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3M GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 GLP10-01-02: Interim Report 02 - Analysis of PFBS, PFHS. and PFOS in Ground Water Samples Collected from Decatur. AL in March/April 2010 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisim ha Kesari P.E., DEE W eston Solutions, Inc. 1400 W eston Way W est Chester, PA 19380 Phone: 610-701-3761 Author Susan W olf 3M Environmental Laboratory Interim Report Completion Date Date o f signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP10-01 -02-02 Total Number of Pages 57 II F ACCREDITED! The testing reported herein meet the requirements of ANS/1SO/IEC17025:2005 "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 9001:2000. Certificate #2052-01 Page 1 of 57 k GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 This page has been reserved for specific country requirements. GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 G LP C ompliance Statement Report Title: Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Ground W ater Samples Collected at Decatur, AL in March/April 2010 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 SiteRelated Monitoring Program. This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below: These are environmental samples where there is no specific test substance, no specific test system and no dosing of a test system. The reference substances have not been characterized under the GLPs and the stability under storage conditions at the test site have not been determined under GLPs. Date Page 3 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Q uality A ssurance Statement Report Title: Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Ground W ater Samples Collected at Decatur, AL in March/April 2010 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 SiteRelated Monitoring Program. This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dates 3/3/10 3/25/10 6/3 /1 0-6/4 /1 0 Phase Protocol In-Phase Audit - Bottle Order Prep Interim Report 02 Data and Report QAU Represe Date Reported to Testing Facility Management Study Director 3/16/10 3/16/10 4/5/10 4/5/10 6/11/10 6/11/10 '^ < 7 -/ Date Page 4 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Ta b le of C o n ten ts GLP Compliance Statem ent................................................................................................................. 3 Quality Assurance Statement................................................................................................................ 4 Table of Contents.................................................................................................................................. 5 List of Tables.......................................................................................................................................... 6 1 Study Information............................................................................................................................ 8 2 Summary......................................................................................................................................... 9 3 Introduction................................................................................................................................... 10 4 Test & Control Substances.......................................................................................................... 11 5 Reference Substances................................................................................................................. 12 6 Test System .................................................................................................................................. 14 7 Method Summary......................................................................................................................... 14 7.1 M ethods........................................................................................................................ 14 7.2 Sample Collection..........................................................................................................14 7.3 Sample Preparation.......................................................................................................14 7.4 Analysis......................................................................................................................... 14 8 Analytical R esults......................................................................................................................... 16 8.1 Calibration..................................................................................................................... 16 8.2 System Suitability..........................................................................................................16 8.3 Limit of Quantitation (LO Q )........................................................................................... 16 8.4 Continuing Calibration................................................................................................... 16 8.5 Blanks............................................................................................................................ 16 8.6 Lab Control Spikes (LC Ss)........................................................................................... 17 8.7 Analytical Method Uncertainty...................................................................................... 19 8.9 Field Matrix Spikes (FMS).............................................................................................. 20 9 Data Summary and Discussion.................................................................................................... 20 Page 5 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 10 Conclusion.................................................................................................................................... 31 11 Data/Sample Retention............................................................................................................... 31 12 Attachm ents.................................................................................................................................. 31 13 Signatures..................................................................................................................................... 32 List of Tables Table 1. Summarized PFBS, PFHS, and PFOS Results (Decatur Groundwater, March/April 2010).....................................................................................10 Table 2. Instrument Parameters............................................................................. 15 Table 3. Liquid Chromatography Conditions.......................................................... 15 Table 4. Mass Transitions.......................................................................................15 Table 5. Limit of Quantitation (LOQ)....................................................................... 16 Table 6. Laboratory Control Spike Recovery..........................................................18 Table 6 continued. Laboratory Control Spike Recovery........................................19 Table 7. Analytical Uncertainty................................................................................19 Table 8. GW203LQ1 Y10 LF ................................................................................ 21 Table 9. GW 220RQ1 Y10 L F ................................................................................21 Table 10. GW220LQ1 Y10 LF..............................................................................22 Table 11. GW 222RQ1 Y10 L F ............................................................................ 22 Table 12. GW227LQ1 Y10 LF............................................................................. 23 Table 13. GW 227RQ1 Y10 L F ............................................................................ 23 Table 14. GW GRS04 Y10 LF...............................................................................24 Table 15. GW310RQ1 Y 1 0 C P ........................................................................... 25. Table 16. GW312RQ1 Y10 C P ........................................................................... 25 Table 17. GW317LQ1 Y 10C P ............................................................................ 26 Table 18. GW 324LQ1 Y10 C P............................................................................ 26 Table 19. GW 327RQ1 Y10 C P ........................................................................... 27 Table 20. GW 328LQ1 Y10 C P ............................................................................ 27 Page 6 of 57 'A GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 21. GW 328RQ1 Y10 C P .............................................................................28 Table 22. GW 330LQ1 Y10 C P..............................................................................28 Table 23. GW 330RQ1 Y10 C P .............................................................................28 Table 24. GW331SQ1 Y10 CP............................................................................. 29 Table25. Trip Blank............................................................................................... 29 Table 26. Rinseate Blanks..................................................................................... 30 Page 7 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Sponsor 3M Company Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j.kesari@ westonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106 Study Personnel W illiam K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clanae@mmm.com): phone (651)-733-9860 Susan Wolf, 3M Analyst Jonathan Steege; analyst Study Dates Study Initiation: March 8,2010 Interim #2 Sample Collection: March 30,2010-A p ril 14,2010 Interim #2 Experimental Termination: May 26, 2010 Interim Report Completion: Date of Interim Report Signing Location of Archives All original raw data and the analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792 Page 8 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 The 3M Environmental Laboratory received groundwater samples from wells located in Decatur, AL, representing 17 different sampling locations. A total of ninety-four sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate groundwater samples from each sampling location. Samples also included lo w , mid and high field matrix spike (FMS) samples for each location, one trip blank containing Milli-QTM water and appropriate trip blank spikes, and five equipment rinseates. Two additional soil-equipment rinseates that were collected as part of project GLP10-01-0201 for analysis of PFBS, PFHS, and PFOS in soils collected from the former sludge incorporation area (FSIA) fields at the Decatur site in March/April 2010, were also included in this analysis. The equipment rinseate blanks did not have FMS samples prepared for determination of PFBS, PFHS or PFOS recovery. All groundwater samples for this project were logged under GLP10-01 -01 -02. The groundwater samples, trip blank and five equipment rinseate blanks were received from Weston personnel on April 15, 2010. The soil-equipment rinseate blanks were received with the FSIA soil shipment on April 01,2010. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project GLP-10-01-02-02. Many of the groundwater samples required dilution to attain PFBS, PFHS, and PFOS concentrations within the range of the curve, in some instances up to a 100-fold dilution were required. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1 The equipment rinseates and the trip blank were below the lower limit of quantitation (LLOQ), indicating adequate control of sample contamination during shipping and sample collections. The PFBS concentration results for all groundwaters ranged over four orders of magnitude from 0.534 ng/mL to 4470 ng/mL. The PFHS concentration results for all groundwaters ranged over four orders of magnitude from 0.691 ng/mL to 6190 ng/mL. The PFOS concentration results for all groundwaters ranged over three orders of magnitude from 2.44 ng/mL to 1750 ng/mL. Page 9 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples from Decatur, AL March/April 2010 Table 1. Summarized PFBS, PFHS, and PFOS Results (Decatur Groundwater, March/April 2010). Sampling Location G W 203LQ1 Y 10 LF G W 220R Q 1 Y 10 LF G W 2 2 0 L Q 1 Y 1 0 LF G W 222R Q 1 Y10 LF G W 2 27 L Q 1 Y 10 LF G W 227RQ1 Y 10 LF G W G RS04Q 1 Y 10 LF GW 310RQ1 Y10 CP GW 312RQ1 Y10 CP GW 317LQ1 Y10 CP GW 324LQ1 Y10 CP GW 327RQ1 Y10 CP G W 328LQ 1Y10 CP GW 328RQ1 Y10 CP GW 330LQ1 Y10 CP GW 330RQ 1 Y10 CP GW 331SQ1 Y10 CP Trip Blank (Milli-QTM W ater) Equipment Rinseate Blanks 1 to 5, 203L DAL D F 05 S S07 2 00 10 (soil equipment rinseate blank) DAL D F 1 1 S S 07 2 00 10 (soil equipment rinseate blank) PFBS Avg. Cone. (ng/mL) RPD 61.9 3 .4 % PFHS Avg. Cone. (ng/mL) RPD 360 0.83% PFOS Avg. Cone. (ng/mL) RPD 852 1 .1 % 7.46 3.5% 32.0 0.63% 46.0 12% 11.1 13% 53.0 4.9% 63.6 3.8% 129 3 .9 % 845 1.3% 974 4.7% 342 4.1% 63.7 4.7% 287 13% 23.8 6.7% 169 0 .0 % 956 7.4% 1 9 3 0 13% 6 1 9 0 9 .0 % <1> 14 00 16% 386 8.0% 424 5.4% 760 5.4% 1220 0 .0 % 946 0.74% 1750 4 .6 % 0.534 0.94% 0.691 0.72% 2.44 3.7% 95.7 2.8% 101 5 .6 % 203 11% 75.8 14% 154 2 .6 % 639 18% 76.8 1 .6 % 25.9 1 .2 % 14.5 0.69% 36.0 1 .9 % 67.7 6.7% 146 19% 504 6.0% 403 1.2% 145 14% 4 4 7 0 2 .5 % <1) 2 5 8 5 .0 % 759 1 .1 % 3 4 9 13% 426 13% 9 2 2 2 1 % (2) < 0 .0 2 5 5 < 0 .0 2 5 8 <0.510 < 0 .0 2 5 5 <0.0258 <0.510 < 0 .0 2 5 5 <0.0258 <0.510 < 0 .0 2 5 5 <0.0258 <0.510 The analytical method uncertainties associated with the reported results are as follows: PFBS 100% 21% , PFHS 100% 25% , and PFOS 100% 4 4% . (1 ) Sampling location did not have an appropriate FM S spike level to sufficiently evaluate analyte recovery. (2) The RPD did not m eet method acceptance criteria of 20% . 1.M t This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate Page 10 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 (PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze ground water samples collected from various wells located in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on-site groundwater conditions. Additionally, two aqueous soil-equipment rinseate samples collected as part of the PFBS, PFHS, and PFOS assessment in soils from former sludge incorporation area (FSIA) fields at the Decatur site in March/April 2010, were also analyzed. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and three field spike samples. Each empty container was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear), PFHS (linear), and PFOS (linear) prior to being sent to the field for sample collection. All sample bottles included the addition of i80 2-PFBS, 180 2-PFHS, and 13Cs-PFOS (internal standards) at a nominal concentration of 1 ng/mL. All sample bottles also included the addition of 13C4-PFOS (surrogate spike) at a nominal concentration of 0.1 ng/mL. See section 8.8 of the report for field matrix spike levels. The aqueous equipment rinseate samples were collected in plain bottles without markings or fortifications, similar to soil sample bottles (see GLP10-0102 Interim Report 01 for details). Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, and for the trip blanks and aqueous soil-equipment rinseate samples. Tables 8-26 summarize the individual sample results and the associated FMS recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. Page 11 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predominantly linear) Perfluorobutane sulfonate C 4F 9S O 3 Potassium Salt 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TC R Number Physical Description Purity PFOS (linear) Perfluorooctane sulfonate C 8F 17S O 3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% PFHS (linear) Perfluorohexane sulfonate C F 13S O 3 Sodium Salt Wellington 4/2/2013 Frozen LPFHxSAM08 TCR08-0018 Crystalline 98% PFOS (linear + branched) Perfluorooctane sulfonate C 8F 17S O 3 Potassium Salt CAS #2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% Page 12 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Reference Substance Chemical Nam e Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TC R Number Physical Description Purity Oj-PFBS Labeled - Perfluorobutane sulfonate C 4F 9S [180 2 ] 0 Ammonium Salt RTI International 3/9/2015 Frozen 11546-107-2 TCR-1013 Liquid 99% Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 13C4-PFOS Perfluorooctane sulfonate 13c 412c 4f 17s o 3 Sodium Salt Wellington 8/18/2011 Frozen MPFPS0808 TCR08-0043 Liquid 98% 18Or PFHS Labeled - Perfluorohexane sulfonate C 6F 13S [180 2 ] 160 - Sodium Salt Wellington 7/24/2011 Frozen MPFHxA0706 TCR-1218 Liquid 98% 13C*-PFOS Perfluorooctane sulfonate 13C 8F 17 s o 3 Sodium Salt Wellington 6/17/2012 Frozen M8PFOS0609 TCR09-0049 Liquid 98% Page 13 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 The test system for this study are ground water samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. Sample Description Key Code. String Number E x a m p le 1 2 3 4 String Descriptor G W 227L Q1 Y10 LF0 S a m p le T yp e S a m p le L o c a tio n W e ll L e v e l S a m p lin g D a te S a m p le T yp e E xam ple G W = G ro u n d W ate r E x a m p le : 2 2 7 L L F R = R e s id u m s h a llo w w a te r-b e a rin g zo n e L = B e d ro c k w ate r-b e a rin g zo n e S = E p ik a rs t m id d le w a te r-b e a rin g z o n e Q 1 Y 1 0 - 1 s t Q u arter, 2010 0 = p rim a ry s a m p le 1 = d u p lic a te s a m p le L S = lo w s p ik e M S = m id s p ik e H S = h ig h s p ik e 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on April 15, 2010 Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with the sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. Samples that required dilution were prepared by dilutions of 1mL sample with 9 mLs of Milli Q water (dilution 1:10). Most sampling locations were diluted 1:100 by further diluting the 1:10 dilution with additional Milli Q water. 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below. Page 14 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 2. Instrument Parameters. Instrum ent Nam e A nalytical M ethod Follow ed A nalysis D ate Llauid C hrom atograph G uard colum n A nalytical colum n Injection Volum e M ass S pectrom eter Ion Source E le c tro d e P olarity S oftw are ETS G in ger E TS -8-044.0 5/17/2010 and 5/26/2010 Agilent 1100 Betasil C 18 (2.1 mm X 100 mm), 5 u Betasil C 18 (2.1 m m X 100 mm), 5u 2 ,5 , o r10u L Applied Biosystems API 5000 Turbo Spray Turbo ion electrode N eg ativ e Analyst 1.4.2 Table 3. Liquid Chromatography Conditions. S tep Num ber 0 1 2 3 4 5 T o ta l Tim e (m in ) 0 1.0 11.0 13.5 14.0 17.0 Table 4. Mass Transitions. F lo w R ate (fd J m in ) 300 300 300 300 300 300 P ercent A (2 m M a m m o n iu m a c e ta te ) 9 7 .0 9 7 .0 5.0 5.0 97.0 97.0 A n a ly te PFBS PFHS PFOS M a s s T ra n s itio n Q 1/Q 3 2 9 9 /8 0 2 9 9 /9 9 2 9 9 /1 3 0 3 9 9 /8 0 3 9 9 /9 9 3 9 9 /1 3 0 4 9 9 /8 0 4 9 9 /9 9 4 9 9 /1 3 0 Dwell tim e was 50 m sec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC ), which was used for quantitation. P e rc e n tB (M e th a n o l) 3.0 3.0 9 5 .0 95.0 3.0 3.0 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 8.1 Calibration Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into prepared in Milli Q water. A total of thirteen spiked standards ranging from 0.025 ng/mL to 50 ng/mL (nominal) were analyzed. Low curve points were disabled for PFOS to meet method blank criteria. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS. Due to the concentration of PFBS, PFHS, and PFOS detected in the samples, isotopically-labeled PFBS, PFHS, and PFOS were not used during instrument calibration. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, and PFOS. 8.3 Limit of Quantitation (LOQ) The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The nominal LOQ for all analytes can be found in Table 4. Table 5. Limit of Quantitation (LOQ). A n alys is D ate 5/17/10 5/26/10 D ilu tio n 1 10 100 200 PFBS LO Q , n g/m L 0.0255 0.255 2.55 NA PFHS LO Q , n g/m L 0.0258 0.258 2.58 51.6 PFOS LO Q , n g/m L 0.510 5.10 51.0 NA 8.4 Continuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All CCVs met method criteria of 100% 25%. 8.5 Blanks Two types of blanks were prepared and analyzed with the samples: method blanks and field/trip blanks. Method blank results were reviewed and used to evaluate method performance and to determine the LOQ for each analyte Page 16 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples from Decatur, AL March/April 2010 8.6 Lab Control Spikes (LCSs) Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into 40 mL of Milli Q water to produce the desired concentration. The spiked water samples were then prepared and analyzed in the same manner as the samples. Due to the analytical reporting limit, the low set of linear PFOS LCS samples could not be quantitated. The method acceptance criteria, average of LCS at each level should be within 100% 20% with an RSD <20%, were met for the PFBS, PFHS, and linear PFOS LCS samples. As the reference materials used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of both linear and branched isomers, additional LCS samples of PFOS (linear + branched) were prepared at three concentrations to evaluate the potential for analytical bias. Due to the analytical reporting limit, the low set of LCS could not be quantitated. The LCS at the mid level met method acceptance criteria, while the high level did not meet method acceptance criteria with an average recovery of 172%. An additonal set of mid, mid-high, and high-level LCS, prepared on a different date with other samples, were analyzed at the end of the analytical run to confirm the recovery of the high-level LCS. The analysis of these samples produced acceptable recoveries for the mid and mid-high LCS, with the average recovery of the high-level LCS at 130%. Based on the recovery of the second set of high-level LCS, it is the opinion of the laboratory that the recovery of the high-level LCS is due to a sample preparation error, and not the result of any significant analytical bias. All PFOS (linear + branched) LCS were used in the determination of the analytical uncertainty. A method deviation is filed with the raw data for PFOS (linear + branched) LCS that did not meet method acceptance criteria. The following calculations were used to generate data in Table 6 for laboratory control spikes. C alculated Concentration LCS Percent Recovery = 100% S pike Concentration standard deviation LC S replicates , 1 LCS% RSD = average LCS recovery Page 17 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 6. Laboratory Control Spike Recovery. ETS-8-044.0 L ab ID PFBS S p ik e d C o n cen tra tio n (n g/m L ) C a lc u la te d C o n cen tra tio n (n g /m L ) % R ecovery S p ik e d C o n cen tra tio n (n g/m L ) LCS-100512-1 LCS-100512-2 LCS-100512-3 Average %RSD 0.204 0.204 0 .2 0 4 0.239 0.227 0.251 117% 5.1% 117 111 123 0.206 0.206 0.206 LCS-100512-4 LCS-100512-5 LCS-100512-6 Average %RSD 5.10 5.10 5.10 4.68 5.42 5.35 101% 7.9% 91.7 106 105 5.15 5.15 5.15 LCS-100512-7 LCS-100512-8 LCS-100512-9 Average %RSD 30.6 30.6 30.6 30.2 30.6 29.3 98.2% 2.2% 98.8 99.9 95.8 30.9 30.9 30.9 PFHS C a lc u la te d C o n cen tra tio n (n g /m L ) 0.244 0.242 0.250 119% 1.5% 4.77 5.43 5.44 101% 7.4% 29.8 29.1 29.5 95.4% 1.1% % R e c o v e iy 118 118 121 92.6 105 106 96.4 94.3 95.5 ETS-8-044.0 L ab ID P F O S (lin e a i) S p ik e d C a lc u la te d C o n cen tra tio n C o n cen tra tio n (n g/m L ) (n g/m L ) % R ecovery L ab ID PFO S (lin e a r+ branched) S p ik e d C a lc u la te d C o n cen tra tio n C o n cen tra tio n (n g/m L ) (n g/m L ) % R ecovery LCS-100512-1 LCS-100512-2 LCS-100512-3 Average %RSD 0.204 0.204 0.204 <0.510 <0.510 <0.510 NA NC LCS-100512-10 0.200 NC LCS-100512-11 0.200 NC LCS-100512-12 0.200 Average %RSD <0.510 <0.510 <0.510 NA NC NC NC LCS-100512-4 LCS-100512-5 LCS-100512-6 Average %RSD 5.10 5.10 5.10 4.90 5.45 5.55 104% 6.7% 96.0 107 109 LCS-100512-13 LCS-100512-14 LCS-100512-15 Average %RSD 5.00 5.00 5.00 5.74 5.85 5.64 115% 1.7% 115 117 113 LCS-100512-7 LCS-100512-8 LCS-100512-9 Average %RSD 30.6 30.6 30.6 30.0 30.2 30.5 98.8% 1.0% 97.9 98.7 99.8 L C S -1 0 0 5 1 2 -1 6 L C S -1 0 0 5 1 2 -1 7 L C S -1 0 0 5 1 2 -1 8 Average %RSD 30.0 30.0 30.0 51.7 49.8 53.4 172% 3.5%(1) 172 166 178 NC = Not Calculated; Concentration detected was less than the analytical LOQ. (1) The average recovery did not m eet method acceptance criteria of 100% 20% . Page 18 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 6 continued. Laboratory Control Spike Recovery. ETS-8-044.0; Prepared with non-study samples P F O S (lin e a r + b ran ch ed) L ab ID S p ik e d C o n cen tra tio n (n g /m L ) C a lc u la te d C o n cen tra tio n (n g /m L ) % R ecovery LCS-100517-16 LCS-100517-17 LCS-100517-18 Average %RSD 5.00 5.00 5.00 4.99 5.27 5.11 102% 2.6% 99.8 105 102 LCS-100517-19 LCS-100517-20 LCS-100517-21 Average %RSD 15.0 15.0 15.0 16.6 16.9 17.5 113% 2.2% 111 113 116 LCS-100517-22 LCS-100517-23 LCS-100517-24 Average %RSD 30.0 30.0 30.0 37.4 40.0 39.9 130% 3.5% (1) 125 133 133 NC = Not Calculated; Concentration detected was less than the analytical LOQ. (1) The average recovery did not m eet method acceptance criteria of 100% 20% . 8.7 Analytical Method Uncertainty Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The most recent 50 data points were used to generate the method uncertainty values listed in Table 7. Table 7. Analytical Uncertainty. Analyte PFBS PFHS PFOS Standard Deviation 10.5 12.4 21.9 M eth o d U n c e rta in ty 100%21% 100%25% 100%44% Page 19 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 8.8 Field Matrix Spikes (FMS) Low, mid and high field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes were generated by adding a measured volume of field sample to a container spiked by the laboratory with PFBS (linear), PFHS (linear), and PFOS (linear) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. The nominal spike level for the low field matrix spike was 1.0 ng/mL, the mid field matrix spike was 100 ng/mL, and the high field marix spike was 1000 ng/mL for all sampling locations. For some sampling locations, the high field matrix spike was not appropriate as compared to the sample concentration. No laboratory matrix spikes were prepared. Field matrix spike levels will be adjusted accordingly for the next sampling event. Due to the high concentration of PFBS, PFHS, and PFOS detected in the samples, the surrogate spike of 13C4-PFOS was not analyzed. FMSReco e ry - ^ amP^e Concentration f FMS - Average Concentration :Field Sample & Field Sample Dup.) *jqqo/ Spike Concentraton The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks and rinseate blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of 30%, demonstrate that the method was appropriate for the given matrix and their respective quantitative ranges. GW GRS04Q1 - The recovery of the high FMS sample for PFOS was 134%. This was the only appropriate field matrix spike level for PFOS. Since the method analytical uncertainty is 100% 44%, no adjustment was made to the analytical uncertainty for PFOS. Page 20 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 8. GW 203LQ1 Y10 LF 3 M U N IS ID D e sc rip tio n G LP10-01 -02-02-051 G LP10-01 -02-02-052 G LP10-01 -02-02-053 G LP10-01 -02-02-054 G LP10-01 -02-02-055 G W 203LQ1 Y10 LF0 G W 203LQ1 Y 10 LF1 G W 203LQ1 Y10 LFLS G W 203LQ1 Y10 LFMS GW 203LQ1 Y10 LFHS A v e ra g e C o n cen tra tio n (ng/m L) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g/m L ) % R ecovery 62.9 60.8 N A <1> N A (1) 1220 NA NA N A (1) N A (1) 114 6 1 .9 n g/m L 3 .4 % C o n cen tratio n (n g/m L ) % R ecovery 358 361 NA (1) NA (1) 1370 NA NA N A (1) N A (1) 103 3 6 0 n g/m L 0 .8 3 % C o n cen tra tio n (n g /m L ) % R ecovery 856 NA 847 NA N A <1) NA (1) N A <1) N A (1) 1700 85.7 8 5 2 n g/m L 1 .1 % NA = Not Applicable (1) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Table 9. GW 220RQ1 Y10 LF 3 M U M S ID D e sc rip tio n G LP 1 0-0 1-02 -02 -080 GLP10-01-02-02-081 G LP 10-0 1-02-02-082 G LP 1 0-0 1-02 -02 -083 G LP 1 0-0 1-02 -02 -084 GW 220RQ 1 Y10 LF0 G W 2 2 0 R Q 1 Y 1 0 LF1 G W 220R Q 1 Y10 LFLS GW 220RQ1 Y10 LFMS G W 220RQ 1 Y10 LFHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g /m L ) % R ecovery 7.59 7.33 8.86 122 1180 NA NA NC 112 115 7.4 6 n g/m L 3 .5 % C o n cen tratio n (n g/m L ) % >Recovery 31.9 32.1 32.9 138 1100 NA NA NC 108 109 3 2 .0 n g/m L 0 .6 3 % C o n cen tra tio n (n g /m L ) % R ecovery 43.2 48.8 44.4 131 1010 NA NA NC 85.9 97.4 4 6 .0 n g/m L 12% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Page 21 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples from Decatur, AL March/April 2010 Table 10. GW 220LQ1 Y10 LF 3 M L IM S ID D escrip tio n G LP10-01-02-02-071 G W 220LQ 1 Y10 LF0 G LP 10-01 -02-02-072 G W 2 2 0 L Q 1 Y 10 LF1 GLP10-01-02-02-073 G W 220LQ 1 Y10 LFLS G LP10-01 -02-02-074 G W 220LQ1 Y 10 LFMS G LP10-01-02-02-075 G W 220LQ1 Y10 LFHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g /m L ) % R ecovery 10.4 NA 11.8 NA 13.5 NC 129 116 1140 111 11.1 n g /m L 13% C o n cen tratio n (n g /m L ) % R ecovery 51.7 54.3 54.4 155 1070 NA NA NC 104 104 5 3 .0 n g/m L 4 .9 % C o n cen tra tio n (n g/m L ) % ,R ecovery 6 4 .8 NA 62.4 NA 6 5 .8 NC 157 94.3 919 86.4 6 3 .6 n g/m L 3.8% NA = Not Applicable NC = Not Calculated; Endogenous sam ple concentration greater than 2x spike level. Table 11. GW 222RQ1 Y10 LF 3 M L IM S ID D e sc rip tio n G LP 10-01-02-02-031 G L P 1 0-01-02-02-032 GLP10-01 -02-02-033 G L P 10-01-02-0 2-0 34 GLP10-O1 -02-02-035 GW 222RQ 1 Y10 LF0 G W 2 2 2 R Q 1 Y 10 LF1 G W 222R Q 1 Y10 LFLS GW 222RQ1 Y10 LFMS GW 222RQ1 Y10 LFHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g /m L ) % R ecovery 131 126 N A (1) N A (1) 1200 NA NA N A <1) N A <1) 105 129 n g /m L 3.9% C o n cen tra tio n (n g /m L ) % R ecovery 839 NA 850 NA NA (1> NA (1) N A (1> N A <1> 1880 105 8 4 5 n g/m L 1 .3 % C o n cen tra tio n (n g /m L ) % R ecovery 951 997 N A <1) N A (1) 2030 NA NA NA (1) NA (1) 107 9 7 4 n g/m L 4.7% NA = Not Applicable (1) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Page 22 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 12. GW 227LQ1 Y10 LF 3 M L IM S ID D e sc rip tio n GLP1O-01 -02-02-085 G W 227LQ 1 Y 10 LF0 G LP10 -0 1 -0 2-02 -08 6 G W 2 2 7 L Q 1 Y 1 0 LF1 GLP10-01-02-02-087 G W 227LQ 1 Y 10 LFLS GLP10-01-02-02-088 GW 227LQ1 Y10 LFMS GLP10-01-02-02-089 GW 227LQ1 Y10 LFHS A v erag e C o n cen tra tio n (n g /m L ) 1 % R P D PFBS PFHS PFOS C o n cen tratio n (n g /m L ) "/ R e c o v e ry 349 335 N A <1) NA (1) 1480 NA NA N A (1) N A (1) 112 3 4 2 n g/m L 4 .1 % C o n cen tra tio n (n g /m L ) % R ecovery 65.2 NA 62.2 NA N A <1) N A <1) N A (1) N A (1) 1120 108 6 3 .7 n g/m L 4 .7 % C o n cen tra tio n (n g/m L ) % R ecovery 305 NA 269 NA N A (1) N A <1) N A (1> N A <1) 1260 98.3 2 8 7 n g/m L 1 3 % NA = Not Applicable (1) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Table 13. GW 227RQ1 Y10 LF 3 M U M S ID D esc rip tio n GLP10-01-02-02-001 G W 227RQ 1 Y 10 LF0 G LP 1 0-0 1 -0 2 -0 2 -0 0 2 G L P 10-01-02-02-003 G L P 10-01-02-02-004 G LP 10-01-02-02-005 G W 2 2 7 R Q 1 Y 1 0 LF1 G W 227R Q 1 Y 10 LFLS G W 227RQ1 Y10 LFMS GW 227RQ 1 Y10 LFHS A v e ra g e C o n c e n tra tio n (n g /m L ) % R PD PFBS PFHS PFOS C o n cen tratio n (n g/m L ) % R ecovery 23.0 NA 24.6 N A (1) N A (1) 1170 NA NA (1) N A (1) 112 2 3 .8 n g/m L 6 .7 % C o n cen tra tio n (n g /m L ) % R ecovery 169 169 N A <1) N A (1) 1210 NA NA N A <1) N A <1) 106 1 6 9 n g/m L 0 .0 % C o n cen tra tio n (n g /m L ) % R ecovery 920 NA 991 N A (1) N A <1> 1950 NA N A <1) N A <1) 100 9 5 6 n g/m L 7.4% NA = Not Applicable (1) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Page 23 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples from Decatur, AL March/Aprll 2010 Table 14. G W G R S 0 4Y 10 L F 3M U N IS ID D e sc rip tio n GLP10-01-02-02-036 G W G RS04Q 1 Y10 LF0 G L P 10-01-02-02-037 G LP 1 0-0 1-02 -02 -038 G W G R S 0 4 Q 1 Y 1 0 LF1 G W G RS04Q 1 Y 10 LFLS G LP10-01-02-02-039 G W G RS04Q 1 Y 10 LFMS GLP10-01-02-02-040 G W G RS04Q 1 Y10 LFHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS P FH S f,) PFOS C o n cen tra tio n (n g/m L ) % R ecovery 1800 NA 2050 n a (2> n a (2) 2730 NA n a (2) n a <2> 78.9 1930 n g/m L 13% C o n cen tra tio n (n g/m L ) % R ecovery 5810 6360 n a <2) n a (2) 7140 NA NA n a <2) n a (2) NC 6 0 9 0 n g /m L 9 .0 % p> C o n cen tratio n (n g /m L ) % R ecovery 1510 NA 1290 n a (2) n a (2) 2730 NA n a <2) N A <2) 13 4(4) 14 00 n g/m L 16% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1 ) PFHS reported from 5/26/10 analysis. (2) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. (3) Sampling location did not have an appropriate field matrix spike level for PFHS. (4) Field matrix spike did not m eet method acceptance criteria of 100% 30% . Since the method analytical uncertainty for PFOS is 100% 44% , no adjustment was m ade to the analytical uncertainty. Page 24 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 15. GW 310RQ1 Y10 CP 3 M L IM S ID D e sc rip tio n GLP10-01-02-02-026 G W 310RQ 1 Y10 CP0 GLP10-01-02-02-027 G W 310RQ 1 Y10 CP1 GLP10-01-02-02-028 G W 310RQ 1 Y10 CPLS GLP10-01-02-02-029 G W 310RQ 1 Y10 CPMS GLP10-01-02-02-030 G W 310R Q 1 Y10 CPHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g /m L ) % R ecovery 401 370 N A <1) N A (1> 1430 NA NA N A <1) N A <1) 102 3 8 6 n g/m L 8.0% C o n cen tra tio n (n g /m L ) % R ecovery 435 NA 412 NA N A <1) N A (1) N A (1) N A <1) 1410 100 4 2 4 n g/m L 5.4% C o n cen tra tio n (n g /m L ) % R ecovery 780 739 N A (1) NA (1) 1730 NA NA N A (1) N A (1> 98.0 76 0 n g/m L 5.4% NA = Not Applicable (1) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sam ple concentrations. Table 16. GW 312RQ1 Y10 CP 3 M L IM S ID D e sc rip tio n G LP 1 0-0 1-02 -02 -090 GLP10-01-02-02-091 G LP 10-01-02-02-092 G LP 1 0-0 1-02 -02 -093 G LP 1 0-0 1-02 -02 -094 GW312RQ1 Y10 CP0 G W 312R Q 1 Y10 CP1 GW 312RQ1 Y10 CPLS GW312RQ1 Y10 CPMS GW312RQ1 Y10 CPHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n C o n cen tra tio n C o n cen tratio n (n g /m L ) % ,R ecovery (n g /m L ) % R ecovery (n g /m L ) % R ecovery 1220 1220 N A (1> N A <1) 2240 NA NA N A (1) N A (1) 100 949 942 N A (1) NA (1) 1970 NA NA N A <1) N A <1> 104 1710 1790 NA (1) NA <1) 2800 NA NA NA <1) NA (1) 106 12 20 n g/m L 0 .0 % 9 4 6 n g/m L 0 .7 4 % 1750 n g/m L 4 .6 % NA = Not Applicable (1 ) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. (2) Sampling location did not have an appropriate field matrix spike level. Page 25 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 17. GW 317LQ1 Y10 CP 3 M U M S ID D escrip tio n GLP10-01-02-02-021 G W 317LQ 1 Y 10 CPO GLP10-01-02-02-022 GW 317LQ1 Y10 CP1 GLP10-01-02-02-023 GW 317LQ1 Y10 CPLS GLP10-01-02-02-024 GW 317LQ1 Y10 CPMS GLP10-01-02-02-025 GW 317LQ1 Y10 CPHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g/m L ) % R ecovery 0.536 NA 0.531 NA 1.78 122 116 113 NA (1) N A (1) 0 .5 3 4 n g/m L 0 .9 4 % C o n cen tra tio n (n g /m L ) % R ecovery 0.688 0.693 1.85 102 NA (1) NA NA 118 103 N A (1) 0.6 91 n g /m L 0 .7 2 % C o n cen tra tio n (n g /m L ) % R ecovery 2.48 2.39 2.98 76.2 N A <1) NA NA NC 74.5 N A (1) 2 .4 4 n g/m L 3 .7 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Table 18. GW 324LQ1 Y10 CP 3 M L IM S ID D e sc rip tio n G LP10-01-02-02-006 G W 324LQ 1 Y10 CPO GLP10-01-02-02-007 GW 324LQ1 Y10 CP1 GLP10-01-02-02-008 GW 324LQ1 Y10 CPLS GLP10-01-02-02-009 G W 324LQ 1 Y10 CPMS GLP10-01-02-02-010 GW 324LQ1 Y10 CPHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g /m L ) % R ecovery 94.3 NA 97.0 NA (1) NA <1) NA N A (1) N A (1) 1170 105 9 5 .7 n g/m L 2.8% C o n cen tra tio n (n g /m L ) % R ecovery 98.3 104 N A (1) NA (1> 1130 NA NA N A <1) N A <1) 105 101 n g /m L 5.6% C o n cen tratio n (n g /m L ) % R ecovery 192 214 N A <1) N A (1) 995 NA NA N A <1) N A <1) 80.0 20 3 n g/m L 1 1 % NA = Not Applicable (1) A dilution o f the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Page 26 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Table 19. GW 327RQ1 Y10 CP 3 M U N IS ID D e sc rip tio n GLP10-01-02-02-061 G W 3 27 R Q 1 Y 10 CPO GLP10-01-02-02-062 G W 327R Q 1 Y10 CP1 GLP10-01-02-02-063 G W 327RQ 1 Y10 CPLS GLP10-01-02-02-064 G W 327RQ 1 Y10 CPMS GLP10-01-02-02-065 G W 327RQ 1 Y10 CPHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g /m L ) % R ecovery 80.9 70.6 N A <1) N A (1) 1270 NA NA N A <1) N A <1) 117 75.8 n g/m L 1 4 % C o n cen tra tio n (n g/m L ) % R ecovery 156 NA 152 NA N A (1) N A <1) N A (1) N A (1) 1220 109 154 n g/m L 2.6% C o n cen tra tio n (n g /m L ) % R ecovery 695 582 NA (1) NA (1) 1490 NA NA N A <1) N A (1) 86.0 63 9 n g/m L 1 8 % N A = Not Applicable (1 ) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Table 20. GW 328LQ1 Y10 CP 3 M U M S ID D e s c rip tio n GLP10-01-02-02-066 GLP1001-02-02-067 GLP10 0 1 0 2 -0 2 -0 6 8 G LP10010202-069 G LP10010202070 G W 328LQ 1 Y 1 0 CPO G W 328LQ 1 Y 10 CP1 GW 328LQ1 Y10 CPLS GW328LQ1 Y10 CPMS GW328LQ1 Y10 CPHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g/m L ) % >Recovery 77 A 76.2 NA (1) N A (1) 1190 NA NA N A (1) N A (1) 109 76.8 n g/m L 1 .6 % C o n cen tratio n (n g/m L ) % R ecovery 26.0 25.7 N A (1> N A (1) 1070 NA NA N A (1) N A (1) 106 2 5 .9 n g/m L 1 .2 % C o n cen tra tio n (n g /m L ) % R ecovery 14.5 NA 14.4 NA N A (1) NA (1) 865 N A (1) N A <1) 85.9 14 .5 n g/m L 0 .6 9 % NA = Not Applicable (1) A dilution o f the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Page 27 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples from Decatur, AL March/April 2010 Table 21. GW 328RQ1 Y10 CP 3 M L IM S ID D e sc rip tio n GLP10-01-02-02-056 G W 328RQ 1 Y10 CP0 GLP10-01-02-02-057 G W 328R Q 1 Y10 CP1 GLP10-01-02-02-058 G W 328RQ 1 Y10 CPLS GLP10-01-02-02-059 G W 328RQ 1 Y10 CPMS GLP10-01-02-02-060 G W 328RQ 1 Y10 CPHS A v erag e C o n cen tra tio n <n g/m L) % R P D PFBS PFHS PFOS C o n cen tra tio n C o n cen tra tio n C o n cen tra tio n (n g/m L ) % R ecovery (n g /m L ) % R ecovery (n g /m L ) % R ecovery 35.6 36.3 N A <1) N A <1) 1230 NA NA N A (1> N A (1) 117 69.9 65.4 N A (1) N A (1) 1120 NA NA N A (1) N A (1> 107 159 132 N A <1) NA <1) 1110 NA NA N A <1) N A <1) 97.4 3 6 .0 n g/m L 1 .9 % 67 .7 n g/m L 6 .7 % 146 n g/m L 1 9 % NA = Not Applicable (1 ) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Table 22. GW 330LQ1 Y10 CP 3 M L IM S ID D e sc rip tio n G LP 1 0-0 1-02 -02 -016 G LP 1 0-0 1-02 -02 -017 G LP 1 0-0 1-02 -02 -018 G LP 1 0-0 1-02 -02 -019 GLP10-01-02-02-020 GW330LQ1 Y10 CP0 G W 330LQ 1 Y10 CP1 GW330LQ1 Y10 CPLS GW330LQ1 Y10 CPMS GW330LQ1 Y10 CPHS A v erag e C o n cen tra tio n (n g /m L ) % R PD PFBS PFHS PFOS C o n cen tratio n (n g /m L ) % R ecovery 519 NA 489 N A (1) NA N A <1) N A <1) N A (1) 1570 105 504 n g /m L 6.0% C o n cen tratio n (n g/m L ) % R ecovery 405 400 NA (1) NA (1) 1460 NA NA N A (1) N A (1) 108 4 0 3 n g/m L 1 .2 % C o n cen tra tio n (n g /m L ) % R ecovery 155 135 N A <1> N A <1> 1100 NA NA N A (1) N A <1) 96.5 14 5 n g/m L 14% NA = Not Applicable (1) A dilution o f the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. Table 23. GW 330RQ1 Y10 CP Page 28 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 3 M U M S ID D escrip tio n G LP 1 0-0 1 -0 2 -0 2 -0 1 1 G LP 1 0-0 1-02 -02 -012 G LP 1 0-0 1-02 -02 -013 G LP 1 0-0 1-02 -02 -014 G LP 1 0-0 1-02 -02 -015 G W 330R Q 1 Y 10 CPO G W 330R Q 1 Y10 CP1 GW 330RQ1 Y10 CPLS GW330RQ1 Y10 CPMS GW330RQ1 Y10 CPHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g/m L ) % R ecovery 4520 NA 4410 NA N A (1> N A <1> N A <1) N A (1) n a (2) n a <2> 4 4 7 0 n g/m L 2 .5 % m C o n cen tra tio n (n g /m L ) % R ecovery 264 251 N A <1> N A <1> 1310 NA NA N A (1) N A <1) 107 2 5 8 n g/m L 5 .0 % C o n cen tra tio n (n g/m L ) % R ecovery 763 755 N A (1) N A (1) 1710 NA NA NA (1) N A (1) 96.1 759 n g/m L 1 .1 % NA = Not Applicable (1 ) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. (2) Analyte concentration exceeded calibration range. Further dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentration. (3) Sampling location did not have an appropriate field matrix spike level. Table 24. GW 331SQ1 Y10 CP 3 M L IM S ID D e sc rip tio n G LP10-01-02-02-046 G W 331S Q 1 Y 10 CPO GLP10-01-02-02-047 G W 331SQ 1 Y10 CP1 GLP10-01-02-02-048 G W 331SQ1 Y10 CPLS GLP10-01-02-02-049 G W 331SQ 1 Y10 CPMS GLP10-01-02-02-050 G W 331SQ1 Y10 CPHS A v e ra g e C o n cen tra tio n (n g /m L ) % R P D PFBS PFHS PFOS C o n cen tra tio n (n g /m L ) % R ecovery 327 371 N A (1) N A (1) NA NA NA (1) N A (1) 1480 111 3 4 9 n g/m L 1 3 % C o n cen tra tio n (n g /m L ) % R ecovery 398 454 NA (1) NA NA N A <1) N A <1) N A (1) 1450 104 4 2 6 n g/m L 13% C o n cen tra tio n (n g /m L ) % R ecovery 824 1020 N A <1> N A (1) 1810 NA NA N A <1> N A (1) 89.7 922 n g/m L 21 % m NA = Not Applicable (1 ) A dilution of the sample was not prepared as the spike level was not expected to be appropriate as compared to the sample concentrations. (2) The R PD did not m eet method acceptance criteria of 20% . Table 25. Trip Blank Page 29 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 3 M U N IS ID G LP 1 0-0 1-02 -02 -076 G LP 1 0-0 1-02 -02 -077 GLP10-01-02-02-078 GLP10-01-02-02-079 D escrip tio n Trip Blank Sample Trip Blank FM S Low Trip Blank FM S Mid Trip Blank FM S High NA = Not Applicable Table 26. Rinseate Blanks PFBS PFHS PFOS C o n cen tra tio n (n g/m L ) < 0 .0 2 5 5 1.28 120 1140 % R ecovery NA 125 118 112 C o n cen tra tio n (n g /m L ) < 0 .0 2 5 8 1.21 112 1070 % R ecovery NA 123 114 109 C o n cen tra tio n (n g /m L ) <0.510 1.21 98.2 925 % R ecovery NA 122 99.2 93.4 3N I U N IS ID GLP10-01-02-02-041 G LP 10-01-02-02-042 G LP 1 0-0 1-02 -02 -043 G LP 1 0-0 1-02 -02 -044 G LP 1 0-0 1-02 -02 -045 GLP10-01-02-01-006 G L P 1 0-0 1-0 2-01 -03 1 PFBS PFHS PFOS D escrip tio n Rinseate Blankl 203L Rinseate Blank2 203L Rinseate Blank3 203L Rinseate Blank4 203L Rinseate Blank5 203L DAL DF05 SS SS07 2 0010 DALDF11 SS SS07 2 0010 C o n cen tra tio n (n g /m L ) < 0 .0 2 5 5 < 0 .0 2 5 5 < 0 .0 2 5 5 < 0 .0 2 5 5 < 0 .0 2 5 5 < 0 .0 2 5 5 <0.0255 % R ecovery NA NA NA NA NA NA NA C o n cen tra tio n (n g /m L ) < 0 .0 2 5 8 < 0 .0 2 5 8 < 0 .0 2 5 8 < 0 .0 2 5 8 <0.0258 <0.0258 <0.0258 % R ecovery NA NA NA NA NA NA NA C o n cen tra tio n (n g/m L ) <0.510 <0.510 <0.510 <0.510 <0.510 <0.510 <0.510 % R ecovery NA NA NA NA NA NA NA NA = Not Applicable Page 30 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for PFBS, PFHS, and PFOS. Analysis was successfully completed following 3M Environmental Laboratory method ETS-8-044.0 described herein. All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. Attachment A: Protocol Amendment #2 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 31 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples from Decatur, AL March/April 2010 Page 32 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Analytical Protocol: GLP10-01-02 Amendment 2 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program PROTOCOL AMENDMENT NO. 2 Amendment Date: March 24, 2010 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project identification GLP10-01-02 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Analytical Protocol: GLP10-01-02 Amendment 2 This amendment modifies the following portion of protocol: "Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program" Protocol reads: No changes to the wording of the protocol are required. A mend to read: No changes to the wording of the protocol are required. This amendment only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis of groundwater samples from Decatur. AL. and conducted as part of the 3M Decatur Phase 3 Program for PFOS. PFHS and PFBS (GLP10-01-02). The anticipated sample collection will occur around the timeframe of March 26. 2010. The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project GLP1Q-01-01-02 and reported as interim report GLP10-01-02-02, (reflecting study GLP10-01-02 and amendment -02). Reason: The reason for this amendment is to document the General Project Outline (GPO) which describes the anticipate groundwater sample collection event to be conducted for the 3M Decatur, AL facility. The G PO is four pages in length and included as attached to this amendment form. GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Analytical Protocol: GLP10-01-02 Amendment 2 Amendment Approval William Reagen, EHS Opns Environmental Lab Management <2 ty o Date Jaisimha Kesari P.E., DEE, Study Director 74 1 oDa~te GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Analytical Protocol: GLP10-01-02 Amendment 2 OM Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: Gary Hohenstein, 3M EHS&Opns From: Susan W olf, 3M EHS&Opns; Environmental Lab cc: William Reagen, 3M EHS&Opns; Environmental Lab Cliffton Jacoby, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions Charles Young, Weston Solutions Tim Frinak, Weston Solutions Date: March 24, 2010 S ubject: Analysis o f Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sedim ent for the 3M Decatur Phase 3 Site-Related M onitoring Program; GLP Interim Report #2 - Decatur 1st Quarter Groundwater Sampling 1 General Project Information Contacts Lab Request Number Six Digit Department Number Project ScheduleFTest Dates 3M Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 aahohensteinmmm.com 3M Environmental Laboratory Management William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaaenOmmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 26Q-5N-17 651 733-9860 cclanae<5>mmm.com Sampling Coordinator Timothy Frinak Weston Solutions Timothv.ftinakiawestonsolutions.com Phone: (3341-332-9123 GLP10-01-02-02 Dept #530711, Project #0022674449 Sampling scheduled for the week of March 29,2010 A ll verbal and written correspondence w ill be directed to Gary Hohenstein, GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Analytical Protocol: GLP10-01-02 Amendment 2 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environm ental Lab) w ill receive and analyze groundwater samples collected from seventeen groundwater w ells fo r Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS). Analyses w ill be conducted under the GLP requirem ents o f EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater sam ples from Decatur, AL w ill be collected by W eston Solutions personnel the week of March 29, 2010. The 3M Environmental Laboratory w ill prepare the sample bottles with all required spikes to ensure that results for PFBS, PFHS, and PFOS are o f a known precision and accuracy. The final report w ill be submitted to Gary Hohenstein and Jai Kesari upon com pletion under interim report GLP10-01-0202. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of March 29, 2010. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Friday, March 26,2010 to the attention of Keith Schmuck., 3M Cordova Environmental Engineer. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ W eston Trailer 3M D ecatur Plant 1400 State Docks Road Decatur, Alabam a 35601 4 Test Parameters The targeted lim it o f quantitation w ill be 0.025 ng/m L (ppb) for PFBS, PFHS, and PFOS. A total o f seventeen sampling locations have been specified. Sampling location descriptions were not available at the time of sample bottle preparation. For each sampling location, a total of five sample bottles will be collected (sample, sample duplicate, low-level field matrix spike, mid-level field matrix spike, and high-level field matrix spike). The "fill to here" line on each 250 mL Nalgene bottle will be 200 m L Four sets of trip blanks consisting o f reagent-grade water, a low-ievei trip blank spike, mid-level field spike and a high-level trip blank spike will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. The low field matrix spike w ill be prepared at 1 ng/mL, the mid field matrix spike at 100 ng/mL, and the high field matrix spike at 1000 ng/mL. Five additional bottles will be prepared to be used for the preparation of the equipment rinseate blanks. A total of 106 sample bottles will be prepared. All sample bottles will include the addition o f 18Q rPFB$, ,a0 2-PFHS, and 13C-PFOS, 1802-PFBS (internal standards) at a nominal concentration of 1 ng/mL. All sample bottles w ill also include the addition of 13C4-PFOS (surrogate spike) at a nominal concentration o f 0.1 ng/mL. 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-Q44.Q "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis '. The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy o f 1003Q%. Field matrix spikes not yielding recoveries wifriin 1Q03G% w ill be addressed in the report and the final accuracy statement may be adjusted accordingly. Alternately, samples may be analyzed by ETS 8-154.3 "Determination o f Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry'*. Method ETS-8-154 has been validated for PFOA and PFOS only; GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Analytical Protocol: GLP10-01-02 Amendment 2 however, specific quality control samples analyzed with the samples will be used to determine overall method precision and accuracy. 6 Reporting Requirements For each sampling location, the report will contain the results for the sample, sample duplicate, and the three field matrix spikes. A single trip blank and three trip blank spikes will be reported for the sampling event as will any equipment blanks prepared in the field. Laboratory control spikes o f reagent water prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks of reagent water prepared at the time o f sample extraction will be used to determine the method detection limit. Any laboratory matrix spikes that may be prepared will also be included in the final report 7 Email Correspondence Attachment A: Sampling Bottle Request Page 6 of 7 PaB 38 of 57 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Analytical Protocol: GLP10-01-02 Amendment 2 Bottle Request - GLP10-01-01 / GLP10-01-02 Q1I0 Decatur Groundwater Sampling 02181.129.145.0001 DATE REQUESTED: 17 March 2010 No. o f Samples 5 12 1 4 Sample Tvpe Groundwater Groundwater Rinseate Sample Trip Blanks Comment Anticipate high VOC concentrations Average Samples Will need HPLC water Anticipate 1 per cooler Note: Some of the wells have limited volume so the smaller the volume requirements the better. BOTTLES REQUIRED BY 26 MARCH 2010 Shipping Address: Martin Smith \ Weston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, AL 35601 256-552-6189 *** Ginger AG01330509 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL R e s u l t s Name. gi00517a.rdb March/April 2010 Data worked up by STW Printing Time: 3:24:04 PM Printing Date: Tuesday, June 29, 2010 Page 40 of 57 Ginger AG01330509 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL R e s u ^t s Nam e. g io o 5 1 7 a . rdb March/April 2010 Printing Date: Tuesday, June 29, 2010 Page 41 of 57 Ginger AG01330509 GLP10-01-02, Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL Resuxts Name- gl00517a rdb March/April 2010 '' Printing Time: 3:24:05 PM Printing Date: Tuesday, June 29, 2010 Page 42 of 57 Ginger AG01330509 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL R e s u lt s Name: qi00517a. rdb March/April 2010 g100517a.rdb (pfbs): "Quadratic" Regression ("1 /x " weighting): y = -1.3e+004 xA2 + 1.71e+006 x + 3.98e+003 (r = 0.9996) _________________________________________________________________________________ Concentration, ng/mL_________________________ Data worked up by STW Printing Time: 3:24:26 PM Page 1 of 1 Printing Date: Tuesday, June 29, 2010 Page 43 of 57 *** Ginger AG01330509 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL ReSults Name: gi00517a.rdb March/April 2010 Data worked up by STW Printing Time: 3:24:45 PM Printing Date: Tuesday/ June 29, 2010 Page 1 of 1 Page 44 of 57 *** Ginger AG01330509 GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL R e s u l t s Name. gi00517a.rdb March/April 2010 Data worked up by STW Printing Time: 3:25:07 PM Printing Date: Tuesday, June 29, 2010 Page 1 of 1 Page 45 of 57 glpio-01-02;interimReioi?S>sjmsnt msy De used' ^ current for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 3M Environm ental L aboratory Method Method o f Analysis for the Determination o f Perfiuorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: Q L j ^ j o ~j Approved By: W illiam K. Reagen, Laboratory Manager Date ETS-8-044.0 Page 1 of 11 Method of Analysis for the Determination of Perfiuorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page46 of 57 glpio-oi-o2; interimRe^RS^rneni may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 1 Scope and Application This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), PerfluorohexanoicAcid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in clean water samples. W ater samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method is considered a perform ance-based method. Data is considered acceptable as long as the defined QC elements are satisfied. Sample collection is not covered under this analytical procedure. 2 Method Summary Clean aqueous samples are analyzed by direct injection using LC/MS/MS. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered. This is a performance-based method. Method accuracy is determined for each sample set using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to each sample matrix. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. Fortification levels for field matrix spikes and for laboratory matrix spikes should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used to determine the statement of accuracy for analytical results. 3 Definitions 3.1 Calibration Standard A solution prepared by spiking a known volume of the Working Standard (WS) into a predetermined amount of ASTM Type I, HPLC grade water, or other suitable water, and analyzed according to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration. 3.2 Laboratory Duplicate Sample (LDS, or Lab Dup) A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures. 3.3 Field Blank (FB)/Trip Blank ASTM Type I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose of the FB is to determine if test substances or other interferences are present in the field environment. This sample is also referred to as a Trip Blank. ETS-8-044.0 Page 2 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 47 of 57 GLPio-oi-o2;interimRepl>ffS>i jment may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 3.4 Field Duplicate Sample (FDS, Field Dup) A sample collected in duplicate at the same time from the same location as the sample. The FDS is handled under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures. 3.5 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to the sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside of the sample container. The FMS should be spiked between approximately 50% and 10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes are added in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a study sample to help determine if the method is in control and whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At least one separate, un-spiked sample must be taken at the same time and place as each FMS. 3.7 Laboratory Control Sample (LCS) An aliquot of control matrix to which known quantities of the target analytes are added in the laboratory at the time of sample extraction. At least two levels are included, one generally at the low end of the calibration curve and one near the mid to upper range of the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared each day samples are extracted. 3.8 Laboratory Matrix Spike (LMS) A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous samples. 3.9 Laboratory Sample A portion or aliquot of a sample received from the field for testing. 3.10 Limit of Quantitation (LOQ) The lower limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix-dependent. The upper limit of quantitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. The highest standard in the calibration curve that meets method criteria is defined as the ULOQ. ETS-8-044.0 Page 3 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 48 of 57 glpio-oi-o2; interimR^oQQjJnient may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 3.11 Method Blank An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus. 3.12 Sample A sample is an aliquot removed from a larger quantity of material intended to represent the original source material. 3.13 Stock Standard Solution (SSS) A concentrated solution of a single-analyte prepared in the laboratory with an assayed reference compound. 3.14 Surrogate A compound similar in chemical composition and behavior to the target analyte(s), but is not normally found in the sample(s). A surrogate compound is typically a target analyte with at least one atom containing an isotopically-labeled substitution. If used, surrogate(s) are added to all samples and quality control samples. Surrogate^) are added to quantitatively evaluate the entire analytical procedure including sample collection, preparation, and analysis. Inclusion of a surrogate analyte is an optional quality control measure and is NOT required. 3.15 Working Standard (WS) A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions. 4 Warnings and Cautions 4.1 Health and Safety The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that might be present. The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses. 4.2 Cautions The analyst must be fam iliar with the laboratory equipment and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or operator manual for additional information and cautions. 5 Interferences During sample preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks. ETS-8-044.0 Page 4 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 49 of 57 glpio-oi-o2; interimRePoRS-inrieni may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to two solvents and equipped with a variable volume injector capable of injecting 5-100 pL connected to a tandem Mass Spectrometer (LC/MS/MS). I Analytical balance capable of reading to 0.0001 g A device to collect raw data for peak integration and quantitation 15-mL and 50-mL disposable polypropylene centrifuge tubes. Gas tight syringes, 25pL, 50pL, 100pL, 250pL, 500pL, 1000pL. 1 mL plastic HPLC autovial. Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 6.2 Chromatographic System Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm Analytical Column: Betasil C 18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Tim e (m ini 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (m L/m inl 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak Area - quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. The previous inform ation is intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met. ETS-8-044.0 Page 5 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 50 of 57 glpio-oi-o2; interimRe^ffS-irnent may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative bn, MRM mode, monitoring the following transitions: A n a lyte Transition Monitored PFBA 213 -> 169 PFPeA 263 ->219 PFHA 3 1 3 -> 2 6 9 and 3 1 3 -> 119 PFHpA 363 -> 319, 363 -> 169 and 363 -> 1 1 9 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 2 1 9 PFDA 513 -> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 2 1 9 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 -> 99 PFHS 399 --^ 80 and 399 --^ 99 PFOS 499 -> 80, 499 -> 99 and 499 -> 130 M ultiple transitions for m onitoring the analytes is an option, as summing m ultiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention tim e criteria are met to assure adequate specificity. The previous information is intended as a guide, alternate instruments and equipment may be used. 7 Reagents and Standards 7.1 Chemicals W ater - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate - A.C.S. Reagent Grade 7.2 Standards Perfluorobutanoic Acid (P F B A -C 4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (PFHA - C6 acid); Oakwood Products, Inc Perfluoroheptanoic Acid (P F H pA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M Perfluorononanoic Acid (PFNA - C9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (P F D A -C 10 acid); Oakwood Products, Inc PerfluoroundecanoicAcid (PFU nA-C 11 acid); Oakwood Products, Inc Perfluorododecanoic Acid (P F D oA - C12 acid); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a ly s is Page 51 of 57 g l p io-oi-o2; interim R eP offS ^merit may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 The previous inform ation is intended as a guide. Reagents and standards from alternate sources may be used. 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)--Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/m L target analyte SSSs--Weigh out 10 mg of analytical standard (corrected fo r p ercent s a lt and p u rity) and dilute to 10OmL with methanol or other suitable solvent, in a 10OmL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. m olecular weight o f anion salt correction factor = m oclecular weight of salt PFOS (K )salt correction factor = ------= 0.9275 538 10 mg C8F17S03"K+with purity 90% = 8.35mg C8F17S03" (10 mg*0.90*0.9275=8.35 mg) 5 pg/m L (5000 ng/m L) m ixed w orking standard--Add 0.5mL each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/m L m ixed w orking standard--Add 1.25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/m L m ixed standard--Add 625pL of the 5 pg/mL-mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage C onditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. ETS-8-044.0 Page 7 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection A n a ly s is Page 52 of 57 2g l p io - o i-o ; interim may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, or other suitable water, using the following table as a guideline. Note: Volumes of water and working standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. C oncentration o f W S, ng/m L 125 125 125 125 250 250 250 250 5000 5000 5000 V olu m e o f W S, fiL 10 15 20 30 20 50 100 200 25 50 100 F in al V olum e o f C alibration S tan d ard (m L o f A S T M Type 1 W ater, o r o th er su itab le w ater) 50 50 50 50 50 50 50 50 50 50 50 F in al C oncentration o f C alibration S tandard, ng/m L (ppb) in A S T M Type 1 W ater, o r o th er su itab le w ater 0.025 0.0375 0.050 0.075 0.100 0.250 0.500 1.00 2.50 5.00 10.0 8 Sample Handling 8.1 Water Sample Preparation This method is applicable to clean water samples. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered. Thoroughly mix sample before removing an aliquot and placing in a labeled plastic autovial. Plastic is preferred over the use of glass autovials, to prevent the possibly of fluorochemical sticking to the glass. Dilute sample, if necessary, with ASTM Type I, HPLC water, or other suitable water. Prepare method QC samples and multiple method blanks and aliquot into labeled plastic autovials. Prepare at least five method blanks. 9 Sample Analysis - LC/MS/MS Analyze the standard curve prior to each set of samples. The standard curve may be plotted using a linear fit, weighted 1/x or unweighted, or by quadratic fil (y = ax2+ bx + c), weighted 1/x or unweighted, using suitable software. The calibration curves may include but should not be forced through zero. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data. High and/or low points may be excluded from the calibration curves to provide a better fit over the range appropriate to the data or because they did not meet the pre-determined acceptance criteria. Low-level curve points should also be excluded if their area counts are not at least twice that of the method and/or solvent blanks. The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may ETS-8-044.0 Page 8 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 53 of 57 GLPio-01-02; interim R^ffS^rnent may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 be within 30%. Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples containing analytes that are quantitated above the concentration of the highest standard in the curve should be further diluted and reanalyzed. 10 Quality Control 10.1 Data Quality Objectives This method and required quality control samples is designed to generate data accurate to 30% with a targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report. 10.2 Method Blanks Method blanks must be prepared with each analysis batch. At least five method blanks must be prepared. Method blanks may be injected multiple times, but no more than 3 injections should be removed from a single method blank. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, and at the end of the analytical run. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts of these method blanks should be calculated and reported. If the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria, or alternatively, the method blanks must be evaluated statistically to determine outliers, or technical justification to eliminate one or more results should be made. 10.3 Sample Replicates Samples duplicates are collected in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks. 10.4 Surrogate Spikes Surrogate spikes are not required but may be used on project specific requirements. 10.5 Lab Control Sample Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each preparation batch. Low lab control spikes should be prepared at concentrations in the range of five to ten times higher than the targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve. The relative standard deviation of the control spikes evaluated independently at each concentration level must be less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire set of samples should be re-injected or re-prepared as appropriate. ETS-8-044.0 Page 9 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 54 of 57 glpio-oi-o2;interim may be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: (Peak Area - Intercept) Analyte found (ng/mL) = xDF Slope DF = factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. Recovery - ana'^ e f unc*(ng/mL) - Average analyte found in sample (ng/mL) x ^ qq Analyte added (ng/mL) 12 Method Performance Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report. 12.1 System Suitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of <5% and a retention time RSD of 2% to be compliant. 12.2 Quantitation C alibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Perform ance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a lysis Page 55 of 57 glpio-oi-o2; interim rnay be used, if current, for 14 days from 06/29/2010 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 D em onstration o f S pecificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/ml_. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions Revision Number Summary o f Changes ETS-8-044.0 Page 11 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 56 of 57 3M Confidential GLP10-01-02; Interim Report 02 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples from Decatur, AL March/April 2010 Record of Deviation/Nonconformance Study / Project No. GLP10-01-02-02 I. Identification Date(s) o f Occurrence: j1 00517a Deviation type (Check one) SOP Protocol Equipm ent Procedure IZI Method IZI GPO Other. II. Description (attach extra pages as needed) Method Requirements: 1. LCS average recovery o f 100% 20%. 2. Sample/Sample Duplicate RPD 20%. 3. FMS recovery o f 100% 30%. Docum ent Number. ETS-8-044.0 Actual procedure/process: (1) LCS average recovery for branched PFOS was >120%. (2) The RPD for PFOS fo r sampling location 331S was 21%. (3) The recovery of the FMS High sample fo r GRS04 for PFOS was 134%. III. Actions Taken (such as am endm ent issued, S O P revision, etc.) Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1) The branched PFOS when quantitated against calibration curve point prepared from linear PFOS have been quantitating around 15-20% higher. The set o f 30 ppb branched LCS prepared w ith the sam ples produced recoveries -170% . The 5 ppb branched LCS recovery w as w ithin acceptance criteria, suggesting that the 30 ppb average recovery may be in error. Three replicates o f branched LCS at 5 ppb, 15 ppb, and 30 ppb, prepared w ith non-study sam ples, were analyzed with the study sam ples to confirm the higher recovery. The results o f the additional sam ples were within the field m atrix spike acceptance criteria o f 100%30%. All LCS were used in the determ ination o f the analytical uncertainty. 2) The RPD value fo r PFOS fo r sampling location 331S w ill be footnoted in the data tables. 3) Since the method analytical uncertainty fo r PFOS is 100% 44% , no adjustm ent was made to the analytical uncertainty for PFOS on GRS04. Actions: Halting o f W ork C lient N otification W ork Recall El Other: Deviations w ill be noted in final report. P ro je ct Lead/P A I A p p ro va l: S u W ithholding o f Report D ate: . S tudy D ire cto r (if G LP ): S p o n so r A p p ro va l (fo r G LP pro to co l d e via tio n s): NA T ech n ica l R e vie w e r (o p tio n a l): N A D a '- M ?)/0 D ate: NA 1 D ate: N A Lab o ra to ry D epartm ent M anager A pp ro va l: D ate: c / jo A o / r J IV. Authorization to Resume Work W here halting o f work occurred, resumption o f work must first be approved b y Laboratory M anagem ent Laboratory D epartm ent M anager A pproval: NA D ate: NA Deviation No. (assigned by S tudy Director o r Team L e ad e r a t the end o f study o r project) Attachm ent A ETS-4-008.7 Page 1 of 1 Documentation o f Deviations and Control o f Nonconform ing Testing Page57<*57