DEQ-CFW_00073044

Perfluoroalkyl ether carboxylic
acids: Occurrence in the Cape Fear
river watershed and fate in drinking
water treatment processes
Mei Sun, Elisa Arevalo, Leigh -Ann Dudley,
Andrew Lindstrom, Mark Strynar, Detlef Knappe
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i NC STATE UP&ERSITY-i Wilmington, April 19, 2017 y4z pRole
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Perfluoroalkyl acids are organic
compounds in which all C=H bonds are
replaced with C=F bonds.
F
F F 10
II H
F S—Q
F LFJ o
n
Long -chain PFASs:
PFCAS: CnF2n+1COOK ►7>_7
PFSAs: CnF2n+1S03H7 r1_>6
F F F F F F 0
F,�\ �OH
F F F F F F F F
F F F F F F F F
S03H
F
F F F F F F F F

Long -chain PFASs have
long half-lives in humans
• Half-lives in humans
— PFOA: 3.8 years
— PFOS: 5.4 years
— PFBS: 4 months
• Toxicokinetic differences for PFOA
—17-19 days in mice
— 4 hours in female rats

To protect the public from adverse health
effects, health based guidelines have been
established
EPA Health Advisory
(chronic exposure)
New Jersey
guidance level (C8)
and recommended
MCL (C9)
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PFOS + C8:
70 ng/L
C8: 40 ng/L
C9: 13 ng/L

Are PFASs a concern in US
drinking water?
Six PFASs were included in the third Unregulated
Contaminant Monitoring Rule (UCMR3)
PerFluoroheptanoic acid (PFHpA, C7) 10
Perfluorooctanoic acid (PFOA, C8) 20
Perfluorononanoic acid (PFNA, C9) 20
Perfluorobutanesulfonic acid (PFSS) 90
Perfluorohexanesulfonic acid (PFHxS) 30
Perfluorooctanesulfonic acid (PFOS) 40
Samples collected from January 2013 —December 2015
Public Water Systems (PWSs) serving >10,000 people

At first glance, UCIVIR3 data suggest
low PFAS detection frequency
UCMR3 requires monitoring for six PFASs in US drinking water.
Monitoring began in 2013, and latest data release was January 2017.
C7
MIRL
•
10
Occurrence
N
0.64
Max. ConcentrationPFAS
(ng/L)
410
• •
concentrations
Saipan, PA, NY,
•
DE, CO
C8
20
1.03
349
PA, M N, Saipan,
DE, WV
C9
20
0.05
56
NJ, DE, PA, MA, NY
P F BS
90
0.05
370
GA, Saipan, CO,
AL, PA
PFHxS
30
0.56
11600
Saipan, AZ, DE,
CO, PA
PFOS
40
0.79
71000
Saipan, DE, CO,
PA, WA
36,972 samples from 4,920 PWSs
PFAS detects: 599 samples (1.6%) from 198 PWSs (4.0%)
Of samples with PFAS detects: 23.4% derived from surface water
Some drinking water samples had PFOA+PFOS levels well above the HAL 6

UCMR3 Data for North Carolina: PFAS detection
frequency higher than for entire US
Compound
(ng/L)
Perfluoroheptanoic acid (PFHpA, C7)
10
29 (max. 60
ng/L)
Perfluorooctanoic acid (PFOA, CS)
20
10 (max. 30
ng/L)
Perfluorononanoic acid (PFNA, C9)
20
0
Perfluorobutanesulfonic acid (PFB,S)
90
0
Perfluorohexanesulfonic acid (PFHxS)
30
5 (max. 110
ng/L)
Perfluorooctanesulfonic acid (PFOS)
40
S (max. 90
ng/L)
1,320 samples from 151 PWSs in NC
PFAS detects: 43 samples (3.3%) from 20 PWSs (13.2%)
Of samples with PFAS detects: 79% derived from surface water
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Elevated PFAS levels affect a
sizeable number of US residents
Hydrological units with
detectable PFASs
IVUI Ut:LWUICU
No data
PFOS+PFOA levels
stimated to exceed the
70 ng/L HAL in the
drinking water of
6 million US residents
Hu et al. ES&T Letters (2016)

...but are we
seeing the
compIete picture?

Sub -classes of PFASs
Examples of
Many
PFASs are
Individual compounds'
PFBA (n-4)
used
in commerce
PFH A(� 6)
PFHpA (n=7)
PFOA (n=8i
PFCAs
PFNA (n-9)
(C F —COOH)
n 2n+i
PFDA(n,-io;
o PFUnA(n=n)
� PFDoA (n=u
> PFTrA (n=-.3)
o PFTeA (n-i4
PFBS (n=4)
PFSAs
PFHxS i' =6'.
(CnF2n+1_SO3H)
o PFOS (n=8)
; PFDS (n-wl
perfluoroalkyl acids
PFBPA n= )
(PFAAs)
PFPAs
PFHxPA (n46)
(CnF2n+i — P03H 2)
PFOPA (n-8)
PFDPA (n-io)
C4/C4 PFPiA (n.m=4)
PFPiAs
C6/C6 PFPiA (n,m=6)
(CnF,n+,—PO,H—Cn,F„„,)
C8IC8 PFPiA (n,m=8)
C6/C8 PFPiA (n-6.m-8)
Number of peer -reviewed
articles since 2002"
o ADONA (CF3-O-C1FE-0-CHFCF,-COOH
PFECAs & PFESAs
° GenX (C3F7-CF(Cl i)-COON)
(CnF2n+l—O—CmF2rn+i—R)
o EEA(C,FS O-C_Fy-O-CFI-COOH)
=` F-538(CI-CFF„-O-C,Fa-SO
o Me (n=4, =N H H
o McFOSA (n=8.R=viCH,,;IH)
o EtFBSA (n-4,R-N(C,H,)H)
PFASs
PASF-based
> FtFOSA;n=3.A-NiC, i.}H1
substances
n McFBSE (n=4-R=N(CH)C,H,,OH)
(C F —R)
n 2n+i
(CnF2n+,—S02—R)
o Me�OSE (ri=8,R=N(CH IC H,C)HI
o EtFBSE(n=4,R=N(C,HjC,H40H)
o EtFOSE (n=8.R=N(C,-1,)C,H4OH)
> over 3000w;�
HsJc,H�o],-POI }
PFASs may
PFAA
loos of others'
have been
precursors
4:2 FTOH (n-4.R-OH)
on the global
6:2 FTOH (n-6,R-OH)
market
fluorotelomer-based
o 9.2 ; TOH (n=8,R=0H1
substances
o 30 z FTOH (n-io,R-OH)
12 2 FTOH ,`n=i2.R=OH1
(CnF2n+i—C2H4—R)
6:2diPAP [(C,F,3C,H40),-PO,HJ
S diPAP''C.7..C,11,101 -PO.H
loos of others
polytetrafluoroethylene (PTFE)
fluoropolymers
poly\nnylidene fluoride (PVDF)
others
fluorinated ethylene propylene (FEP)
Wang et al. ES&T (2017)
perfluorcalkexylpolymer(PFA)
perfluoro
of ethers (PFPEs)
928
698
1081
1186
4066
1496
1407
1069
1016
426
587
654
1081
3507
340
3
33
31
35
4
12
12
8
4
26
6
14
25
134
7
259
24
116
4
146
8
106
375
412
165
42
23
25

Two series of PFECAs were recently
discovered in the Cape Fear River
x106 -ESI EIC(189773) Scan Frag+8OOV :'IorkhsSa*K
3 f
F
2 O ar
I.
F F
0
x10 s -ESI EIC(228 97411Scar, Frag-80 O. ":iorkhst0ata3 e F
F
O
1 F
F 0.
F
0
F
x*:' -ESI E1=;2-8 9709) Scar Frag-SC OT':.bMtstData3 c F F
F
F�F �
f
F O
F
x10 • I-ESI EIC(328.96, , Scan Fra9.80 OV VkrrkWDM3 d
2
0
x10 3 -ESI EIC(378 96`5) Scan Frog-W DV %,krk1tat0ata3 d
7.5 '
7
2.5
a102 -E9EIC(alY.9C1�5sw�Fny':=i..nwLatG+t+"
Strynar et al. ES&T (2015)
F
F
F F F F F "GenX"
O
F 1
F il0
6.5 75 85 7
Crays vs Aoaaadion Tams (min)
F F F
F
F
F F F
F O
F
F F F F
O
F
f �
f
F

■
7
Two series of PFECAs were recently
discovered in the Cape Fear River
.10
45
35
3
213
2
'S
,
o:
0
0
0
0
0
0
0
0
0
0
.0
2
,
0
.10
EtC(7E4 9123) Scan Frp-aO OV W-kt..tD." e
6980 0
F F F F F
F /O`�p /O\/(p� ,pH
F F/x\ f
ESI EK(622 92a9) Scan Frp-a0 Ov �•/«k1..tON.6 tl
r•(1)
t O
t
F F\ F F\
' F_x OH
t /
t i F F F F
mown. v..wc w..twn 1 nn. mn
-FGI LK(490 f4651 Se.n Frp�aO M,v«YI..tON.0 A
3 2 41. n
S
t F O F F
s OH
F
1 F
s
•ES, EIC-058 %211 50— F-9-80 UV w«k1..tU.f.6 e
1 262
Cants. T.—Imn1
Strynar et al. ES&T (2015)
O
F L
F, f
OH
O
F
Molecular Formula C6HF,,O,
Monotaotopic Main 377 9598 Do
[M-H}- 376.9625 Do
Molecular Formula C,HF90,
Monoisotopic Mass: 311.98W Da
[M-H]-: 310.9W8 Do
Molecular Formula C,HF,O,
Mono,aotopic Mass 245.9763 Do
(M•H].. 244.9690 Da
Molecular Formula: C,HF,O,
Monasotopic Mass. 179.9546 Do
[M-H]-: 178.9773 Do

Cf)
DEQ-CFW 00073056

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Cape Fear River Basin
Haw
River
N
Com unity A
�I {
Deep River
Flow direction
Community B
Capc Fear River
( Op ID " ` �1 SDJ wl I--
NI4 ,�1 PI
NV ; VT� NE v' IAILIN.OH I_P.R-, �M� PFAS Surface water sampling site
G, _ j co Ks.`„_._KyLiv� �°� for PAC test
A
- T* l2lanUiaCtllrlrig
NM �a .'-'— BC,
ti .. ,MS }` �°" plant
._TX
r ~+ FL\
tia
North Carolina
CommunityC
Cape Fear river basin
0 25 50 100 km
• Largest
watershed in
NC
• Supplies
~1.5M people
with drinking
water

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Sampling Protocol
• Samples collected in 1-L HDPE bottles
Two sampling approaches
— Daily composite samples of source water at
three drinking water treatment plants
— Grab samples to track PFAS fate in drinking
water treatment plant
• No preservative
• Storage at room temperature
• Analysis within 7 days of sample collection
CO
En
00

PFAS Analytical Method
• PFAS concentrations measured by LC-MS/MS
• Large -volume direct injection (900 pL)
• Sample and standard preparation:
— filtration with a 0.45-pm glass fiber filter
— addition of mass -labeled internal standards
— addition of formic acid
• Calibration curves ranged from 10 - 750 ng/L
• Limit of quantitation was 10 ng/L for all PFASs
except C10 and PFOS (25 ng/L)
P.
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CO

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PFAS Occurrence in the CFR Watershed
■ PFOA
■ PFHxS
Community
Community B
Community C
■ PFPeA ■ PFHxA R PFHpA
PFNA " PFDA ■ PFBS
■ PFOS ■ PFPrOPrA = "GenX"
n=127
F "GenX"
- F
F F FF FF
n=76 OH
F O
IF O
0
200
j
n=35
Average concentration in drinking water source (ng/L)
Sun et al. (2016) ES&T Letters

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No measurable PFAS removal by
conventional and advanced treatment
Raw water
Pre -ozone effluent
Settled water
Settled -ozone effluent
BAC effluent
Finished water
x
C4 ■ CS C6 I C7 a CB
Raw TOC: 6.0 mg/L, 03: 3.1 mg/L
Settled TOC: 1.9 mg/L, 03: 1.3 mg/L
MP UV: 25 mJ/Cm2, FAC: 1.3 mg/L, 17 h
200 400 600 800
PFAS Concentration (ng/L)
C9 _ C10 ■ PFBS ■ PFHS ■ PFOS ■ GenX

0
0
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CO
0
N
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
0 is
O
F
F OH
F F
PFMOAA
F
F 0
F F
0
0
, W F OH
- I A Y__� F
PF02HxA
0 50,000 100,000 1507000 2007000 2507000 3007000
Peak area counts of emerging PFASs
at a WTP in Community C
■ PFPrOPrA PFMOAA PFMOPrA ■ PFMOBA PF02HxA PF030A ■ PF04DA
Sun et al. (2016) ES&T Letters

What about
activated carbon?.
PAC: thermally activated, wood -based
PAC Doses: 30, 60, 100 mg/L
Contact time: 60 minutes
Water: Cape Fear River (TOC: 9.0 mg/L)
PFECAs: Native levels
0
PFCAs and PFSAs: Spiked at 1000 ng/L
W
W

Adsorbability of PFASs varies greatly. The PFECAs
that were present at the highest concentrations
were essentially non -adsorbable
100%
■ 30 mg/L
80%
o~°9 60 mg/L
c�° 100 mg/L
y 40%
=-
20%
w
w 0% 11 1 Lill
-20%
�Z
o� w
PFCAs Mono -ether PFECAs Multi -ether PFECAs PFSAs
Sun et al. (2016) ES&T Letters

1000/0
.�
80%
of
60%
CIO
O-j
40%
E
0
20%
�
w
o
V �p
/0
L
Q
-20%
w
3
PFAS adsorbability:
PFSA>PFCA>PFECA
v
/ GenX
--m-PFCAs - o-Mono-ether PFECAs
Sun et al. (2016) ES&T Letters
PFOA
7 9
Chain length
-f-Multi-ether PFECAs
III
:-PFSAs

Proposed
sampling plan
1,4-Dioxane and PFAS Fate in
Urban Water Cycle

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Objective 1: Determine fate of 1,4-dioxane and perfluoroalkyl
substances (PFASs) in the urban water cycle
The Drinking Water Cycle
Source
(aquifer, lake,
etc.)
Water
System ,10
Distribution
System
Sewer
Lines
Wastewater Plant
f
Discharge
Homes or Businesses
Septic
System
Identify residence times/water ages at suitable sampling points
to trace a parcel of water through the water/wastewater system

Objective 2: Determine fate of 1,4-dioxane and PFASs during
aquifer storage and recovery (ASR)
Sample monthly for one ASR cycle (ASR and monitoring wells)
• Recharge
• Storage
• Recovery
BiweeklyIII
Temperature, pH, turbidity, Total organic carbon,
specific conductance, dissolved trihalomethanes
oxygen, redox potential, residual
chlorine (during recharge)
Nitrate, nitrite, ammonium, 1,4-dioxane, PFASs,
sulfate, chloride, bromide, dissolved organic carbon,
fluoride Uu254 absorbance
Objective 3: Determine possible association of 1,4-dioxane
and PFASs with biosolids
Measure 1,4-dioxane and PFAS concentrations in aqueous and
solid phases of biosolids. Determine partition coefficients.

Target Audiences for Results
• CFPUA staff
— Data expected to illustrate treatment/ operational
challenges associated with PFASs and 1,4-dioxane
— Demonstrate need for source control — eliminate
PFASs and 1,4-dioxane at upstream NPDES
discharge locations
• North Carolina DEQ
— Raise awareness about treatment challenges with
emerging contaminants
0
— Expand scope of current 1,4-dioxane working group
m to start looking at possibilities for controlling PFAS
p
C
C3 0 sources
W

Acknowledgments
• National Science Foundation (Award #1550222)
• North Carolina Urban Water Consortium
• Adam Pickett, Chris Smith, Michael Richardson,
Ben Kearns at participating utilities
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