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GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 GLP10-01-02: Interim Report 07 - Analysis of PFBS. PFHS. and PFOS in Ground Water Samples Collected at the Former Sludge Incorporation Area (FSIA) located in Decatur. AL in June/Julv 2010 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisimha Kesari P.E., DEE W eston Solutions, Inc. 1400 W eston Way W est Chester, PA 19380 Phone: 610-701-3761 . . Author Susan W olf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP10-01-02-07 Total Number of Pages 68 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 Page 1 of 68 GLP10-01-02; Interim Report 07 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 36 Page 2 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 GLP Compliance Statement Report Title: Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Ground Water Samples Collected at the Former Sludge Incorporation Area (FSIA) at 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. Jaisimha Kesari, P.E., DEE, Study Director Date Page 3 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Quality A ssurance Statement Report Title: Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Ground Water Samples Collected at the Former Sludge Incorporation Area (FSIA) at 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 10/1,10/4, and 10/5/10 Phase Interim Report 07 Data and Report Date Reported to Testing Facility Management Study Director 10/ 11/10 10/ 11/10 Date Page 4 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Ta b le of Contents 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.......................................................................................................... 11 5 Reference Substances................................................................................................................. 12 6 Test System.................................................................................................................................. 13 7 Method Summary......................................................................................................................... 13 7.1 M ethods........................................................................................................................13 7.2 Sample Collection......................................................................................................... 13 7.3 Sample Preparation...................................................................................................... 13 7.4 Analysis.........................................................................................................................13 8 Analytical R esults......................................................................................................................... 14 8.1 Calibration..................................................................................................................... 14 8.2 System Suitability......................................................................................................... 15 8.3 Limit of Quantitation (LOQ)...........................................................................................15 8.4 Continuing Calibration...................................................................................................15 8.5 Blanks............................................................................................................................15 8.6 Lab Control Spikes (LC Ss)...........................................................................................16 8.7 Analytical Method Uncertainty...................................................................................... 18 8.9 Field Matrix Spikes (FMS)..............................................................................................19 9 Data Summary and Discussion.................................................................................................... 19 Page 5 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 10 Conclusion....................................................................................................................................35 11 Data/Sample Retention................................................ ;.............................................................35 12 Attachm ents..................................................................................................................................35 13 Signatures.....................................................................................................................................36 L ist of Tables Table 1. Summarized PFBS, PFHS, and PFOS Results (FSIA Groundwater, June/July 2010). 10 Table 2. Sample Description Key Code....................................................................................... 13 Table 3. Instrument Parameters...................................................................................................14 Table 4. Liquid Chromatography Conditions................................................................................14 Table 5. Mass Transitions.................................................................:......................................... 14 Table 6. Limit of Quantitation (LOQ)............................................................................................ 15 Table 7. Laboratory Control Spike Recovery.............................................................................. 17 Table 8. Analytical Uncertainty.................................................................................................... 19 Table 9. Field Matrix Spike Levels...............................................................................................19 Table 10. DAL 130R Q2 Y10 SF................................................................................................. 21 Table 11. DAL130L Q 2 Y 1 0 S F ................................................................................................. 22 Table 12. DAL 130S Q2 Y10 SF................................................................................................. 23 Table 13. DAL131RQ 2 Y 10S F................................................................................................. 23 Table 14. D AL131LQ 2 Y 1 0 S F ................................................................................. 24 Table 15. DAL 131S Q2 Y10 SF................................................................................................. 24 Table 16. DAL 132R Q2 Y10 SF................................................................................................. 25 Table 17. DAL 132L Q2 Y10 S F ................................................................................................. 25 Table 18. DAL 132S Q2 Y10 SF................................................................................................. 26 Table 19. DAL 133R Q2 Y10 SF................................................................................................. 26 Table 20. DAL 133L Q2 Y10 S F ................................................................................................. 27 Table 21. DAL 133S Q2 Y10 SF................................................................................................. 27 Page 6 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 22. DAL 134R Q2 Y10 SF..................................................................................................28 Table 23. DAL 134L Q2 Y10 S F ..................................................................................................28 Table 24. DAL 134S Q2 Y10 SF..................................................................................................29 Table 25. DAL135R Q2 Y 10S F ....................................................................... Table 26. DAL 135L Q2 Y10 S F ..................................................................................................30 Table 27. DAL 135S Q2 Y10 SF..................................................................................................30 Table 28. DAL 136L Q2 Y10 S F .................................................................................................. 31 Table 29. DAL136S Q2 Y 10S F .................................................................................................. 31 Table 30. DAL 137L Q2 Y10 S F ..................................................................................................32 Table 30. DAL 137S Q2 Y10 SF..................................................................................................32 Table 32. DAL 138S Q2 Y10 SF..................................................................................................33 Table 33. DAL 138L Q2 Y10 S F ..................................................................................................33 Table 34. Trip Blank..................................................................................................................... 34 Table 35. Rinseate Blanks........................................................................................................... 34 29 Page 7 of 68 GLP10-01-02; Interim Report 07 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@ w estonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106 Study Personnel W illiam K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clanae@mmm.com): phone (651)-733-9860 Susan Wolf, 3M Analyst Jonathan Steege; analyst Study Dates Study Initiation: March 8, 2010 Interim 07 Experimental Termination: September 17, 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 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 2 Summary The 3M Environmental Laboratory received ground water samples from wells located at the Former Sludge Incorporation Area (FSIA) in Decatur, AL, representing twenty-four different sampling locations. A total of one hundred twenty-four sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate groundwater samples from each sampling location. Samples also included at least two field matrix spike (FMS) samples for each location, one trip blank 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 ground water samples, trip blank and two equipment rinseate blanks were collected on June 30, July 1 and July 2,2010, and received from Weston personnel on July 6,2010. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project GLP-10-01 -02-07. Many of the ground water samples required dilution to attain PFBS, PFHS, and/or POFS concentrations within the range of the curve, in some instances up to 100-fold dilution were required. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The equipment rinseates and the trip blank were below the lower limit of quantitation (LLOQ), indicating adequate control of sample contamination during shipping and sample collections. The PFBS concentration results for all ground waters ranged over three orders of magnitude from 0.0463 ng/mL to 75.1 ng/mL. The PFHS concentration results for all ground waters ranged over three orders of magnitude from <0.103 ng/mL to 754 ng/mL. The PFOS concentration results for all ground waters ranged over four orders of magnitude from 0.427 ng/mL to 1720 ng/mL. Page 9 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 1. Summarized PFBS, PFHS, and PFOS Results (FSIA Groundwater, June/July 2010). Sampling Location DAL 130R Q2 Y10 SF 100701 PFBS Avg. Cone. (ng/mL) RPD 16.6 1.2% PFHS Avg. Cone. (ng/mL) RPD 119 0.0% PFOS Avg. Cone. (ng/mL) RPD 532 8.5% DAL130L Q2 Y10SF 100701 1.53 2.0% 13.0 2.0% 74.4 2.3% (1) DAL130S Q2Y10SF 100701 3.57 2.0% 12.1 16% 72.1 0.69% DAL 131RQ2 Y10SF 100701 75.1 0.53% 345 1.2% 1720 1.4% DAL131LQ2 Y10SF 100630 2.94 6.8% 19.3 3.6% 33.6 1.6% DAL 131S Q2 Y10 SF 100630 1.06 0.95% 5.49 1.5% 8.25 3.9% DAL 132RQ2Y10SF 100701 7.64 1.0% 36.0 1.9% 263 0.76% DAL132L Q2Y10SF 100701 10.0 5.2% 78.2 3.7% 240 2.1% (2) DAL 132S Q2 Y10 SF 100701 32.6 4.9% 211 0.0% 861 0.58% DAL 133R Q2 Y10 SF 100701 7.70 2.1% 45.6 1.1% 77.5 9.2% DAL 133L Q2 Y10 SF 100702 6.75 1.9% 39.4 0.76% 144 7.6% DAL 133S Q2 Y10 SF 100701 12.7 0.79% 77.1 4.2% 228 5.4% DAL 134R Q2 Y10 SF 100702 59.1 1.7% 441 2.3% 1180 2.3% DAL 134L Q2 Y10 SF 100702 12.8 0.78% 106 1.9% 491 2.7% (2) DAL 134S Q2Y10SF 100702 0.0938 13% 1.33 6.0% 12.6 7.2% DAL 135R Q2 Y10 SF 100702 83.0 0.48% 754 1.9% 1040 1.8% DAL 135L Q2 Y10 SF 100702 6.36 0.63% 37.9 8.4% 55.4 9.9% DAL 135S Q2 Y10 SF 100702 0.735 3.5% 5.88 5.4% 7.16 8.1% DAL 136L Q2 Y10 SF 100630 2.91 3.8% 11.7 2.6% 89.7 4.4% DAL 136S Q2 Y10 SF 100630 3.49 1.1% 19.3 1.0% 106 6.0% DAL 137L Q2 Y10 SF 100701 0.0847 16% <0.103 0.734 14% DAL137S Q2Y10SF 100701 0.119 7.6% <0.103 0.427 3.7%(1> DAL 138S Q2 Y10 SF 100630 5.72 3.3% 16.9 1.8% 216 0.42% DAL 138L Q2 Y10 SF 100630 0.0463 27% (3) <0.103 0.791 3.7% Trip Blank (Milli-QTM Water) <0.0306 <0.103 <0.102 Equipment Rinseate Blanks, 137L and 131R <0.0306 <0.103 <0.102 The analytical method uncertainties associated with the reported results are as follows: PFBS 100% 19%, PFHS 100% 20%, and PFOS 100% 37%. (1) The analytical uncertainty has been adjusted for PFOS based on FMS recovery for: DAL 130L to 100% 45% and DAL 137S to 100% 38%. See discussion in section 9 of the report. (2) Sampling location did not have an appropriate FMS spike level to sufficiently evaluate analyte recovery. (3) The RPD did not meet method acceptance criteria of 20%. Page 10 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 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 samples collected from various wells located at the Former Sludge incorporation Area (FSAI) in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on site groundwater conditions. 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. 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". Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, and for the trip blanks and aqueous soil-equipment rinseate samples. Tables 10-33 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 There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. Page 11 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 5 Reference Substances 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 C4FgS03 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 C8F1 7 S O 3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% PFHS (lin ear) Perfluorohexane sulfonate C e F 13SO 3 Sodium Salt Wellington 4/2/2013 Frozen LPFHXSAM08 TCR08-0018 Crystalline 98% PFOS (lin ea r + branched) Perfluorooctane sulfonate C 8F17SO 3 Potassium Salt CAS # 2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% Page 12 of 68 GLP10-01-02; Interim Report 07 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 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 3 4 String Descriptor DAL 131S Q2Y10 SFO Sampling Location Sampling Point Well Level Sampling Date Sample Type Example DAL = Decatur, AL Example: 131S R = Residum shallow water-bearing zone L = Bedrock water-bearing zone S = Epikarst middle water-bearing zone Q2Y10 - 2nd Quarter, 2010 0=primary sample 1=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 W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on July 6, 2010 Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with the sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. Samples that required dilution were prepared by dilutions of 1mL sample with 9 mLs of Milli Q water (dilution 1:10). Most sampling locations were diluted 1:100 by further diluting the 1:10 dilution with additional Milli Q water. 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below. Page 13 of 68 GLP10-01-02; Interim Report 07 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 Olile ETS-8-044.0 7/15/2010 Agilent 1100 Betasil C18 (2.1 mm X 100 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5u 2 or 10 uL Applied Biosystems API 4000 Turbo Spray Turbo Ion electrode Negative Analyst 1.4.2 ETS MaryAnn ETS-8-044.0 9/17/10 Agilent 1100 Betasil C18 (2.1 mm X 100 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5n 5 or 10 uL Applied Biosystems API 5000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Table 4. Liquid Chromatography Conditions. Step Number 0 1 2 3 4 5 Total Time (min) 0 1.0 14.5 15.5 16.5 20.0 Flow Rate (fdJmln) 300 300 300 300 300 300 Percent A (2 mM ammonium acetate) 90.0 90.0 10.0 10.0 90.0 90.0 PercentB (Methanol) 10.0 10.0 90.0 90.0 10.0 10.0 Table 5. Mass Transitions. Analyte PFBS PFHS PFOS Mass Transition Q1/Q3 299/80 299/99 399/80 399/99 399/130 499/80 499/99 499/130 Dwell time was 125 or 50 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram'' (TIC), which was used for quantitation. 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 Page 14 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Milli Q water. A total of fifteen spiked standards ranging from 0.025 ng/mL to 100 ng/mL (nominal) were prepared, however, the 9/17/10 analysis did not contain the two highest curve points. Low or high curve points may have been disabled to meet method 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. 7/15/10 Analysis for 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 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 PFO.S for both the 7/15/10 and 9/17/10 analysis. 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 for both the 7/15/10 and 9/17/10 analysis. 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 of Quantitation (LOQ). Analysis Date 7/15/10 9/17/10 Dilution 1 10 100 1 PFBS LOQ, ng/mL 0.0306 0.306 3.06 0.0255 PFHS LOQ, ng/mL 0.103 1.03 10.3 0.0258 PFOS LOQ, ng/mL 0.102 1.02 10.2 0.510 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% with the exception of the following: 7/15/10 Analysis; Twenty-one CCVs were analyzed during the course of the run with three CCVs not meeting method acceptance criteria with recoveries of 70.8%, 73.6%, and 73.3% for PFHS. Reported samples bracketed by these CCVs include: 132S, 134R, 135S, and 135L. 8.5 Blanks Two types of blanks were prepared and analyzed with the samples: method blanks and field/trip blanks. Method blank results were reviewed and used to evaluate method performance and to determine the LOQ for each analyte Page 15 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 8.6 Lab Control Spikes (LCSs) Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into 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, average of LCS at each level should be within 100% 20% with an RSD <20%Acceptance criteria was met for the PFBS, PFHS, and linear PFOS for LCS samples analyzed on 7/15/10. Acceptance criteria was not met for the low set of linear PFOS LCS analyzed on 9/17/10 with an average recovery of 191 %. The mid and high sets of linear PFOS LCS met method acceptance criteria, as did all three sets of LCS for PFBS and PFHS. The 9/17/10 analysis included a number of samples that contained PFOS concentrations greater than the calibration range. It is believed that the high recovery for the low set of LCS is due to analyte carry-over as the low set of LCS were analyzed immediately after these samples. As the reference materials used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of both linear and branched isomers, additional LCS samples of PFOS (linear + branched) were prepared at three concentrations to evaluate the potential for analytical bias. The LCS analyzed on 7/15/10 at the low and mid levels met method acceptance criteria, while the high level did not meet method acceptance criteria with an average recovery of 122%. The LCS analyzed on 9/17/10 at the mid and high levels met method acceptance criteria, while the low level did not meet method acceptance criteria with an average recovery of 125%. All PFOS (linear + branched) LCS were used in the determination of the analytical uncertainty. A method deviation is filed with the raw data for PFOS (linear and linear + branched) LCS that did not meet method acceptance criteria. The following calculations were used to generate data in Table 7 for laboratory control spikes. Calculated Concentration LCS Percent Recovery --------------------------------------- 100% Spike Concentration standard deviation LCS replicates LCS% RSD = 100% average LCS recovery Page 16 of 68 GLP10-01-02; Interim Report 07 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 7/15/10 PFBS Lab ID Spiked Calculated Spiked Concentration Concentration Concentration (ng/mL) (ng/mL) XoRecovery (ng/mL) LCS-100707-1 LCS-100707-2 LCS-100707-3 0.510 0.510 0.510 0.506 99.3 0.515 0.534 105 0.515 0.530 104 0.515 Average %RSD 103 3.0% LCS-100707-4 LCS-100707-5 LCS-100707-6 5.10 5.10 5.10 5.13 101 5.15 4.90 96.1 5.15 5.23 103 5.15 Average %RSD 100% 3.5% LCS-100707-7 30.6 28.4 92.7 30.9 LCS-100707-8 LCS-100707-9 30.6 30.6 27.9 91.0 30.9 28.6 93.6 30.9 Average %RSD 92.4% 1.4% PFHS Calculated Concentration (ng/mL) 0.463 0.455 0.480 90.4% 2.8% 5.64 5.59 5.73 110% 1.4% 30.7 29.9 30.4 98.1% 1.3% XoRecovery 89.8 88.3 93.2 110 108 111 . 99.3 96.7 98.3 ETS-8-044.0 Analyzed 7/15/10 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) XoRecovery LCS-100707-1 LCS-100707-2 LCS-100707-3 0.510 0.510 0.510 0.480 0.447 0.470 94.1 LCS-100707-10 87.6 LCS-100707-11 92.2 LCS-100707-12 0.500 0.500 0.500 0.493 0.431 0.419 98.6 86.2 83.8 Average %RSD 91.3% 3.6% Average %RSD 89.5% 8.9% LCS-100707-4 5.10 5.48 107 LCS-100707-13 5.00 5.84 117 LCS-100707-5 5.10 5.43 106 LCS-100707-14 5.00 5.67 113 LCS-100707-6 5.10 5.46 107 LCS-100707-15 5.00 5.83 117 Average %RSD 107% 0.46% Average %RSD 116% 1.7% LCS-100707-7 LCS-100707-8 LCS-100707-9 30.6 30.6 30.6 30.1 98.4 LCS-100707-16 30.0 30.6 100 LCS-100707-17 30.0 30.7 100 LCS-100707-18 30.0 37.8 126 36.0 120 36.3 121 Average %RSD 99.6% 1.1% Average %RSD 122% 2.6%'11 (1) The average recovery did not meet method acceptance criteria of 100% 20%. Page 17 of 68 GLP10-01-02; Interim Report 07 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 9/17/10 PFBS Lab ID Spiked Calculated Spiked Concentration Concentration Concentration (ng/mL) (ng/mL) XRecovery (ng/mL) LCS-100916-1 LCS-100916-2 LCS-100916-3 0.510 0.510 0.510 0.474 93.0 0.515 0.583 114 0.515 0.592 116 0.515 Average %RSD 108% 12% LCS-100916-4 LCS-100916-5 LCS-100916-6 5.10 5.10 5.10 5.07 99.4 5.15 5.98 117 5.15 6.14 120 5.15 Average %RSD 112% 9.9% LCS-100916-7 LCS-100916-8 LCS-100916-9 15.3 15.3 15.3 16.9 110 15.5 16.1 105 15.5 16.7 109 15.5 Average %RSD 108% 2.4% PFHS Calculated Concentration (ng/mL) 0.461 0.565 0.563 103% 11% 4.66 5.50 5.54 102% 9.7% 15.7 15.8 15.3 101% 1.7% %Recovery 89.5 110 109 90.5 107 108 101 102 98.6 ETS-8-044.0 Analyzed 9/17/10 PFOS (linear) PFOS (linear + branched) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) VoRecovery Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery LCS-100916-1 LCS-100916-2 LCS-100916-3 0.510 0.510 0.510 1.10 1.01 0.821 216 LCS-100916-10 0.500 197 LCS-100916-11 0.500 161 LCS-100916-12 0.500 0.678 0.669 0.527 136 134 105 Average %RSD 191% 1 5% 11,21 Average %RSD 125% 14% 111 LCS-100916-4 LCS-100916-5 LCS-100916-6 5.10 5.10 5.10 4.32 84.7 LCS-100916-13 5.00 4.93 96.8 LCS-100916-14 5.00 5.18 102 LCS-100916-15 5.00 4.87 97.4 4.97 99.4 4.84 96.8 Average %RSD 94.5% 9.4% Average %RSD 97.9% 1.4% LCS-100916-7 LCS-100916-8 LCS-100916-9 15.3 15.3 15.3 14.0 91.3 LCS-100916-16 15.0 14.7 96.1 LCS-100916-17 15.0 13.6 88.9 LCS-100916-18 15.0 14.9 99.5 15.2 102 15.0 100 Average %RSD 92.1% 4.0% Average %RSD 101% 1.3% (1) The average recovery did not meet method acceptance criteria of 100% 20%. (2) The high recovery is most likely due to carry over, which is likely due to samples analyzed prior to LCS samples which had PFOS concentrations exceeding the calibration range. 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 8. Page 18 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 8. Analytical Uncertainty. Analyte PFBS PFHS PFOS Standard Deviation 9.39 9.76 18.6 Method Uncertainty 100%19% 100%20% 100%37% 8.8 Field Matrix Spikes (FMS) Low, mid and high field matrix spikes (FMS) were collected at each sampling point (low and high FMS only at 131R, 134R, and 135R) 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. Table 9. Field Matrix Spike Levels. Sampling Location Spike Level PFBS, ng/mL PFHS, ng/mL PFOS, ng/mL Low 0.102 0.103 0.102 136R, 137R, 137s, 137L, 138L Mid 1.02 1.03 1.02 High 10.2 10.3 10.2 Low 1.02 1.03 1.02 130L, 131L, 132L, 133R, 134S, 134L, 136S<1) Mid High 10.2 10.3 10.2 102 103 102 130R, 130S, 131S, 132R, 132S, 133S, 133L, Low 10.2 10.3 10.2 135S, 135L<1), 136L, 138S (1), 138R Mid 102 103 102 High 1020 1030 1020 131R, 134R, 135R Low 102 103 102 High 1020 1030 1020 Low 1.02 1.03 1.02 Trip Blank Mid Mid-High 10.2 10.3 10.2 102 103 102 High 1020 1030 1020 (1) One of the spiked bottles in this sampling set was overfilled by more than 10%. The field matrix spike true value has been adjusted accordingly. FMS Recovery - ^ amP*e Concentration o f F M S - Average Concentration: Field Sample & Field Sample Dup.) t ^ Spike Concentraton 9 Data Summary and Discussion 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. Page 19 of 68 ,, GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 DAL 130L - The recovery of the high FMS sample for PFOS was 54.8%. The mid spike was not calculated since the detected concentration was 10x higher than the expected concentration. The analytical uncertainty has been adjusted for PFOS based on the recovery of the high FMS to 100% 45%. DAL 132L - The high FMS spike level at 102 ng/mL was not an appropriate spike level to sufficiently evaluate PFOS recovery. DAL 134L - The high FMS spike level at 102 ng/mL was not an appropriate spike level to sufficiently evaluate PFOS recovery. DAL 135L - The recovery of the mid FMS sample for PFOS was 68.2%. The high FMS sample did meet method acceptance criteria with a recovery of 91.1%. The mid spike was the most appropriate spike level as compared to the sample concentration, however, no adjustment will be made to the analytical uncertainty as the method uncertainty for PFOS is 100% 37%. DAL 1 3 6 L -T h e recovery of the mid FMS sample for PFOS was 65.6%. The high FMS sample did meet method acceptance criteria with a recovery of 79.4%. The mid spike was the most appropriate spike level as compared to the sample concentration, however, no adjustment will be made to the analytical uncertainty as the method uncertainty for PFOS is 100% 37%. DAL 137L - The recovery of the low FMS sample for PFHS was 149%. The mid and high FMS samples did meet method acceptance criteria with recoveries of 119% and 103%, respectively. The samples contain trace PFHS below the method LOQ of 0.103 ng/mL, which most likely accounts for the high recovery of the low FMS sample (spike level 0.103 ng/mL). Since the mid FMS met method acceptance criteria, and was an appropriate spike level as compared to the sample concentration, no adjustment will be made to the analytical uncertainty. DAL 137S - The recovery of the low FMS sample for PFHS was 186%. The mid and high FMS samples did meet method acceptance criteria with recoveries of 123% and 108%, respectively. The samples contain PFHS just below the method LOQ of 0.103 ng/mL, which most likely accounts for the high recovery of the low FMS sample (spike level 0.103 ng/mL). Since the mid FMS met method acceptance criteria, and was an appropriate spike level as compared to the sample concentration, no adjustment will be made to the analytical uncertainty. The recovery of the mid FMS sample for PFOS was 61.5%. The high FMS sample did meet method acceptance criteria with a recovery of 83.9%. Since the mid spike was the most appropriate spike level as compared to the sample concentration, the analytical uncertainty has been adjusted for PFOS to 100% 38%. DAL 138L - The recovery of the low FMS sample for PFHS was 203%. The mid and high FMS samples did meet method acceptance criteria with recoveries of 124% and 101%, respectively. The samples contain PFHS just below the method LOQ of 0.103 ng/mL, which most likely accounts for the high recovery of the low FMS sample (spike level 0.103 ng/mL). Since the mid FMS met method acceptance criteria, and was an appropriate spike level as compared to the sample concentration, no adjustment will be made to the analytical uncertainty. Page 20 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 10. DAL 130R Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-001 DAL130RQ2Y10 SF 0 GLP10-01-02-07-002 DAL 130R Q2 Y10 SF 1 GLP10-01-02-07-003 DAL130RQ2Y10 SF LS GLP10-01-02-07-004 DAL130RQ2Y10 SF MS GLP10-01-02-07-005 DAL130RQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) XRecovery 16.5 NA 16.7 NA 27.4 106 N A (1) NA (1) N A (1> N A (1) 16.6 ng/mL 1.2% Concentration (ng/mL) XRecovery 119 NA 119 NA 130 NC 218 96.1 979 83.5 119 ng/mL 0.0% Concentration (ng/mL) XRecovery 554 NA 509 NA 498 NC 598 NC 1350 79.9 532 ng/mL 8.5% NA = Not Applicable NC = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:100 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Page 21 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 11. DAL 130L Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-011 DAL 130LQ2Y10 SF 0 GLP10-01-02-07-012 DAL130LQ2Y10 SF 1 GLP10-01-02-07-013 DAL 130LQ2 Y10 SF LS GLP10-01-02-07-014 DAL130LQ2Y10 SF MS GLP10-01-02-07-015 DAL130LQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 1.51 NA 1.54 NA 2.61 106 463 NA<1) 130 126 1.53 ng/mL 2.0% Concentration (ng/mL) %Recovery 12.9 NA 13.1 NA 14.1 NC 432 NA(1) 134 117 13.0 ng/mL 1.5% Concentration (ng/mL) %Recovery 75.2 NA 73.5 NA 75.2 NC 476 NA(1) 130 54.8 (2) 74.4 ng/mL 2.3% m NA = Not Applicable NC = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. PFBS, PFHS, and PFOS were analyzed on 7/15/10 with a 1:10 dilution. (1) Suspect the sample bottle was prepared in correctly. The MS concentration detected is not consistent with the spike level (nominal concentration o f 10 ng/mL). (2) The field matrix spike did not meet method acceptance criteria of 100% 30%. (3) The analytical uncertainty for PFOS has been adjusted for FMS recovery to 100% 45%. Page 22 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 12. DAL 130S Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MLIMSID Description GLP10-01-02-07-006 DAL130SQ2Y10 SF 0 GLP10-01-02-07-007 DAL130SQ2Y10 SF 1 GLP10-01-02-07-008 DAL130SQ2Y10 SF LS GLP10-01-02-07-009 DAL130SQ2Y10 SF MS GLP10-01-02-07-010 DAL130SQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 3.53 NA 3.60 NA 14.0 102 N A (1) N A (1) NA (1) N A (1) 3.57 ng/mL 2.0% Concentration (ng/mL) %Recovery 11.1 NA 13.0 NA 22.9 105 113 98.0 924 88.5 12.1 ng/mL 16% Concentration (ng/mL) %Recovery 72.3 NA 71.8 NA 84.5 NC 152 78.2 937 84.8 72.1 ng/mL 0.69% NA = Not Applicable NC = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:100 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Table 13. DAL 131R Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-016 DAL131RQ2Y10 SF 0 GLP10-01-02-07-017 DAL 131RQ2Y10 SF 1 GLP10-01-02-07-018 DAL 131RQ2Y10 SF LS GLP10-01-02-07-019 DAL131RQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 74.9 NA 75.3 NA 179 102 N A (1> N A <1) 75.1 ng/mL 0.53% Concentration (ng/mL) %Recovery 343 NA 347 NA 447 NC 1160 79.1 345 ng/mL 1.2% Concentration (ng/mL) %Recovery 1710 NA 1730 NA 1820 NC 2430 69.8 1720 ng/mL 1.4% NA = Not Applicable NC = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1;100 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Page 23 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 14. DAL 131L Q2 Y10 SF (Sampled 6/30/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-025 DAL 131LQ2 Y10 SF 0 GLP10-01-02-07-026 DAL 131LQ2 Y10 SF 1 GLP10-01-02-07-027 DAL 131LQ2Y10 SF LS GLP10-01-02-07-028 DAL131LQ2Y10 SF MS GLP10-01-02-07-029 DAL131LQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 2.84 NA 3.04 NA 4.18 NC 13.2 101 88.4 83.8 2.94 ng/mL 6.8% Concentration (ng/mL) %Recovery 18.9 NA 19.6 NA 20.7 NC 30.2 106 104 82.3 19.3 ng/mL 3.6% Concentration (ng/mL) %Recovery 33.9 NA 33.4 NA 34.9 NC 43.9 NC 112 76.9 33.6 ng/mL 1.6% NA = Not Applicable NC = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. PFBS, PFHS, and PFOS were analyzed on 7/15/10 with a 1:10 dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Table 15. DAL 131S Q2 Y10 SF (Sampled 6/30/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-020 DAL131SQ2Y10 SF 0 GLP10-01-02-07-021 DAL 131S Q2 Y10 SF 1 GLP10-01-02-07-022 DAL 131S Q2 Y10 SF LS GLP10-01-02-07-023 DAL 131S Q2 Y10 SF MS GLP10-01-02-07-024 DAL 131S Q2 Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 1.06 NA 1.05 NA 11.0 97.5 NA (1) N A <1) NA (1) N A (1) 1.06 ng/mL 0.95% Concentration (ng/mL) %Recovery 5.53 NA 5.45 NA 14.3 85.5 N A (1) N A (1> NA <1) NA<1) 5.49 ng/mL 1.5% Concentration (ng/mL) %Recovery 8.41 NA 8.09 NA 18.2 97.5 N A(1> N A (1) NA (1) N A (1) 8.25 ng/mL 3.9% NA = Not Applicable PFBS, PFHS, and PFOS were analyzed on 9/17/10 without dilution. . (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Page 24 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 16. DAL 132R Q2 Y10 SF (Sampled 7/1/10) PFBS PFHSf1) PFOS 3MUMSID Description GLP10-01-02-07-030 DAL132RQ2Y10 SF 0 GLP10-01-02-07-031 DAL 132RQ2Y10 SF 1 GLP10-01-02-07-032 DAL 132RQ2Y10 SF LS GLP10-01-02-07-033 DAL 132RQ2Y10 SF MS GLP10-01-02-07-034 DAL 132RQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 7.60 NA 7.68 NA 17.5 96.7 N A (1) N A (1) NA (1) NA (1) 7.64 ng/mL 1.0% Concentration (ng/mL) %Recovery 36.3 NA 35.6 NA 44.8 NC 133 94.2 865 80.5 36.0 ng/mL 1.9% Concentration (ng/mL) %Recovery 262 NA 264 NA 274 NC 333 NC 1070 79.3 263 ng/mL 0.76% N A = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:100 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Table 17. DAL 132L Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MLIMSID Description GLP10-01-02-07-040 DAL132LQ2Y10 SF 0 GLP10-01-02-07-041 DAL132LQ2Y10 SF 1 GLP10-01-02-07-042 DAL132LQ2Y10 SF LS GLP10-01-02-07-043 DAL 132LQ2 Y10 SF MS GLP10-01-02-07-044 DAL132LQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 10.3 NA 9.78 NA 11.2 NC 18.9 86.9 102 90.2 10.0 ng/mL 5.2% Concentration (ng/mL) %Recovery 76.7 NA 79.6 NA 79.7 NC 84.9 NC 177 96.0 78.2ng/mL 3.7% Concentration (ng/mL) %Recovery 238 NA 243 NA 257 NC 270 NC 379 NC 240 ng/mL 2.1% <1> NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFBS, PFHS, and PFOS were analyzed on 7/15/10 with a 1:10 dilution. (1) Sampling location did not have an appropriate FMS spike level to sufficiently evaluate PFOS recovery. Page 25 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 18. DAL 132S Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MLIMSID Description GLP10-01-02-07-035 DAL132SQ2Y10 SF 0 GLP10-01-02-07-036 DAL132SQ2Y10 SF 1 GLP10-01-02-07-037 DAL132SQ2Y10 SF LS GLP10-01-02-07-038 DAL132SQ2Y10 SF MS GLP10-01-02-07-039 DAL132SQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 31.8 NA 33.4 NA 44.8 NC 135 100 NA (1) N A (1) 32.6 ng/mL 4.9% Concentration (ng/mL) %Recovery 211 NA 211 NA 213 NC 287 NC 1100 86.3 211 ng/mL 0.0% Concentration (ng/mL) %Recovery 863 NA 858 NA 825 NC 873 NC 1660 77.9 861 ng/mL 0.58% N A= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS wsre analyzed on 7/15/10 with a 1:100 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution o f the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Table 19. DAL 133R Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MLIMSID Description GLP10-01-02-07-045 DAL133RQ2Y10 SF 0 GLP10-01-02-07-046 DAL 133RQ2 Y10 SF 1 GLP10-01-02-07-047 DAL 133RQ2Y10 SF LS GLP10-01-02-07-048 DAL 133RQ2Y10 SF MS GLP10-01-02-07-049 DAL 133RQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 7.78 NA 7.62 NA 8.87 NC 18.2 103 N A (1) N A (1) 7.70 ng/mL 2.1% Concentration (ng/mL) %Recovery 45.8 NA 45.3 NA 44.6 NC 52.9 NC 128 80.0 45.6 ng/mL 1.1% Concentration (ng/mL) %Recovery 73.9 NA 81.0 NA 71.0 NC 84.2 NC 160 80.9 77.5 ng/mL 9.2% NA= NotApplicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:10 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Page 26 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Table 20. DAL 133L Q2 Y10 SF (Sampled 7/2/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-055 DAL132LQ2Y10 SF 0 GLP10-01-02-07-056 DAL 132LQ2 Y10 SF 1 GLP10-01-02-07-057 DAL132LQ2Y10 SF LS GLP10-01-02-07-058 DAL 132LQ2 Y10 SF MS GLP10-01-02-07-059 DAL 132LQ2 Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 6.81 NA 6.68 NA 16.7 97.6 NA (1) N A (1) NA (1) N A (1) 6.75 ng/mL 1.9% Concentration (ng/mL) %Recovery 39.5 NA 39.2 NA 48.3 NC 145 103 914 84.9 39.4 ng/mL 0.76% Concentration (ng/mL) %Recovery 139 NA 149 NA 161 NC 274 128 1030 86.8 144 ng/mL 7.6% N A= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:50 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Table 21. DAL 133S Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-050 DAL133SQ2Y10 SF 0 GLP10-01-02-07-051 DAL133SQ2Y10 SF 1 GLP10-01-02-07-052 DAL133SQ2Y10 SF LS GLP10-01-02-07-053 DAL133SQ2Y10 SF MS GLP10-01-02-07-054 DAL133SQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 12.6 NA 12.7 NA 21.8 89.7 N A <1> NA (1) NA <1> NA <1) 12.7 ng/mL 0.79% Concentration (ng/mL) %Recovery 75.5 NA 78.7 NA 89.5 NC 173 93.1 990 88.6 77.1 ng/mL 4.2% Concentration (ng/mL) %>Recovery 221 NA 234 NA 230 NC 337 107 1180 93.2 228 ng/mL 5.4% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:50 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Page 27 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 22. DAL 134R Q2 Y10 SF (Sampled 7/2/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-060 DAL134RQ2Y10 SF 0 GLP10-01-02-07-061 DAL 134RQ2 Y10 SF 1 GLP10-01-02-07-062 DAL134RQ2Y10 SF LS GLP10-01-02-07-063 DAL 134RQ2 Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 58.6 NA 59.6 NA 157 96.0 NA <1) N A <1) 59.1 ng/mL 1.7% Concentration (ng/mL) %Recovery 436 NA 446 NA 521 NC 1270 80.5 441 ng/mL 2.3% Concentration (ng/mL) %Recovery 1170 NA 1190 NA 1140 NC 1900 70.3 1180 ng/mL 2.3% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:100 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Table 23. DAL 134L Q2 Y10 SF (Sampled 7/2/10) PFBS PFHS PFOS 3MLIMSID Description GLP10-01-02-07-075 DAL134LQ2Y10 SF 0 GLP10-01-02-07-076 DAL134LQ2 Y10 SF 1 GLP10-01-02-07-077 DAL134LQ2Y10 SF LS GLP10-01-02-07-078 DAL134LQ2Y10 SF MS GLP10-01-02-07-079 DAL 134LQ2 Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 12.7 NA 12.8 NA 13.8 NC 22.5 95.6 NA (1> N A (1) 12.8 ng/mL 0.78% Concentration (ng/mL) XRecovery 107 NA 105 NA 107 NC 112 NC 184 75.7 106 ng/mL 1.9% Concentration (ng/mL) %Recovery 484 NA 497 NA 503 NC 470 NC 535 NC 491 ng/mL 2.7% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:10 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. (2) Sampling location did not have an appropriate FMS spike level to sufficiently evaluate PFOS recovery. Page 28 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 24. DAL 134S Q2 Y10 SF (Sampled 7/2/10) PFBS PFHS PFOS 3NILINIS ID Description GLP10-01-02-07-070 DAL134SQ2Y10 SF 0 GLP10-01-02-07-071 DAL134SQ2Y10 SF 1 GLP10-01-02-07-072 DAL134SQ2Y10 SF LS GLP10-01-02-07-073 DAL134SQ2Y10 SF MS GLP10-01-02-07-074 DAL134SQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 0.100 NA 0.0876 NA 1.21 109 10.9 106 87.8 86.0 0.0938 ng/mL 13% Concentration (ng/mL) VoRecovery 1.37 NA 1.29 NA 2.43 107 12.7 110 91.4 87.4 1.33 ng/mL 6.0% Concentration (ng/mL) VoRecovery 13.1 NA 12.2 NA 13.1 NC 23.4 106 101 86.3 12.6 ng/mL 7.2% N A= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFBS, PFHS and PFOS were analyzed on 7/15/10 with a 1:5 dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Table 25. DAL 135R Q2 Y10 SF (Sampled 7/2/10) PFBS PFHS PFOS 3NILINIS ID Description GLP10-01-02-07-064 DAL135RQ2Y10 SF 0 GLP10-01-02-07-065 DAL135RQ2Y10 SF 1 GLP10-01-02-07-066 DAL135RQ2Y10 SF LS GLP10-01-02-07-067 DAL135RQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 82.8 NA 83.2 NA 185 100 NA <1) NA(1) 83.0 ng/mL 0.48% Concentration (ng/mL) %Recovery 761 NA 747 NA 853 NC 1610 83.1 754 ng/mL 1.9% Concentration (ng/mL) VoRecovery 1030 NA 1050 NA 1190 NC 1890 83.2 1040 ng/mL 1.8% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:100 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Page 29 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 26. DAL 135L Q2 Y10 SF (Sampled 7/2/10) PFBS PFHS PFOS 3MLIMSID Description GLP10-01-02-07-085 GLP10-01-02-07-086 GLP10-01-02-07-087 DAL135LQ2Y10 SF 0 DAL 135LQ2Y10 SF 1 DAL135LQ2Y10 SF LS GLP10-01-02-07-088 DAL135LQ2Y10 SF MS GLP10-01-02-07-089 DAL 135LQ2 Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 6.38 NA 6.34 NA 15.6 90.6 NA (1) N A (1) N A (1) N A <1) 6.36 ng/mL 0.63% Concentration (ng/mL) %Recovery 36.3 NA 39.5 NA 49.6 NC 132 103 922 85.8 37.9 ng/mL 8.4% Concentration (ng/mL) %Recovery 52.6 NA 58.1 NA 62.2 NC 117 68.2 (2) 985 91.1 55.4 ng/mL 9.9% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:100 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. (2) The field matrix spike did not m eet method acceptance criteria of 100% 30%. Table 27. DAL 135S Q2 Y10 SF (Sampled 7/2/10) PFBS PFHS PFOS 3MUMSID Description Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery GLP10-01-02-07-080 DAL135SQ2Y10 SF 0 0.748 NA 5.72 NA GLP10-01-02-07-081 DAL135SQ2Y10 SF 1 0.722 NA 6.04 NA GLP10-01-02-07-082 DAL135SQ2Y10 SF LS 11.0 101 15.2 90.5 GLP10-01-02-07-083 DAL135SQ2Y10 SF MS GLP10-01-02-07-084 DAL135SQ2Y10 SF HS NA (1) N A (1) NA (1) NA (1) N A (1> NA (1) N A (1) N A (1) Average Concentration (ng/mL) %RPD 0.735 ng/mL 3.5% 5.88 ng/mL 5.4% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFBS, PFHS and PFOS were analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Concentration (ng/mL) %Recovery 6.87 NA 7.45 NA 16.5 91.6 N A <1) N A (1) N A (1> N A <1) 7.16 ng/mL 8.1% Page 30 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 28. DAL 136L Q2 Y10 SF (6/30/10) PFBS PFHS PFOS 3MLIMSID Description GLP10-01-02-07-095 DAL136LQ2Y10 SF 0 GLP10-01-02-07-096 DAL 136LQ2Y10 SF 1 GLP10-01-02-07-097 DAL 136LQ2Y10 SF LS GLP10-01-02-07-098 DAL136LQ2Y10 SF MS GLP10-01-02-07-099 DAL 136LQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 2.96 NA 2.85 NA 13.7 106 N A <1) NA(1) N A (1) NA (1) 2.91 ng/mL 3.8% Concentration (ng/mL) %Recovery 11.8 NA 11.5 NA 20.7 87.9 108 93.5 856 82.0 11.7 ng/mL 2.6% Concentration (ng/mL) %Recovery 87.7 NA 91.6 NA 93.8 NC 157 65.6 (2> 899 79.4 89.7 ng/mL 4.4% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:50 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. (2) The field matrix spike did not m eet method acceptance criteria. Table 29. DAL 136S Q2 Y10 SF (Sampled 6/30/10) PFBS PFHS PFOS 3MLIMSID Description Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery GLP10-01-02-07-090 DAL 136S Q2 Y10 SF 0 3.47 NA 19.2 NA GLP10-01-02-07-091 DAL 136S Q2 Y10 SF 1 3.51 NA 19.4 NA GLP10-01-02-07-092 DAL 136S Q2Y10 SF LS 4.78 NC 20.0 NC GLP10-01-02-07-093 DAL 136S Q2Y10 SF MS 14.1 104 29.1 95.1 GLP10-01-02-07-094 DAL 136S Q2Y10 SF HS NA (1) NA (1) 98.8 85.7 Average Concentration (ng/mL) %RPD 3.49 ng/mL 1.1% 19.3 ng/mL 1.0% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:10 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Concentration (ng/mL) %Recovery 103 NA 109 NA 110 NC 110 NC 183 83.9 106 ng/mL 6.0% Page 31 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 30. DAL 137L Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MLIMSID Description GLP10-01-02-07-105 DAL137LQ2Y10 SF 0 GLP10-01-02-07-106 DAL 137LQ2 Y10 SF 1 GLP10-01-02-07-107 DAL 137LQ2 Y10 SF LS GLP10-01-02-07-108 DAL 137LQ2 Y10 SF MS GLP10-01-02-07-109 DAL137LQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 0.0914 NA 0.0780 NA 0.203 116 1.21 110 10.6 103 0.0847 ng/mL 16% Concentration (ng/mL) %Recovery <0.103 NA <0.103 NA 0.153 149 (1) 1.23 119 10.6 103 <0.103 ng/mL Concentration (ng/mL) %Recovery 0.684 NA 0.784 NA 0.886 NC 1.85 109 10.6 96.5 0.734 ng/mL 14% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFBS, PFHS and PFOS were analyzed on 7/15/10 without dilution. (1) The field matrix spike did not meet method acceptance criteria. Table 31. DAL 137S Q2 Y10 SF (Sampled 7/1/10) PFBS PFHS PFOS 3MLIMSID Description Concentration (ng/mL) %Recovery GLP10-01-02-07-100 DAL137SQ2Y10 SF 0 0.123 NA GLP10-01-02-07-101 DAL137SQ2Y10 SF 1 0.114 NA GLP10-01-02-07-102 DAL137SQ2Y10 SF LS 0.232 111 GLP10-01-02-07-103 DAL137SQ2Y10 SF MS 1.38 124 GLP10-01-02-07-104 DAL137SQ2Y10 SF HS 11.6 113 Average Concentration (ng/mL) %RPD 0.119 ng/mL 7.6% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFBS, PFHS and PFOS were analyzed on 7/15/10 without dilution. (1) The field matrix spike did not meet method acceptance criteria. (2) The analytical uncertainty for PFOS has been adjusted for FMS recovery to 100% 38%. Concentration (ng/mL) %Recovery <0.103 NA <0.103 NA 0.192 186 (1) 1.27 123 11.1 108 <0.103 ng/mL Concentration (ng/mL) %Recovery 0.435 NA 0.419 NA 0.562 NC 1.05 61.5 (1) 8.99. 83.9 0.427 ng/mL 3.7% Page 32 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 32. DAL 138S Q2 Y10 SF (Sampled 6/30/10) PFBS PFHS PFOS 3MUMSID Description GLP10-01-02-07-110 DAL138SQ2Y10 SF 0 GLP10-01-02-07-111 DAL138SQ2Y10 SF 1 GLP10-01-02-07-112 DAL138SQ2Y10 SF LS GLP10-01-02-07-113 DAL138SQ2Y10 SF MS GLP10-01-02-07-114 DAL138SQ2Y10 SF HS Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 5.81 NA 5.62 NA 15.5 106 N A (1) N A (1) N A (1) N A <1) 5.72 ng/mL 3.3% Concentration (ng/mL) %Recovery 17.0 NA 16.7 NA 27.8 NC 116 96.3 888 84.6 16.9 ng/mL 1.8% Concentration (ng/mL) %Recovery 216 NA 217 NA 240 NC 319 NC 1091 85.7 216 ng/mL 0.42% NA = Not Applicable NO = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFHS and PFOS were analyzed on 7/15/10 with a 1:50 dilution. PFBS was analyzed on 9/17/10 without dilution. (1) A dilution of the sample was not prepared as the spike level was not appropriate as compared to the sample concentrations. Table 33. DAL 138L Q2 Y10 SF (Sampled 6/30/10) PFBS PFHS PFOS 3MUMSID Description Concentration (ng/mL) %Recovery GLP10-01-02-07-115 DAL 138LQ2 Y10 SF 0 0.0525 NA GLP10-01-02-07-116 DAL 138LQ2Y10 SF 1 0.0401 NA GLP10-01-02-07-117 DAL 138LQ2 Y10 SF LS 0.153 105 GLP10-01-02-07-118 DAL138LQ2Y10 SF MS 1.19 112 GLP10-01-02-07-119 DAL138LQ2 Y10 SF HS 11.2 109 Average Concentration (ng/mL) %RPD 0.0463 ng/mL 2 r / , <1> NA= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PFBS, PFHS and PFOS were analyzed on 7/15/10 without dilution. (1) The RPD did not meet method acceptance criteria of 20%. (2) The field matrix spike did not meet method acceptance criteria. Concentration (ng/mL) %Recovery <0.103 NA <0.103 NA 0.209 203 (2) 1.28 124 10.4 101 <0.103 ng/mL Concentration (ng/mL) %Recovery 0.805 NA 0.776 NA 0.805 NC 1.66 85.1 9.71 87.5 0.791 ng/mL 3.7% Page 33 of 68 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Table 34. Trip Blank 3M UNIS ID GLP10-01-02-07-124 GLP10-01-02-07-120 GLP10-01-02-07-121 GLP10-01-02-07-122 GLP10-01-02-07-123 Description Trip Blank Sample Trip Blank LS Trip Blank MS Trip Blank MHS Trip Blank HS PFBS PFHS PFOS Concentration (ng/mL) <0.0306 1.35 12.7 117 1170 %Recovery NA 132 (1) 125 115 115 Concentration (ng/mL) <0.103 1.22 11.4 108 1090 %Recovery NA 118 111 105 106 Concentration (ng/mL) <0.510 1.19 11.6 114 900 %Recovery NA 117 114 112 88.2 NA= Not Applicable (1) The field matrix spike did not meet method acceptance criteria. Table 35. Rinseate Blanks 3MLIMSID GLP10-01-02-07-068 GLP10-01-02-07-069 Description DAL137L Q2 Y10SF RB DAL131RQ2 Y10SF RB PFBS Concentration (ng/mL) <0.0306 <0.0306 PFHS Concentration (ng/mL) <0.103 <0.103 PFOS Concentration (ng/mL) <0.102 <0.102 Page 34 of 68 GLP10-01-02; Interim Report 07 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/Sampie Retention All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 12 Attachments Attachment A: Protocol Amendment #2 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 35 of 68 GLP10-01-02; Interim Report 07 . Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 13 Signatures Cleston Lange, Ph.D., 3M Principal Analytical Investigator 2 .& /P Date Page 36 of 68 Attachment A GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/Julv 2010 y Analytical Protocol: GLP10-01-02 Amendment 07 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. 07 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 Former Sludge Incorporation Area (FSIA) Groundwater Page 1 of 9 Page 37 of 68 Attachment A GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in W ater Samples from Decatur, AL June/Julv 2010 y Analytical Protocol: GLP1Q-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, [(1,2,3,4,5,6,7,8-13C8)-PFOS] will be added at a fixed concentration to each sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation of PFOS and the surrogate. A stable isotope-labeled internal standard, K180 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 of PFBS. A mend to read: A stable isotope-labeled surrogate [(1,2,3,4-13C,f)-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, [(1,2,3,4,5,6,7,8-13C8)-PFOS] may be added at a fixed concentration to each sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation of 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 of PFHS. A stable isotope-labeled internal standard, [(^O ^-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 for the sampling points of interest, foe data will be reviewed to determine if foe use of internal standards and surrogate is appropriate for the current sampling event. Page 2 of 9 Page 38 of 68 Attachment A Protocol heads: GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Analytical Protocol: GLP10-01-02 Amendment 07 No changes to the wording o f the protocol are required. A mend to read: No changes to the wording of the protocol are required. This amendment only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis o f groundwater samples from Decatur, AL, and conducted as part o f the 3M Decatur Phase 3 Program fo r PFOS, PFHS and PFBS (GLP10-01-02). The anticipated sample collection w ill occur around the tim efram e o f June 21,2010. The groundwater samples for this sampling event w ill be entered into the 3M Environm ental Laboratory LlMS as project GLP10-01-01-07 and reported as interim report GLP10-01-02-02, (reflecting study GLP10-0107 and amendment -07). Reason: The reason for this am endm ent is to docum ent the General Project Outline (GPO) which describes the anticipate groundwater sample collection event to be conducted for the 3M Decatur, AL facility. The GPO is four pages in length and included as attached to this amendment form. Page 3 of 9 Page 39 of 68 Attachment A GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Analytical Protocol: GLP10-01-02 Amendment 07 Amendment Approval Page 4 of 9 Page 40 of 68 Attachment A GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Analytical Protocol: GLP10-01-02 Amendment 07 3 M Environmental Health & Safety Operations, Environmental Laboratory Genera! P roject O utline To: From: 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 o f Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sedim ent for the 3M Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 07 - Form er Sludge Incorporation Area (FSIA) Groundwater 1 General Project Information Contacts Lab Request Number Six Digit Department Number Project Schedule/Test Dates 3M Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone:(651)737-3570 aahohensteinimmm.com 3M Environmental Laboratory Management William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaaenSDmmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 ccfanaefffimmm.com Sampling Coordinator Timothy Frinak Weston Solutions Timothv.frinaki5>westonso!utions.com Phone: (3341-332-9123 GLP10-01-02-07 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 5 of 9 Page 41 of 68 Attachment A GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Analytical Protocol: GLP10-01-02 Amendment 07 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) w ill receive and analyze groundwater samples collected from twenty-seven groundwater w ells for Perfiuorobutanesuffonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) from the Form er Sludge Incorporation Area (FSIA). Analyses w ill be conducted under the GLP requirem ents o f EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples 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 submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP10-01-0207. 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-seven sampling locations have been specified. For each sampling location, a sample, sample duplicate and a minimum of two field matrix spikes will be collected. Table 1 indicates the well ID and corresponding field spike levels. The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. Three sets of trip blanks consisting of reagent-grade water, a low-level trip blank spike, mid-level field spike, mid-high 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. Two additional bottles will be prepared to be used for the preparation of the equipment rinseate blanks. A total of 145 sample bottles will be prepared. Page 6 of 9 Page 42 of 68 Attachment A GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in W ater Samples from Decatur, AL June/July 2010 . - Analytical Protocol: GLP10-01-02 Amendment 07 Table 1. Sampling Locations and Field Matrix Spike levels. Well No. Sample Level Spike Cone. (ng/mL) 136R, 137R, 137S, 137L, 138L 130L, 131L, 132L, 133R, 134S, 134L, 136S 130R, 130S, 131S, 132R, 132S, 133S, 133L, 135S, 1351,136L, 138S, 138R 131R, 134R, 135R Trip Blank Set 1,2, and 3 Low Mid High Low Mid High Low Mid High Low High Low Mid Mid-High High 0.1 1.0 10 1 10 too 10 100 1000 100 1000 1 10 100 1000 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 o f 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 arid High Performance Liquid Chromatography/Mass Spectrometry". Method ETS-8-154 has been validated for PFGA and PFOS only; however, specific quality control samples analyzed with foe samples will be used to determine overall method precision and accuracy. 6 Reporting Requirements For each sampling location, foe report will contain the results for foe sample, sample duplicate, and field matrix spikes. Trip blank and trip blank spikes will be reported for foe 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 preparation will also be reported and used to evaluate foe overall method accuracy and precision. Method blanks of reagent water prepared at foe time of sample preparation will be used to determine foe method detection limit. For those sampling locations where foe 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 7 Email Correspondence Attachment A: Sampling Bottle Request Page 7 of 9 Page 43 of 68 Attachment A GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in W ater Samples from Decatur, AL June/July 2010 . ,. _ __ Analytical Protocol: GLP10-01-02 Amendment 07 Project Duration: 21 June through 2 July 2010 Ship Containers to: Weston Solutions, inc. Field Office 3M Decatur Plant 1400 State Docks Road Decatur, Al 35601 256-552-6189 Attn: Martin Smith Date Required: 18-Jun-10 Sample Media Groundwater Samples 27 Sample Container Requirements Duplicate Samples Rinsate Blank Sets na 2 Trip Blank Sets See Note 1 Note 1: One trip blank w ill be required fo r each shipping container returned to the laboratory. It should be noted that ice will be required for shipments of soil / sediment samples which may result in an increase in the number of shipping containers {and trip blanks) required. Note 2: Rinsate Blank Sets should be accompanied with an appropriate volume o f water to accomplish the sampling. The volume should account for spillage during the rinsing process. Note 3: Please note that any bottle sets not used due to unique field conditions will be isolated and returned to the laboratory labeled for disposal. ' Page 8 of 9 Page 44 of 68 Attachment A W ells Included in This Sampling Event: GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/Juiy 201 o Analytical Protocol: GLP10-01-02 Amendment 07 Page 9 of 9 Page 45 of 68 Ollie: U00110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Page 46 of 68 *011ie: UOO110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Page 47 of 68 01lie: U00110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Page 48 of 68 *011ie: U00110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Page 49 of 68 *011ie: U00110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Page 50 of 68 *011ie: U00110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Page 51 of 68 01lie : U00110402 Attachment B Data work-up performed by STW Page 4 of 4 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Page 52 of 68 Ollie: U00110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Page 53 of 68 *011ie: U00110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Page 54 of 68 *011ie: U00110402 Attachment B Page 3 of 3 GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Printing Time: 8:36:45 AM Printing Date: Monday, October 25, 2010 Page 55 of 68 *01lie : U00110402 Attachment B GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS In Water Samples from Decatur, AL June/July 2010 Page 56 of 68 ' Attachment C DocBRM!-fjiPo;!rjMfeTfmgi$3ii,o^ 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: 0 ^ / ( 1 {o ~ l Approved By: W illiam K. Reagen, Laboratory Manager O / > Date ETS-8-044.0 P a g e t of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 57 of 68 Attachment C Dociw&iRQ;rjmk@niErMl,oW current, for 14 days from 10/25/20 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. W ater samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In 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 58 of 68 Attachment C Docifficra^jiRoai^fecmi^ct.oW 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 Lim it 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 59 of 68 Attachment C 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 60 of 68 Attachment C DocssittM'Oii!)1RQ2}'jfttWfnKspisti,o?i 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 C 18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: 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 (m L/m in) 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak Area - quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. The previous inform ation is intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met. ETS-8-044.0 Page 5 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 61 of 68 Attachment C DocigiwtwfoTOai'jfifetiiiKSFwI.oWcurrent, 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: A n a ly te Transition Monitored PFBA 213 -> 169 PFPeA 263 ->219 PFHA 3 1 3 -> 2 6 9 and 3 1 3 -> 119 PFHpA 363 -> 319, 363 -> 169 and 363 -> 119 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 2 1 9 PFDA 513 -> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 2 1 9 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 -> 99 PFHS 399 --^ 80 and 399 --^ 99 PFOS 499 -> 80, 499 -> 99 and 499 -> 130 M ultiple transitions for monitoring the analytes is an option, as summing m ultiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention 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 W ater - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate - A.C.S. Reagent Grade 7.2 Standards Perfluorobutanoic Acid (P F B A - C4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (PFHA - C6 acid); Oakwood Products, Inc . Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M Perfluorononanoic Acid (PFNA - C9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (PFDA - C10 acid); Oakwood Products, Inc Perfluoroundecanoic Acid (PFU nA-C 11 acid); Oakwood Products, Inc Perfluorododecanoic Acid (P FD oA -C 12acid); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 62 of 68 Attachment C DocitsttRiwtqci^'jhtefnsg^.oW current, for 14 days from 10/25/2010 Analysis of PFBS, PFHS, and PFOS in W ater 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 p e rc e n t s a lt a n d p u rity ) and dilute to 10OmL with methanol or other suitable solvent, in a 10OmL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. salt correction factor = molecular weight of anion moclecular weight of salt PFOS (K +)salt correction factor = ------= 0.9275 538 10 mg C8F17S03'K+with purity 90% = 8.35mg C8F17S03~(10 mg*0.90*0.9275=8.35 mg) 5 pg/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 63 of 68 Attachment C Doce&?3ii)mTjMteiniBi8^,oW 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, pL 10 15 20 30 20 50 100 200 25 50 100 Final Volume of Calibration Standard (mL o f ASTM Type 1Water, or other suitable water) 50 50 50 50 50 50 50 50 50 50 50 Final Concentration of 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 64 of 68 Attachment C Docwwl)a^teniiai,oM: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 65 of 68 Attachment C Dociiwt)aMhtbiOTpal,oW 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: (Peak Area - Intercept) Analyte found (ng/mL) = xDF Slope DF = factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) Recovery = x100 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 66 of 68 Attachment C D o c t)t103'jiifen s ,0?f 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 67 of 68 ftcM<&ntial GLP10-01-02; Interim Report 07 Analysis of PFBS, PFHS, and PFOS in Water Samples from Decatur, AL June/July 2010 Record of Deviation/Nonconformance I. Identification Study / Project No. Date(s) of Occurrence: Document Number: GLP10-01-02-07 o100715b and m l 00917a ETS-8-044.0 Deviation type SOP Equipment Procedure 13 Method (Check one) Protocol_______13 GPO_________________ Other: II. Description (attach extra p a g e s as needed) Method Requirements: (1) CCV recovery within 100% 25%. (2) LCS average recovery of 100% 20%. (3) Sample/Sample Duplicate RPD 20%. (4) ..............FMS recovery of 100% 30%........... Actual procedure/process: ( 1) Twenty-one CCVs were analyzed during the course of the run with three CCVs not meeting method acceptance criteria with recoveries of 70.8%, 73.6%, and 73.3% for PFHS (o100715b). (2) LCS average recovery for the high set of linear and branched PFOS was 122% (s100715b). LCS average recovery for the low set of linear PFOS was 121% and 125% for the low set of linear and branched PFOS (m100917a). (3) The RPD value for PFBS for 138L was 27%. (4) The following locations did not have an appropriate FMS level for PFOS: DAL 132L and DAL 134L. The following FMS level did not meet method acceptance criteria: the high FMS for PFOS on DAL 130L (54.8%), the mid FMS for PFOS DAL 135L (68.2%), the mid FMS for PFOS on DAL 136L (65.6%), the low FMS for PFHS on DAL 137S (149%), the low FMS for PFHS on DAL 137S (186%), the mid FMS for PFOS on DAL 137S (61.5%), and the low FMS for PFHS on DAL 138L (203%).___________________ (such as amIIeIn.dmAecnttiiossnuesd,TSaOkPernevision, etc.) C orrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1) Reported samples bracketed by the three CCVs for PFHS that did not meet method acceptance criteria (132S, 134R, 135S, and 135L) will be noted in the final report. 2) The 9/17/10 analysis included a number of samples that contained PFOS concentrations greater than the calibration range. It is believed that the high recovery for the low set of LCS is due to analyte carry over as the low set of LCS were analyzed immediately these samples. 3) The RPD value for PFBS for 138L with a value >20% will be footnoted in the data tables. 4) Sampling locations without an appropriate spike level for PFOS will be footnoted in the final report (DAL 132L and DAL 134L). Sampling locations DAL 135L and 136L had FMS recoveries for PFOS that did not meet method acceptance criteria (68.2% and 65.6%), however, since the method analytical uncertainty for PFOS is 100% 37%, no adjustment was made to the analytical uncertainty. Sampling locations DAL 137L, DAL 137S, and DAL 138L had high recoveries for the low FMS for PFHS, however, the samples contained PFHS just below the method LOQ of 0.103 ng/mL, which most likely accounts for the high recovery of the low FMS samples. The mid and high FMS levels for these sampling locations met method acceptance criteria. For sampling locations DAL 130L and DAL 137S, the analytical uncertainty will be adjusted based on the recovery of the most appropriate spike level. Actions: Halting of Work Client Notification Work Recall Withholding of Report 0 Other: Deviations will be noted in fi report. Project Lead/PAI Approval: Study Director (if GLP): Date: S p onsor A pproval (for G L P p ro to c o l deviations): NA Technical Reviewer (optional): NA Date: NA Date: NA Laboratory Departm ent M anager Approval: Date: 9 5'QC7~2~C'/0 Where halting of work occuIrVre.d, Areusutmhpotiroinzaoftwioonrk mtousRt feirsstubemaeppWrovoerdkby Laboratory Management Laboratory Departm ent M anager Approval: NA | Date: NA Deviation No. (assigned by Study Director or Team Leader at the end of study or project) Attachment A ETS-4-008.7 Page 1 of 1 Documentation of Deviations and Control of Nonconforming Testing Page 68 of 68