HomeMy WebLinkAboutDEQp00020500,g`cEo sr''rE�
A UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
\� z NATIONAL EXPOSURE RFSEA.RCH LA[30R.ATORY
RESEARCH I RIANGLE PARI;, PIC 27711
August 31, 2017
MEMORANDUM
C)PP)t)'c GF
SUBJECT: Laboratory PFAS Results for NC DEQ Cape Fear Watershed Sampling:
Preliminary Non -Targeted Analysi
FROM: Timothy J. Buckley, Dire or
Exposure Methods and urements D'vision
THRU: Jennifer Orme-Zavaleta, Director
National Exposure Research Labor
TO: Linda Culpepper, Deputy Director
Division of Water Resources
North Carolina Department of Environmental Quality
Enclosed please find our fourth report of PFAS concentrations in Cape Fear River water
samples collected under the direction of NC DEQ. This report includes preliminary findings
from our non -targeted analyses. These results were presented and discussed during your visit
August 28, 2017 to our Laboratory in Research Triangle Park, N.C.
Thank you for inviting us to be a part of this c5ort that addresses a very important public
health concern in North Carolina. These results represent the effort of many within our lab, but I
would especially like to acknowledge Drs. Mark Strynar, Andy Lindstrom, James McCord, and
Seth Newton in conducting the laboratory analyses, Dr. Myriam Medina. -Vera who provided
invaluable support and coordination, and Ms. Sania Tong Argao who supported and oversaw
quality assurance.
If you have any questions or concerns, do not hesitate to contact me at (919) 541-2454 or
email bucklev.tizlurtlhvriUel),i.',.civ- I look forward to our continued work together.
Enclosure
CC: Becky B. Allenbach, USEPA Region 4
Jeff Morris, USEPA OPPT
Betsy Behl, USEPA, OW
Peter Grevatt, USEPA, OW
August 31, 2017
Summary of Results
Our preliminary non -targeted results are limited to samples from the Chemours outfall
and finished water from the Sweeney Water Treatment Plant for weeks 1— 6. We chose these
sites because we believe the concentrations observed bound this portion of the watershed.
Furthermore, we did not want to delay our reporting due to the additional time required to
assemble and interpret results from the other locations. We are continuing to work on a
comprehensive report that will include targeted and non -targeted analysis results at all locations
over the seven weeks of sampling.
We include five analytes in this initial non -targeted analysis report (Table 1). An
important limitation to our non -targeted analysis results is that these results are considered semi-
quantitative. We cannot know the exact concentration because no authentic standards are
available for these chemicals. However, we are very confident of the chemical identity based on
the high resolution mass spectrometry and knowledge of Chemours' chemical products.
Table 1. Analytes Measured Non -Targeted LC/TOFMS Analysis
i Monoisotopic
Short Name Chemical Name !, Formula CAS no. Mass (Da)
PFESA
j Perfluoro-3,6-dioxa4-methyl-
Byproduct I
17-octene-l-sulfonic acid
F.thanesulfonic acid, 2-[1-
[difluoro(1,2,2,2-
PFESA
PFESAuct
tetrafluoroethoxy)methyl]-1,2,
2
Byprod2,2-tetrafluoroethoxy]-1,1,2,2-
I tetrafluoro-
PFMOAA
I (2,2-difluoro-2-
(trifluoromethoxy)acetic acid)
PFO2HxA
i Perfluoro-3,5-dioxahexanoic
acid
PF030A
! perfluoro-3,5,7-trioxaoctanoic
acid
C7HF1305S j 29311-67-9 443.9337
i
C7H2Fi405S 749836-20-2 463.9399
C3HF503 674713-5 179.9846
C41IF704 39492-88-1
245.9763
CSHF90s 39492-89-2 311.9680
We provide semi -quantitative "concentrations" in two forms (Table 2). The first is the
peak area that is associated with the monoisotopic mass for each compound. The peak area is
generally proportional to the analyte concentration and it is useful in interpreting changes in
concentration over time and between locations for a given analyte. For example, for PFMOAA
measured in Sweeney Finished water, we see the peak area change from —4.5 million to 3,000
counts from week 1 to 6. This can be interpreted as roughly a 1,500 -fold decrease in
concentration without knowing the exact concentration. The second way we provide a semi-
quantitative estimate of concentration is to scale the non -targeted analyte based on the measured
concentration of GenX.
(NTA] _ [GenX] * NTAPAGenXpA
Where: [NTA] is the concentration of the non -targeted analyte (ng/L)
4
August 31, 2017
[GenX] is the concentration of GenX (ng/L)
NTAPA is the integrated peak area for the non -targeted analyte
GenXPA is the integrated peak area for GenX
In essence, we are assuming that the mass spectrometer responds to the non -targeted
analyte as if it were GenX. The actual instrument response may be weaker or stronger resulting
in an under- or over -estimation of the non -targeted concentration. Our experience with this class
of analytes suggests that estimates of this fashion are accurate to within —1 0 -fold of the estimated
value.
The non -targeted analyte estimated concentrations are particularly uncertain at the
Chemours outfall during weeks 1-3. Concentrations were so high that even after samples were
diluted 20X, we exceeded our calibration curve for GenX and were also likely saturating the
mass spectrometer for both GenX and non -targeted analytes. The semi -quantitative estimate for
the non -targeted analytes are particularly uncertain and likely underestimated. These results are
shown in Table 2 and have been flagged accordingly.
Whether considering peak area or estimated concentration, the non -targeted results show
two very different time profiles. For three of the analytes, concentrations at the outfall and
Sweeney finished water show a precipitous drop very similar to what was observed for GenX
(Figures 1-4). These results suggest that whatever mitigation strategy used to reduce GenX, was
also effective for these three chemicals. The second time profile is for two perfluoroethersulfonic
acid (PFESA) byproducts. We believe these chemicals are a byproduct of Nafion production. In
contrast to the GenX-related chemicals, for these two chemicals, we do not observe a clear
decreasing trend in concentration (Figures 5 & 6). These results suggest the discharge of these
chemicals was unaffected by whatever strategies were used to mitigate GenX discharge.
Concentrations of the PFESAs range from 2,900 to 73,900 ng/L at the Chemours outfall and 53
to 7,860 ng/I, in Sweeney finished drinking water. Note that these concentrations are in the same
range as GenX originally noted in Sun et al., 2016.'
In Figure 7, the plots show the two different types of time profiles for the six analytes.
Each analyte is graphed as a relative percentage of its maximum intensity over the sampling
period. For the PFESAs byproducts, this maximum period occurred in the middle of sampling,
while for the other analytes, the maximum was during the first week.
As with GenX, our QA/QC results for the non -targeted results are within expected
tolerances. We did not detect any of the analytes in field blanks, indicating that no field or lab
contamination took place. Because there are no standards for these analytes, we have no
assessment of accuracy, but duplicate analyses were within 20 percent. The laboratory methods
for the results reported here are described in Sun et al., 20161 and Strynar et al., 20152.
1 Sun M; Arevalo E, Strynar M; Lindstrom A; Richardson M; Kearns B; Pickett A; Smith C; Knape DRU: Legacy and Emerging
Perlluomalkyl Substances Are Important Drinking Water Contaminants in the Cape Fear River Watershed of North Carolina. Environmental
Science & Technology Letters. 2016
ZStrynar M, Dagnino S, McMahen R, Hang S, Lindstrom A, Andersen E McMillan L, Turman M, Ferrer 1, Ball C. Identification of Novel
Per luoroalkyl Ether C'artxwylic Acids (PFECAs) and Sulfonic Acids (Pi 6SAs) in Natural Waters Using Accurate Mass Time -of -}light Mass
Spectrometry (TOFMS). Environ Sci Tcchnol. 2015
August 31, 2017
Table 2. Semi -Quantitative Estimates of GenX and Non -Targeted Analyte Concentrations
(ng/L) Measured at Chemours Outfall and Sweeney Finished Drinking Water During Sampling
Weeks 1- 6.
Non -Target
PFMOAA
PF02HxA
PF030A
GenX
PFESA Byproduct 1
PFESA Byproduct 2
PFMOAA
PF02HxA
PF030A
GenX
PFESA Byproduct 1
PFESA Byproduct 2
PFMOAA
PF02HxA
PF030A
GenX
PFESA Byproduct 1
PFESA Byproduct 2
PFMOAA
PF02HxA
PF030A
GenX
PFESA Byproduct 1
PFESA Byproduct 2
PFMOAA
PF02HxA
PF030A
GenX
PFESA Byproduct 1
PFESA Byproduct 2
Location
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Sweeney
Sweeney
Sweeney
Sweeney
Sweeney
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Sweeney
Sweeney
Sweeney
Sweeney
Sweeney
Sweeney
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Chemours Outfall 002
Sample
Week
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
_ 2
-- 3
3
3
3
3
3
NTA Area I GenX Area I GenX Conc. I NTA Conc. I Flag
63,712,278
182,599,647
51,940,394
10,363,496
1,380,791
14,039,048
4,560,543
1,265,760
293,854
21,356
664,104
37,373,851
71,331,553
19,111,355
8,345,860
1,895,442
13,230,172
1,059,209
738,362
251,372
10,129
14,447
437,286
11,265,308
10,284,502
1,545,961
9,390,564
5,721,468
17,252,514
4
10,363,496
10,363,496
10,363,496
10,363,496
10,363,496
10,363,496
293,854
293,854
293,854
293,854
293,854
243,854
8,345,860
8,345,860
8,345,860
8,345,860
8,345,860
10,129
10,129
10,129
10,129
10,129
10,129
9,390,564
9,390,564
9,390,564
9,390,564
9,390,564
9,390,564
21,760
21,760
21,760
21,760
21,760
21,760
726
726
726
726
726
726
15,250
15,250
15,250
15,250
15,250
15,250
100
100
100
100
100
100
21,530
21,530
21,530
21,530
21,530
21,530
134,000
383,000
109,000
21,800
2,900
29,500
11,300
8,880
3,130
726
53
1,640
68,300
130,000
34,900
15,300
3,460
24,200
10,500
7,290
2,480
100
143
4,320
25,800
23,600
3,540
21,500
13,100
39,600
1
i
1
1
1
1
2
z
2
2
z
2
1
1
1
1
1
1
1
1
1
1
1
1
August 31, 2017
Non -Target
Analyte
Location
SampleNTA
Week
Area
GenX Area
GenX Conc.
(ng/L)
NTA Conc.
(ng/L)
Flag
NOTE: For week#3, there was insufficient sample available fora Sweeny finished water analysis.
For week#4, there was insufficient sample available for a Chemours outfall 002 water analysis.
Chemours Outfall 002
PFMOAA
Sweeney
4
82,181
21,348
81
312
PF02HxA
Sweeney
4
210,440
21,348
81
798
PF030A
Sweeney
4
168,842
21,348
81
641
GenX
Sweeney
4
21,348
21,348
81
81
PFESA Byproduct 1
Sweeney
4
31,581
21,348
81
120
PFESA Byproduct 2
Sweeney
4
522,627
21,348
81
2,360
PFMOAA
Chemours Outfall 002
5
558,337
287,302
713
1,390
3
PF02HxA
Chemours Outfall 002
5
366,856
287,302
713
910
3
PF030A
Chemours Outfall 002
5
175,874
287,302
713
436
3
GenX
Chemours Outfall 002
5
287,302
287,302
713
713
3
PFESA Byproduct 1
Chemours Outfall 002
5
11,797,348
287,302
713
4,460
3
PFESA Byproduct 2
Chemours Outfall 002
5
15,762,943
287,302
713
39,100
3
PFMOAA
Sweeney
5
3,405
8,630
95
37
PF02HxA
Sweeney
5
100,174
8,630
95
1,100
PF030A
Sweeney
5
63,750
8,630
95
702
GenX
Sweeney
5
8,630
8,630
95
95
PFESA Byproduct 1
Sweeney
5
14,352
8,630
95
158
PFESA Byproduct 2
Sweeney
5
713,541
8,630
95
7,860
PFMOAA
Chemours Outfall 002
6
113,443
16,637
102
696
PF02HxA
Chemours Outfall 002
6
70,333
16,637
102
431
PF030A
Chemours Outfall 002
6
14,038
16,637
102
86
GenX
Chemours Outfall 002
6
16,637
16,637
102
102
PFESA Byproduct 1
Chemours Outfall 002
6
2,569,948
16,637
102
15,800
PFESA Byproduct 2
Chemours Outfall 002
6
12,055,574
16,637
102
73,900
PFMOAA
Sweeney
6
3,312
11,030
70
21
PF02HxA
Sweeney
6
185,715
11,030
70
1,170
PF030A
Sweeney
6
123,515
11,030
70
778
GenX
Sweeney
6
11,030
11,030
70
70
PFESA Byproduct 1
Sweeney
6
11,504
11,030
70
72
PFESA Byproduct 2
Sweeney
6
741,742
11,030
70
4,670
Flag
1= Sample was diluted 20X and diluted sample exceeded the calibration curve for GenX
2 = Sample was diluted 5X
3 = Sample was diluted 20X
800
700
600
500
�d 3
400''
T
C
avi 300
3
200
100
0
1
12000
10000
` soc
on
c
5 6000 ,3
T
C I
cu
W
N 4000
fy; e
2000
0
1
Figure 1. GenX Concentration (ng/L) Profile
L Sweeney Chemours
2 3 4 5 6
Sample Week
Figure 2. PFMOAA Concentration (ng/1) Profile
2 3 4
Sample Week
6
August 31, 2017
25000
20000
15000 =
O
H
10000 0
E
a
.c
v
5000
U
160000
140000
Sweeney Chemours
120000
5 6
J
bA
100000
w
80000 p
60000 E
aj
U
40000
20000
0
August 31, 2.017
Figure 3. PF02HxA Concentration (n<g/L) Profile
3500
3000
2500
b0
C
a 2000
SH
? f
1500
0
v
vi
1000
500
0
1
Figure 4. P 030A Concentration (ng/L) Profile
1.20000
liiweeney Chemours 100000
2 3 4 .5
Sample Week
7
6
J
80000 on
C
60000 p
N
0
0
40000
U
2.0000
0
10000
450000
9000
400000
Sweeney Chemours
8000
350000
7000
—'
300000
00
c
6000
250000 42
5000
O
v
200000 3
c
4000
0
3
150000 a
3000
v
100000
2000
50000
1000'
0
s ''
0
1 )
3 4 5 6
Sample Week
3500
3000
2500
b0
C
a 2000
SH
? f
1500
0
v
vi
1000
500
0
1
Figure 4. P 030A Concentration (ng/L) Profile
1.20000
liiweeney Chemours 100000
2 3 4 .5
Sample Week
7
6
J
80000 on
C
60000 p
N
0
0
40000
U
2.0000
0
180
160
140
120
c
CL
100
0 80
c
a
N 60
40
20
0
Figure 5. PFESA Byproduct I Concentration (ng/J,) Profile
Sweeney Chemours
1 2 3 4 5 6
Sample Week
Figure 6..PFF,SA Byproduct 2 Concentration (ng/L) Profile
9000
8000
7000
6000
c
5000
ai 4000
c
Oj
N 3000:
2000
1000
0
1 2
sweeney Chemours
3 4 5
Sample Week
L
It
August 31, 2017
18000
16000
14000
12000 to
10000 T
O
8000
0
6000 t
v
4000
2000
0
80000
70000
60000
J
Op
50000
40000 p
0
30000 E
a
L
U
20000
10000
0
. , r
August 31, 2017
Figure 7. Relative change (compared to highest measured value) in PFAS concentration
over weeks 1 – G for GenX and NTAs at the Chemours outfall and Sweeney Finished
Drinking Water. GcnX and NTAs in Panels A,D,E, & F show a consistent decreasing
profile. The PFESA Byproduct concentrations are variable and do not show a clear trend.
_ — _ __ - -- - --
GenX J PFESA Byproduct 1 PFESA Byproduct 2
100 _— w
50-
25
0
N
N
C 0
0
Q.
N
0
100
CO
a)
W
75
111
25
0
Chemours Outfall 002
Sweeney
2 4 6
2 4 6
Sampling Week
9
2 4 6