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3M GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 GLP10-01-02: Interim Report 06 - Analysis o f PFBS. PFHS. and PFOS in Groundwater/Surface Water Samples Collected as Part of the Avenue A Investigation Area in Decatur. AL in June/Julv 2010 Study Title Analysis of Perfiuorooctane 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 Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 Author Susan Wolf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP10-01-02-06 Total Number o f Pages 67 The testing reported herein meet the requirements of ISO/IEC 17025-2005 "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 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 This page has been reserved for specific country requirements. Page 2 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 GLP C o m p lia n c e S tatem ent Report Title: Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Groundwater/Surface Water Samples Collected as Part of the Avenue A Investigation Area in Decatur, AL in June/July 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 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Q uality A ssurance Statement Report Title: Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Groundwater/Surface Water Samples Collected as Part of the Avenue A Investigation Area in Decatur, AL in June/July 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 9/23, 9/24, 9/27, and 9/28/10 Phase Data and Interim Report Date Reported to Testing Facility Management Study Director 10/ 12/10 10/ 12/10 Date Page 4 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table of C ontents 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................................................................................................................................... 11 4 Test & Control Substances.......................................................................................................... 12 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 )................................................. 8.4 Continuing Calibration................................................. 16 17 8.5 Blanks............................................................................................................................17 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.................................................................................................... 21 Page 5 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 10 Conclusion.................................................................................................................................... 37 11 Data/Sample Retention................................................................................................................ 37 12 Attachm ents.................................................................................................................................. 37 13 Signatures..................................................................................................................................... 38 L ist o f Ta b les Table 1. Summarized PFBS, PFHS, and PFOS Results (Avenue A Investigation, June/July 2010). 10 Table 2. Sample Description Key Code........................................................................................... 14 Table 3. Instrument Parameters....................................................................................................... 15 Table 4. Liquid Chromatography Conditions..................................................................................... 15 Table 5. Mass Transitions..................................................................................................................15 Table 6. Limit of Quantitation (LOQ).................................................................................................16 Table 7. Laboratory Control Spike Recovery....................................................................................18 Table 8. Analytical Uncertainty.......................................................................................................... 20 Table 9. DALSW SW 01 100623...................................................................................................... 22 Table 10. DAL SW SW02 100622................................................................................................... 22 Table 11. DAL SW SW03 100622................................................................................................... 23 Table 12. DAL SW SW 04 100622.................................................................................................... 23 Table 13. DAL SW SW05 100622.................................................................................................... 24 Table 14. DAL SW SW06 100622................................................................................................... 24 Table 15. DAL SW SW07 100622................................................................................................... 25 Table 16. DAL SW SW08 100623.................................................................................................... 25 Table 17. DAL SW SW09 100623............... ....................................................................................26 Table 18. DAL SW SW10 100623.................................................................................................... 26 Table 19. DALSW SW 11 100623.................................................................................................... 27 Table 20. DAL SW SW12 100623.................................................................................................... 28 Table 21. DALGW GP01 100709.................................................................................................... 28 Page 6 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 22. DAL GW GP02 100709.................................................................................................... 29 Table 23. DAL GW GP03 100709.................................................................................................... 29 Table 24. DAL GW GP04 100709................................................. 30 Table 25. DAL GW GP05 100709.................................................................................................... 31 Table 26. DAL GW GP07 100709.................................................................................................... 31 Table 27. DAL GW GP08 100709.................................................................................................... 32 Table 28. DAL GW GP09 100709.................................................................................................... 32 Table 29. DAL GW GP10 100709.................................................................................. 33 Table 30. DAL GW GP11 100708.................................................................................................... 33 Table 31. DAL GW GP12 100708.................................................................................................... 34 Table 32. DAL GW 216R 100716..................................................................................................... 34 Table 33. Trip B lank..........................................................................................................................35 Table 34. Rinseate Blanks............. ................................................................................................. 36 Page 7 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 1 Study Information 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, fclanqe@mmm.comL phone (651)-733-9860 Susan Wolf, 3M Analyst Jonathan Steege; analyst Study Dates Study Initiation: March 8, 2010 Interim Report 06 Experimental Termination: September 10, 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 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 2 Summary The 3M Environmental Laboratory received groundwater and surface water samples collected as part of the Avenue A Investigation area in Decatur, AL, representing twenty-four different sampling locations. A total of one hundred thirty-four sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate water samples from each sampling location. Samples also included at least two field matrix spike (FMS) samples for each location, three trip blanks containing M illi-QTM water and appropriate trip blank spikes, and two equipment rinseates. The equipment rinseate blanks did not have FMS samples prepared for determination of PFBS, PFHS, and PFOS recovery. The surface water samples, one set of trip blanks and equipment rinseate blanks were received from Weston personnel on June 25,2010. The groundwater samples and one set of trip blanks were received on July 13, 2010. The groundwater samples from location 216R and one set of trip blanks were received on July 22, 2010. All water samples for this project were logged under GLP10-01 -01-06. In addition, soil-equipment rinseate blanks from GLP10-01-02-03 (Wetlands Edge Environment Center - WEEC Swamp), GLP10-01 -02-05 (Avenue A Investigation - Soils), and GLP10-01-02-08 (Phase 3 Offsite Soil) are also reported herein. 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-10-01-02-06. Most of the water samples required dilution to attain PFBS, PFHS, and PFOS concentrations within the range of the curve, in some instances up to a 200-fold dilution was required. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1 The equipment rinseates and trip blanks were below the lower limit of quantitation (LLOQ) collected with the water samples for GLP1001-02-06, indicating adequate control of sample contamination during shipping and sample collections. The soil-equipment rinseate blanks from GLP10-01-02-03, GLP10-01-02-05, and GLP10-01-02-08 were below the LLOQ with the exception of one soil-equipment rinseate blank collected under GLP1001-02-03 which had a detected concentration just above the LLOQ. The PFBS concentration results for all groundwater and surface water samples ranged over three orders of magnitude from 0.764 ng/mL to 279 ng/mL. The PFHS concentration results for all groundwater and surface water sample ranged over three orders of magnitude from 3.68 ng/mL to 1130 ng/mL. The PFOS concentration results for all groundwater and surface water samples ranged over two orders of magnitude from 17.5 ng/mL to 1780 ng/mL. Page 9 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 1. Summarized PFBS, PFHS, and PFOS Results (Avenue Investigation, June/July 2010). Sampling Location DALSWSW01 100623 DAL SWSW02 100622 DAL SWSW03 100622 DAL SWSW04 100622 DAL SWSW05 100622 DAL SWSW06 100622 DAL SWSW07 100622 DAL SWSW08 100623 DAL SWSW09 100623 DAL SW SW 10100623 DALSWSW11 100623 DAL SW SW 12 100623 DALGWGP01 100709 DAL GW GP02 100709 DAL GW GP03 100709 DAL GW GP04 100709 DAL GW GP05 100709 DAL GW GP07 100709 DAL GW GP08 100709 DAL GW GP09 100709 DAL GW GP10 100709 DALGWGP11 100708 DAL GWGP12 100708 DALGW 216R 100712 PFBS Avg. Cone. (ng/mL) RPD 15.0 4.0% 7.68 5.1% 9.57 1.2% 13.7 5.8% 20.9 1.9% 17.4 4.6% 1 0 . 8 0 .0 % 40.7 4.2% 279 2.5% 22.5 4.4% 102 3.0% 0.764 2.4% 5.02 0.20% 21.1 13% 66.4 0.45% 19.1 0.0% 30.0 0.0% 20.7 3.9% 6.36 1.1% 20.7 1.9% 447 2.5% 67.0 3.1% 2.59 58% (2) 10.6 1.9% PFHS Avg. Cone. (ng/mL) RPD 120 1.7% 52.0 0.19% , 72.2 2.1% 86.5 2.0% 102 3.9% 77.5 0.77% 47.9 1.0% 166 3.6% 643 9.0% 233 2.6% 1130 0.89% 3.68 0.54% 7.63 3.7% 11.2 13% 413 0.24% (1) 85.8 8 .6 % 158 5.7% 171 2.9% 70.2 7.8% 36.0 13% 420 3.3% 330 1.8% 11.2 44% <2) 30.5 3.0% PFOS Avg. Cone. (ng/mL) RPD 248 4.0% 213 7.7% 197 1.1% 192 2.2% 392 3.6% 228 1 .1 % 129 2.2% 266 1.9% 382 2.1% 389 1.0% 850 3.2% 104 2.0% 26.2 5.3% 17.5 20% 373 17% <1) 152 30% (2) 3 8 2 18% 1780 4.5% 1420 4.9% 95.5 33% (2) 127 31% <2) 660 6 .1 % 48.8 67% <2) 119 9.2% The analytical method uncertainties associated with the reported results are as follows: PFBS 100% 21%, PFHS 100% 23%, and PFOS 100% 41% . (1) Sampling location did not have an appropriate FMS spike level to sufficiently evaluate analyte recovery. (2) The RPD did not meet method acceptance criteria of 20%. (3) Sample GLP10-01-02-03-009 (DAL-SD-WESB4-RB) PFOS result was 0.260 ng/mL. Page 10 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Table 1 continued. Summarized PFBS, PFHS, and PFOS Results (Avenue A Investigation, June/July 2010). Sampling Location Trip Blank and (Milli-QTM Water) Equipment rinseate blanks GLP10-01-01-03 Soil-Equipment rinseate blanks GLP10-01-01-05 Soil-Equipment rinseate blanks GLP10-01-01-08 Soil-Equipment rinseate blanks PFBS Avg. Cone. (ng/mL) RPD <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 PFHS Avg. Cone. (ng/mL) RPD <0.103 <0.103 <0.103 <0.103 <0.103 PFOS Avg. Cone. (ng/mL) RPD <0.255 <0.255 <0.255 (3) <0.255 <0.255 The analytical method uncertainties associated with the reported results are as follows: PFBS 100% 21%, PFHS 100% 25%, and PFOS 100% 44% . (1) The RPD did not meet method acceptance criteria of 20%. (2) Sampling location did not have an appropriate FMS spike level to sufficiently evaluate analyte recovery. (3) Sample GLP10-01 -02-03-009 (DAL-SD-WESB4-RB) PFOS result was 0.260 ng/mL. 3 Introduction 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 (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 and surface water samples collected as part of the Avenue A Investigation in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on-site groundwater conditions. In addition, three aqueous soil-equipment rinseate samples from GLP10-0101-03 (Wetlands Edge Environment C enter-W EEC Swamp), six soil-equipment rinseate samples from GLP10-01-01-05 (Avenue A Investigation - Soils), and one soil-equipment rinseate sample from GLP10-01-01-08 (Phase 3 Offsite Soil) are also reported herein. 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 13C8-PFOS (internal standards) at a nominal concentration of 1 ng/mL. However, due to the levels of PFBS, PFHS, and PFOS detected in the samples, the use of internal standards was not used for quantitation. 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. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Page 11 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, trip blanks, groundwater-equipment rinseate samples, and aqueous soil-equipment rinseate samples. Tables 9-34 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 4 '-Test & Control.Substances 'r' There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predom inantly linear) Perfluorobutane sulfonate C4 F9 SO3 Potassium Salt 3M ' 1/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOS (lin ear) Perfluorooctane sulfonate C8 F17SO3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% PFHS (lin ear) Perfluorohexane sulfonate CF13S O 3 Sodium Salt Wellington 4/2/2013 Frozen LPFHxSAM08 TCR08-0018 Crystalline 98% PFOS (lin ea r + branched) Perfluorooctane sulfonate C8 F 17SO 3 Potassium Salt CAS # 2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% Page 12 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 1, o 2-p f b s Labeled - Perfluorobutane sulfonate C4 F9S[180 2]0Ammonium Salt RTI International 3/9/2015 Frozen 11546-107-2 TCR-1013 Liquid 99% 1*Or PFHS Labeled - Perfluorohexane sulfonate C6 Fi 3 S[180 2 ]160 - Sodium Salt Wellington 7/24/2011 Frozen MPFHXA0706 TCR-1218 Liquid 98% R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 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 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 6 Test System The test system for this study are surface water and 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. Table 2. Sample Description Key Code. String Number Example 1 2 4 String Descriptor DAL S W S W 0 7 0 100622 Sample Type Sample Location Sampling Date Sample Type Example SUV= Surface Water Example: SW07 100622- June 22, 2010 0=primary sample DB=duplicate sample LS = low spike MS = mid spike HS = high spike 7 Method Summary : 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In Water 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 June 25, July 13, and July 22, 2010. Samples were stored refrigerated at the laboratory after receipt. One set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were returned with each batch of 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). A few sampling locations were diluted 1:20 by diluting 0.5mL of sample with 9.5 mLs of 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 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 3. Instrument Parameters. Instrument Name Analytical Method Followed Analysis Date Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS Stan , ETS-8-044.0 8/04/2010 Agilent 1100 Betasil C18 (2.1 mm X 100 mm), 5 n Betasil C18 (2.1 mm X 100 mm), 5g 10 uL Applied Biosystems API 4000 Turbo Spray Turbo Ion electrode Negative Analyst 1.4.2 Table 4. Liquid Chromatography Conditions. ETS MaryAnn ETS-8-044.0 9/10/10 Agilent 1100 Betasil C18 (2.1 mm X 100 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5u 2 o r10uL Applied Blosystems API 5000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Step Number 0 1 2 3 4 5 0 1 2 3 4 5 Total Time (min) 0 1.0 11.0 13.5 14.0 17.0 0 2.0 14.5 15.5 16.5 20.0 Flow Rate (fdJmin) Percent A (2 mM ammonium acetate) 8/4/10 Analysis 300 80.0 300 80.0 300 10.0 300 10.0 300 80.0 300 80.0 9/10/10 Analysis 300 90.0 300 90.0 300 5.0 300 5.0 300 90.0 300 90.0 PercentB (Methanol) 20.0 20.0 90.0 90.0 20.0 20.0 10.0 10.0 95.0 95.0 10.0 10.0 Table 5. Mass Transitions. Analyte PFBS PFHS PFOS Mass Transition Q1/Q3 299/80 299/99 399/80 399/99 499/80 499/99 499/130 Dwell time was 50 or 125 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation. Page 15 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 8 Analytical Results 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 fifeen spiked standards ranging from 0.025 ng/mL to 100 ng/mL (nominal) were analyzed. Low and/or high curve points were disabled as needed to meet calibration acceptance 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. PFOS: The calibration curve was constructed using the linear isomer of PFOS only. Since the samples were expected to contain both linear and branched isomers of PFOS, LCS and GLP10-01-02-06 samples were quantitated by processing the PFOS linear and branched isomers separately and summing the calculated concentrations together to generate the final PFOS concentration. This was done to help minimize any potential analytical bias due to quantitating linear and branched isomers of PFOS against a predominately linear reference standard for PFOS. 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 6. Table 6. Limit o f Quantitation (LOQ). Analysis Date 8/4/10 9/10/10 Dilution 1 10 20 1 200 PFBS LOQ, ng/mL 0.0255 0.255 0.510 0.0306 NA PFHS LOQ, ng/mL 0.103 1.03 2.06 0.103 NA PFOS LOQ, ng/mL 0.255 2.55 5.10 NA 20.4 Page 16 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 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 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. The method acceptance criteria states that the average of LCS at each level should be within 100% 20% with an RSD 20%. 8/4/10 Analysis: Method acceptance criteria was met for the PFBS, PFHS, and the mid and high set of linear PFOS LCS samples. The low set of linear PFOS LCS had an average recovery of 121 %. 9/10/10 Analysis: Method acceptance criteria was met for all three levels of LCS for PFBS. The mid and high LCS met method acceptance criteria for PFHS and PFOS. The average recovery for the low set of LCS for PFHS was 73.5% and not calculated for PFOS as the detected values were <LOQ. 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 and branched) were prepared at three concentrations to evaluate the potential for analytical bias. 8/4/10 Analysis: The low, mid, and high set of LCS (linear + branched ) did not meet method acceptance criteria with an average recovery of 166%, 128%, and 141 %, respectively. 9/10/10 Analysis: The mid set of LCS (linear + branched), met method acceptance criteria, while the low set (57.4%) and high set (123%), did not meet method acceptance criteria. Based on the recovery of the linear and branched PFOA LCS, it is the opinion of the laboratory that the recovery discrepency of the linear and branched isomers of PFOA indicates an analytical bias. Because of this bias, the method uncertainty will be adjusted to 100% 41 %, based on the highest recovery of the linear and branched LCS, at the spike level most appropriate as compared to the on-column concentrations of PFOS detected in the samples. In this case, the 30 ppb LCS (linear + branched) analyzed on 8/4/10 with an average recovery of 141%. A method deviation addressing the LCS recoveries is included in the raw data package. The following calculations were used to generate data in Table 7 for laboratory control spikes. LCS Percent Recovery C alculated C oncentration . 1gg0/0 Spike Concentration LCS% RSD = standard deviation LCS replicates . 1Q0% average LCS recovery Page 17 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 7. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 8/4/10 Lab ID LCS-100726-1 LCS-100726-2 LCS-100726-3 Average %RSD LCS-100726-4 LCS-100726-5 LCS-100726-6 Average %RSD LCS-100726-7 LCS-100726-8 LCS-100726-9 Average %RSD PFBS Spiked Concentration (ng/mL) 0.510 0.510 0.510 Calculated Concentration (ng/mL) 0.558 0.593 0.572 5.10 5.10 5.10 113% 2.7% 4.59 5.64 5.64 30.6 30.6 30.6 104% 12% 32.1 32.9 32.4 106% 0.94% Spiked Concentration YoRecovery (ng/mL) 1 1 0 0.515 116 0.515 1 1 2 0.515 90.0 111 111 5.15 5.15 5.15 105 30.9 107 30.9 106 30.9 PFHS Calculated Concentration (ng/mL) 0.513 0.613 0.531 107% 9.7% 4.70 5.63 5.84 104% 11% 32.6 33.4 33.4 107% 1.1% YoRecovery 100 119 103 91.2 109 113 106 108 108 ETS-8-044.0 Analyzed 8/4/10 PFOS (linear) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) LCS-100726-1 LCS-100726-2 LCS-100726-3 0.510 0.510 0.510 0.590 0.652 0.613 Average %RSD 121% 5.1%(1> LCS-100726-4 LCS-100726-5 LCS-100726-6 5.10 5.10 5.10 4.67 5.70 5.81 Average %RSD 106% 1 2 % LCS-100726-7 LCS-100726-8 LCS-100726-9 30.6 30.6 30.6 34.5 34.9 34.9 Average %RSD 114% 0.66% YoRecovery Lab ID 116 LCS-100726-10 128 LCS-100726-11 1 2 0 LCS-100726-12 Average %RSD 91.6 LCS-100726-13 1 1 2 LCS-100726-14 114 LCS-100726-15 Average %RSD 113 LCS-100726-16 114 LCS-100726-17 114 LCS-100726-18 Average %RSD PFOS (linear + branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) YoRecovery 0.500 0.844 169 0.500 0.500 0.829 0.817 166 163 5.00 5.00 5.00 166% 1 .6 % 111 6.28 6.49 6.38 126 130 128 30.0 128% 1 .6 % '" 42.2 141 30.0 30.0 41.9 43.1 140 144 141%1.5%(1) (1) The average recovery did not meet method acceptance criteria of 100% 20%. Page 18 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 9/10/10 Lab ID LCS-100910-1 LCS-100910-2 LCS-100910-3 Average %RSD LCS-100910-4 LCS-100910-5 LCS-100910-6 Average %RSD LCS-100910-7 LCS-100910-8 LCS-100910-9 Average %RSD Spiked Concentration (ng/mL) 0.204 0.204 0.204 5.10 5.10 5.10 15.3 15.3 15.3 PFBS Calculated Spiked Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.185 0.231 0.245 108% 14% 90.7 113 120 0.206 0.206 0.206 5.17 5.79 5.43 107% 5.7% 101 113 106 5.15 5.15 5.15 14.8 17.3 17.1 107% 8.2% 96.9 113 111 15.5 15.5 15.5 PFHS Calculated Concentration (ng/mL) <0.103 0.144 0.159 73.5% 7.0%(1) 5.20 5.77 5.45 106% 5.2% 14.9 16.6 16.7 104% 6.4% VoRecovery NA 69.8 77.1 101 112 106 96.1 107 108 ETS-8-044.0 Analyzed 9/10/10 PFOS (linear) PFOS (linear + branched) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) VoRecovery LCS-100910-1 LCS-100910-2 LCS-100910-3 Average %RSD 0.204 0.204 0.204 <0 . 1 0 2 <0 . 1 0 2 <0 . 1 0 2 NA NA LCS-100910-10 NA LCS-100910-11 NA LCS-100910-12 Average %RSD 0.495 0.495 0.495 0.302 0.278 0.273 57.4% 5.3% ,1) 60.9 56.2 55.2 LCS-100910-4 LCS-100910-5 LCS-100910-6 Average %RSD 5.10 5.10 5.10 4.44 4.97 4.65 91.9% 5.7% 87.1 97.5 91.1 LCS-100910-13 LCS-100910-14 LCS-100910-15 Average %RSD 4.95 4.95 4.95 4.92 5.02 5.81 106% 9.2% 99.3 101 117 LCS-100910-7 LCS-100910-8 LCS-100910-9 Average %RSD 15.3 15.3 15.3 13.7 15.5 16.2 98.8% 8.6% 89.5 101 106 LCS-100910-16 LCS-100910-17 LCS-100910-18 Average %RSD 14.8 14.8 14.8 17.8 18.3 18.3 123% 1.9%(1) 120 124 124 (1) The average recovery did not meet 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 for PFBS and PFHS. For PFOS, the analytical uncertainty Page 19 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 was determined based on the quality control data generated with the project samples (Table 6) and was used to evaluate method accuracy and precision. Due to the analytical high bias observed during the quantitation of the linear + branched PFOS against a calibration curve constructed from the analysis of calibration standards containing linear PFOS only, an analytical uncertainty of 41 % is applied to all PFOS sample results for this project. Table 8. A n a lytica l U ncertainty. Analyte Standard Deviation Method Uncertainty PFBS 10.6 100%21% PFHS 11.6 100%23% PFOS N A (1) 100%41% (1) NA = Not Applicable. See section 8.6 of the report for a discussion on the assigning of the method uncertainty for PFOS. 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 10 ng/mL, and the high field marix spike was 100 ng/mL for all sampling locations. For some sampling locations, the high field matrix spike was not appropriate as compared to the sample concentration. Field matrix spike levels will be adjusted accordingly for the next sampling event. FMS Recovery - ^ amP'e Concentration o f F M S- Average Concentration :Field Sample & Field Sample Dup.) t ^ Spike Concentraton 8.9 Laboratory Matrix Spikes (LMS) Samples were analyzed under project GLP10-01-01-06 for PFOA. Results from that analysis found that the high FMS level was not sufficient for several of the surface water sampling locations for PFOA. Since it was presumed that the levels of PFOS in these samples would be similar to the PFOA results, laboratory matrix spikes were prepared for GLP10-01-01-06 were analyzed instead of the FMS samples prepared with the sample set. Laboratory matrix spike were prepared and analyzed for the following sample locations: 200ppb LMS: DAL SW SW01, DAL SW SW04, DAL SW SW05, and DAL SW SW08, 400ppb LMS; DAL SW SW10 and DAL SW SW11, 500ppb LMS; DAL SW SW09, and 1500ppb LMS; DAL GW GP07 and DAL GW GP08 Laboratory 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. Page 20 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 LMS Recovery 9 Data (LMS Sample Concentration - Average Concentration : Sample & Sample Pup.) t 100% LMS Spike Concentraton w * r us' s,on:& 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 21 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 9. DALSWSW01 100623 PFBS PFHS PFOS 3 M U M S ID Description GLP10-01 -02-06-035 DALSW SW 01 0 100623 GLP10-01 -02-06-036 DALSW SW 01 DB 100623 GLP10-01 -02-06-037 DALSW SW 01 LS 100623 GLP10-01 -02-06-038 DAL SW SW01 MS 100623 GLP10-01 -02-06-039 DALSW SW 01 HS 100623 GLP10-01 -02-06-036 LMS DAL SW SW01 DB - 200ppb LMS Average Concentration (ng/mL) %RPD Concentration (ng/mL) XRecovery 15.3 14.7 N A <1) N A <1) N A (1) 246 NA NA N A 0) N A <1) N A <1) 113 15.0 ng/mL 4.0% Concentration (ng/mL) %Recovery 119 NA 121 N A <1> NA N A (1) N A (1) N A (1) N A <1) N A <1) 345 109 120 ng/mL 1.7% Concentration (ng/mL) %Recovery 243 253 N A <1) N A (1) N A (1) 505 NA NA N A (1) N A (1) N A (1) 126 248 ng/mL 4.0% NA = Not Applicable (1) The sample was not analyzed. Table 10. DAL SW SW02 100622 PFBS PFHS PFOS 3MUM SID Description Concentration (ng/mL) YoRecovery GLP10-01 -02-06-030 GLP10-01 -02-06-031 GLP10-01 -02-06-032 DAL SW SW02 0 100622 DAL SW SW02 DB 100622 DAL SW SW02 LS 100622 7.48 7.87 NA (1) NA NA N A (1) GLP 10-01-02-06-033 DAL SW SW02 LS 100622 GLP 10-01 -02-06-034 DAL SW SW02 HS 100622 Average Concentration (ng/mL) %RPD N A (1) N A (1) 119 109 7.68 ng/mL 5.1% Concentration (ng/mL) %Recovery 51.9 NA 52.0 N A <1> NA N A (1> N A (1) 161 N A (1> 106 52.0 ng/mL 0.19% Concentration (ng/mL) YoRecovery 221 NA 205 NA N A (1) N A <1) NA (1) N A <1) 307 92.4 213 ng/mL 7.7% NA = Not Applicable (1) The sample was not analyzed. Page 22 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 11. DAL SW SW03 100622 PFBS PFHS PFOS 3MUM SID Description Concentration (ng/mL) %Recovery GLP10-01-02-06-021 DAL SW SW03 0 100622 9.51 NA GLP10-01 -02-06-022 DAL S W SW 03 DB 100622 9.62 NA GLP10-01 -02-06-023 DAL SW SW 03 LS 100622 N A (1) N A (1) GLP10-01 -02-06-024 DAL SW SW03 MS 100622 GLP10-01-02-06-025 DAL SW SW03 HS 100622 N A (1) 120 NA (1) 108 Average Concentration (ng/mL) %RPD 9.57 ng/mL 1.2% Concentration (ng/mL) %Recovery 71.4 NA 72.9 NA NA <1) N A (1) NA <1) 184 N A <1) 109 72.2 ng/mL 2.1% Concentration (ng/mL) %Recovery 196 NA 198 NA NA (1) N A (1) 278 N A (1) N A (1) 80.1 197 ng/mL 1.1% N A = Not Applicable (1) The sample was not analyzed. Table 12. DAL SW SW04 100622 PFBS PFHS PFOS 3 M U M S ID Description GLP10-01-02-06-016 DAL SW SW 04 0 100622 G L P 10-0 1-02-06-017 DAL SW SW04 DB 100622 GLP10-01-02-06-018 GLP10-01 -02-06-019 DAL SW SW04 LS 100622 DAL SW SW04 MS 100622 GLP10-01-02-06-020 GLP10-01-02-06-017; LMS DAL SW SW04 HS 100622 DAL SW SW04 DB - 200ppb LMS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 14.1 NA 13.3 NA NA <1) NA (1) NA (1) N A <1) NA <1) NA (1) 230 106 13.7 ng/mL 5.8% Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery 87.3 85.6 N A (1) N A (1) N A (1) 320 NA NA N A <1) NA (1) NA (1) 113 190 194 NA (1) NA (1) N A (1) 413 NA NA NA (1) N A (1) N A (1) 108 86.5 ng/mL 2.0% 192 ng/mL 2.2% NA = Not Applicable (1) The sample was not analyzed. Page 23 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Table 13. DAL SW SW05 100622 PFBS PFHS PFOS 3 M L IM S ID Description G L P 10-01-02-06-011 DAL SW SW 05 0 100622 G L P 10-0 1-02-06-012 DAL SW SW05 DB 100622 G L P 10-0 1-02-06-013 G L P 10-0 1-02-06-014 DAL SW SW05 LS 100622 DAL SW SW05 MS 100622 GLP10-01-02-06-015 DAL SW SW05 HS 100622 GLP 10-01 -02-06-012; LMS DAL SW SW05 DB - 200ppb LMS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 2 1 .1 20.7 NA NA N A (1) N A <1) N A (1) N A (1) N A (1) N A (1) 247 1 1 1 20.9 ng/mL 1.9% Concentration (ng/mL) %Recovery 104 NA 100 NA (1) NA N A <1) N A (1) N A <1) N A (1) N A (1) 327 109 102 ng/mL 3.9% Concentration (ng/mL) %Recovery 399 385 N A (1> N A (1) N A (1! 615 NA NA N A <1) N A <1) N A (1) 109 392 ng/mL 3.6% NA = Not Applicable (1) The sample was not analyzed. Table 14. DAL SW SW06 100622 PFBS PFHS PFOS 3M U M S ID Description Concentration (ng/mL) %Recovery GLP10-01-02-06-006 DAL SW SW 06 0 100622 17.8 NA GLP10-01-02-06-007 DAL SW SW06 DB 100622 17.0 NA GLP10-01-02-06-008 D A L S W S W 0 6 L S 100622 NA (1) N A <1) GLP10-01 -02-06-009 DAL SW SW06 MS 100622 GLP10-01-02-06-010 DAL SW SW06 HS 100622 NA (1) 131 N A <1) 111 Average Concentration (ng/mL) %RPD 17.4 ng/mL 4.6%, Concentration (ng/mL) %Recovery 77.8 77.2 N A <1> NA <1> 190 NA NA N A <1) N A (1) 109 77.5 ng/mL 0.77% Concentration (ng/mL) %Recovery 229 NA 227 NA N A (1) N A (1) 325 N A (1> NA (1> 95.3 228 ng/mL 1.1% NA = Not Applicable (1) The sample was not analyzed. Page 24 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 15. DAL SW SW07 100622 PFBS PFHSf1> PFOS 3M UNIS ID Description Concentration (ng/mL) %Recovery GLP10-01-02-06-001 DAL S W SW 06 0 100622 10.8 NA GLP10-01 -02-06-002 DAL SW SW06 DB 100622 10.8 NA GLP10-01 -02-06-003 DAL SW SW06 LS 100622 N A (1) N A (1) GLP10-01-02-06-004 DAL SW SW06 MS 100622 N A (1> N A (1) GLP10-01 -02-06-005 DAL SW SW06 HS 100622 129 116 Average Concentration (ng/mL) %RPD 10.8 ng/mL 0.0% Concentration (ng/mL) %Recovery 47.6 NA 48.1 NA N A (1) N A (1) N A (1) 174 N A (1) 122 47.9 ng/mL 1.0% Concentration (ng/mL) %Recovery 128 NA 131 N A (1) NA N A <1) N A (1) 222 NA (1) 90.8 129 ng/mL 2.2% NA = Not Applicable (1) The sample was not analyzed. Table 16. DAL SW SW08 100623 3M L IM S ID Description GLP 10-01 -02-06-045 DAL SW SW08 0 100623 GLP 10-01-02-06-046 GLP 10-01 -02-06-047 GLP10-01-02-06-048 GLP10-01 -02-06-049 DAL SW SW08 DB 100623 DAL SW SW08 LS 100623 DAL SW SW08 MS 100623 DAL SW SW08 HS 100623 GLP10-01 -02-06-046; LMS DAL SW SW08 DB - 200ppb LMS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration Concentration Concentration (ng/mL) %Recovety (ng/mL) %Recovery (ng/mL) YoRecovery 39.8 NA 169 NA 268 NA 41.5 NA 163 NA 263 NA N A (1) N A <1) N A (1) N A (1) N A (1) N A (1) NA <1) NA (1) N A <1) NA (1) NA (1) N A (1) N A <1) 264 N A (1> 109 N A <1) 392 NA (1) 110 NA (1) 504 N A (1) 117 4 0.7ng/mL 4.2% 166 ng/mL 3.6% 266 ng/mL 1.9% NA= Not Applicable (1) The sample was not analyzed. Page 25 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 17. DAL SW SW09 100623 PFBS PFHS PFOS 3M UNIS ID Description GLP10-01-02-06-050 DAL SW SW09 0 100623 G L P 10-01-02-06-051 DAL SW SW09 DB 100623 GLP10-01 -02-06-052 DAL SW SW09 LS 100623 GLP10-01 -02-06-053 DAL SW SW09 MS 100623 GLP10-01 -02-06-054 DAL SW SW09 HS 100623 GLP10-01-02-06-051 ; LMS DAL SW SW09 DB - 500ppb LMS Average Concentration (ng/mL) %RPD Concentration (ng/mL) XRecovery 275 282 N A (1) N A (1) N A (1) 808 NA NA N A <1) N A (1) N A <1> 104 279 ng/mL 2.5% Concentration (ng/mL) XRecovery 672 NA 614 NA N A <1) N A (1) N A <1) NA (1) N A <1) N A (1) 1200 108 643 ng/mL 9.0% Concentration (ng/mL) XRecovery 386 NA 378 N A (1) NA NA (1) N A (1) N A (1) NA (1) N A <1) 960 113 382 ng/mL 2.1% NA = Not Applicable (1) The sample was not analyzed. Table 18. DAL SW SW10 100623 PFBS PFHS PFOS 3M U M S ID Description GLP 10-01-02-06-060 G LP10-01-02-06-061 GLP10-01 -02-06-062 DAL SW SW 10 0 100623 D A LS W S W 10 DB 100623 D A LS W S W 10 LS 100623 G L P 10-01-02-06-063 GLP10-01-02-06-064 DAL SW SW10 MS 100623 D A LS W S W 10 HS 100623 GLP10-01-02-06-061; LMS DAL SW SW10 DB - 400ppb LMS Average Concentration (ng/mL) %RPD Concentration (ng/mL) XRecovery 23.0 22.0 NA NA N A (1> N A <1> NA (1) NA <1> N A (1) N A <1) 420 97.4 22.5 ng/mL 4.4% Concentration (ng/mL) XRecovery 236 230 N A <1) N A (1) N A <1) 661 NA NA NA (1) N A (1) NA <1) 104 233 ng/mL 2.6% Concentration (ng/mL) XRecovery 387 NA 391 NA N A (1> N A (1) N A (1> N A <1) N A (1> 805 N A <1) 102 389 ng/mL 1.0% NA = Not Applicable (1) The sample was not analyzed. Page 26 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 19. DAL SW SW11 100623 PFBS PFHS PFOS 3M UM SID Description GLP10-01 -02-06-055 DAL SWSW11 0 100623 GLP10-01 -02-06-056 DALSW SW 11 DB 100623 GLP10-01 -02-06-057 DALSW SW 11 LS 100623 GLP10-01 -02-06-058 DALSW SW 11 MS 100623 GLP10-01 -02-06-059 DAL SW SW 11 HS 100623 GLP10-01 -02-06-056; LMS DALSW SW 11 DB -5 0 0 p p b L M S Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 103 NA 100 N A (1) NA NA <1) N A (1) N A <1) N A <1) N A (1) 641 106 102 ng/mL 3.0% Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery 1 1 2 0 NA 863 NA 1130 NA 836 NA N A (1) N A (1) N A (1) N A <1) N A (1) N A (1) N A (1) N A <1) N A (1) 1830 N A (1) NC N A (1) 1400 N A (1) 108 1130 ng/mL 0.89% p) 850 ng/mL 3.2% NA = Not Applicable NC = Not Calculated; Endogenous concentration greater than 2x spike level. (1) The sample was not analyzed. (2) Sampling location did not have an appropriate field matrix spike level. Page 27 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 20. DAL SW SW12 100623 PFBS PFHS PFOS 3MUM SID Description Concentration (ng/mL) %Recovery GLP10-01 -02-06-040 DAL SW SW 12 0 100623 0.773 NA GLP10-01-02-06-041 DAL SW SW 12 DB 100623 0.755 NA GLP10-01-02-06-042 DAL SW SW12 LS 100623 N A <1) N A (1) GLP10-01 -02-06-043 D A L S W S W 1 2 M S 100623 12.4 114 GLP10-01-02-06-044 D ALSW SW 12 HS 100623 114 111 Average Concentration (ng/mL) %RPD 0.764 ng/mL 2.4% Concentration (ng/mL) %Recovery 3.69 NA 3,67 NA N A (1) 15.3 113 N A (1) 113 106 3.68 ng/mL 0.54% Concentration (ng/mL) %Recovery 103 NA 105 N A (1) NA N A <1) 118 NC 168 63.5 (2) 104 ng/mL 2.0% NA = Not Applicable NC = Not Calculated; Endogenous concentration greater than 2x spike level. (1) The sample was not analyzed. (2) Field matrix spike did not meet method acceptance criteria o f 100% 30%. Table 21. DAL GW GP01 100709 PFBS PFHS PFOS 3 M L IM S ID Description Concentration (ng/mL) %Recovery GLP10-01-02-06-070 G LP1 0 - 0 1 -02-06-071 GLP10-01-02-06-072 GLP 10-01 -02-06-073 G L P 10-01-02-06-074 DAL GWGP01 0 1007009 DALGW GP01 DB 100709 DALG W GP01 LS 100709 DAL GWGP01 MS 100709 DALG W GP01 HS 100709 5.01 5.02 6.60 17.1 123 NA NA NC 118 116 Average Concentration (ng/mL) %RPD 5.02 ng/mL 0.20% Concentration (ng/mL) %Recovery 7.49 NA 7.22 NA 9.33 NC 19.5 118 121 110 7.36 ng/mL 3.7% Concentration (ng/mL) %Recovery 26.9 NA 25.5 NA (1) NA N A (1) NA (1) 115 N A <1) 87.3 26.2 ng/mL 5.3% NA= Not Applicable (1) The sample was not analyzed. Page 28 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 22. DAL GW GP02 100709 PFBS PFHS PFOS 3M UNIS ID Description Concentration (ng/mL) %Recovery GLP10-01-02-06-075 DAL GW GP02 0 1007009 19.7 NA GLP10-01-02-06-076 GLP10-01 -02-06-077 GLP10-01-02-06-078 DAL GW GP02 DB 100709 D A LG W G P 02LS 100709 DAL GW G P02 MS 100709 22.4 N A <1) N A (1) NA N A (1) N A <1) GLP10-01-02-06-079 DAL GW GP02 HS 100709 Average Concentration (ng/mL) %RPD 134 . 1 1 1 21.1 ng/mL 13% Concentration (ng/mL) %Recovery 10.4 NA 11.9 NA N A (1) N A (1) N A (1) NA 0) 127 1 1 2 11.2 ng/mL 13% Concentration (ng/mL) %Recovery 15.7 19.3 N A (1) N A (1) 87.6 NA NA N A (1) N A (1) 68.7 (2) 17.5 ng/mL 20% N A= Not Applicable (1) The sample was not analyzed. (2) Field matrix spike did not meet method acceptance criteria of 100% 30%. Table 23. DAL GW GP03 100709 PFBS PFHS PFOS 3M UNIS ID Description Concentration (ng/mL) %Recovery GLP10-01-02-06-080 DAL GW GP03 0 1007009 GLP10-01-02-06-081 DAL GW GP03 DB 100709 6 6.2 66.5 NA NA GLP10-01-02-06-082 DAL GW GP03 LS 100709 N A <1) N A <1> GLP10-01-02-06-083 DAL GW GP03 MS 100709 GLP10-01 -02-06-084 DAL G W G P03 HS 100709 N A <1) 180 N A <1) 111 Average Concentration (ng/mL) %RPD 66.4 ng/mL 0.45% Concentration (ng/mL) %Recovery 413 412 N A <1) N A <1> 571 NA NA N A (1) N A <1) NC 413 ng/mL 0.24% Concentration (ng/mL) %Recovery 341 NA 405 N A (1) NA N A <1) N A (1) N A <1) 678 NC 373 ng/mL 1 7 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) The sample was not analyzed. (2) Sampling location did not have an appropriate field matrix spike level for PFFIS or PFOS. Page 29 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 24. DAL GW GP04 100709 PFBS PFHS PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery GLP10-01 -02-06-085 GLP10-01-02-06-086 GLP10-01-02-06-087 GLP10-01-02-06-088 GLP10-01 -02-06-089 DAL GW GP04 0 1007009 DAL GW GP04 DB 100709 DAL G W G P 0 4 L S 100709 DAL GW GP04 MS 100709 DAL GW GP04 HS 100709 19.1 19.1 N A (1) N A (1) 136 NA NA N A (1) N A (1> 115 Average Concentration (ng/mL) %RPD 19.1 ng/mL 0.0% Concentration (ng/mL) %Recovery 89.5 NA 82.1 NA N A (1) N A <1) N A <1) 232 N A <1) 142 <2> 85.8 ng/mL 8 .6 % Concentration (ng/mL) VoRecovery 175 NA 130 NA NA <1> N A (1) N A <1> N A (1> 296 141 <2> 152 ng/mL 30% m N A= Not Applicable (1) The sample was not analyzed. (2) Field matrix spike did not meet method acceptance criteria o f 100% 30%. (3) The analytical uncertainty has been adjusted for field matrix spike recovery to 100% 42% for PFHS and 100% 41 % for PFOS. (4) The sample/sample duplicate RPD did not meet method acceptance criteria of <20%. Page 30 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 25. DAL GW GP05 100709 PFBS PFHS PFOS 3 M L IM S ID Description Concentration (ng/mL) %Recovery GLP10-01 -02-06-090 DAL GW GP05 0 1007009 30.0 NA GLP10-01-02-06-091 DAL G W G P 05D B 100709 30.0 NA GLP10-01-02-06-092 DAL GW GP05 LS 100709 GLP10-01 -02-06-093 DAL G W G P 05M S 100709 N A (1) N A (1) NA (1) NA (1) GLP10-01 -02-06-094 DAL GW G P05 HS 100709 141 109 Average Concentration (ng/mL) %RPD 30.0 ng/mL 0.0% Concentration (ng/mL) %Recovery 162 NA 153 NA NA (1) NA (1) N A (1) N A (1) 280 119 158 ng/mL 5.7% Concentration (ng/mL) %Recovery 416 NA 347 N A (1) NA N A (1) N A (1) N A (1) 515 NC 382 ng/mL 18% m N A = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) The sample was not analyzed. (2) Sampling location did not have an appropriate field matrix spike level for PFOS. Table 26, DAL GW GP07 100709 PFBS PFHS PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery GLP10-01 -02-06-095 DAL GW GP07 0 1007009 20.3 NA GLP10-01-02-06-096 G L P 10-01-02-06-097 DAL GW GP07 DB 100709 DAL GW GP07 LS 100709 2 1 .1 N A <1> NA N A (1) GLP10-01-02-06-098 DALG W G P07 MS 100709 GLP10-01-02-06-099 DAL GW GP07 HS 100709 GLP10-01 -02-06-095 LMS DAL G W G P07 0; 1500ppb LMS NA <1> 137 NA (1) NA (1) 114 N A (1) Average Concentration (ng/mL) %RPD 20.7 ng/mL 3.9% Concentration (ng/mL) %Recovery 173 NA 168 N A (1) N A (1) NA N A (1) N A (1) 298 N A <1> 124 NA (1) 171 ng/mL 2.9% Concentration (ng/mL) %Recovery 1740 NA 1820 N A (1) NA N A (1) N A (1) N A (1) 3660 N A (1) NA (1) 123 1780 ng/mL 4.5% NA = Not Applicable (1) The sample was not analyzed. Page 31 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 27. DAL GW GP08 100709 PFBS PFHS PFOS 3M UNIS ID Description Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery G L P 10-0 1-02-06-100 DAL GW GP08 0 1007009 GLP10-01-02-06-101 D A LG W G P 08 DB 100709 GLP10-01-02-06-102 DAL G W G P08 LS 100709 GLP10-01 -02-06-103 DAL G W G P08M S 100709 GLP10-01 -02-06-104 DAL GW GP08 HS 100709 GLP10-01 -02-06-100 LMS DAL G W G P08 0; 1500ppb LMS 6.39 6.32 N A (1) N A (1) 118 N A (1) NA NA N A <1) N A <1) 109 N A <1) 67.4 72.9 N A (1) N A (1) 173 N A (1) NA NA N A <1) N A (1) 99.9 N A (1) 1380 1450 N A (1) N A <1) N A (1) 3210 NA NA NA (1) N A (1> NA <1) 117 Average Concentration (ng/mL) %RPD 6.36 ng/mL 1.1% 70.2 ng/mL 7.8% 1420 ng/mL 4.9% NA = Not Applicable (1) The sample was not analyzed. Table 28. DAL GW GP09 100709 3NI UNIS ID Description GLP10-01-02-06-105 DAL GWGP09 0 1007009 GLP10-01-02-06-106 DAL GW G P09 DB 100709 GLP10-01 -02-06-107 DAL GW GP09 LS 100709 GLP 10-01 -02-06-108 DAL G W G P 09M S 100709 GLP10-01 -02-06-109 DAL GW GP09 HS 100709 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 20.9 20.5 N A <1) N A <1) 128 NA NA NA (1) N A <1) 105 20.7 ng/mL 1.9% Concentration (ng/mL) %Recovery 33.7 38.3 NA NA N A (1) N A <1) 147 NA <1) NA (1) 108 36.0 ng/mL 13% Concentration (ng/mL) %Recovery 79.9 NA 111 NA N A (1) N A <1) N A <1) NA <1) 188 90.6 95.5 ng/mL 33% TM NA = Not Applicable (1) The sample was not analyzed. (2) The sample/sample duplicate RPD did not meet method acceptance criteria of <20%. Page 32 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 29. DAL GW GP10 100709 3MUM SID Description G L P 10-01-02-06-1 10 DAL GW GP10 0 1007009 GLP10-01-02-06-111 D A LG W G P 10 DB 100709 GLP10-01-02-06-112 D A LG W G P 10LS 100709 GLP10-01-02-06-113 DAL GW GP10 MS 100709 GLP10-01-02-06-114 DAL GW GP10 HS 100709 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 441 NA 452 NA NA <1) NA <1) N A (1) N A (1) 541 NC 447 ng/mL 2.5% Concentration (ng/mL) %Recovery 427 NA 413 NA N A <1) NA <1) N A (1) N A <1) 532 NC 4 2 0 ng/mL 3.3% Concentration (ng/mL) %Recovery 146 NA 107 NA N A (1) NA (1) N A <1> 200 N A <1) 72.1 127ng/mL 3 1 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) The sample was not analyzed. (2) Sampling location did not have an appropriate field matrix spike level for PFS or PFHS. (3) The sample/sample duplicate RPD did not meet method acceptance criteria of <20%. Table 30. DAL GW GP11 100708 PFBS PFHS PFOS 3M U M S ID Description Concentration (ng/mL) %Recovery GLP10-01-02-06-115 GLP10-01 -02-06-116 DAL GWGP11 0 1007008 DALGW GP11 DB 100708 65.9 68.0 NA NA GLP10-01-02-06-117 GLP10-01-02-06-118 GLP10-01-02-06-119 D ALG W G P11 LS 100708 DALGW GP11 MS 100708 D ALG W G P11 HS 100708 N A <1> N A <1> 181 N A <1) N A (1) 112 Average Concentration (ng/mL) %RPD 67.0 ng/mL 3.1% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) The sample was not analyzed. (2) Sampling location did not have an appropriate field matrix spike level for PFS or PFHS. Concentration (ng/mL) %Recovery 327 NA 333 NA N A (1) NA <1) N A (1) N A (1) 486 NC 330 ng/mL 1 .8 % Concentration (ng/mL) %Recovery 640 NA 680 N A (1) NA NA (1) N A (1) NA (1) 1076 NC 660 ng/mL 6 .1 % Page 33 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 31. DAL GW GP12 100708 3 M L IM S ID Description GLP10-01-02-06-120 GLP10-01-02-06-121 DAL GW GP12 0 1007008 DAL GW G P12 DB 100708 GLP10-01-02-06-122 D A LG W G P 12 LS 100708 GLP 10-01-02-06-123 DAL GW GP12 MS 100708 GLP10-01-02-06-124 DAL GW G P12 HS 100708 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 1.84 NA 3.33 NA 3.92 NC 14.4 116 117 112 2.59 ng/mL 58% p> Concentration (ng/mL) %Recovery 8.78 NA 13.7 NA 13.8 NC 24.4 126 128 111 11.2 ng/mL 44%TM Concentration (ng/mL) %Recovery 32.4 NA 65.1 NA N A (1) N A <1) N A <1) N A (1) 148 96.9 48.8 ng/mL 67% TM NA = Not Applicable (1) The sample was not analyzed. (2) The sample/sample duplicate RPD did not meet method acceptance criteria of 20%. Table 32. DAL GW 216R 100716 3M L IM S ID Description GLP10-01-02-06-130 GLP10-01-02-06-131 GLP10-01 -02-06-132 DAL GW 216R 0 1007016 DAL GW 216R DB 100716 DAL G W 216R LS 100716 GLP10-01-02-06-133 GLP10-01 -02-06-134 DAL GW 216R MS 100716 DAL G W 216R HS 100716 Average Concentration (ng/mL) %RPD NA = Not Applicable (1) The sample was not analyzed. PFBS PFHS PFOS Concentration (ng/mL) %Recovery 10.5 10.7 N A <1> N A <1) 118 NA NA N A (1> NA <1) 105 10.6 ng/mL 1.9% Concentration (ng/mL) YoRecovery 30.9 30.0 N A (1) NA NA N A (1) NA <1) 141 N A <1) 107 30.5 ng/mL 3.0% Concentration (ng/mL) YoRecovery 114 NA 125 NA (1) NA N A (1> NA (1) N A (1) 192 71.6 119 ng/mL 9.2% Page 34 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 33. Trip Blank 3M UNIS ID GLP10-01-02-06-026 GLP10-01-02-06-027 GLP10-01-02-06-028 GLP10-01-02-06-029 GLP10-01-02-06-066 GLP10-01-02-06-067 GLP10-01-02-06-068 GLP1001-02-06-069 GLP10-01-02-06-125 GLP10-01-02-06-126 GLP10-01-02-06-127 GLP10-01-02-06-128 ( NA = Not Applicable Description DAL SW TRIP1 0100622 DAL SW TRIP1 LS 100622 DALSW TRIP1 MS 100622 DAL SW TRIP1 HS 100622 DALGW TRIP1 0 100708 DALGW TRIP1 LS 100708 DALGW TRIP1 MS 100708 DALGW TRIP1 HS 100708 DAL GW TRIP2 0100716 DAL GW TRIP2 LS 100716 DAL GW TRIP2 MS 100716 DAL GW TRIP2 HS 100716 PFBS PFHS PFOS Concentration (ng/mL) <0.0255 1.21 11.4 120 <0.102 1.21 11.9 121 <0.102 1.16 11.4 112 %Recovery NA 119 112 118 NA 119 117 119 NA 114 112 110 Concentration (ng/mL) <0.103 1.19 11.6 119 <0.258 1.15 11.6 119 <0.258 1.12 11.7 115 YoRecovery NA 116 113 116 NA 112 113 116 NA 109 114 112 Concentration (ng/mL) <0.255 1.22 10.9 101 <0.255 1.13 10.6 102 <0.255 1.22 10.9 102 YoRecovery NA 120 107 99.0 NA 111 104 100 NA 120 107 100 Page 35 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Table 34. Rinseate Blanks 3MUM SID GLP10-01-01-06-065 GLP10-01-01-06-129 GLP10-01-01-03-009 GLP10-01-01-03-015 GLP10-01-01-03-021 GLP10-01-01-05-008 GLP10-01-01-05-020 GLP10-01-01-05-053 GLP10-01-01-05-086 GLP10-01-01-05-100 GLP10-01-01-05-110 GLP10-01-01-08-010 NA = Not Applicable Description DAL SW SW10 RB 100623 DALG W 216R RB 100716 D AL-SD -W ESB4-R B-0000 D AL-SD -W ESC 4-R B-0000 DAL-SS-WEU01 -RB-0000 DAL SD SD03 RB 100625 DAL SD SD08 RB 100625 DAL SS SS06 RB 100707 DAL SS GP06 RB 100709 DAL SS GP09 RB 100708 DALSSG P11 RB 100708 DAL-SS-OSS08-RB-0010 PFBS PFHS PFOS Concentration (ng/mL) <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 <0.0255 %Recovery NA NA NA NA NA NA NA NA NA NA NA NA Concentration (ng/mL) <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 %Recovery NA NA NA NA NA NA NA NA NA NA NA NA Concentration (ng/mL) <0.255 <0.255 0.260 <0.255 <0.255 <0.255 <0.255 <0.255 <0.255 <0.255 <0.255 <0.255 %Recovery NA NA NA NA NA NA NA NA NA NA NA NA Page 36 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 10 Conclusion 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. 11 Data/Sample Retention 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 06 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 37 of 67 13 Signatures GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Cleston Lange, Ph.D., 3M Principal Analytical Investigator Date 2 ? 0 0 /ctyo William K Reagen, Ph.D., 3M Environmental Laboratory Department Manager Date Page 38 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/Juiy 2010 Analytical Protocol: GLP10-01-02 Amendment 06 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. 06 Amendment Date: June 16, 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 Sampling Event Avenue A Investigation - Surface W ater and Groundwater Page 1 of 6 Page 39 of 67 G LP10-01-02; Interim Report 06 Analysis o f PFBS, PFHS, and PFOS In W ater Sam ples from Decatur, AL J u n e /J u lvy20 1 0 Analytical Protocol: GLP10-01-02 , Amendment 07 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: Section 9.2.1 : A stable isotope-labeled surrogate [(1,2,3,4-13C4)-PFOS] will also be added at a fixed level to each sample, LMS, LCS, procedural blank, and at variable known concentrations in calibration standards, and quantified to evaluate surrogate recoveries. A stable isotope-labeled internal standard, [(1,2,3,4,5,6,7,8-13Ce}-PFOS] will be added at a fixed concentration to each sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation o f PFOS and the surrogate. A stable isotope-labeled internal standard, [(180 2)-PFHS] will be added at a fixed concentration to each sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation of PFHS. A stable isotope-labeled internal standard, [(180 2)-PFBS] will be added at a fixed concentration to each sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation o f PFBS. A mend to read: A stable isotope-labeled surrogate [(1,2,3,4-13C4)-PFOS] may also be added at a fixed level to each sample, LMS, LCS, procedural blank, and at variable known concentrations In calibration standards, and quantified to evaluate surrogate recoveries. A stable isotope-labeled internal standard, [(1,2,3,4,5,6,7,8-53C8)-PFOS] may be added at a fixed concentration to each sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation o f PFOS and the surrogate. A stable isotope-labeled internal standard, [(180 2)-PFHS] may be added at a fixed concentration to each sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation o f PFHS A stable isotope-labeled internal standard, [(1802)-PFBS] may be added at a fixed concentration to each sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation of PFBS. The use of internal standards and surrogate are only appropriate for those sampling locations with PFBA, PFHS, and PFOS concentrations in the low ppb range. Prior to each sampling event, if previously obtained PFBS, PFHS, and PFOS data is available fer tile sampling points o f interest, the date will be reviewed to determine if the use o f internal standards and surrogate is appropriate for the current sampling event. Page 2 of 9 Page 40 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/Juiy 201 o Analytical Protocol: GLP10-01-02 Amendment 06 Amendment Approval Page 3 of 6 Page 41 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/Julv 2010 Analytical Protocol: GLP10-01-02 Amendment 06 Environmental Health & Safety Operations, Environmental Laboratory General P roject O utline To: F rom : cc: Date: S ubject: Gary Hohenstein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab 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 June 16,2010 Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sedim ent for the 3M Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 06 - Avenue A Investigation 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 aahohenstein mmm.com 3M Environmental Laboratory Management William K. Reagen 3M EHS Opns, Environmental Laboratory 26G-5N-17 651 733-9739 wkreaaen<3>mmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cclanaeifflmmm.com Sampling Coordinator Timothy Frinak Weston Solutions Timothv.frinakfwestonsolutions.com Phone: (334)-332-9123 GLP10-01-02-06 Dept #530711, Project #0022674449 Sampling scheduled for the week of June 21, 2010 A ll verbal and written correspondence will be directed to Gary Hohenstein. Page 4 of 6 Page 42 of 67 G LP10-01-02; Interim Report 06 A nalysis o f PFBS, PFHS, and PFOS in W ater Sam ples from Decatur, AL June/Julv 2010 Analytical Protocol: GLP10-01-02 Amendment 06 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environm ental Lab) w ill receive and analyze surface water and groundwater sam ples collected from twenty-five sampling locations for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) as part o f the Avenue A Investigation. 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 June 21,2010. The 3M Environm ental Laboratory w ill prepare the sample bottles w ith 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 subm itted to Gary Hohenstein and Jai Kesari upon com pletion under interim report GLP10-01-0206. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of June 21, 2010. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Friday, June 18,2010. Sample bottles should be stored refrigerated on-site until sample collection, Martin Smith \ W eston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 4 Test Parameters The targeted limit of quantitation will be 0.025 ng/m L (ppb) for PFBS, PFHS, and PFOS. A total of twenty-five 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 mL. Three sets of trip blanks consisting o f reagent-grade water, a low-level 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 will be prepared at 1 hg/mL, the mid field matrix spike at 10 ng/mL, and the high field matrix spike at 100 ng/mL. Five additional bottles will be prepared to be used fo r tee preparation o f the equipment rinseate blanks. A total of 142 sample bottles will be prepared. Page 5 of 6 Page 43 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Analytical Protocol: GLP10-01-02 Amendment 06 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "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 of 10030%. Field matrix spikes not yielding recoveries within 10030% will 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 of 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; however, specific quality control Samples analyzed with tee 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. Trip blank and trip blank spikes will be reported for the sampling event as will any equipment/rinseate 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 of sample extraction will be used to determine the method detection limit. For those sampling locations where the field matrix spike level was not appropriate, due to higher than expected analyte concentrations, a laboratory matrix spike may be prepared and will be included in the final report. Page 6 of 6 Page 44 of 67 Scan API4000 V1660305 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Page 45 of 67 Stan API4000 V1660305 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 s100804a.rdb (PFHS): "Quadratic" Regression ("1 /x " weighting): y = -1.49e+003 xA2 + 3.98e+005 x + 2.74e+004 (r = 0.9998) Area, counts 2.6e7 2.5e72.4e7 2.3e72.2e7 2.1e72.0e71.9e71.8e7 1.7e71.6e7 1.5e71.4e71.3e71.2e71.1e71.0e79.0e68.0e6 7.0e6 6.0e6 5.0e64.0e63.0e6 2.0e61.0e6- 0.0 / / / 0 5 To 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 Concentration, ng/mL *Data work-up performed by STW Printing Time: 1:16:22 PM Page 1 of 1 Printing Date: Friday, October 22, 2010 Page 46 of 67 Stan API4000 V1660305 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Page 47 of 67 ***Stan API4000 V1660305 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 *Data work-up performed by STW Page 1 of 4 Printing Time: 1:15:16 PM Printing Date: Friday, October 22, 2010 Page 48 of 67 Scan API4000 V1660305 Page 2 of 4 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Page 49 of 67 ***stan API4000 V166030S GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Page 50 of 67 *Stan API4000 V1660305 Page 4 of 4 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Printing Date: Friday, October 22, 2010 Page 51 o f 67 Stan API4000 V1660305 Page 1 of 3 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Page 52 of 67 Stan API4000 V1660305 Page 2 of 3 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Page 53 of 67 Stan API4000 V1660305 *Data work-up performed by STW Page 3 of 3 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Printing Time: 1:18:15 PM Printing Date: Friday, October 22, 2010 Stan API4000 V1660305 *Data work-up performed by STW Page 1 of 1 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Printing Date: Friday, October 22, 2010 Page 55 of 67 DocGmrti{02Sitt&eBrt'o6f current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 3M Environm ental Laboratory Method Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: Q y Approved By: ...*g W illiam K, Reagen, Laboratory Manager Date ETS-8-044.0 Page 1 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 56 of 67 DocQERaKtn8ai/ttto a^flloef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 1 Scope and Application This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (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. Water 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 Water 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 57 of 67 DocacRfiirtifei^ijitteiKcparipef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 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 Water by LC/MS/MS; Direct Injection Analysis Page 58 of 67 DocGra0Hbi!fit&i 85$lpef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 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(s) 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 familiar 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 Water by LC/MS/MS; Direct Injection Analysis Page 59 of 67 DocGraFtfiratjit&i a^aaloef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 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 C18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Time (min) 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 (mL/min) 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 information 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 Water by LC/MS/MS; Direct Injection Analysis Page 60 of 67 Docomsrtiwaijftte gpsloef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: Analyte Transition Monitored PFBA 213 -> 169 PFPeA 263->219 PFHA 313 --> 269 and 313 -> 119 PFHpA 363 -> 319, 363 -> 169 and 363 -> 119 PFOA 413 -> 369, 413 -> 219 and 413 - 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 219 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 Multiple transitions for monitoring the analytes is an option, as summing multiple 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 time 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 Water - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate -A .C .S . Reagent Grade 7.2 Standards Perfluorobutanoic Acid (PFBA - C4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (P F H A -C 6 acid); Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M Perfluorononanoic Acid (P F N A -C 9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (P F D A -C 10 acid); Oakwood Products, Inc Perfluoroundecanoic Acid (PFUnA-C11 acid); Oakwood Products, Inc Perfluorododecanoic Acid (P FD oA -C 12 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 Water by LC/MS/MS; Direct Injection Analysis Page 61 of 67 DocQCRfiGKtuTO^te B^s&doef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 The previous information 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/mL target analyte SSSs-- Weigh out 10 mg of analytical standard (corrected fo r percent salt and purity) and dilute to 100mL with methanol or other suitable solvent, in a 100mL 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. molecular weight of anion salt correction factor moclecular weight of salt PFOS (K +)salt correction factor = ------= 0.9275 538 10 mg C8Fi7S03'K+with purity 90% = 8.35mg CsF^SC^- (10 mg*0.90*0.9275=8.35 mg) 5 pg/mL (5000 ng/mL) mixed working standard-- Add 0.5mL each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/mL mixed working 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/mL mixed 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 Conditions-- 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 Analysis Page 62 of 67 DocGER*artiiroijttte s^ftrtpef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL. June/July 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. Concentration o f WS, ng/mL 125 125 125 125 250 250 250 250 5000 5000 5000 Volume o f WS, fd10 15 20 30 20 50 100 200 25 50 100 Final Volume of Calibration Standard (mL o f ASTIVI Type 1 Water, or other suitable water) 50 50 50 50 50 50 50 50 50 50 50 Final Concentration o f Calibration Standard, ng/mL (ppb) in ASTM Type 1 Water, or other suitable water 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 Water by LC/MS/MS; Direct Injection Analysis Page 63 of 67 DocQmrtiraiyit&i8i s^solpef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 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 Water by LC/MS/MS; Direct Injection Analysis Page 64 of 67 DocQm?8D?dinsaijute8ffp.i5iQef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 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: Analyte found (ng/mL) = ---------------------------- -- x DF 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. Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) Recovery = X 100 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 Calibration 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 Performance: 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 Water by LC/MS/MS; Direct Injection Analysis Page 65 of 67 DocamartiiGB*i$ft&w>e^ealgef current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Demonstration o f Specificity: 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 of Changes ETS-8-044.0 Page 11 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 66 of 67 GLP10-01-02; Interim Report 06 Analysis of PFBS, PFHS, and PFOS in W ater Samples from Decatur, AL \ June/July 2010 I. Identification Study / Project No. Date(s) of Occurrence: GLP10-01-02-06 s100804a and m l 00910a Deviation type (Check one) iSOP Protocol Equipment Procedure 0 Method 0 GPO Other: II. Description (attach extra pages as needed) Method Requirements: 1. LCS average recovery of 100% 20%. 2. Sample/Sample Duplicate RPD 20%. 3. LMS/FMS recovery of 100% 30%. Document Number: ETS-8-044.0 Actual pracedure/process: (1) LCS average recovery for linear and branched PFOS was >120% (s100804a). LCS average recovery for the low set of LCS for PFHS, and the low and high set of linear and branched PFOS was outside acceptance criteria (m100910a). (2) The RPD for PFOS for sampling location GP04 was 30%, GP09 PFOS RPD was 33%, GP10 PFOS RPD was 31%, GP12 RPD for PFBS, PFHS, and PFOS was >50%. (3) The recovery of the high FMS sample for SW12 for PFOS was 63.5%. The recovery of the high FMS sample for GP02 for PFOS was 68.7%. The recovery of the high FMS sample for GP04 for PFOS was 141%. III. Actions Taken __________________ ______ (such as amendment issued, SOP revision, etc.)_________________________ Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1) The linear + branched PFOS LCS when quantitated against a calibration curve prepared from linear PFOS have been quantitating around 15-30% higher. By quantitating the linear and branched isomers of PFOS separately, against a linear PFOS curve, and summing the resulting concentrations, appears to help reduce the recovery of the linear + branched PFOS high LCS at 30ppb 8%. A slight increase was seen in the recovery of the low and mid linear + branched PFOS LCS, and an 18% decrease in the recovery of low set of linear PFOS LCS. The method analytical uncertainty was assigned based on the average recovery of the high set of linear + branched PFOS LCS (141%), since the sample on-column concentrations most closely matched the 30 ppb LCS. LCS average recoveries outside method acceptance criteria will be footnoted in the final report. 2) The RPD value for sampling locations with RPD values >20% will be footnoted in the data tables. 3) Since the method analytical uncertainty for PFOS is 100% 41%, no adjustment was made to the analytical uncertainty for PFOS on SW12, GP02, and GP04. Actions: Halting of Work Client Notification Work Recall 0 Other: Deviations will be noted in final report. P roject Lead/PA I A pproval: S u s a n W o lf J I 'X Withholding of Report Study Director (if GLP): i ^ Q T . c & S p onsor A pproval (for G u P p r io c o l deviations): NA Technical Reviewer (optional): NA Date: NA Date: NA Laboratory Departm ent M anager Approval: Date: -- ' " IV. Authorization to Resume Work Where halting of work occurred, resumption of work must first be approved by Laboratory Management Laboratory Departm ent M anager Approval: NA Date: NA Deviation N o ._____ 1_________ (assigned by Study Director or Team Leader at the end of study or project) Page 67 of 67