Document VjaENae9O99Bxa99LdV4ZVLBp

AR226-3641 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151 Final Report Analysis of PFO A , P FO S , P FH S, and PFBS From Newly Constructed W ells at the O akdale, 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 lACCBEOITEDI Certificate #2052-01 The testing reported herein meet the requirements of ISO/tED 17025-1999 "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 1 OF 18 000006 3M ENVIRONMENTAL LABORATORY REPORT NO. 06-0151 3M E nvironm ental Laboratory 3M Environmental Laboratory Manager: William 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 Samples from Newly Constructed W ells near the Oakdale, Minnesota Disposal Site March 1 3 ,2 0 0 6 1 Introduction/Summary The 3M Environmental Laboratory extracted and analyzed ground w ater 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 w ere returned to the 3M Environmental Laboratory for analysis of perfluorooctanoate (PFO A ), perfluorooctane sulfonate (P FO S ), perfluorohexane sulfonate (PFHS), and perfluorobutane sulfonate (PFBS) under laboratory project number E 06-0151 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 sample 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 sample results. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report. 1J L 1a ccred ited ! Certificate #2052-01 The testing reported herein meet the requirements of ISO /IED 17025-1999 "General Requirements fo r the Competence o f Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that compiles w ith this International Standard also operate in accordance with ISO 9001/ISO 9002 (1994). 3M CONFIDENTIAL " i 'V 'y ` 000007 PAGE 2 OF 18 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151 Table 1. Sample Results Summary. 3M U M SID Sample Description mPPOA Concentration (ng/mL) <*PFOS VippHS PPFBS Concentration Concentration Concentration (ng/mL) (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 NA E06-0151-086 OKMN GWS SP42 0 060302 <0.0250 <0.0249 <0.0252 <0.0397 E06-0151-087 OKMN GWS SP42 DB 060302 <0.0250 <0.0249 <0.0252 <0.0397 Average <0.0260 <0.0249 ' <0.0252 <0.0397 %RPD Sample/Sample Dup NA NA NA NA E06-0151-090 E06-0151-091 OKMN GWS PL43 0 060302 V ! <0X)250 : OKMN GWS PL43 DB 060302 ,. -,<0.0250 ; , . <0.0249: -,:<0.0249' <0.0252 <0.0252 - <0.0397 <0.0397 Average1: <0.0250 ` <0.0249 <0.0252 <0.0397 %RPO Sample/Sample Dup ' ' NA NA NA NA E06-0151-094 ! OKMN GWS RW39 0 060302 : <0.0250' ' ' <0.0249 ' <0.0252 <0.0397 E06-0151-095 OKMN GWS RW39 DB 060302 ' <0.0250 . <0.0249 <0.0252 <0.0397 Average <0.0250 <0.0249 <0.0252 , <0.0397 %RPD Sample/Sample Dup NA NA NA NA E06-0151-098 - - OKMN GWS:PC4&0 060303 - 0.592 . ..- 0.390 0.0649 <0.0397 E06-0151-098 v ' OKMN GWS PC45 0 060303 - . ' 0.522 . 0.464 - ' ' 0.0635 <0.0397 E06-0151-099 T OKM N GWS PC45 DB 060303 - 1 V 0:514 , -,. . -t '- " ':! Average 0.643 ' '' 0.449 ' i! ' 0.0547 ` 0.434 0.0610 J <0.0397 <0.0397 % RSb Sample/Sample Dp/Lab bp 1 7.9 ' 9J 9.1' NA E06-0151-102 OKMN GWS SP44 0 060303 <0.0250 <0.0249 <0.0252 <0.0397 E06-0151-103 0 z 1 s i -<0.0250 <0.0249 <0.0252 <0.0397 " y \i Average-., <0.0250 = <0.0249' i <0.0252 <0.0397 %RPD Sample/Sample Dup * * ,^ N A ; J - -iNA! ' \ NA NA E06-0151-106 E06-0151-107 OKMN GWS RW38 0 060303 OKMN GWS RW38 DB 060303 0.0525 0.0556 0.187 0.195 <0.0252 <0.0252 <0.0397 <0.0397 Average 0.0540 0.191 <0.0252 <0.0397 %RPD Sample/Sample Dup 5.7 42 NA NA E06-0151-110 OKMN GWS RW37 0 060303 0.312 2.47 <0.0252 <0.0397 E06-0151-110 OKMN GWS RW37 0 060303 0.282 2.51 <0.0252 <0.0397 E06-0151-111 OKMN GWS RW37 DB 060303 0.298 2.56 <0.0252 <0.0397 Average 0.297 2.51 <0.0252 <0.0397 %RSD Sample/Sample Dup/Lab.Dup . so. ; ' J -'.1 .8 NA NA E06-0151-114 OKMN GWS PL.41 0 060303 0.0766 ` ' ' 0.0268 <0.0252 <0.0397 E06-0151-115 OKMN GWS PL41 DB 060303 0.0796 <0.0249 <0.0252 <0.0397 Average 0.0781 "*0.0268 <0.0252 <0.0397 %RPD Sample/Sample Dup 3.8 NA NA NA (1) The analytical uncertainty for PFOA was 1005.8% based on method accuracy and precision. See Section 3.7 for additional explanation. The limit of 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 3 M ENVIRONMENTAL 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 of 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 limit 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 f0.0249 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 limit ofquantitation (LOQ) was 0.0252 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 0.0252 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 limit of quantitation (LOQ) was 0.0397 ng/mL. Results and average values are rounded to three significant figures according to EPA rounding roles. %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 all three results (sample, laboratory duplicate, and sample duplicate). (6) The average value listed is the concentration for the 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. 2 Methods - Analytical and Preparatory 2.1 Sample Collection Sam ples w ere 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 (PFO A, PFO S, PFH S, and PFBS). Collected sam ple bottles w ere returned to the laboratory at am bient 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 w ere 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 Matrix Spike Trip Blank High Matrix Spike Nominal Final Volume (m U 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 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 St. Peter 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. Observations Well Identification Sediment Color ' SedimentAmount Other RW37 Grey-brown " 'Moderate Strong petroleum odor present RW38 Rust-brown Ught NA RW39 . Rust-brown v ! ' ' Ught NA RW40 Rust-brown ' " 'Modfate NA PL41 Rust-brown' " 'Moderate NA SP42 ' RuSt-brown . " 'Moderate NA PL43 , Rust-brown ! ......... " 'Moderate NA SP44 Grev-brown . ..."'Moderate ( NA PC45 (1) (2) Rust-brown p'Uqht NA Moderate: after centrifugation of a 40 mL aliquot, solids roughly the size of a pea remained after removal of the supernatant. 1f Light: after centrifugation of a 40 mL aliquot, solids present, but minimal. 2.2 Extraction All samples, calibration standards, and associated quality control sam ples'w ere extracted using the procedure outlined in E TS -8-154.1 "Determination of Perfluorinated Acids, Aldohols, Amides, and Sulfonates in W ater by Solid Phase Extractions and High Perform ance Liquid Chromatography/Mass Spectrometry". Briefly, 4 0 mL of sample 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. T he loaded SPE cartridges w ere then eluted with 5 mL of methanol. This extraction procedure concentrates the samples 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 as 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, sam ple 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 w as deem ed necessary. E TS -8-154.1 does not describe sample centrifugation prior to extraction. This method modification was 3M CONFIDENTIAL PAGE 5 OF 18 000010 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151 necessary as the sediment completely clogged the SPE cartridges almost immediately preventing complete loading of the w ater 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 w ere 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 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 w ere 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) w ere 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 the new calibration curve. 2.3 Analysis Ail 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 Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode P o la rity Software ETSStan Agilent 1100 Betasil C18 (2.1 mm.X100 mm), 5 um Betasil C18 (2.1 mm X 100 mm), 5 um 5uL Applied Biosvstems 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 Row Rate QJJmin) 300 300 300 300 300 300 Percent A (2 mM ammonium acetate) 80.0 80.0 10.0 10.0 80.0 80.0 P ercents (Methanol) 20.0 20.0 90.0 90.0 20.0 20.0 3M CONFIDENTIAL PAGE 6 OF 18 OO0O11 3M ENVIRONMENTAL LABORATORY REPORT NO. E0&-0151 Table 7. Mass Transitions Analyte (,,PFBS (,)PFHS 0)PFOS (,|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 methanoiic stock solutions containing PFOA, PFO S, PFH S, and PFBS into 40 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 met the method calibration accuracy requirement of 25% . The 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 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 PFO A, 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. T h e sam e standard w as analyzed in triplicate at the end of the analytical sequence. All analytes m et 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 the instrument response and the initial calibration curve was still in control. All C CVs produced recoveries within 100% 25% , which met method criteria. 3M CONFIDENTIAL PAGE 7 OF 18 000012 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 w ere prepared by loading 4 0 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 fo r Extractions performed on 3/6/2006. Sample Name Sample Comment Sample ID s060306a025 s060306a026 s060306a027 s060306a028 Method Blank-1 Method Blank-2 Method Blank-3 Method Blank-4 MB-060306-1 MB-060306-2 MB-060306-3 MB-060306-4 s060306a029 Method Blank-5 MB-060306-5 S060306a030 s060306a031 s060306a032 Method Blank-6 Method Blank-7 Method Blank-8 MB-060306-6 MB-060306-7 MB-060306-8 Area Counts ofhighestmethod 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 0X7252 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 w ere 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 Field/Trip Blanks Prior to sam ple collection, one sample container was filled with 450 mL of A STM 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 w ere prepared and analyzed in triplicate. LCSs were prepared by spiking known amounts of the analytes into 4 0 mL of A STM Type I water 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 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 determ ine overall method uncertainty in Section 3.7. Table 9 sum m arizes the LCS recovery results from the March 6 ,2 0 0 6 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 PFOS 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 10 ppb Lab Control Spike LCS-060306-3 LCS-060306-4 10 ppb Lab Control Spike LCS-060306-5 10 Dbb 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 : 1.00 1.01 0.961 9.19 9.65 , 9.85 . 97.4%J3.3% 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 Calculated Cone. (ng/mL) 1.04 1.03 1.00 9.91 10.2 10.1 102%l.8% % Recovery 104 103 100 99.4 102 101 PFHS Sample Description Lab ID Spiked Cone. (ng/mL) 1 ppb Lab Control Spike LCS-060306-f 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 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%iS.S% 07 ' 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%B.1% 105 106 104 92.4 94.0 95.7 (1) All results and average values listed tq three significant figures according to EPA rounding rules. %RSD values given to two significant figures. Due to rounding,'values may vary slightly-from those in the raw data. Calculated Concentration LCS Percent Recovery = 100% Spike Concentration standard deviation LCS replicated . ^0QO^ average LCS recovery 3.7 Analytical Uncertainty Both the accuracy (percent recovery) and precision (% R S D ) 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 SD ) is then used 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 3M CONFIDENTIAL PAGE 9 OF 18 000014 3MENVIRONMENTAL 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 PFO S, 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.) ,, 1Qoy 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 SD ) of the sample and sam ple duplicate (and laboratory duplicate - if applicable). All field matrix spike recoveries were within 100+30% for all 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% . 3M CONFIDENTIAL PAGE 10 OF 18 3MENVIRONMENTAL LABORATORY REPORT NO. E06-0151 Table 10. (1>Sample Results for OKMN GWS RW40. PiFOA PFOS PiCHS PFBS 3MUMSID Description Cone. (ng/mL) %Recovery Cone. (ng/mL) %Recovery Cone. (ng/mL) /^Recovery Cone. (ng/mL) %Recovety 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= NotApplicable. (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 m uM sm Description Cone. %Recovery Cone. (ng/mL) %Recovery Cone. (ng/mL) %Recoverv Cone. (ng/mL) %Recovety E06-0151-086 OKMN GWS SP42 0 060302 <0.0250 NA <0.0249 NA <0 0252 - NA <0.0397 NA E06-0151-087 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 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. 3M CONFIDENTIAL PAGE 11 OF 18 m o o iG 3M ENVIRONMENTAL LAVORA TORY REPORT NO. E06-051 Table 12. (1|Sample Results for OKMN GWS PL43. PFOA PFOS PFHS PFBS 3M UM SID Description Cone. <ng/mL) %Recoverv Cone. (ng/mL) %Recovetv Cone. (ng/mL) /Recovery Cone. (ng/mL) /Recovery 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 E06D151-092 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 ail 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 M U M S ID Description Cone. (ng/mL) "/Recovery Cone. (ng/mL) "/Recovery Cone. (ngfinL) `/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 <0.0259 <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 o o o o i? Table 14. (1>Sample Results for OKMN GWS PC45. 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151 / I PFOA PFOS PFHS PFBS 3M U M S ID Description Cone. (ng/mL) "/Recovery Cone. (ngfinlj %Recovery Cone. (ng/mL) "/Recovery Cone. (ng/mL) "/Recovery E06-0151-098 OKMN GWS PC45 0060303 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 E06-0151-098'2' 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 . 94.Q . 15.2 . !3|148 10.3 102 9.74 98.2 <4|E06-0151098-LMS Low Laboratory Matrix Spike at 1 ng/mL 1.59 105 1.41 97.5 1.07 100 0.944 95.1 WE06-015109B-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/mL) %RS0 0,5437.9 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 tire sample. All three 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 the 40 m l sample aliquqt prior to centrifugation. 3M CONFIDENTIAL PAGE 13 OF 18 000018 3M ENVIRONMENTAL LABORATORYi REPORT NO. E06-0151 Table 15. (1,Sample Results for OKMN GWS SP44. PFOA PFOS PFHS PFBS 3M U M S ID Description Cone. (ng/mL) %Recovery Cone. (ng/mL) %Recoverv Cone. (ng/mL) %Recoverv Cone. (ng/mL) ^R ecovery 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 m IM S ID Description Cone. (ng/mL) %Recovery Cone. (ng/mL) "/.Recovery Cone. (ngAnL) "/R ec o v ery 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= NotApplicable. (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 UT 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151 Table 17. (1|Sample Results for OKMN GWS RW37. PFOA PFOS PFHS PFBS 3M UM SID Description Cone. (ngfaiL) . YoRecoverv Cone. (ng/mL) %Recovery Cone. (ngAnL) YoRecoverv Cone. (ng/mL) YoRecovery E06-0151-110 OKMN GWS RW37 0 060303 0.282 NA 2.51 NA <0.0252 NA <0.0397 NA E06-0151-111 OKMN GWS RW37 DB 060303 0.298 NA 2.56 NA <0.0252 NA <0.0397 NA E06-0151-110121 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 Laboratory Matrix Spike 110-LMS Low at1 ng/mL 1.47 117 3.71 120 0.983 97.7 0.941 94.8 (3|E06-0151110-LMS Hah Laboratory Matrix Spike at 10 ng/mL 9.62 ... 93.3 12.3 98.2 8.91 88.6 8.82 88.9 Average Concentration (ng/mL) YoRSD 0.2971 5.0 2 .5 1 1 1 <0.0252 <0.0397 NA= Not Applicable. (1) Table displays rounded values for all concerrtrationsand 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 ofthe 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 00002a 3MENVIRONMENTAL LABORATORY ' REPORT NO. E06-0151 Table 18. (1>Sample Results for OKMN GWS RW39. PFOA PF(OS PFHS PFBS 3M UM SID Description Cone. (ngtoiL) %Recovery Cone. (ngAnL) %Recovery Cone. (ng/mL) %Recoverv 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-O151-117 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 p>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 fo r the Trip Blank. PFOA PF(OS PFHS PFBS 3M UM SID Description Cone. (ng/mL) /Recovery Cone. (ng/mL) /Recovery Cone. (ng/mL) %Recovery Cone. (ng/mL) ^R ecovery 121Extracted 33-06 E06-0151-079 E06-0151-080 E06-0151-081 Extracted 3-6-06 OKMN PWTRIP2 0 060302 OKMN PWTRIP2 LS 060302 OKMN PWTRIP2 HS 060302 <0.0250 0.808 7.47 NA 80.9 74.8 <0.0249 NA <0.0252 0.788 79.0 0.808 8.25 82.7 8.04 NA <0.0397 NA 80.3 0.783 78.9 79.9 7.67 77.3 E06-0151-079 OKMN PWTRIP2 0 060302 <0.0250 NA <0.0249 NA <0.0252 NA <0.0397 NA E06-0151-080 OKMN PWTRIP2 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 cun prepared on 3-6-06. 3M CONFIDENTIAL PAGE 16 OF 18 000021 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0151 S Conclusion PFOA, PFO S, PFHS, 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. The accuracy and precision were then used to estimate the analytical uncertainty for the results (100 5.8% for PFOA; 100 3.7% for PFO S, 100 8.6% for PFH S, and 100 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 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 3V LABOnATOT^' F F & O F T N 'O 0 6 i> 5 : 7 S /g n a tu re s \ ; ' 'i | ,< Susan T W oif. 3M S erncr 0 h e m is t \ \/ ..... Uk-Cs........................ J._.:....F 7 ,.u ' M icheiie 0 . M aiinsky, P h.C r 3 $ p e ctn ica ! L e a d /j { 'i v<2rv V * W i;|iam K Reageru Ph D E rM ronm enial Labonatcrv M anagem ent ,'> / / ( / ><. b a ie i f i S / /.Y . ' Oafe y/ s /'S /c C . Q ata The 3 M E n v iu r.m e n ta i La bcra to ry s QuauSy A ssurance U n ii has a u d ite j th data and reper fa r iti DroieCv -' Jf ' - j/y W 4-"'' /' , , / Q ualrty A s s tra fe Represem a&ye D a te m CON^OfeNfRA. :ACh '.Cf- ?S 000023