Document MGd5pJ8KE6rDQxJkDq5dNVD9y
P M226-/93S
Proven Results.
i \
m Analytical Report
itf 3M Company Analysis o f PFOA and PFOS in W ater Samples from O akdale M unicipality E05-0074
m Exygen Report No. L0004351 Testing Laboratory
Exygen Research 3058 Research Drive
State College, PA 16801
* Requester Gary A. Hohenstein
-- Environmental Manager, Special Projects EHS Operations 3M Company Building 42-2E-27
St. Paul, MN 55106
m
PAGE 10 F 5
^ ^ k 3 0 5 8 Research Drive 4 F m S t a t e College, PA 1 6 8 0 1 , USA
^ T : 800.281.3219
m F : 814.272.1019 exygen.com
a
m
m 1 Introduction
Results are reported for the analysis of perfluorooctanoic acid (PFOA) and g perfluorooctanesulfonate (PFOS) in water samples received at Exygen as requested by Gary
Hohenstein of 3M Company. The Exygen project number assigned to the samples Is L0004351. Table I lists the target analytes quantitated for the samples.
^ Tablet. Target Analytes for Quantitation
Parameter
Acronym
Formula
a
Perfluorooctanoic Acid
PFOA
C7F16COOH
a Perfluorooctanesulfonate
PFOS
C8F17S 0 3'
2 Sample Receipt
a Thirty-five samples were received at Exygen in 500 mL white plastic narrow-mouth bottles. At
the request of 3M, all samples were analyzed. A copy of all sample log-in information is presented in Attachment C.
The samples were received on 01/26/05. The samples were shipped ambient via UPS. The samples were stored refrigerated from time of receipt until analysis.
i
3 Methods - Analytical and Preparatory
0 3.1 W ater Sam ple Preparation
m Solid phase extraction (SPE) was used to prepare the water samples for LC/MS/MS analysis. Forty milliliters of the water sample was transferred to a C1BSPE cartridge. The cartridge was washed with 5 mL of a 40% methanol: 60% water wash. The cartridge was eluted with 5 mL of 100% methanol. A portion of the extract was transferred to autosampler 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 f li 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 for a characteristic amount of time. Following HPLC separation, mass spectrometry provides a rapid ^ and accurate means for analyzing a wide range of organic compounds. Molecules are ionized, fragmented, and detected. The ions characteristic of the compounds are observed and quantitated against extracted standards.
PAGE 2 OF5
An HP1100 system interfaced to an Applied Biosystems API 4000 was used to analyze the sample extracts for quantitation.
Isomer separation was obtained using a gradient elution through a Thermo Fluophase RP, 50 x 2.1 mm x 5pm column. The sum of the isomers is reported as a single value for each of the analytes.
The following gradient was performed:
m Mobile Phase (A):
2mM Ammonium Acetate in Water
Mobile Phase (B):
Methanol
m MTime 0.0
%A 65
35
1.0 65
35
m 8.0 25 10.0 25
75 75
11.0 65
35
18.0 65
35
The following parameters were used for operation of the mass spectrometer:
Parameter
Setting
Ionization Mode
Electrospray
Polarity Transitions Monitored
Negative 413->369 (PFOA), 499->80 (PFOS),
415->370 (13C-PFOA)
Gas Temperature
350C
Drying Gas (N2)
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 at 0, 25, 50, 100, 250, * 500, and 1000 ng/L (ppt) for LC/MS/MS analysis. Calibration standards are prepared using the same SPE procedure used for samples. The instrument response versus the concentration was plotted for each point. Using linear regression with 1/x weighting, the slope, -- y-intercept and coefficient of determination (r2) were determined. A calibration curve is acceptable if r2 > 0.985.
For the results reported here, calibration criteria were met. The calibration curves are included in the raw data in Attachment D.
PAGE3 OF5
m
4.2 Surrogates
"C13C PFOA is used as a surrogate for the water samples. rvO A was added to the empty
sample containers before the bottles were sent to the field for sampling. In the field, the bottles were filled to a volumetric fill line with the sample.
13C PFOA recoveries can be found in Attachment 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 method accuracy. The laboratory control spikes must 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 (0.1 ng/mL) and high matrix spike (1.0 ng/mL) were prepared for every water sample In the field. Compounds were added to the empty sample containers before the bottles were sent to the field for sampling. Matrix spikes are used to assess method accuracy In the matrix. The matrix spikes should show recoveries between 70-'* 30%. For the results reported here, the matrix 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 sample results are reported along with the sample results in Attachment A.
5 Data Summary
Please see Attachment A for a detailed listing of the analytical results. The results are reported in parts per billion (ng/mL) for PFOA and PFOS.
6 Statement of Accuracy
Based on results of laboratory control spikes, field matrix spikes, and surrogate spikes, the analytical accuracy for PFOS and PFOA results is 30%, except for sample O-W2-208463 which is 50%. Laboratory control spikes, surrogate spikes and field matrix spikes showed recoveries within these ranges, with the following exceptions:
The PFOA and PFOS recovery in 0-W5-127287 Low Spike, 0-W9-151575 Low Spike, and O-W8-572808 Low Spike could not be calculated because the inherent sample concentration in this sample was over 3 times greater than the spiking concentration.
PAGE4 OF 5
The PFOS recovery for sample 0-W1-208462 Low Spike was 177%. The PFOS concentration in this sample is reported as NQ (Not Quantifiable), meaning that the measured concentration is belween 0.025 ng/mL and the Limit of Quantitation (LOQ) that is 0.050 ng/mL.
The PFOS recovery for sample O-W2-208463 Low Spike was 208%. The PFOS concentration for this sample is reported as NQ.
The PFOS recoveries for samples O-W3-208454 Low Spike and Whispering Oaks Mobile Park High Spike were 134%. The PFOS concentrations for these samples are reported as ND, meaning that PFOS is not detected at or above 0.025 ng/mL.
Samples 0-W5-127287 Low Spike, 0-W9-15175 Dup, 0-W7-463534, 0-W8572608. and Whispering Oaks Mobile Home Park showed surrogate recoveries between 131% and 138%.
Specific sample recoveries are given in Attachment B.
7 Data/Sample Retention
Samples will be returned to 3M 60 days after final reporting. All electronic data is archived on retrievable media and hard copy reports are stored in data folders maintained by Exygen. Hardcopy data is stored for a minimum of five years. The client will be notified 30 days prior to the disposal of hardcopy data.
8 Attachments
7.1 Attachment A: Analytical Results
7.2 AttachmentB: Spike Recovery Data
7.3 Attachm ent C: Chain o f Custody Forms
7.4 Attachment D: Raw Analytical Data
9 Signatures
PAGE5 OFS
Date Date
SECTION A
i
Proven Results.
<
Sum m ary o f PFOA and PFOS in W ater Samples E05-0074 i
Analyte Found (ng/mL)
m C8 Acid PFOA
C8 Sulfonate PFOS
Exygen ID_____ \ ______ Sample ID_____________ Perfluorooctanoic Acid_______ Perfluorooctanesulfonate
L4351-1 L4351-2
0-W 5-127287 \ 0-W 5-127287 Dup
0.821 0.736
1.12 1.01
L4351-5
. 0-W9-15175
L4351-6
Q-W9-15175 Dup
0.825 0.892
L4351-9
Q-W1 -208462
0.0746
Ml
L4351-10 L4351-13
O-W1-208462 Dup O-VV2-208463
0.0790 0.0773
L4351-14
O-W2-^08463 Dup
0.0750
L4351-17
0-W7-463534
0.285
II
L4351-18
0-W7-463534 Dup
0.274
L4351-21
O-W8-572.608
0.668
L4351-22
O-W8-572608. Dup
0.647
li
L4351-25
O-W3-208484
L4351-26
O-W3-208454 Dtip
ND ND
L4351-29
Whispering OAKS Mobile Park
ND
il
L4351-30 Whispering OAKS Mobile Piark Dup
L4351-33
E05-0074 Trip Blank ,
ND ND
0.583 0.653
NQ 0.0514
NQ ND 0.276 0.269 1.02 0.977 ND ND ND ND ND
ND = Not detected at or above 0 .0 25 ng/mL. NQ = Not quantifiable = M easured concentration between 0.025 ng/mL and the Limit of
Quantitation (L O Q ) which is 0 .0 5 0 ng/mL.
m
*i
J&30.350568 Research D rive
State College, PA 16801 USA
V,T: 814.272.1039 F: 814.231.1580
* exygen.com
SECTION B
1Exygen
w i ^ R E S E A FR C H
Precise Research. Proven Results.
Field M atrix Spike Recovery Summary fo r PFOA and PFOS In W ater E05-0074
m
C8 Acid PFOA
C8 Sulfonate PFOS
Amount Amt Found Amount
Amt Found Amount
Sample
Spiked in Sample Recovered Recovery in Sample Recovered Recovery
iW
Description 0-W5-127287 Low Spike
(ng/mL) (ng/mL) (ng/mL) (%)
(ng/mL) (ng/mL) (%)
(L4 3 5 1 -3 ,0.1 ppb Spike)
0.1 0.821 0.971
*
1.12 1.34 *
0-W5-127287 High Spike
(L 4 3 5 1 -4 ,1 ppb Spike}
1 0.821 1.86 104 1.12 1.98 86
0-W9-151575 Low Spike {L4351-7,b,1 ppbSpike)
0.1 0.825 0.859
*
0.583
0.636
*
m 0-W9-151575 High Spike
(L 4 3 5 1 -8 ,1 ppb,Spike)
1 0.825 2.03 121 0.583 1.89 131
a
0-W1-208462 Low .Spike (L4351-11, o.l ppbSpike)
0.1
0.0746
0.203
128
NQ
0.177
177
0-W1-208462 High Spike
(L4351-12.1 ppb Spike)
1 0.0748 1.22 115 NQ 1.29 129
ii
O-W2-208463 Low Spike
(L4351 -15.0.1 ppb Spike)
0.1
0.0773
0.225
148
NQ
0.208
208
i t O-W2-208463 High Spike
(L43S1-10.1 ppb Spike)
\ 1 0.0773 1.45 137 NQ 1.43 143
0-W7-463534 Low Spike
i
(L4351 -19 ,0.1 ppb Spike)
01
0.285
0.403
118
0.276
0.398
122
0-W7-463534 High Spike (L 4351-20,1ppbSpike)
1 0.285 1.48 120 0.276 1.57 129
O-W8-572608 Low Spike (L4351-23, 0.1 ppbSpike)
0.1
0.668
0.668
*
1.02 0.855 *
O-W8-572608 High Spike
(L43S 1-24,1 ppbSpike)
1 0.660 1.93 126 1.02 2.29 127
O -W 3 -2 0 8 4 5 4 L o w S p ik e
(L4351-27.0.1 ppbSpike)
0.1
ND ' 0.124
124
ND
0.134
134
m O-W3-208454 High Spike
{L4351-28,1 ppb Spike)
1 ND 1.22 122 ND 1.28 128
W hispering O AKS M obile Park Low Spike
(L 4 3 5 1 -3 1 ,0.1 p p b Spike)
0.1
ND
0.0819
82
ND
0.0931
93
W hispering O AKS Mobile Park High Spike
(L43S1-32.1 ppb Spike)
1
ND
1.23 123
ND
1.34 134
m*
E05-0074 Trip Blank Low Spk
(L4351-34,0.1 ppb Spike)
0.1
ND
0.119
1)9
ND
0.130
130
m
E05-0074 Trip Blank High Spk
(L4351-35,1 ppb Spike)
1
ND
1.09
109
ND
1.30 130
* 'S am p le residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot b e calculated
ND = Not detected at or above 0 025 ng/mL.
N Q = Not quantifiable = M easured concentration between 0 .025 ng/mL and the Limit of
Quantitation (LO Q ) which Is 0.0 5 0 ng/mL.
J ^ 3 30055f8 Research D rive x# m stSatatts College, PA 16801, USA
V,T: 800.281.3219 F: 814.272.1019 exygen.com
5
Proven Results.
Surrogate Spike Recovery Summary for 13C-PFOA in Water E05-0074
13c -p f o a
Amount Amount
Exygen ID
Sample D e scrip tio n
Spiked Recovered Recovery
(ng/mL) (ng/mL)
(% )
m L4351-1 L4351-2
O-WS-127287 0-W 5-127287 Dup
0.5 0.584 0.5 0.530
117 106
L4351-3
0-W 5-127287 Low Spk
0.5 0.655
131
L4351-4
0-W 5-127287 High Spk
0.5 0.537
107
0
L4351-5
0-W9-15175
0.5 0.608
122
L4351-6
0-W9-15175 Dup
0.5 0.674
135
L4351-7
0-W9-15175 Low Spk
0.5 0.512
102
L4351-8
Q-W9-15175 High Spk
0.5 0.590
118
L4351-9
0-W 1-208462
0.5 0.575
115
0
L4351-10
O-W 1-208462 Dup
0.5 0.643
129
L4351-11
O-W1-208462 Low Spk
0.5 0.644
129
L4351-12
0-W1-28462 High Spk
0.5 0.587
117
0
L4351-13
O-W2-208463
0.5 0.559
112
L4351-14
O-W2-20463 Dup
0.5 0.519
104
L4351-15
O-W2-208463 Low Spk
0.5 0.735
147
0
L4351-16
0-W2-208463 High Spk
0.5 0.623
125
L4351-17
0-W 7-463534
0.5 0.680
136
mmi
L4351-18 L4351-19
0-W7-463534 Dp 0-W7-463534 Low Spk
0.5 0.647 0.5 0.639
129 128
L4351-20
0-W7-463534 High Spk
0.5 0.591
118
0
L4351-21
O-W8-572608
0.5 0.692
138
L4351-22
O -W 8-572608 Dup
0.5 0.567
113
L4351-23
O-W8-572608 Low Spk
0.5 0.515
103
m
L4351-24
O-W8-572608 High Spk
0.5 0.609
122
L4351-25
O-W3-208454
0.5 0.528
106
L4351-26
O-W3-208454 Dup
0.5 0.564
113
*i
L4351-27
O-W3-208454 Low Spk
0.5 0.624
125
L4351-28
O-W3-208454 High Spk
0.5 0.592
118
M
L4351-29
Whispering OAKS Mobile Park
0.5 0.671
134
L4351-30 Whispering OAKS Mobile Park Dup 0.5 0.357
71
L4351-31 Whispering OAKS Mobile Park Low Spk
0.5 . 0.414
83
m L4351-32 Whispering OAKS Mobile Park High Spk
0.5
0.617
123
L4351-33
E05-0074 Trip Blank
0.5 0.528
106
L4351-34
E05-0074 Trip Blank Low Spk
0.5 0.542
108
0
L4351-35
E05-0074 Trip Blank High Spk
0.5 6,531
106
m J ^ 3 0 5 8 Research D rive TM M m u ta te College, PA 16801, USA
800.281.3219 F : 814.272.1019 M exygen.com
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