Document R2EeyvREJ4yKrp3EzpRxjoE7
AR226-3647
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
Phone: (651)778-5150 Fax: (651) 778-7203
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 d ie A2LA Certificate #20524)1. Testing that compiles with this International Standard also operate in accordance with ISO 9001/ISO 9002 (1994).
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3 M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
3 M E nvironm ental Laboratory 3M Environmental Laboratory Manager: W iliam K. Reagen, Ph.D. 3M Technical Lead: Michelle Malinsky, Ph.D. Report Author Michelle Malinsky/Susan W olf 3M Environmental Laboratory Professional Service Personnel
Gabriel McMurtry, Pace Analytical, Lab Ops Cindy Carlson, Pace Analytical, Lab Ops
Analytical Report E06-0151
Ground W ater Sam ples from Newly Constructed W ells near the Oakdale, Minnesota Disposal Site March 13, 2006
1 Introduction/Summary
The 3M Environmental Laboratory extracted and analyzed ground w ater samples collected by Weston Solutions, Inc. personnel on March 2 -3 ,2 0 0 6 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 (PFO A ), perfluoroodane sulfonate (P FO S ), perfluorohexane sulfonate (PFHS), and perfluorobutane sulfonate (PFBS) under laboratory project number E 06-0161 using 3M Environmental Laboratory Method ETS 8-154.1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in W ater by Solid Phase Extractions and High Perform ance Liquid Chromatography/Mass Spectrometry".
The 3M Environmental Laboratory prepared sets of sample containers for nine sampling locations. Each sam ple set consisted of a field sample, field sample duplicate, low field spike (1.0 ng/mL) and high field spike (10 ng/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 w ere extracted on March 3 ,2 0 0 6 and analyzed on March 3 ,2 0 0 6 and on March 6, 2006. Table 1 below summarizes the sam ple results. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.
lK
[accredited]
Certificate #2052-01
The testing reported herein meet the requirements of ISO /IED 17025-1999 "General Requirements for the Competence of 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).
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Table 1. Sample Results Summary.
M U M S ID
S anple Description
n PFOA Concentration
(ng/mL)
PFOS Concentration
(ng/m L)
VPFHS Concentration
(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
%RPD Sample/Sample Dup
NA
E06-0151-086 E060151-087
OKMN GWS SP42 0 060302 OKMN GWS SP42 DB 060302
<b.0250 <0.0250
Average %RPD Sample/Sample Dup
<0.0250 NA
E06-0151-090 E06-0151-091
OKMN GWS PL43 0 060302 OKMN GWS PL43 DB 060302
v > <0.0250 . -<0.0250
Average ' %RPO Sample/Sample Dup
<0.0250 NA
E06-0151-094 E06-0151-095
! OKMN GWS RW39 0 060302 OKMN GWS RW39 DB 060302
1 <0.0250' ' J <0.0250 ;
Average
<0.0250
%RPD Sample/Sample Dup
NA
E06-0151-098 - E06-0151-098 '>' E06-0151-099 7;
OKMN G W S.P045'0 060303 OKM NGW SPC45 0 060303 : OKMN GWS PC45 DB 060303 ^
0.592 . 0.522 ; 0.514
' ` ' Average % R Sb Sample/Sample O liW tab Dup
0.543 ' 7.9
E06-0151-102 E06-0151-103
OKMN GWS SP44 0 060303 OKMN GWS-SP44 DB 060303
<0.0250 .<0.0250
r x i v j Average-.
<0.0250
%RPD Sample/Sample Dup *
.N A
E06-0151-106 E06-0151-107
OKMN GWS RW38 0 060303 OKMN GWS RW38 DB 060303
0.0525 0.0556
Average %RPO Sample/Sample Dup
0.0540 5.7
E06-0151-110 E06-0151-110 E06-0151-111
OKMN GWS RW37 0 060303 OKMN GWS RW37 0 060303 OKMN GWS RW37 DB 060303
0.312 0.282 0.298
E06-0151-114 E06-0151-115
Average %RSD Sample/Sample Dup/LabDuo
OKMN GWS PL41 0 060303 OKMN GWS PL41 DB 060303
0.297 5.o ;
0.0766 ' 0.0796
Average %RPD Sample/Sample Dup
0.0781 3.8
NA NA
<0.0249 <0.0249
<0.0252 <0.0252
<0.0249
<0.0252
NA NA
. <0.0249
- <0.0252
- .<0.0249'
<0.0252
<0.0249
<0.0252
1 NA
NA
<0.0249' `
<0.0252
<0.0249
<0.0252 '
<0.0249
<0.0252
NA NA
0.390
0.0649
0.464 - 1' 0.0635
1 0.449 ' : ; l` 0.0547
0 .4 3 4 '': '
0.0610
9.0 91
<0.0249
<0.0252
<0.0249 . <0.0252
<0.0249
. ' <0.0252
' -:NA: ' '.
NA
0.187
<0.0252
0.195
<0.0252
0.191
<0.0252
4.2 NA
2.47
<0.0252
2.51 <0.0252
2.56
<0.0252
2.51 , ` ,,1.8
' 0.0268
<0.0252 NA
<0.0252
<0.0249
<0.0252
0.0268 NA
<0.0252 NA
* PFBS Concentration
(ng/mL)
<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
NA <0.0397 <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
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.
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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 of 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 o f 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 1008.6% based on method accuracy and precision. See Section 3.7 for additional explanation. The lim it o f quantitation (LOQ) was 0.0252 ng/mL. Results and average values are rounded to three significant figures according to EPA rounding mies. %RPD values are rounded to two significant figures. Because o f rounding, values may vary slightly from those listed in the raw data. Samples with reported results less than the LOQ o f 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 o f quantitation (LOQ) was 0.0397 ng/mL. Results and average values are rounded to three significant figures according to EPA rounding mies. %RPD values are rounded to two significant figures. Because o f rounding, values may vary slightly from those listed in the raw data. Samples with reported results less than the LOQ o f 0.0397 ng/mL may or may not have PFBS p resent, 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 aft three results (sample, laboratory duplicate, and sample duplicate).
(6) The average value listed is the concentration for file sample or sample duplicate that produced a vale above the LOQ. A true average and %RPD between the sample and sample duplicate was not determined.
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, PFO S, PFHS, and PFBS). Collected sample bottles w ere returned to the laboratory at ambient conditions on March 3 ,2 0 0 6 . 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
N om inal Final Volume
(mL)
450 450 450 450 450 450 450
PFOA
NA NA 0.999 9.99 NA 0.999 9.99
Final Concentration (ng/mL)
PFOS
PFHS
NA NA 0.997 9.97 NA 0.997 9.97
NA NA 1.01 1Q.1 NA 1.01 10.1
PFBS
NA NA 0.992 9.92 NA 0.992 9.92
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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 S t Petes' Sandstone well Prairie du Chein well Oakdale Minnesota site . Groundwater Sample Sample Duplicate Low Spike High Spike
The ground w ater samples, sample duplicates, and field matrix spikes returned for analysis all had visible sediment present which "colored" the w ater sample when shaken to disperse the solids. All collected samples w ere centrifuged to rem ove particulate before extraction. S ee Section 2.2 for more information. Additionally, the samples associated with R W 37 generated a fairly strong petroleum odor. The table below describes additional observations noted for each of the sam ple locations.
Table 4. Sample Observations.
O bservations
Well Identification
Sediment Color
' SedimentAm ount
O ther
RW37
Grey-brown
'"M oderate
Strong petroleum odor present
RW38
Rust-brown
^L ig h t
NA
RW39
R ust-brow n"
<. ' ^Light
NA
RW40
Rust-brown
'"M oderate
NA
PL41
Rust-brown 1
'"M oderate
NA
SP42
Rust-brown
.( ''Moderate
NA
PL43
, Rust-brown
............ . '"M oderate .
NA
SP44
Grey-brown
, ..'"M oderate ,
NA
PC45 ( 1}
(2)
Rust-brown
Ught
NA
Moderate: after centrifugation of a 40 mL aliquot, solids roughly the size o f a pea remained after removal of the
supernatant.
` ,i i-
''
Light: after centrifugation of a 40 mL aliquot, solids present, but minimal.
2.2 Extraction
All samples, calibration standards, and associated quality control samples w ere extracted using the procedure outlined in E TS -8-154.1 "Determination of Perfiuorinated Acids, Alcbhols, Amides, and Sulfonates in W ater by Solid Phase Extractions and High Perform ance Liquid Chrom atography/Mass Spectrometry". Briefly, 4 0 mL of sam ple w ere loaded onto a pre-conditioned W aters C 18 solid phase extraction (S P E) cartridge (Sep-Pak, 1.0 g, 6 cc) using a vacuum manifold. The loaded SPE cartridges w ere then eluted with 5 mL of methanol. This extraction procedure concentrates the sam ples by a factor of eight. (Initial volume = 4 0 mL, final volume = 5 mL). The calibration standards, lab control spikes, method blanks, and trip blank sample and spikes w ere extracted a s described above. Because the collected ground w ater 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 w ere retained if further extraction was deem ed necessary. E TS -8-154.1 does not describe sample centrifugation prior to extraction. This method modification was
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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 w ere 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 ,2 0 0 6 and that this standard was not the sam e one used to prepare the collection bottle spikes. On March 6 ,2 0 0 6 , a new extracted calibration curve was prepared using the sam e (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 (E 06-0151 -098 and E 06-0151-0110) were also re-extracted. Furthermore, low and high lab matrix spikes at 1 and 10 ng/mL w ere 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 ,2 0 0 6 ) against the the new curve (March 6 ,2 0 0 6 ) demonstrated that a systematic bias of 20-30% was present in the first analysis. All sample extracts from March 3 ,2 0 0 6 were then reanalyzed against the new curve. All results presented here are from the March 6 ,2 0 0 6 analysis against tiie new calibration curve.
2.3 Analysis
All sample and quality control extracts w ere analyzed for the target analytes using high performance liquid chromatography/ tandem mass spectrometry (H PLC /M S/M S). 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 n a lytica l colum n In jection Volum e M ass Spectrom eter ion Source E le c tro d e P olarity Softw are
ETSStan Agilent 1100 Betasil C18 (2.1 mm.X100 mm), 5 urn Betasil C18 (2.1 mm X 100 mm), 5 urn
5 uL Applied Biosystems API 4000
Turbo Spray Z-sprav Negative
Analyst 1.4.1
Table 6. Liquid Chromatography Gradient Program
Step N um ber
0 1 2 3 4 5
Total Time (m in)
0 1.0 14.5 15.5 16.5 20.0
Flow Rate (fi/m in )
300 300 300 300 300 300
Percent A (2 m M 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
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Table 7. Mass Transitions
A n alyte 0)PFBS (1)PFHS '"PFO S
0)PFOA
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)
125 125 125 125 125 125 125 125 125 125
'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 w ere prepared by spiking known amounts of methanolic stock solutions containing PFO A, PFO S, PFH S, and PFBS into 4 0 mL of A STM type I water. Each spiked water standard was then extracted in the sam e m anner as the collected samples. A total of tw elve 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 point. Each extracted calibration standard used to generate the final calibration curve m et the method calibration accuracy requirem ent of 25% . The correlation coefficients (r) w ere greater than 0.999 for all analytes.
3.2 Limit of Quantitation (LOQ)
The LOQ for this analysis, as defined in E TS -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, PFO S, PFH S, 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 the 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 sam e standard was analyzed in triplicate at the end of foe analytical sequence. All analytes met method acceptance criteria of less than 5% relative standard deviation (R S D ) for peak area and less than 2% R SD for retention tim e 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) w ere analyzed to confirm that foe instrument response and the initial calibration curve was still in control. All C CVs produced recoveries within 100% 25% , which m et method criteria.
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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 w ere prepared by loading 40 mL of ASTM Type I w ater onto a C 18 SPE cartridge and eluting with 5 mL of methanol using the sam e extraction procedure as the samples. Method blanks w ere 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-060306-5
s060306a030
Method Blank-6
MB-060306-6
s060306a031
Method Blank-7
MB-060306-7
s060306a032
Method Blank-6
MB-060306-8
A n a Counts o f highest m ethod blank m ultiplied by (wo
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 3904 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 w ere less than half the area counts of the calibration standard used to establish the LOQ.
3.5.3 FleW/Trip Blanks
Prior to sample collection, one sam ple container was filled with 450 mL of A STM Type I water, sealed, and shipped to the sam ple 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 w ere 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 w ere prepared and analyzed in triplicate. LCSs were prepared by spiking known amounts of the analytes into 40 mL of A STM Type I w ater to produce the desired concentration. The spiked w ater samples were then extracted and analyzed in the same m anner as the samples. Analysis of triplicate LCSs at the two specified levels cross-validates the
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analytical method as used here for any modifications/deviations from ETS 8-154.1. Additionally, LCS results will be used to determ ine overall method uncertainty in Section 3.7. Table 9 summarizes the LCS recovery results from the March 6 ,2 0 0 6 extraction set.. LCS recoveries from the March 3 ,2 0 0 6 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
A verage %Recovery % RSD
Spiked Cone. (ng/m L)
0.999 0.999 0.999 9.99 9.99 9.99
Calculated Cone.
(ng/m L)
% Recovery
1.00 1.01 0.961 9.19 9.65 , 9.85 97.4% &.3%
100 101 96.2 92.1 96.6 98.6
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
Ltd) ID
Spiked Cone. (ng/mL)
1 ppb Lab Control Spike
LCS-060306-1'
1 ppb Lab Control Spike
LCS-060306-2
1 ppb Lab Control Spike
L C S 6 6 0 3 0 6 -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
A verage %Recovery %RSD
1.01 1.01 ! 1.01 10.1 10.1 10.1
Calculated Cone.
(ng/m L)
% Recovery
1.08 1.11 1.08 9.85 9.93 9.84 103%5.5%
0 7 110 107 97.7. 98.5 97.6
Spiked Cone. (ng/m L)
0.992 0.992 0.992 9.92 9.92 9.92
PFBS
Calculated Cone. (ng/m L)
% Recovery
1.04 1.05 1.03 9.17 9.32 9.49 99.4% J.1%
105 106 104 92.4 94.0 95.7
(1) A ll results and avefage values listed to three significant figures according to EPA rounding rules. %RSD values given to two significant figures. Due to rounding,-values may vary slighfly from those in the raw data.
,, Calculated Concentration LCS Percent Recovery ----------------------------------------
100%
Spike C oncentration
LCS% RSD = t andem deviation LCS replicates . 1Q()% averageLC S recovery
3.7 Analytical Uncertainty
Both the accuracy (percent recovery) and precision (% R SD ) of the lab control spikes w ere used to estim ate the overall method's analytical uncertainty for a given analyte. For exam ple, the overall accuracy and precision for PFO A based on LCS results was 97.4% 3.3% . The measured precision (% R S D ) is thenused to determ ine the range of the accuracy.
Exam ple: 97.4*(0.033) = 3.25 97.4 + 3.25 = 100.7; 9 7 .4 -3 .2 5 = 94.20
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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 PFO A is given as 100 5.8% for these results. For PFO S, PFH S, 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 w ere 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.
(Calculated Sample Concentration - Average Concentration : Field Sample & Field Sample P u p .), FMS Recovery =
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 (R P D ) or relative percent standard deviation (R S D ) of the sam ple and sample duplicate (and laboratory duplicate - if applicable). All field matrix spike recoveries were within 10030% for ail analytes except for the high level PFO S field matrix spike associated with PC45 (LIM S ID # E 06-0151-101) which produced a recovery of 148% . The analytical accuracy for the PFO S 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 10030% .
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Table 10. (1>Sample Results for OKMN GWS RW40.
PiFOA
P Ico s
P iCHS
PFBS
3M U M S 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
EO&0151-O85 OKMN GWS RW40 HS 060302
726
72.7
9.93
99.6
9.05
90.0
8.4 84.6
Average Concentration (ng/mL) % RPO
<0.0250
<0.0249
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays pounded values tor 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
M U M S ID
Description
Cone. (ng/mL)
% R eco vety
Cone. (natoiL)
`/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
E06D151-087 OKMN GWS SP42 OB 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
725
72.6
10.1
101
8.54
84.9
821
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.
3M CONFIDENTIAL
PAGE 11 OF 18
000016
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Table 12. (1>Sample Results for OKMN GWS PL43.
P F OA
PFOS
P F HS
P F BS
3M U M S ID
Description
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
%Recoverv
Cone. (ng/mL)
/ R ecovery
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
Aversele 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.
PF OA
PFOS
P F HS
PFBS
M U M S ID
Description
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
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 tor all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPO 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
000017
PAGE 12 OF 18
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Table 14. (1,Sample Results for OKMN GWS PC45.
P i-O A
PFO S
P F HS
PFB S
M U M S ID
Description
Cone. (ng/mL)
%R ecovery
Cone. (ng/mL)
^R ecovery
Cone. (ng/mL)
"/Recovery
Cone. (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
NA
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
90.6
1.64
121
1.11
105
1.05 106
E06-0151-101 OKMN GWS PC45 HS 060303
9.93 .
910 . .
15.2 . . i3,148
10.3
102
9.74
98.2
<4t0 6 -0 1 5 1 098-LMS Low
Laboratory Matite Spike at 1 ng/mL
1.59 105 1.41 97.5 1.07 100 0.944 95.1
!... {
CO 4-
'"E06-0151098-LMS High
Laboratory Matrix Spike at 10 ng/mL -
108 11.0 106 10.5 104 9.05 912
Average Concentration (ng/mL) % RSD .
,5
0 ,5 4 3 7 .9
0 .4349.0
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 RPO values may vary
slightly from foe values in the raw data.
(2) Sample results are from a duplicate laboratory extraction o f the sample. A ll three replicate values used to determine average and %RSD.
(3) FMS recovery exceeded method acceptance criteria o f 10030%.
(4) Laboratory matrix spikes were prepared by spiking the 40 mL sample aiiqgpt prior to centrifugation.
3M CONFIDENTIAL
PAGE 13 OF 18
000018
3M ENVIRONMENTAL LABQR/\TORY > REPORT NO. E06-0151
Table 15. (1>Sample Results for OKMN GWS SP44.
PFOA
PFOS
PFHS
PFBS
M U M S ID
Description
Cone. (ng/mL)
"/,,Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
/",,Recovery
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 Die 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
P F HS
PFBS
M U M S ID
Description
Cone. (ng/mL)
"/,,Recovery
Cone. (ng/mL)
"/,,Recovery
Cone. (ngAnL)
%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
* ? V.iv..;
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Table 17. <1>Sample Results for OKMN GWS RW37.
PFOA
PFOS
P F HS
PFBS
3M U M S ID
Description
Cone. (ngfaiL) .
%Recoverv
Cone. (na/mL)
%Recovery
Cone. (ng/mL)
% R ecovety
Cone. (ngfoiL)
X R eco very
E06-0151-110 OKMN GWS RVV37 0 060303
0.282
NA
2.51
NA <0.0252 NA <0.0397 NA
E06-015-111 OKMN GWS RW37 DB 060303
0298
NA
2.56
NA <0.0252 NA <0.0397 NA
E06-0151-11012' OKMN GWS RW37 0 060303
0,312
NA
2.47
NA <0.0252 NA <0.0397 NA
E06-0151-112 OKMN 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
" 06-0151110-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 at 10 nq/mL
9.62 .
93.3
12.3
98.2
8.91
88.6
8.82
88.9
Average C oncentration ing/m L) %RSD
0.297 5 .0
2.51 1.8
<0.0252
<0.0397
NA= Not Applicable.
(1) Table displays rounded values for aHconcentrations 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 o f the sample. A ll 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
3MENVIRONMENTAL LABORATORY REPORT NO. E06-0151
Table 18. |1>Sample Results for OKMN GWS RW39.
PFOA
PF(OS
PFHS
PFBS
3M U M S ID
Description
Cone. (ng/mL)
%Recovery
Cone. (ng/mL)
YRecoverv
Cone. (ng/m L)
/ R eco ve ry
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
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
PFiOS
PF HS
PFBS
3M U M S ID
Description
Cone. (ng*nL)
%Recoverv
Cone. (ngtotL)
^R ecovery
Cone. (ng/m L)
%R e co ve ry
Cone. (ng/mL)
%Recovery
mExtracted 3-3-06
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
0.808
80.9
0.788 79.0 0.808
80.3 0.783 78.9
E06-0151-081
OKMN PW TRIP2 HS 060302
7.47
74.8
8.25
82.7
8.04
79.9 7.67 77.3
Extracted 3-6-06
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
3MENVIRONMENTAL LABORATORY REPORT NO. E06-0151
5 Conclusion
PFO A, PFO S, PFH S, and PFBS results for the collected samples w ere presented in Table 1. Laboratory control spikes w ere used to determ ine the method accuracy and precision for all analytes. T he accuracy and precision were then used to estim ate the analytical uncertainty for the results (100
5.8% for PFOA; 100 3.7% for PFO S, 100 8.6% for PFH S, apd 1 0 0 6 .6 % for PFBS). Field matrix
spike recoveries within 100 30% demonstrated that the analytical method was appropriate for the given sam ple matrix.
g Data / Sample Retention
All remaining sam ple and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.
3M CONFIDENTIAL * V ^ ^ 'V
PAGE 17 OF 18
000022
sw sMVimuuEbTAi. LAQomror*'' <?FPO<?TNC eOB O-b :
7 Signatures
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Wiliam K Reagen, Ph 0 , Errvtromerta! laboratory Management
3 /'S /c C
Date
The 3M Envronrnental laboratory's Quality Assurance Unit has audited the data and nsac*t for this
o r c - je c t
.R . : i / '.
Quality Assum es Represemafcye
Date
A O b O:- *3
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