Document DDO2r3DoRkXLLyk03k5D4679n
AR226-3635
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Final Report
Analysis of PFOA, PFOS, PFHS, and PFBS From Newly Constructed Wells at the Oakdale, Minnesota
Disposal Site
Laboratory Request Number: E06-0151
Method Requirement: 3M Method ETS-8-154.1 (modified)
Testing Laboratory 3M EHS Operations 3M Environmental Laboratory
Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106
Requester Gary Hohenstein 3M Building 42-02-E-27
PO Box 3331 Saint Paul, MN 55133-3331
P h o n e :(6 5 1 )7 7 8 -5 1 5 0 Fax: (651) 778-7203
Iaccredited! Certificate #2052-01
The testing reported herein meet the requirements of ISO /IED 17025-1999 "General Requirements for the Competence o f Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that compiles with this International Standard also operate in accordance with ISO 9001/ISO 9002 (1994).
3M CONFIDENTIAL
PAGE 1 OF 18 i
000006
3 M ENVIRONMENTAL LABORATORY REPORT NO. E0&0151
3M Environm ental Laboratory 3M Environmental Laboratory Manager: William K. Reagen, Ph.D. 3M Technical Lead: Michelle Malinsky, Ph.D. Report Author: Michelle Malinsky/Susan Wolf 3M Environmental Laboratory Professional Service Personnel
Gabriel McMurtry, Pace Analytical, Lab Ops Cindy Carlson, Pace Analytical, Lab Ops
Analytical Report E06-0151
Ground Water Samples from Newly Constructed Wells near the Oakdale, Minnesota Disposal Site March 13,2006
1 Introduction/Summary
The 3M Environmental Laboratory extracted and analyzed ground water samples collected by Weston Solutions, Inc. personnel on March 2-3,2006 from newly constructed wells on and/or near the Oakdale, Minnesota 3M disposal site. Samples were returned to the 3M Environmental Laboratory for analysis of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS), and perfluorobutane sulfonate (PFBS) under laboratory project number E06-G151 using 3M , Environmental Laboratory Method ETS 8-154.1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry".
The 3M Environmental Laboratory prepared sets of sample containers for nine sampling locations.
Each sample set consisted of a field sample, field sample duplicate, low field spike (1.0 ng/mL) and .
high field spike (1Qng/mL). Each empty container was marked with a "fill to here" line which
,
corresponded to a final volume of 450 mL. Containers reserved for field matrix spikes were fortified
with an appropriate matrix spike solution containing the four target analytes prior to being sent to the
field for sample collection.
All samples were extracted on March 3,2006 and analyzed on March 3,2006 and on March 6, 2006. Table 1 below summarizes the sample results. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.
The testing reported herein meet the requirements of ISO /IED17025-1999 "General Requirements for the Competence o f Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001/ISO 9002 (1994).
3M CONFIDENTIAL
PAGE 2 OF 18
3M ENVIRONMENTAL LABORA TORY REPORT NO. E06-0151
Table 1. Sample Results Summary.
3M L IM S ID
Sample Description
mPFOA Concentration
(ng/mL)
PFOS Concentration
y (ng/mL)
PFHS '
**PFBS
Concentration Concentration
(ng/mL)
(ng/mL)
E06-0151-082 E06-0151-083
OKMN GWS RW40 0 060302 OKMN GWS RW40 DB 060302
Average
<0.0250 <0.0250 <0.0250
<0.0249 <0.0249 <0,0249
<0.0252 <0.0252 <0.0252
<0.0397 <0.0397 <0.0397
%RPD Sample/Sample Dup
NA
NA
NA
E06-0151-086
OKMN GWS SP42 0 060302
<0,0,250
<0.0249
<0.0252
E06-0151-087
OKMN GWS SP42 DB 060302
<0.0250
<0.0249
<0.0252
Average
<0.0250
<0.0249
<0.0252
%RPD Sample/Sample Dup
NA
NA NA
E06-0151-090
OKMN GWS PL43 0 060302
^ <0.0250
, f0 i0 2 4 9 i . ; <0.0252
E06-0151-091
OKMN GWS PL43 DB 060302 - , -<0.0250
:.;.<0.0249?
<0.0252
A.
Average1: s <0.0250
' <0.0249
<0.0252
%RF"D Sample/Sample Dup
NA
" ' NA -
NA
E06-0151-094
! OKMN GWS RW39 0 060302
<0.0250 ' 1 ; <0.0249
<0.025,2
E06-0151-095
OKMN GWS RW39 DB 060302
' <0.0250
<0.0249
<0.0252
Average
<0.0250
<0.0249
<0.0252
%RPD Sample/Sample Dup
NA
NA NA
E06-0151r098 - - OKMN GW S.P045 0 060303
0.592
0.390 ,.v ' 0.0649
E06-0151-098 v - -OKMN GWS PC45 0 060303 i
. 0.522
0.464 - " 0.0635
E06-0151-099 t- 'OKMN GWS PC45 DB 060303 ^
0.514 '
0.449 ' : ' 0.0547
i
' ; ' ,r'
' ' f- " 1; Average; ' 0.543
!
0.434
0.0610
4t>Rs6 Sample/Sample Dup/l_ab Dup
C. 7 9
' 9.0 '
9.1'
E06-0151-102
OKMN GWS SP44 0 060303
<0.0250
<0.0249
<0.0252
E06-0151-103 ... OKMN GW SSP44 DB 060303
<0.0250
<0.0249
<0.0252
,>
A w a ie ;
<0.0250 / <0.0249 J l <0.0252
%RPD Sample/Sample D u p .
..N A
' - 'N A ' a.
NA
E06-0151-106
OKMN GWS RW38 0 060303
0.0525
0.187
<0.0252
E06-0151-107
OKMN GWS RW38 DB 060303
0.0556
0.195
<0.0252
Average
0.0540
0.191
<0.0252
%RPD Sample/Sample Dup
5.7
4.2
NA
E06-0151-110
OKMN GWS RW37 0 060303
0.312
2.47
<0.0252
E06-0151-110
OKMN GWS RW37 0 060303
0.282
2.51 <0.0252
E06-0151-111
OKMN GWS RW37 DB 060303
0.298
2.56
<0.0252
E06-0151-114
Average %RSD Sample/Sample Dup/Lab.Dup
OKMN GWS PL41 0 060303
0-297 5.0 ;
0.0766' ' '
2.51 1-8 '0.0268
<0.0252 NA
<0.0252
E06-0151-115
OKMN GWS PL41 DB 060303
0.0796
<0.0249
<0.0252
Average
0.0781
(6|0.0268
<0.0252
%RPD Sample/Sample Dup
3.8
NA NA
NA <0.0397 <0.0397 <0.0397
NA : ,<0.0397
<0.0397 <0.0397
NA <0.0397 <0.0397 , <0.0397
NA <0.0397 <0.0397 <0.0397 <0.0397
N <0.0397 <0.0397 <0.0397
NA <0.0397 <0.0397 <0.0397
NA <0.0397 <0.0397 <0.0397 <0.0397
NA <0.0397 <0.0397 <0.0397
NA
(1) The analytical uncertainty for PFOA was 1005.8% based on method accuracy and precision. See Section 3.7 for additional explanation. The lim it o f quantitation (LOQ) was 0.0250 ng/mL. Results and average values are rounded to three significant figures according to EPA rounding rules. %RPD values are rounded to two significant figures.
3M CONFIDENTIAL
PAGE 3 OF 18
000008
3MENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Because of rounding, values may vary slightly from those listed in the raw data. Samples with reported results less than the LOQ o f 0.0250 ng/mL may or may not have PFOA present. Results less than the LOQ are not quantified.
(2) The analytical uncertainty for PFOS was 1003.7 % based on method accuracy and precision. See Section 3.7 for additional explanation. The lim it o f quantitation (LOQ) was 0.0249 ng/mL. Results and average values are rounded to three significant figures according to EPA rounding rules. %RPD values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Samples with reported results less than the LOQ of 0.0249 ng/mL may or may not have PFOS present. Results less than the LOQ are not quantified.
(3) The analytical uncertainty for PFHS was 100+8.6% based on method accuracy and precision. See Section 3.7 for additional explanation. The lim it of quantitation (LOQ) was 0.0252 ng/mL. Results and average values are roiinded to three significant figures according to EPA rounding rules. %RPD values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Samples with reported results less than the LOQ of 0.0252 ng/mL may or may not have PFHS present. Results less than the LOQ are not quantified.
(4) The analytical uncertainty for PFBS was 1006.6 % based on method accuracy and precision. See Section 3.7 for additional explanation. The lim it of quantitation (LOQ) was 0.0397 ng/mL. Results and average values are rounded to three significant figures according to EPA rounding rules. %RPD values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Samples with reported results less than the LOQ of 0.0397 ng/mL may or may not have PFBS present., Results less than the LOQ are not quantified.
(5) Sample results are for a laboratory extraction duplicate. The relative standard deviation (%RSD) is reported using ail three results (sample, laboratory duplicate, and sample duplicate).
(6) The average value iisted is the concentration for the sample or sample duplicate that produced a value above the ' LOQ. A true average and %RPD between the sample and sample duplicate was not determined.
2 Methods - Analytical and Preparatory
2.1 Sample Collection
Samples were collected in NalgeneTM (low-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Prior to sample collection, bottles designated for field matrix spikes were spiked in the laboratory with a known volume of an appropriate matrix spiking solution containing the analytes of interest (PFOA, PFOS, PFHS, and PFBS). Collected sample bottles were returned to the laboratory at ambient conditions on March 3, 2006. Table 2 below details the bottles prepared and the corresponding spike levels for each sampling location. Samples were collected from nine individual sites. Table 3 provides the key code for the sample descriptions.
Table 2. Sample Collection and Spike Information.
Description
Sample Sample Duplicate Low Field Matrix Spike High Field Matrix Spike Trip Blank Trip Blank Low M atrix Spike Trip Blank High Matrix Spike
Nominal Final Volume
tmL)
PFOA
450 NA
450 450
' NA 0.999
450 9.99
450 NA
450 0.999
450 :
9.99
Final Concentration (ng/mL)
PFOS
PFHS
NA NA 0.997 9.97 NA 0.997 9.97
NA ' NA 1.01 10.1 NA 1.01 10.1
PFBS
NA NA 0.992 9.92 NA 0.992 9.92
3M CONFIDENTIAL
PAGE 4 OF 18
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Table 3. Sample Description Key Code.
Sample ID Code RW PL SP PC OKMN . GW 0 DB LS HS
Definition ' Residuum well
Platteville Limestone well 1S t Peter Sandstone well Prairie du Chein well Oakdale Minnesota site . i .. i -. Groundwater-Sample Sample . Duplicate Low Spike High Spike
The ground water samples, sample duplicates, and field matrix spikes returned for analysis all had visible sediment present which "colored" the water sample, whep shakent0 disperse the solids. All collected samples were centrifuged to remove particulate Before extraction. See Section 2.2 for more information. Additionally, the samples associated with RW37 generated a fairly strong petroleum odor. The table below describes additional observations noted for each of the sample locations.
Table 4. Sample Observations.
Observations
Well Identification
Sediment Color
Sediment Amount
Other
RW37
Grey-brown
(,)Moderate
Strong petroleum odor present
RW38
Rust-brown
" Light
NA
RW39
: - Rust-brown '
!
" Light
'/-
NA
RW40
Rust-brown :: M
'^M oderate '
NA
PL41 :
` i: Rifst-browri
" Moderate
NA
SP42
Rut-brow ' / .. . ^'Moderate ' NA
PL43 ' ?
, Rust-brown " .
... (,>Moderate ...
NA ,
SP44
Grev-brown
......" M oderate., ,. .
NA
PC45 (1)
(2)
Rust-brown
" Light
NA
Moderate: after centrifugation of a 40 mL aliquot, sojids roughly the size of a pea remained after removal of the
supernatant.
1 ' h r: `
. / ! - n ' !
Light: after centrifugation of a 40 mL aliquot, solids present, but minimal.
2.2 Extraction
All samples, calibration standards, and associated quality control samples were extracted using the procedure outlined in ETS-8-154.1 "Determination of Perfluorinated Acids, Alcbhols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry". Briefly, 40 mL of sample were loaded onto a pre-conditioned Waters C18 solid phase extraction (SPE) cartridge (Sep-Pak, 1.0 g, 6 cc) using a vacuum manifold. The loaded SPE cartridges were then eluted with 5 mL of methanol. This extraction procedure concentrates the samples by a factor of eight. (Initial volume = 40 mL, final volume = 5 mL). The calibration standards, lab control spikes, method blanks, and trip blank sample and spikes were extracted as described above. Because the collected ground water samples contained visibly significant amounts of sediment/particulate, the 40 mL aliquot was centrifuged at 3500 rpm for ten minutes for all samples, sample duplicates, low field , matrix spikes and high field matrix spikes prior to extraction. After centrifugation, the supernatant was loaded onto the SPE cartridge for extraction similar to the calibration standards and laboratory quality control samples. The remaining solids were retained if further extraction was deemed necessary. ETS-8-154.1 does not describe sample centrifugation prior to extraction. This method modification was
3M CONFIDENTIAL
PAGE 5 OF 18
OOOOlQ
3M ENVIRONMENTAL LABORATORY REPORT NO. EOS-0151
necessary as the sediment completely clogged the SPE cartridges almost immediately preventing complete loading of the water sample. The final methanol sample extracts had a slight yellowish color. Recoveries of laboratory matrix spikes and field sample matrix spikes demonstrated that the centrifugation step did not significantly impact the method performance.
Samples were extracted and initially analyzed on March 3,2006. The trip blank spikes for all four analytes produced recoveries of approximately 60%. Additionally, most field sample matrix spike recoveries were between 60-80%. Upon further review of the data, it was determined that an older standard was used to prepare the upper range of the calibration curve on March 3,2006 and that this standard was not the same one used to prepare the collection bottle spikes. On March 6,2006, a new extracted calibration curve was prepared using the same (newer) standard used to prepare the collection bottle spikes. Method blanks and lab control spikes at 1 ng/mL and 10 ng/mL were also prepared with the new curve. Additionally, the trip blank and trip blank field matrix spikes along with two samples (E06-0151-098 and E06-0151-0110) were also re-extracted. Furthermore, low and high lab matrix spikes at 1 and 10 ng/mL were prepared for the two samples selected for re-extraction. For the lab matrix spiked samples, an appropriate amount of spiking standard was added to the 40 mL sample aliquot before it was centrifuged to remove the solids. Analysis of selected calibration points from the first curve (March 3, 2006) against the the new curve (March 6,2006) demonstrated that a systematic bias of 20-30% was present in the first analysis. All sample extracts from March 3,2006 were then reanalyzed against the new curve. All results presented here are from the March 6,2006 analysis against the new calibration curve.
2.3 Analysis
All sample and quality control extracts were analyzed for the target analytes using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below.
Table 5. Instrument Parameters
Instrum ent Name Liquid C hrom atograph G uard colum n A nalytical colum n In jection Volum e M ass S pectrom eter Ion Source E le c tro d e P olarity S o ftw a re
ETSStan Agilent 1100 Betasil C18 (2.1 mm.X100 mm), 5 urn Betasil C18 (2.1 mm X 100 mm), 5 urn
5uL Applied Biosystems API 4000
Turbo Spray Z-spray Negative
Analyst 1.4.1
Table 6. Liquid Chromatography Gradient Program
Step Number
0 1 2 3 4 5
Total Time (min)
0 1.0 14.5 15.5 16.5 20.0
Flow Rate (pL/rnin)
300 300 300 300 300 300
Percent A (2 mM ammonium acetate)
80.0 80.0 10.0 10.0 80.0 80.0
Percent B (Methanol}
20.0 20.0 90.0 90.0 20.0 20.0
3M CONFIDENTIAL
PAGE 6 OF 18
O O O O ll
3MENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Table 7. Mass Transitions
Analyte '"P F B S `"PFHS '"P FO S
` "P F O A
Mass Transition Q1/Q3 299/80 299/99 399/80 399/99 499/130 499/99 499/80 413/369 413/219 413/169
Dwell Time (msec)
125 125 125 125 125 125 125 125 ' ' 125 ' ' `- 'M 125
` Individual transitions were summed to produce a "total ion chromatogram" (TIC). The TICs were used for quantitation.
3 Data Analysis
3.1 Calibration
Calibration standards were prepared by spiking known amounts of methanolic stock solutions ; containing PFOA, PFOS, PFHS, and PFBS into 40 mL of ASTM type I water. Each spiked water ; standard was then extracted in the same manner as the collected samples. A total of twelve spiked standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data was not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve p in t. Each extracted calibration standard used to generate the final calibration curve met the method calibration accuracy requirement of 25%. Th correlation coefficients (r) were greater than 0.999 for all analytes.
3.2 Limit of Quantitation (LOQ)
The LOQ for this analysis, as defined in ETS-8-154.1, is the lowest non-zero calibration standard in the curve in which the area counts are twice those of the method blank(s). The limit of quantitation for PFOA, PFOS, PFHS, and PFBS is 0.0250 ng/mL, 0,0249 ng/mL, 0.0252 ng/mL, and 0.0397 ng/mL respectively Area count comparision for the method blanks and th lowest calibration standard will be provided in Section 3.5.1.
3.3 System Suitability
Fiver replicate injections of the 5 ng/mL extracted-calibration standard was analyzed at the beginning of the analytical sequence to demonstrate overall system suitability. The same standard was analyzed in triplicate at the end of the analytical sequence. All analytes met method acceptance criteria of less than 5% relative standard deviation (RSD) for peak area and less than 2% RSD for retention time for both opening and closing system suitability injections.
3.4 Continuing Calibration
During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve was still in control. All CCVs produced recoveries within 100%25%, which met method criteria.
3M CONFIDENTIAL
PAGE 7 OF 18 O O O O 2
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
3.5 Blanks
Three types of blanks were prepared and analyzed with the samples: method blanks, solvent blanks, and field/trip blanks. Each blank type is described below.
3.5.1 Method Blanks
Several method blanks were prepared by loading 40 mL of ASTM Type I water onto a C18 SPE cartridge and eluting with 5 mL of methanol using the same extraction procedure as the samples. Method blanks were prepared to evaluate the levels of background contamination in the overall extraction process (reagent water, glassware, SPE cartridges, etc.) Table 8 lists the area counts for the method blanks and the LOQ standard associated with the given data set.
Table 8. Method Blank Area Counts for Extractions performed on 3/6/2006.
Sample Name
Sample Comment
Sample ID
s060306a025
Method Blank-1
MB-060306-1
s060306a026
Method Blank-2
MB-060306-2
s060306a027
Method Blank-3
MB-060306-3
s060306a028
Method Blank-4
MB-060306-4
s060306a029
Method Blank-5
MB-0S0306-5
s060306a030
Method Blank-6
MB-060306-6
s060306a031
Method Blank-7
MB-060306-7
s060306a032
Method Blank-8
MB-060306-8
Area Counts o f highest method blank multiplied bv two
Area Counts LOQ standard
LOQ concentration, ng/mL
PFOA 11741 11689 11131 6189 8872 5558 20205 15076 40410 50284 0.0250
Area Counts
PFOS (,,2880
1412 1814 993 1510 655 1982 1802 3964 5254 0.0249
PFHS 5939 2265 5101 1824 1613 1218 5292 4387 11878 21147 0.0252
PFBS 13417 4009 18787 4178 4717 1874 11821 14398 37574 54306 0.0397
(1) Determined to be a statistical outlier at the 80% confidence level using Dixon's Q-test. Area value not used to establish the LOQ for PFOS.
3.5.2 Solvent Blanks
Several methanol solvent blanks were analyzed to assess system contamination and/or instrument carryover. Analyte peak area counts in all blank samples Were less than half the area counts of the calibration standard used to establish the LOQ.
3.5.3 Field/Trip Blanks
Prior to sample collection, one sample container was filled with 450 mL of ASTM Type I water, sealed, and shipped to the sample collection site along with the empty containers. This sample was analyzed as field/trip blank. The trip blank serves as an additional method blank that accounts for any storage conditions and/or holding time issues that the samples may experience. The target analytes were not detected above the stated LOQ in the trip blank.
3.6 Lab Control Spikes (LCSs)
For the extractions performed on March 3, 2006, low (0.25 ng/mL. nominal concentration) and high (7.5 ng/mL nominal concentration) lab control spikes were prepared and analyzed in triplicate. LCSs were prepared by spiking known amounts of the analytes into 40 mL of ASTM Type I water to produce the desired concentration. The spiked water samples were then extracted and analyzed in the same manner as the samples. Analysis of triplicate LCSs at the two specified levels cross-validates the
3M CONFIDENTIAL
PAGE 8 OF 18
000013
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
analytical method as used here for any modifications/deviations from ETS 8-154.1. Additionally, LCS results will be used to determine overall method uncertainty in Section 3.7. Table 9 summarizes the LCS recovery results from the March 6,2006 extraction set.. LCS recoveries from the March 3,2006 extraction are not given here as no sample results were reported from this run.
Table 9. <1)Lab Control Spike Results.
PFOA
Sample Description
Lab ID
1 ppb Lab Control Spike
LCS-060306-1
1 ppb Lab Control Spike
LCS-060306-2
1 ppb Lab Control Spike
LCS-060306-3
10 ppb Lab Control Spike LCS-060306-4
10 ppb Lab Control Spike LCS-060306-5
10 ppb Lab Control Spike LCS-060306-6
Average %Recovery %RSD
Spiked Cone. (ng/mL)
0.999 0.999 0.999 9,99 9.99 9.99
Calculated Cone.
(ng/mL)
% Recovery
> i.oo.
1.01 0.961 9.19 9,6)5. , 9.85
<
100 101 96.2 92.1 96.6 98.6
97.4%J3.3%
Spiked Cone. (ng/mL)
0.997 0.997 0.997 9.97 9.97 9.97
PFOS
Calculated Cone. (ng/mL)
' 1.04 1.03 1.00 9.91 10.2 10.1
102%1.8%
% Recovery
104 103 100 99.4 102 101
PFHS
Sample Description
Lab ID
Spiked Coric. (ng/mL)
1 ppb Lab Control Spike
LCS-060306-1
1 ppb Lab Control Spike
LCS-060306-2:
1 ppb Lab Control Spike
LCS4360306-3 : !
10 ppb Lab Control,.Spike LCS-060308-4
10 ppb Lab Control Spike LCS-060306-5
10 ppb Lab Control Spike LCS-060306-6
Average %Recovery %RSD
1.01 1.01 1.01 10.1 10.1 10.1
Calculated : Cone.
(ng/mL)
% Recovery
1.08 ' 1.11 1.08 9.85 9.93 9.84 103%Y5.5%
107 ' 110 107 97.7, 98.5 97.6
Spiked Cone. (ng/mL)
0.992 0.992 0.992 9.92 9.92 9.92
PFBS
Calculated Cone. (ng/mL)
% Recovery
1.04 1.05 1.03 9.17 9.32 9.49 99.4%36.1%
105 106 104 92.4 94.0 95.7
(1) All results and average values listed tg three significant figures according to EP rounding rules. %RSD .values given to two significant figures. Due to rounding, values may va iy eilghtty'-frorin those ln the raw data.
100Calculated Concentration
LCS Percent Recovery =
%
Spike Concentration
LCS% RSD = gtendardd e v j^ n L C S repiicateS . ^ average IC S recovery
3.7 Analytical Uncertainty
Both the accuracy (percent recovery) and precision (%RSD) of the lab control spikes were used to
estimate the overall method's analytical uncertainty for a given analyte. For example, the overall
accuracy and precision for PFOA based on LCS results was 97.4% 3.3%. The measured precision
(%RSD) is then used to determine the range of the accuracy.
Example:
97.4*(0.033) = 3.25
97.4 + 3.25 = 100.7; 97.4-3.25 = 94.20
..
3M CONFIDENTIAL r& fit'' t
PAGE 9 OF 18
000014
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Thus, LCS accuracy results range from 94.2% to 100.7%. The absolute difference of the low and high ends of this range when compared 100%, are then calculated.
100.7%-100% = 0.70% 100%-94.2% = 5.8%.
The most conservative (largest) absolute difference is then used as the analytical uncertainty for the given analyte. Therefore, the analytical uncertainty for PFOA is given as 100 5.8% for these results. For PFOS, PFHS, and PFBS, the analytical uncertainty, as defined here, is 100 3.7%, 100 8.6%, and 100 6.6% , respectively.
3.8 Field Matrix Spikes (FMS)
Low (nominal concentration of 1.0 ng/mL) and high (nominal concentration 10 ng/mL) field matrix spikes were collected at each sampling point to verify that the analytical method is applicable.to the collected matrix. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not interfere with the extraction and analysis of the analytes of interest. Field matrix spike results will be presented in the next section with the sample data.
FMS Recovery - (Calculated Sample Concentration - Average Concentration : Field Sample & Field Sample Pup.) ,, Spike Concentrator!
4 Data Summary
The tables (Tables 10-19) below summarize the sample results, field matrix spike recoveries, and lab matrix spike reovoeries (if applicable) for the nine locations as well as the Trip Blank. Each table provides the average concentration and the relative percent difference (RPD) or relative percent standard deviation (RSD) of the sample and sample duplicate (and laboratory duplicate - if applicable). All field matrix spike recoveries were within 10030% for all analytes except for the high level PFOS field matrix spike associated with PC45 (LIMS ID# E06-0151-101) which produced a recovery of 148%. The analytical accuracy for the PFOS results associated with this well have not been adjusted as the low field matrix spike, as well as the low and high level lab matrix spikes, produced recoveries within 100130%.
3M CONFIDENTIAL
S M 'S ? *
PAGE 10 OF 18
OG0 O1 S
3M ENVIRONMENTAL LABORA TORY REPORT NO. E06-0151
Table 10. (1,Sample Results for OKMN GWS RW40.
PiFO A
Pi= o s
PiP S
PFBS
3M IM IS ID Description
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
E06-0151-082 OKMN GWS RW40 0 060302
<0.0250
NA
<0.0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-083 OKMN GWS RW40 DB 060302
<0.0250
NA
<0:0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-084 OKMN GWS RW40 LS 060302
1.15
115
1.22
122
1.15
114
0.976
98.4
E06-0151-085 OKMN GWS RW40 HS 060302
7.26
72.7
9.93
99.6
9.05
90.0
8.4 84.6
Average Concentration {ng/mL) %RPD
<0.0250
<0.0249
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data. %RPD values not given with both the sample and sample duplicate concentrations are less than the reported LOQ.
Table 11. (1)Sample Results for OKMN GWS SP42.
PFOA
PFOS
PFHS
PFBS
3 M U M S ID
Description
Cone. (ng/mL)
"/Recovery
Cone. (ngftnL)
%Recovery
Cone. (ng/mL)
"/Recovery
Cone. (ng/mL)
%Recovery
E06-0151-086 OKMN GWS SP42 0 060302
<0.0250
NA
<0.0249
NA
<0.0252 - " NA
<0.0397
NA
E06-Q151-087 OKMN GWS SP42 DB 060302
<0.0250
NA
<0.0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-088 OKMN GWS SP42 LS 060302
0.93
93.1
1.18
118
1.03
102 0.963 97.0
E06-0151-089 OKMN GWS SP42 HS 060302
7.25
72.6
10.1
101
8.54
84.9
8.21
82.7
Average Concentration (ng/mL) %RPD
<0.0250
<0.0249
<0.0252
<0.0397
NA= Not Applicable.
;
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data. %RPD values not given with both the sample and sample duplicate concentrations are less than the reported LOQ.
000016
3M CONFIDENTIAL
PAGE 11 OF 18
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Table 12. (1)Sample Results for OKMN GWS PL43.
PFOA
PFOS
PFHS
PFBS
3M UM SID
Description
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
VoRecoverv
E06-0151-090 OKMN GWS PL43 0 060302
<0.0250
NA
<0.0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-091 OKMN GWS PL43 DB 060302
<0.0250
NA
<0.0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-092 OKMN GWS PL43 LS 060302
1.02
102
1.2
120
1.09
108
0.982
99.0
E06-0151-093 OKMN GWS PL43 HS 060302
8.29
83.0
11.7
117
10.1
100
9.31 93.8
Average Concentration (ng/mL) % RPD
<0.0250
<0.0249
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data. %RPD values not given with both the sample and sample duplicate concentrations are less than the reported LOQ.
Table 13. (1)Sample Results for OKMN GWS RW39.
PFOA
PFOS
PFHS
PFBS
3MLIMSID
Description
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
E06-0151-094 OKMN GWS RW39 0 060302
<0.0250
NA
<0.0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-095 OKMN GWS RW39 DB 060302
<0.0250
NA
<0.0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-096 OKMN GWS RW39 LS 060302
0.954
95.5
1.07
107 0.968 96.2 0.951 95.8
E06-0151-097 OKMN GWS RW39 HS 060302
7.43
74.4
10.5
105
9.52
94.6
9.25 93.2
Average Concentration (ng/mL) % RPD
<0.0250
<0.0249
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data. %RPD values not given with both the sample and sample duplicate concentrations are less than the reported LOQ.
3M CONFIDENTIAL
PAGE 12 OF 18
000017
Table 14. (1>Sample Results for OKMN GWS PC45.
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
nm m s
PFO A
PFO S
PF HS
PF BS
3 M U M S ID
Description
Com. (ng/mL)
%Recovery
Com. 1
(ng/mL)
%Recovery
Com. (ng/mL)
%Recovery
Com. (ng/mL)
"/Recovery
E06-0151-098 OKMN GWS PC45 0 060303
0.522
NA - -
0.464
NA 0.0649 NA <0.0397 NA
E06-0151-099 OKMN GWS PC45 DB 060303
0.514
N
0.449
NA 0.0547 NA <0.0397 NA
E06-0151-098121 OKMN GWS PC45 0 060303 .
0.592
NA
0.390
NA 0.0635 NA <0.0397 NA
E06-0151-100 OKMN GWS PC45 LS 060303
.1.45
903
1.64
121
1.11
105
1.05
106
E06-0151-101 OKMN GWS PC45 HS 060303
9.93
94.0
. 15.2
. . i3i148
10.3
102
9 .7 4 .
98.2
(41E06-0151098-LMS Low
Laboratory Matrix Spike at 1 nq/mL
1.59 105 1.41 97.5 1.07 100 0.944 95.1
mE06-0151098-LMS High
Laboratory Matrix Spike at 10 ng/mL ~
11.3 108 11.0 106 10.5 104 9.05 91.2
Average Concentration (ng/m L)% RS0 -, v - - , s ... 0.543 7.9
0.434 9 .0
0.0610 9.1
<0.0397
NA= Not Applicable. (1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures). %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data. (2) Sample results are from a duplicate laboratory extraction of the sample. A ll friree replicate values used to determine average and %RSD.
(3) FMS recovery exceeded method acceptance criteria of 100+30%. (4) Laboratory matrix spikes were prepared by spiking foe 40 mL sample aliquot priorto centrifugation.
3M CONFIDENTIAL
PAGE 13 OF 18
000018
3M ENVIRONMENTAL LABORATORY ., REPORT y o . E06-0151
Table 15. (1>Sample Results for OKMN GWS SP44.
PFOA
PFOS
PFHS
PFBS
3M L IM S ID
Description
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recoverv
E06-0151-102 OKMN GWS SP44 0 060303
<0.0250
NA
<0.0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-103 OKMN GWS SP44 DB 060303
<0.0250
NA
<0.0249
NA
<0.0252
NA
<0.0397
NA
E06-0151-104 OKMN GWS SP44 LS 060303
0.943
94.4
1.08
108 0.991 98.5 0.942 94.9
E06-0151-105 OKMN GWS SP44 HS 060303
8.82
88.3
11.9
119
9.60 95.4 9.16
92.3
Average Concentration (ng/mL) % RPD
<0.0250
<0.0249
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data. %RPD values not given with both the sample and sample duplicate concentrations are less than the reported LOQ.
Table 16. (1,Sample Results for OKMN GWS RW38.
PFOA
PFOS
PFHS
PFBS
3M UM SID
Description
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
E06-0151-106 OKMN GWS RW38 0 060303
0.0525
NA
0.187
NA <0.0252 NA <0.0397 NA
E06-0151-107 OKMN GWS RW38 DB 060303
0.0556
NA
0.195
NA <0.0252 NA <0.0397 NA
E06-0151-108 OKMN GWS RW38 LS 060303
1.02
96.7
1.42
123
1.06
105 0.969 97.6
E06-0151-109 OKMN GWS RW38 HS 060303
7.94
78.9
10.2
100
9.27
92.1
8.86
89.3
Average Concentration (ng/mL) %RPD
0.0540 5 .7
0.191 4.2
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary,
slightly from the values in the raw data. %RPD values not given with both the sample and sample duplicate concentrations are less than the reported LOQ.
3M CONFIDENTIAL
PAGE 14 OF 18
000019
3 M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
000039
Table 17. (1iSample Resulte for OKMN GWS RW37.
PFOA
PFOS
PFHS
PFBS
3M IM S ID
Description
Cone. (ng/mL) .
%Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recoverv
E06-0151-110 OKMN GWS RW37 0 060303
0.282
NA .
2.51 ......... NA
<0.0252
NA
<0.0397
NA
E06-015-111 OKMN GWS RW37 DB 060303
0.298
NA
2.56
NA <0.0252 NA <0.0397 NA
E06-0151-110 OKMN GWS RW37 0 060303
0.312
NA
2.47
NA <0.0252 NA <0.0397 NA
E06-0151-112 KMN GWS RW37 LS 060303
1.22
92.3 3.43 '92.2
1.19
118
1.16
117
E06-0151-113 OKMN GWS RW37 HS 060303
' 7.73
74.4
11.7
92.1
10.2
101
9.83
99.1
|3|E06-0151110-LMS Low
Laboratory Matrix Spike at 1 ng/mL
1.47
- 117
3.71
120 0.983 97.7 0.941 94.8
,3|E06-0151110-LMS High
Laboratory Matrix Spike at10na/m L
9.62 93.3 12.3 98.2 8.91 88.6 8.82 88.9
Average Concentration (ng/mL) %RSD
0.2975.0
2.51 1.8
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data.
(2) Sample results are from a duplicate laboratory extraction of the sample. All three replicate values used to determine average and %RSD.
(3) Laboratory matrix spikes were prepared by spiking a 40 mL sample aliquot prior to centrifugation.
3M CONFIDENTIAL
PAGE 15 OF 18
000020
3M ENVIRONMENTAL LABORATORY REPqRWQ^E06-0151
Table 18. (1,Sample Results for OKMN GWS RW39.
PFOA
PFOS
PFHS
PFBS
3M UM SID
Description
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recoverv
E06-0151-114 OKMN GWS PL41 0 060303
0.0766
NA
0.0268
NA <0.0252
NA <0.0397 NA
E06-0151-115 OKMN GWS PL41 DB 060303
0.0796
NA <0.0249 NA <0.0252 NA <0.0397 NA
E06-0151-116 OKMN GWS PL41 LS 060303
1.11
103
1.13 111 1.10
109 0.995 100
E06-0151-117 OKMN GWS PL41 HS 060303
9.93
98.6
12.1 121 11.7
116 10.3 104
Average Concentration (ng/mL) %RPD
0.0781 3.8
<2>0.0268
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data. %RPD values not given with both the sample and sample duplicate concentrations are less than the reported LOQ.
(2) The average value reported reflects the single result that was above the LOQ. A true sample average and %RSD were not determined.
Table 19. <1,Sample Results for the Trip Blank.
PFOA
PFOS
PFHS
PFBS
3M U M S ID
Description
Cone. (ng/mL)
% Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
121Extracted 3-3-06
E06-0151-079
OKMN PW TRIP2 0060302
E06-0151-080
OKMN PW TRIP2 LS 060302
E06-0151-081
OKMN PW TRIP2 HS 060302
Extracted 3-6-06
<0.0250 0.808 7.47
NA 80.9 74.8
<0.0249 0.788 8.25
NA 79.0 82.7
<0.0252 0.808 8.04
NA <0.0397 NA 80.3 0.783 78.9 79.9 7.67 77.3
E06-0151-079
OKMN PW TRIP2 0 060302
<0.0250
NA
<0.0249 NA <0.0252
NA <0.0397 NA
E06-0151-080
OKMN PW TRIP2 LS 060302
1.04
104
0.928
93.0
1.04
103 0.982 99.0
E06-0151-081
OKMN PW TRIP2 HS 060302
9.04
90.5
10.2 102 10.0 99.4 9.58 96.5
NA= Not Applicable.
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
slightly from the values in the raw data. %RPD values not given with both the sample and sample duplicate concentrations are less than the reported LOQ.
(2) Samples extracted on 3-3-06 but analyzed against the calibration curve prepared on 3-6-06.
3M CONFIDENTIAL
PAGE 16 OF 18
000021
3M ENVIRONMENTAL LABORATORY REPORT NO. EQ&-0151
5 Conclusion
PFOA, PFOS,' PFHS, and PFBS results for the collected samples were presented in Table 1. Laboratory control spikes were used to determine the method accuracy and precision for all analytes. The accuracy and precision were then used to estimate the analytical uncertainty for the results (100
5.8% for PFOA; 100 3.7% for PFOS, 100 8.6% for PFHS, and 100 6.6% for PFBS). Field matrix
spike recoveries within 100 30% demonstrated that the analytical method was appropriate for the given sample matrix.
q Data / Sample Retention
All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.
3M CONFIDENTIAL
PAGE 17 OF 18
000022
W ;.r :
v a m m m s N T A i. L A B o m ro n *
S r P w r K o a'&ixi,:
7 Signatures
>W......- V
- A'i. . i > '
Susar T W o 3 M See cr Chemist, e . ' L /
Date
'`\ ' | / /
/
..... ............................. ............................................. .. T....... .................... >?A.r.i,.
Mchele 0. Matinsfcy. PhCfS^lft'hriica! Lead/ ;
Hate
___ -- -1 W#arr K Heaven. PtiD, Ernrfronpefital tafcrate-y Mtsoagemer t
J /ts /o Oste
The 3M Env-ranir,entai Laboratc-ry s Guo.}yAssurance Unit has audited ths data and revert far this
onset
.
' :
/] . A i
/'.,
Gusfcty Asstracce Representative
D ale
5M C C V 'F .O u v m
t" S s 'O r i<5
000023
