPPpG
P 5, PFpP
Page 9of12
DEQ-CFW 00002942

5000
4000
J
3000
U 1000
M
• Community C •
•
f -�- — — — 40- -i
PFP�P`P PPS PFPe PF� PP��PPPoP PP�PePOP q PFPF�P0Ox C'
PF
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 25th percentile, respectively; the middle line represents the
median; upper and lower bars represent the 901h and loth percentile, respectively; and dots
represent outliers (>900, or <10th percentile).
Page 10 of 12
DEQ-CFW 00002943

2 SE 07 2500
►WiNUiRA
E
1.5E+07
3
0
c 1.0E+07
v
5.0E+06
0 0E+00
2000
1500
1000
a
W
500
0
6/15/13 7/30/13 9/13/13 10/28/13 12/12/13
5. E+07
4. E+07
E
3. E+07
3
0
w
c:
2. E+07
a�
1. E+07
0. E+00
500
400
J
300
200
a
w
100
0
6/15/13 7/30/13 9/13/13 10/28/13 12/12/13
U. E+07
5. E+07
v
4.E+07
o
3. E+07
c
v
2. E+07
1.E+07
0 E+00
6000
5000
4000
txO
3000 N
2000 w
1000
0
6/1/13 7/1/13 7/31/13 8/30/13 9/29/13
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
DEQ-CFW 00002944

iwr
a
80%
60%
40%
E
°C 20%
0% IAF
0 20 40 60 80 100 120 140
time (min)
-4-PFBA - D-PFPeA-i---PFHxA-)t-PFHpA-*-PFOA
* PFNA -<>-PFDA -a-PFBS O-PFHxS-*-PFOS
100%
80%
60%
m
40%
cc 20%
0% It
-20%
0 20 40 60 80 100 120 140
time (min)
-0-PFBA -4*-PFPeA--*-PFHxA -*-PFHpA-*-PFOA
*N -PFNA -0-PFDA -O-PFBS-O-PFHS-k-PFOS
100%
80%
e
60%
m
E40%
E
°C 20%
0%
-20%
0 20 40 60 80 100 120 140
time (min)
-�-PFBA -4*--PFPeA-A-PFHxA -*-PFHpA-#f-PFOA
PFNA-Q-PFDA -a-PFBS -*.-PFHxS -*-PFOS
lw,/.
80% b
60%
E40Y0 �p--
20%
0% 4
-20%
0 20 40 60 80 100 120 140
time (min)
tPFMOPrA-FPFMOBA PFPrOPrA
-P-PF02HxA-G-PF030A -C> PF04DA
1W7b
d
80%
60%
A
oc 20% —
0%
-20%
0 20 40 60 80 100 120 140
time (min)
tPFMOPrA-WPFMOBA PFPrOPrA
-0-PF02HxA -0-PF030A PF04DA
aw-ro
80°% f
X 60% --0
140% -
-� -:
d
20%
0%
-20%
0 20 40 60 80 100 120 140
time (min)
PFMOPrA -WPFMOBA PFPrOPrA
-0-PF02HxA--a-PF030A 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
DEQ-CFW 00002945

a
b O 4 'do
/l� ►� i C L-��
DEQ-CFW 00002946

DEQ-CFW 00002947

Recently discovered perfluoroalkyl ether carboxylic
acids occur at substantially higher concentrations
than traditional PFASs and GenX
Raw water
Pre -ozone effluent
Settled water
Settled -ozone effluent
BAC effluent
Finished water
F
II I I O
F F F
II
� o
I
0
F O I F Oh
I F
' O F PF02HxA
I F
I
F OH
F F
PFMOAA
I'
0 50,000 100,000 150,000 200,000 250,000 300,000
Peak area counts of emerging PFASs
at a WTP in Community C
■ PFPrOPrA PFMOAA PFMOPrA ■ PFMOBA PF02HxA PF030A a PF04DA
Sun et al. (2016) ES&T Letters

0
0
6
n
I
0
0
0
0
N
Legac}F PFASs
212.8 � 168.8
13C4-PFBA
262.9 218.8
13C2- PFHxA
313.6 -> 268.8
13C2- PFHxA
WFH"A
362.9-+318.8
13C4- PFDA
413.0�368.8
13C4- PFDA
463.0->418.8
13C4- PFOA
513.1 - + 68.8
13C2-PFDA
PFBS
299.1 --+ 98.8
1802-PFHxS
PFHxS
399.1-+ 98.8
1802-PFHxS
PFOS
498.9 — 98.8
13C4-PFOS
PFECAs,
PFMOAA
180.0 -+ 85.0
N/A
PFMOPrA
229.1-> 184.9
N/A
PFMOAA
279.0 -+ 234.8
N/A
PFPrOPrA
329.0 -> 284.7
13C2- PFHxA
PFO2HxA
245.1-+ 85.0
N/A
PFO3OA
311. -3, 849
N/A
PFO4DA
377.1--+85.0
N/A
Perfluoro-n-[1,2,3,4-13C4]butanoic acid
13C4-PFBA
Perfluoro-n-[1,2-13C2]hexanoic acid
13C2-PFHxA
Perfluoro-n-[1,2,3,4-13C2]octanoic acid
(13C4-PFOA)
Internal standardsPerfluoro-n-[1,2-13G]decanoic acid
(13C2-PFDA)
Sodium perfluoro-l-
hexane[18O2]sulfonate (1802-PFHxS)
Sodium perfluoro-l-[1,2,3,4-i3C.]octane
sulfonate (13C4-PFOS)
217 0 -+ 172
Not applicable
315.1--> 269.8
417.0 -+ 372.0
515.1 -> 469.8
4031 -+ 83 8
502.9 --* 79.9