DEQ-CFW_00073023

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 Sun1,2- ", Elisa Areval02, Mark Strynar3, Andrew Lindstrom3, Michael Richardson4, Ben
Kearns4, Adam Pickett5, 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 00073023

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 00073024

Table S1. Perfluoroalkyl substances (PFASs) detected in the Cape Fear River (CFR) watershed
carbonsMolecular It of Chain length
Compound weight Formula CAS perfluorinated (including all
• and S)
Perfluorocarboxylic acids (PFCAs)
Perfluorobuanoic 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
C6HFnO2
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
Perfluoroheanoic acid (PFDA)
514.1
CioHFi9O2
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
C8HFi7SO3
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
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
CAHF704
39492-88-1
3
6
Perfluoro(3,5,7-trioxaoctanoic) acid (PF030A)
312.0
CsHF905
39492-89-2
4
8
Perfluoro(3,5,7,9-tetraoxadecanoic) acid (PF04DA)
378.1
C6HF1106
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 /L
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/cmz
Free chlorine dose
1.26 mg/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) Mobile Phase A°a (v/v)
1 •
Mobile Phase B0%
Flow Rate (mL/min)
1•
•
1•
1 • 1
•1
1 •
1 1 , 1
•1 .
1 •
1 � 1 •
•1
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 00073026

Table S5. MS transitions for PFAS Analysis
Legacy PFASs
Compound
PFBA
MS/MS
Transition
212.8 168.8
Internal
standard
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
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
PFECAs
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
PFO2HxA
245.1 --),85.0
N/A
PFO3OA
311. 84.9
N/A
PFO4DA
377.1 85.0
N/A
Internal standards
Perfluoro-n-[1,2,3,4-13C4]butanoic acid
(13C4-PFBA)
217.0 172 ->
Not applicable
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
Perfluoro-n-[1,2-13C2]decanoic acid
(13C2-PFDA)
515.1 469.8
Sodium perfluoro-1-
hexane["02]sulfonate (1802-PFHxS)
403.1 83.8
Sodium perfluoro-1-[1,2,3,413C4]octane
sulfonate (13C4-PFOS)
502.9 79.9 ->
Page 5 of 12
DEQ-CFW 00073027

Table S6. Maximum,
minimum,
mean and median concentrations
(ng/L) of PFASs at three drinking
water intakes.
min
medianmax
-.median
PFBA
99
<10
26
33
38
<10
12
12
104
<10
12
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
1: 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 T, PFASs.
** Other PFECAs were present in water samples from community C but could not be quantified and were therefore not included in
PFASs
Page 6 of 12

F O
FO
�
-F
F OH
F F
PFMOAA
F F F O
O
F�
F F F OH
F
F
PFMOBA
PF02HxA
F F O
O
F�
F F OH
F
F
PFMOPrA
\ /F F\ / \ /F F F
F x O j� O x O�O OH
F \ // F F \ F F
PF04DA O
PFPrOPrA
rrusuA
Figure S1. Molecular structures of PFECAs evaluated in this study
Page 7 of 12
DEQ-CFW 00073029

Cape Fear River watershed
Haw
River
Comm A N
DV%rTP
Deep River
Flow direction
Community B DVVTP 13
North Carolina Cape Fear River
` SPFAS Surface water sampling site
Cape Fear river basin manufacturing, for PAC test
MN — plant Community C.,
�OR ro so M DVVTP f
WY W --f'Ny Vr NH---
[A
NE PA
IL IN OH
NV UT CO ►
Ke MO IDE
CA K TH KY
NC z;
AZ NM sc
MS AL
TX LA
FL,,
100 km
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-00073030

1200
1000
_ 800
rn
c
c
0 600
m
c
400
0
200
v
Community
I
QQQ`oQcPQQ� QFQe QF� QQ�pPQQpPQQ�PQQpPQQQ, QQ�.�SQQ01QQOPkQQ05
QF
200
150
J
0)
0 100
c�
c
c
50
co
0 in
•
Community B •
•
QQQ�OQ�PQF6 QQQe QF� QQ,�'pPPFOPPF�PPFaPQFQ' ',? � oI O`'
QF
Page 9 of 12
DEQ-CFW 00073031

5000
4000
J
3000
c
0
c�
2000
N
c
0
U
1000
0
• Community C •
• •
•
JL -9- .�.
PPP��P�p'PF6 PFPe PF� PF�pPPP�PPP�PPP�PPP� PF���PF�PF�PxPP��
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 751h and 25th percentile, respectively; the middle line represents the
median; upper and lower bars represent the 901h and 10th percentile, respectively; and dots
represent outliers (>90th or <1011, percentile).
Page 10 of 12
DEQ-CFW 00073032

2.5 E+07
2.0E+07
a
1.5E+07
3
0
1.0E+07
�o
aU
5.0E+06
0 0E+00
2500
2000
1500 0
V)
1000 LL
a
w
500
0
6/15/13 7/30/13 9/13/13 10/28/13 12/12/13
S00
5. E+07
a
4. E+07
m
3. E+07
3
0
2.E+07
�o
v
5
1. E+07
0. E+00
400
J
300
N
N
200 LL
a
w
100
0
6/15/13 7/30/13 9/13/13 10/28/13 12/12/13
6000
6/15/13 7/30/13 9/13/13 10/28/13 12/12/13
6000
6. E+07
5. E+07
4. E+07
o
3. E+07
2. E+07
1. E+07
0 E+00
5000
4000
ao
3000 c A
a
LL
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 00073033

awio
a
80%
M
40%
w
20%
0%
-20%
4 1 -.,4
0 20 40 60 80 100 120 140
time (min)
-+-PFBA t PFPeA PFHxA-*-PFHpA-*--PFOA
tPFNA-0•-PFDA-o-PFBS--O-PFHxS-I-PFOS
100%
C
80%
X 60%
A
9 40%
E
d
°C 20%
0% It
-20%
0
20 40
60 80
100
120 140
time (min)
-f-PFBA
-s-PFPeA
f PFHxA
-k-PFHpA
-*-PFOA
-i-PFNA
-0-PFDA
---PFBS
-O-PFHS
-i-PFOS
100%
80%
ar�a�---
60%
A
�O 40% -
E
m
°C 20%
0% IIA
-20%--
0
20 40
60 80
100
120 140
time (min)
-0-PFBA
-I*--PFPeA
PFHxA
-)E-PFHpA
-*-PFOA
t PFNA
-o-PFDA
-o-PFBS
-0-PFHxS
-t PFOS
lw�
80%
60%
m
40%
d
°C 20%
0%
-20%
300%
80%
60%
A
'0 40%
E
v
20%
0%
-20%
0
M
0 20 40 60 80
time (min)
4 PFMOPrA-FPFMOBA
-0-PF02HxA -U-PF030A
100
SG°o
60%
A
6 40%
E
a,
s 20%
0%
-20%
100 120 140
PFPrOPrA
PF04DA
20 40 60 80 100 120 140
time (min)
-10,-PFMOPrA-*-PFMOBA tPFPrOPrA
-P-PF02HxA -{-} PF030A-0-PF04DA
f .�
y
0 20 40 60 80 100 120 140
time (min)
-*--PFMOPrA i-PFMOBA-A-PFPrOPrA
-*-PF02HxA-0-PF030A O-PF040A
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 00073034