Document MJorE6jwRa2Yy5BRG8KJpbgXM
P roven Results.
At22Jb-mO>
Analytical Report
\ 3M Company
Analysis of PFOA and PFOS in Water Samples from Cottage Grove ^ Municipality E04-0910 ^ Exygen Report No. L0004153 Revised
-- Testing Laboratory
Exygen Research 3058 Research Drive 4 State College, PA 16801
4 Requester
G ary A. Hohenstein
4 Manager, Environmental Operations
EHS Oprations 3M Company
gj Building 42-2E -27 St. Paul, M N 5 l0 6
PAGE 10 F 5
^ ^ ^ 3 0 5 8 Research Drive 4 F m l S t a t e College, PA 16801, USA
m j : 800.281.3219
m R 814.272.1019 exygen.com
1 introduction
In this revised report, results are reported fo r the analysis of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) in water samples received at Exygen as requested by Gary Hohenstein of 3M Company. The report was revised to update the requester information and to make m inor changes to the text of the report. Analytical results were not changed in this revision.
The Exygen project number assigned to the samples is L0004153. Table I lists the target analytes quantitated for the samples.
Table I. Target Analytes fo r Quantitation
P aram eter
Acronvm
F orm ula
Perfluorooctanoic acid
PFOA
C ^C O O H
Perfluorooctanesulfonate
PFOS
c 8f 17s o 3h
2 Sample Receipt
Forty-three sam ples were received at Exygen in 500 mL white plastic narrow-m outh bottles. At the request o f 3M, all samples were analyzed. A copy of all sam ple log-in information is presented in Attachm ent A.
The samples were received on 12/30/04. The samples were shipped am bient via UPS. The sam ples were stored refrigerated from tim e of receipt until analysis.
3 Methods - Analytical and Preparatory
3.1 Water Sample Preparation
Solid phase extraction (SPE) was used to prepare the w ater samples fo r LC/MS/MS analysis. Forty m illiliters of the water sample was transferred to a C i8 SPE cartridge. The cartridge was washed with 5 m L of a 40% methanol: 60% water wash. The cartridge was eluted with 5 m L of 100% methanol. A portion of the extract was transferred to autosam pler vials and analyzed using electrospray LC/MS/MS.
3.2 Sample Analysis by LC/MS/MS
In High Pressure Liquid Chromatography (HPLC), an aliquot of extract is injected and passed through a liquid-phase chromatographic column. Based on the affinity of the analyte for the stationary phase in the column relative to the liquid mobile phase, the analyte is retained fo r a
PAGE2 OFS
characteristic am ount of tim e. Following HPLC separation, mass spectrom etry provides a rapid and accurate means fo r analyzing a wide range of organic compounds. M olecules are ionized, fragm ented, and detected. Th ions characteristic of the compounds are observed and quantitated against extracted standards.
An HP1100 system interfaced to an Applied Biosystems API 4000 was used to analyze the
sample extracts for quantitation.
.
Isom er separation was obtained using a gradient elution through a Therm o Ruophase RP, 50 x 2.1 mm x 5pm column. The sum of the isomers is reported as a single value fo r each of the analytes.
The following gradient was performed:
Mobile Phase (A): M obile Phase (B):
2mM Ammonium Acetate in W ater Methanol
Tim e 0 .0 1.0 8.0 10.0 11.0 18.0
%A 65 65 25 25 65 65
%B 35 35 75 75 35 35
The following param eters were used for operation of the mass spectrom eter:
P aram eter Ionization Mode Polarity Transitions Monitored
Gas Tem perature Drying Gas (N2)
S etting
Electrospray Negative 413->369 (PFOA), 499->80 (PFOS), 415->370 (13C-PFOA) 350C 7.0 L/min
4 Analysis
4.1 Calibration
A 7-point calibration curve was analyzed initially and throughout the analytical sequence for PFOA, PFOS and 13C PFOA. The calibration points were prepared a t 0 ,2 5 ,5 0 ,1 0 0 ,2 5 0 ,5 0 0 , and 1000 ng/L (ppt) for LC/MS/MS analysis. Calibration standards are prepared using the sam e SPE procedure used fo r samples. The instrument response versus the concentration was plotted fo r each point. Using linear regression with 1/x weighting, the slope, y-intercept and coefficient of determ ination ( r ) were determined. A calibration curve is acceptable if r2 > 0.985.
For the results reported here, calibration criteria were m e t The calibration curves are included in the raw data in Attachm ent C.
PAGE3 OF5
4.2 Surrogates
13C PFOA is used as a surrogate fo r the water samples. 13C PFOA was added to the empty sam ple containers before the bottles were sent to the field fo r sampling. In the field, the bottles were filled to a volum etric fill line with the sample.
,3C PFOA recoveries can be found in Attachm ent B.
4.3 Laboratory Control Spikes
Laboratory control spikes in the analytical set were prepared by adding a known concentration of PFOA, 13C-PFOA, and PFOS to laboratory reagents. Laboratory control spikes are used to assess m ethod accuracy. The laboratory control spikes m ust show recoveries between 70130% or the data is rejected. For the results reported here, the laboratory control spikes were within the acceptable range.
4.4 Field Matrix Spikes
A low and high m atrix spike was prepared for every water sample in the field. Compounds were added to the em pty sample containers before the bottles were sent to the field for sam pling. Matrix spikes are used to assess m ethod accuracy in the m atrix. The m atrix spikes should show recoveries between 70-130%. For the results reported here, the m atrix spikes were within the acceptable range, except as noted in Section 6 of this report.
4.5 Sample Related Comments
All water samples were collected in duplicate. Duplicate sam ple results are reported along with the sam ple results in Attachm ent B.
5 Data Summary
Please see Attachm ent B fo r a detailed listing of the analytical results. The results are reported in parts per billion (ng/mL) fo r PFOA and PFOS.
6 Statement o fAccuracy
Based on results of laboratory control spikes, field m atrix spikes, and surrogate spikes, the analytical accuracy for PFOS and PFOA results is 30%. All surrogate spike recoveries and all PFOS field m atrix spike recoveries were within this range. All PFOA field m atrix spike recoveries were w ithin this range with 4 exceptions.
The PFOA recovery for sample CG-W5-2Q8806 High Spike w as 65%.
The PFOA recovery for sample CG-W 3-208807 Low Spike was 298%
The PFOA recovery fo r sample CG-W 7-201127 High Spike w as 58%
The PFOA recovery for sample CG -W 10-191904 High Spike was 65%
PAGE4OFS
4 In each of these cases the second field m atrix spike showed recovery between 70 and 130%. Specific sample recoveries are given in Attachm ent B.
4
7 Data/Sampie Retention
iri Samples will be returned to 3M Corporation 60 days after final reporting. All electronic data is archived on retrievable media and hard copy reports are stored in data folders m aintained by Exygen. Hardcopy data is stored for a minimum of five years. The client w ill be notified 30 days prior to the disposal of hardcopy data.
lil 8 Attachments
7.1 Attachment A: Analytical Results <4
7.2 Attachm ent B: Spike Recovery Data 7.3 Attachment C: Chain of Custody Forms ii 7.4 Attachment D: Raw Analytical Data
9 Signatures
ii
*
m
m PAGES OF5
ill
/8
Section A
P roven Results.
m
\ Summary of PFOA and PFOS in Water Samples E04-0910
Exygen ID
Sample ID
Analyte Found (ng/mL)
C8 Acid PFOA
C8 Sulfonate PFOS
Perfiuorooctanoic Acid
Perfluorooctanesulfonate
L4153-1 L4153-2 L4153-5 L4153-6 L4153-9 L4153-10 L4153-13 L4153-14 L4153-17 L4153-18 L4153-21 L4153-22 L4153-25 L4153-26 L 4 153-29 L 4 153-30 L 4 153-33 L4153-34 L 4 1 5 3 -3 7 L4153-38 L4153-41
. CG-W 6-201238 G-W 6-201238 Dup
CG -W 9-165602 CG -W 9-165602 Dup
C G -W 5-208806 CG-W 5-208806 Dup
C G -W 3r208807 CG-W 3-28807 Dup
CG-W7-2Q.1227 CG -W 7-201227 Dup
C G -W 8-110464 C G -W 8-110464 Dup
C G -W 11-655944 C G -W 11-655944 Dup
CG-W 10-191904 C G -W 10-191904 Dup
CG-W 2-208809 CG -W 2-208809 Dup
CG-W 1-208808 CG -W 1-208808 Dup
T rip Blank-CG
,
ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
4
ND = Not detected at or above 0.025 ng/mL. NQ = Not quantifiable = Measured concentration between 0.025 ng/mL and the Limit of
Quantitation (LOQ) which is 0.050 ng/mL.
at
m
* ^^L3.300558 Research Drive
m m s Statafte College, PA 16801, USA
J: 814.272.1039
V>
F: 814.231.1580 exygen.com
Section B
Field Matrix Spike Recovery Summary for PFOA and PFOS in Water E04-0910
CBAcid PFOA
____C8 Sulfonate PFOS
Amount Amt Found Amount
Amt Found Amount
Sample
Spiked in Sample Recovered Recovery in Sample Recovered Recovery
hi
Description
_.(n0/mL) (ng/mL) (ng/mL)
(%)
(ng/mL) (ng/mL)
(%)
CG-W6-20.1238 Low Spike
(1.4153-3,0.1 ppbSpike)
0.1
ND
0.106
106
ND
0.119
119
CG-W6-201238 High Spike
(L4153-4,5ppb Spike)
5 ND 5.77 115 ND 5.71 114
CG-W9-165602 Low Spike
(L4153-7,0.1 ppb spike)
0.1
ND
0.109
109
ND
0.122
122
l i CG-W9-165602 High,Spike
(L4153-8,5 ppbSplk)
5 ND 5.84 117 ND 5.68 114
CG-W5-208806 Low Spike
I
(L4153-11,0.1 ppbSpike)
0.1
ND
0.118
118
ND
0.127
127
CG-W5-208806 High Spike .
(L4153-12, 5ppbSpike)
5 ND 3.27 65 ND 4.79 96
CG-W3-208807 Low Spike (1.4153-15,0.1 ppb Spike)
0.1
ND
0.298
298
ND
0.123
123
CG-W3-208807 High Spike
(L4153-15,5 ppbSpike)
\ 5 ND 3.69 74 ND 5.19 104
CG-W7-201227 Low Spike
(L4153-10,0.1 ppbSpike)
Oil
ND
0.126
126
ND
0.116
116
CG-W7-201227 High Spike
(L4153-20,5 ppb Spike)
5 \ ND
2.89 58
ND
5.39 108
CG-W8-110464 Low Spike
(L4153-23, 0.1 ppb Spike)
0.1 \ ND
0.0985
99
ND
0.0973
97
CG-W8-110464 High Spike
A
(L4153-24,5 ppb Spike)
5 ND 3.56 71 ND 5.43 109
CG-W11-655944 Low Spike (M153-27,0.1 ppbSpike)
0.1
ND',
0.105
105
ND
0.131
131
CG-W11-655944 High Spike
(1.4153-25,5 ppbSpike)
5 ND 3.75 75 ND 6.31 126
CG-W10-191904 Low Spike
(L41S3-31,0.1 ppbSpike)
0.1
ND '0.110 110
ND
0.125
125
CG-W10-191904 High Spike (L4153-32,5 ppb Spike)
5 ND 3.2.6 65 ND 5.40 108
CG-W2-208809 Low Spike
m
(1.4133-35,0.1 ppbSpike)
0.1
ND
0.113
113
ND
0.121
121
CG-W2-208809 High Spike
(L4153-38, 5ppb Spike)
5 ND 3.51 70 ND 5.67 113
m CG-W1 -208808 Low Spike
(L4153-3, 0.1 ppbSpike)
0.1
ND
0.0894
89
ND
0.114
114
CG-W1-208808 High Spike
(L4153-40,5 ppbSpike)
5 ND 3.59 72 \ ND 5.73 115
m Trip Biank-CG Low Spk
(04153-42,0.1 ppbSpike)
0.1
ND
0.0879
88
ND
0.105
105
Trip Blank-CG High Spk
(L4153-43, 5ppbSpike)
5 ND 4.82 96 ND 5.16 103
N D = No! detected at or above 0.025 ng/mL.
J^305f NQ = Not quantifiable = Measured concentration between 0.025 ng/mL and the Limit of
3058 Research D rive
Quantitation (LO Q ) which is 0.050 ng/mL.
jr m s tSatatte College, PA 16801, USA
VT: 800.281.3219 F: 814.272.1019
A exygen.com
i Surrogate Spike Recovery Summary for 13C-PFOA in Water E04-0910
1IC-PFOA
Amount Amount
*
Exygen
Sample
Spiked Recovered Recovery
ID
Description
(ng/mL) (ng/mL)
(%)
L4153-1
CG-W6-201238
0.5 0.543
109
Ifl
L4153-2
CG-W6-201238 Dup
0.5 0.500
100
153-3 CG-W6-201238 Low Spk
0.5
0.560
112
L453-4 CG-W6-201238 High Spk
0.5
0.541
108
li
L4153r5 L4153-B
CG-W9-165602 CG-W9-165602 Dup
0.5 0.489 0.5 0.513
96 103
L4153-7 , CG-W9-165602 Low Spk
0.5
0.575
115
L4153-8 , CG-W9-165602 High Spk
0.5
0.593
119
1
L4153-9
CG-W5-208806
0.5 0.547
109
L4153-10
CG-W5-208806 Dup
0.5 0.507
101
L4153-11 CG-W5-208806 Low Spk
0.5
0.553
111
i
L4153-12 CG-W5-208806 High Spk
0.5
0.424
85
L4153-13
GG-W3-208807
0.5 0.490
98
L4153-14
CG-W3-208807 Dup
0.5 0.518
104
L4153-15 CG-W3-208807 Low Spk
0.5
0.535
107
L4153-16 CG-W3-25807 High Spk
0.5
0.486
97
L4153-17
CG-W^201227
0.5 0.514
103
L4153-18
CG-W7-201227 Dup
0.5 0.583
117
i
L4153-19 CG-W7-201227 Low Spk
0.5
0.598
120
L4153-20 CG-W7-201227 High Spk
0.5
0.469
94
L4153-21
CG-W8-110464
0.5 0.478
96
g
L4153-22
CG-W8-110464 Dup
0.5 0.568
114
L4153-23 CG-W8-110464 Low Spk
0.5
0.459
92
L4153-24 CG-W8-110464 High Spk
0.5
0.547
109
ii
L4153-25 L4153-26
CG-W11-655944 CG-W11-655944 Dup .
0.5 0.5
0.575 0.548
115 110
L4153-27 CG-W 11-655944 Low Spk
0.5
0.615
123
L4153-28 CG-W11-655944 High Spk \ 0.5
0.587
117
m
L4153-29
CG-W10-191904
0.5 0.578
116
L4153-30
CG-W10-191904 Dup
0.5
0.577
115
L4153-31 CG-W10-191904 Low Spk
0.5
0.567
113
L4153-32 CG-W10-191904 High Spk
0.5
0.537
107
L4153-33
CG-W2-208809
0.5 , 0.579
116
L4153-34
CG-W2-208809 Dup
0.5 0.526
105
L4153-35 CG-W2-208809 Low Spk
0.5
0.545
109
4
L4153-36 CG-W2-208809 High Spk
0.5
0.541
108
L4153-37
CG-W1-208808
0.5 0.551
110
L4153-38
CG-W1-208808 Dup
0.5 0.527
105
ri
L4153-39 CG-W1-208808 Low Spk
0.5
0.548
110
L4153-40 CG-W1-208808 High Spk
0.5
0.528,
106
L4153-41
Trip Blank-CG
0.5
0.532 \
106
ftf L4153-42 Trip Blank-CG Low Spk 0.5 0.482 . 96
L4153-43 Trip Blank-CG High Spk
0.5
0.525
105
^ ^ 3 0 5 8 Research D rive m . State College, PA 16801, USA
800.281.3219 m F : 814.272.1019
exygen.com
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