DEQp00020813

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',z, ", Elisa Arevaloz, Mark Strynar3, Andrew Lindstrom3, Michael Richardson4, Ben
Kearns4, Adam Picketts, Chris Smith6, and Detlef R.U. Knappe2
Department of Civil and Environmental Engineering
University of North Carolina at Charlotte
Charlotte, North Carolina 28223, USA
z 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
I 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

Analytical standards: PFASs studied in this research are listed in Table Sl. 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

Table S1. Perfluoroalkyl substances (PFASs) detected in the Cape Fear River (CFR) watershed
Page 3 of 12
O ' :
Molecular
► p► ►• ► '► (including all
weight carbons1 and S)
Perfluorocarboxylic acids (PFCAs)
Perfluorobutanoic acid (PFBA)
214.0
C07a
375-22-4
3
4
Perfluoropentanoic acid (PFPeA)
264.0
GHFA
2706-90-3
4
5
Perfluorohexanoic acid (PFHxA)
314.1
QHF1102
307-24-4
5
6
Perfluoroheptanoic acid (PFHpA)
364.1
C7HF1301
375-85-9
6
7
Perfluorooctanoic acid (PFOA)
414.1
GHF1502
335-67-1
7
8
Perfluorononanoic acid (PFNA)
464.1
C9HF1702
375-95-1
8
9
Perfluorodecanoic acid (PFDA)
5141
C1oHF190z
335-76-2
9
10
Perfluorosulfonic acids (PFSAs)
Perfluorobutane sulfonic acid (PFBS)
300.1
C4HF9SO33
375-73-5
4
5
Perfluorohexane sulfonic acid (PFHxS)
400.1
C6HF13SO3
355-46-4
6
7
Perfluorooctane sulfonic acid (PFOS)
500.1
GHF603
1763-234
8
9
Perfluoroalkyl ether carboxylic acids with one ether group (mono -ether PFECAs)
Perfluoro-2-methoxyacetic acid (PFMOAA)
180.0
QHF503
674-13-5
2
4
Perfluoro-3-methoxypropanoic acid (PFMOPrA)
230.0
GHF703
377-73-1
3
5
Perfluoro-4-methoxybutanoic acid (PFMOBA)
280.0
OHFA
863090-89-5
4
6
Perfluoro-2-propoxypropanoic acid (PFPrOPrA)
330.1
GHF1103
13252-13-6
5
7
Perfluoroalkyl ether carboxylic acids with multiple ether group (multi -ether PFECAs)
Perfluoro(3,5-dioxahexanoic) acid (PF02HxA)
246.0
GHF704
39492-88-1
3
6
Perfluoro(3,5,7-trioxaoctanoic) acid (PF030A)
312.0
GHF905
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
ValLie
Raw water ozone dose
3.1 m
Raw water total organic carbon concentration
6.0 m /L
Aluminum sulfate coagulant dose
43 m
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 Ch
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'O' (v/v)
Mobile Phase B°o
Flow Rate (ml/min)
1
'
1•
a
1
-
IMM
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

Table S5. MS transitions for PFAS Analysis
Page 5 of 12
Legacy PFASs
CompoundMS/MS
PFBA
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--4 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-l-
hexane[102]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

Table S6. Maximum,
minimum, mean and median concentrations
(nA) of PFASs at three drinking
water intakes,
max
min
median
mean
max
min
median
mean
max
104
min median
<10
12
mean—,
22
PFBA
99 <10 26 33
38 <10 12 12
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
QO
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
QO
PFDA
35
Q5
<25
<25
0-5
<25
Q5
Q5
Q5
Q5
Q5
Q5
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
Q5
29
44
43
<25
Q5
Q5
40
Q5
Q5
Q5
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
E 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 Z 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
O
FY',F OH
F F
PFMOAA
F F F O
0 -
F
F F F OH
F
F
PFMOAA
F F O
O
�
F OH
F
F F
F
PFMOPrA
PFPrOPrA
PF02HxA PF030A
F F F F\ /F
F OH
F F F F -�'fF
PF04DA O
Figure S1. Molecular structures of PFECAs evaluated in this study
Page 7 of 12

Haw
River
I I I r
Cape Fear River watershed
amurW,v A
DWTP4
Deep River
Flow direction
N
Community B DWTP
North Carolina Cape Fear River
IIFAS Surface water sampling site
for PAC test
Cape Fear river basin manufacturing
-r "-- - plant Community C:�
NO
WIN 4M DVrFP
WO
on 0 NY VT NH C'11 -'e Fear
River
Surface water I
manufacturing
plant
IA
ILCT
CO MO KY VVV
CA
OK NC
LAZ TN NM AR
MIS AL GA
TX LA
100 kin
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

1200
1000
800
U
200
0
Q�P�OQiPQF6 QFPe QFC PQ'�QPQQoPQQ�PQQOPQQ� QF�*5PF0�QFOPxPQO�
PF
200
150
rn
c
p 100
c�
L
c
CD
U
C
0 50
U
0
QtP QgP QeP �i�' j.QP QOP QIP FOP FQ'S `�`*' QO`' PPgS QOc
QPP�O P QF QF QF P P P P QF P QPOvl P
P
Page 9 of 12

5000
4000
3000
C
0
= 2000
0
U
C
O
V 1000
U
• Community C •
•
PPP�OoPPFO QFPe QFC PP��PPPoPPP�PPPOPPP� QF��9QP55PF�PkPF��
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 90th and 10th percentile, respectively; and dots
represent outliers (>9011, or <10th percentile).
Page 10 of 12

2.5E+07
2.0E+07
WE
5.0E+06
Community A
• Mean flow
e I PFASs
0
ee
n
0
o e e Aq
0%e
2500
2000
1500
1000 n4LL
w
W
0.0E+00 ' —mn4°° — 0
6/15/13 7/30/13 9/13/13 10/28/13 12/12/13
5.E+07
4.E+07
m
3.E+07
3
O
r- 2.E+07
ro
v
1.E+07
0. E+00
Community B
• Mean flow
e 2 PFASs
• e
• e n e bA
e e
500
e•e
J
300
N
200 U-
100 100
0
6/15/13 7/30/13 9/13/13 10/28/13 12/12/13
LeRMIYA
5.E+07
-a
4.E+07
o 3.E+07
C
2.E+07
1. E+07
0.E+00
6/1/13 7/1/13 7/31/13 8/30/13 9/29/13
6000
5000
4000
c
3000 cn
a
LL
2000 w
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

iwW
a
80%
9 60%
m
40%
u
20%
0%
-20%
0 20 40 60 80 100 120 140
time (min)
+PFBA -o-PFPeA ,_ PFHxA-*EPFHpA-*-PFOA
•- PFNA -<>-PFDA-a-PFBS-o-PFHxS-A-PFOS
100%
c----- �
80%
a, 60%
a
40%
E
20%
0%
-20%
0 20 40 60 80 100 120 140
time (min)
--*-PFBA -a-MeA PFHxA-*-PFHpA - PFOA
-4p,-PFNA-Q-PFDA -.o-PFBS-0-PFHS-t-PFOS
100%
80% e / ����
� 60%
40%
E
v
Cr 20%
0%
.20%
0 20 40 60 80 100 120 140
time (min)
-f-PFBA -a-PFPeA PFHxA-9E-PFHpA -*-PFOA
PFNA-O--PFDA-a-PFBS PFHxS f PFOS
1W70
80%
60%
40%
E
W
¢ 20%
0%
-20%
100%
80%
60%
W
40%
E
v
20%
0%
-20%
0
V
0 20 40 60 80
time (min)
-0-PFMOPrA -WPFMOBA
-0-PF02HxA -0-PFO30A
100 120 140
PFPrOPrA
PF04DA
iw,r.
80%
Z9 60%
m
40%
E
Ix 20%
0%
-20%
20 40 60 80 100 120 140
time (min)
tPFMOPrA-f-PFMOBA PFPrOPrA
-O-PFO2HxA -F,}-PF030A PF04DA
f
0 20 40 60 80 100 120 140
time (min)
-+PFMOPrA f-PFMOBA PFPrOPrA
::-PF02HxA -0 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.
Techflol. 2007, 41, (15), 5271-5276.
Page 12 of 12