Document mq5yNdemNG8r4Y372QdDeeRmQ

3M GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 GLP10-01-02. Interim Report 10: Analysis of PFBS. PFHS. and PFOS in Groundwater Samples Collected at Off-Site Wells located in Decatur. AL in October 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 Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 Author Susan Wolf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP10-01-02-10 Total Number of Pages 57 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 1 Page 1 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 This page has been reserved for specific country requirements. Page 2 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 GLP C o m p l ia n c e S ta te m e n t Report Title: GLP10-01-02, Interim Report 10. Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at Off-Site Wells located in Decatur, AL in October 2010 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 SiteRelated Monitoring Program. This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below: These are environmental samples where there is no specific test substance, no specific test system and no dosing of a test system. The reference substances have not been characterized under the GLPs and the stability under storage conditions at the test site have not been determined under GLPs. Date Page 3 of 57 GLP10-01-02; Interim Report 10 Analysis of PFBS, PFHS, and PFOS in Grundwater from Decatur, AL October 2010 Q uality A ssurance Statement Report Title: GLP10-01-02, Interim Report 10. Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Off-Site Wells located in Decatur, AL in October 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 report and the accompanying data were audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated below. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dates 1 2 /2 /1 0 -1 2 /3 /1 0 Phase Data and Interim Report Date Reported to Testing Facility M anagem ent Study Director 12/23/10 12/23/10 Page 4 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Ta b le of C o n ten ts GLP Compliance Statement................................................................................................. !............. 3 Quality Assurance Statement......................................................................................... :.................... 4 Table of Contents.................................................................................................................................5 List of Tables..........................................................................................................................................6 1 Study Information............................................................................................................................ 8 2 Summary......................................................................................................................................... 9 3 Introduction............................................................................... 10 4 Test & Control Substances.......................................................................................................... 10 5 Reference Substances................................................................................................................. 11 6 Test System.................................................................................................................................. 13 7 Method Summary......................................................................................................................... 13 7.1 Methods................................................... ................................................................... 13 7.2 Sample Collection......................................................................................................... 13 7.3 Sample Preparation.......................................................................................................13 7.4 Analysis......................................................................................................................... 13 8 Analytical Results.........................................................................................................................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 (LCSs)...........................................................................................15 8.7 Analytical Method Uncertainty...................................................................................... 17 8.8 Field Matrix Spikes (FMS)............................................................................................. 17 Page 5 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 9 Data Summary and Discussion.................................................................................................... 17 10 Conclusion....................................................................................................................................26 11 Data/SampleRetention................................................................................................................ 26 12 Attachments..................................................................................................................................26 13 Signatures..................................................................................................................................... 27 L ist o f Ta b les Table 1. Summarized PFBS, PFHS, and PFOS Results (Off-Site Groundwater, Decatur, AL, October 2010)....................................................................................................... 9 Table 2. Instrument Parameters..............................................................................................14 Table 3. Liquid Chromatography Conditions...........................................................................14 Table 4. Mass Transitions....................................................................................................... 14 Table 5. Limit of Quantitation (LOQ)....................................................................................... 15 Table 6. Laboratory Control Spike Recovery.......................................................................... 16 Table 7. Analytical Uncertainty................................................................................................ 17 Table 8. Field Matrix Spike Levels...........................................................................................17 Table 9. DAL GW 602L101029..............................................................................................18 Table 10. DAL GW 602S 101029...........................................................................................18 Table 11. DAL GW 603L 101029............................................................................................19 Table 12. DAL GW 603S 101028...........................................................................................19 Table 13. DAL GW 604 L 101029..........................................................................................20 Table 14. DAL GW604S 101029...................... :.................................................................. 20 Table 15. DAL GW605R 101029.......................................................................................... 21 Table 16. DAL GW 605 L 101029........................................................................................... 21 Table 17. DAL GW 607R 101028.......................................................................................... 22 Table 18. DAL GW 607L 101028........................................................................................... 22 Table 19. DAL GW 609R 101027.......................................................................................... 23 Table 20. DAL GW 609 L 101027........................................................................................... 23 Page 6 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Table 21. DAL GW 611R 101027.......................................................................................... 24 Table22. DALGW 611L 101027........................................................................................... 24 Table23. Trip Blank................................................................................................................25 Table 24. DAL GW 602S RB 101029.....................................................................................25 Page 7 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 1 Study inforni'aiion ! ;, `f tT Sponsor 3M Company Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone:(651)737-3570 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j.kesari@westonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106 Study Personnel William K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clange@mmm.com): phone (651)-733-9860 Susan Wolf, 3M Analyst Chelsie Grochow; Analyst Study Dates Study Initiation: March 8, 2010 Interim Report 10 Experimental Termination: November 09, 2010 Interim Report Completion: Date of Interim Report Signing Location of Archives All original raw data and the analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792 Page 8 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 2 Summary The 3M Environmental Laboratory received groundwater samples from wells located at Off-Site Wells located in Decatur, AL, representing fourteen different sampling locations. A total of forty-five sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS) analysis, and included duplicate groundwater samples from each sampling location. Samples also included one field matrix spike (FMS) samples for each location, one trip blank containing Milli-QTM water, a trip blank spike, and one equipment rinseate sample. The equipment rinseate blank did not have FMS samples prepared for determination of PFBS, PFHS, and PFOS recovery. The groundwater samples, trip blank and one equipment rinseate blank were received from Weston personnel on October 29,2010 and November 4, 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 -02-10. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The equipment rinseate 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 from 0.0615 ng/mL to 0.480 ng/mL. The PFHS concentration results for all ground waters ranged from 0.0396 ng/mL to 0.622 ng/mL. The PFOS concentration results for all ground waters ranged from 0.0.0404 ng/mL to 2.41 ng/mL. The method uncertainty for PFBS is 100% 16%, PFHS 100% 16%, and PFOS 100% 21%. Table 1. Sum m arized PFOA Results (Off-Site G roundwater, Decatur, AL, O ctober 2010) Avg. PFBS Avg. PFHS Avg. PFOS Sample ID Concentration Concentration Concentration (ng/mL) RPD (ng/mL) RPD (ng/mL) RPD DAL GW 602L 101029 0.0813 0.49% 0.291 2 7 % [al 0.744 8.6% DAL GW 602S 101029 0.239 12% 0.127 6.3% 0.710 1 7% DAL GW 603L 101029 0.112 19% 0.109 1 4% 0.102 5.2% DAL GW 603S 101028 0.158 7.6% 0.122 3.3% 0.220 6.8% DAL GW 604L 101029 0.279 17% 0.215 14% 1.46 3.4% DAL GW 604S 101029 0.303 14% 0.224 8.5% 0.472 8.9% DAL GW 605R 101029 0.119 2 3% fai 0.0661 3.2% 0.0403 [bl DAL GW 605L 101029 0.406 0.49% 0.622 2 3% [al 0.522 2.5% DAL GW 607R 101028 0.0870 0.12% 0.0707 13% 0.0611 4.6% DAL GW 607L 101028 0.0615 2.8% 0.0823 38% [al 0.0920 8.2% DAL GW 609L 101027 0.259 8.9% 0.477 1.0% 2.41 5.0% [cl DAL GW 609R 101027 0.480 14% 0.154 37% [al 0.164 39% [al DAL GW 611R 101027 0.191 6.3% 0.0396 32% [al 0.580 7.2% DAL GW 611L 101027 0.317 1.3% 0.167 0.60% 0.933 5.1% Trip Blank (Milli-QTM Water) < 0.0250 < 0.0250 < 0.0400 Equipment rinseate blanks < 0.0250 < 0.0250 < 0.0400 N/A; not applicable [a] The sample/sample duplicate RPD was 20%. [b] A RPD could not be calculated as one of the sample replicates was <LOQ. [c] Sampling location did not have an appropriate FMS spike level to sufficiently evaluate PFOS recovery. Page 9 of 57 GLP10-01-02; Interim Report 10 Analysis of PFBS, PFHS, and PFOS In Groundwater from Decatur, AL October 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 off-site wells located in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on-site groundwater conditions. The 3M Environmental Laboratory prepared sample bottles (250 mL high-density polyethylene) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample bottle sets for each groundwater sampling location included a field sample, field sample duplicate, and a field spike sample. Each empty container for groundwater samplings 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, PFHS, and PFOS prior to being sent to the field for sample collection. All sample bottles also included the addition of internal standards 180 2-PFBS, 180 2PFHS, and 13C4-PFOS at a nominal concentration of 1 ng/mL. All sample bottles also included the addition of surrogate spike 13C4-PFOS at a nominal concentration of 0.1 ng/mL. See section 8.8 of the report for field matrix spike levels. 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 groundwater samples collected, the trip blank, and equipment rinseate samples. Tables 9-24 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 10 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 ieference Substances The analytical reference substances used for this study are listed below. fTi| Ijj R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predom inantly lin ear) Perfluorobutane sulfonate C4F9SO3 Potassium Salt 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% PFOS (lin ear) Perfluorooctane sulfonate C8F17SO3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% PFHS (lin ear) Perfluorohexane sulfonate C6F13SO3 Sodium Salt Wellington 4/2/2013 Frozen LPFHXSAM08 TCR08-0018 Crystalline 98% PFOS (lin ea r + branched) Perfluorooctane sulfonate C8F17SO3 Potassium Salt CAS #2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% Page 11 of 57 GLP10-01 -02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 1bo 2-p f b s Labeled - Perfluorobutane sulfonate C4F9S[180 2]0- Ammonium Salt RTI International 3/9/2015 Frozen 11546-107-2 TCR-1022, TCR-1028 and TCR-1033 Liquid 99% 1, Or PFHS Labeled - Perfluorohexane sulfonate C6F13S[1802]160- Sodium Salt Wellington 04/29/2013 Frozen MPFC-C-0410 TCR10-0037 Liquid N A(1) R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 1sC ,-P F O S Perfluorooctane sulfonate 13C8F17 s o 3 Sodium Salt Wellington 04/29/2013 Frozen MPFC-C-0410 TCR10-0037 Liquid N A <1) (1) Compound is part of a custom mixture of mass-labeled perfluorinated compounds at a concentration of 5.0 pg/mL. Page 12 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Test System There was not a test system for this study in the classic sense of a GLP study. This study was conducted for analysis of ground water samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" environmental samples. Sample Description Key Code. String Number Example 1 2 3 4 5 6 String Descriptor DAL GW602S 0101029 Sample Location Sample Type Well ID Well Level Sampling Date Sample Type Example DAL= Decatur, Alabama GW= Groundwater Example: 602 R = Residum shallow water-bearing zone L = Bedrock water-bearing zlne S = Epikarst middle water-bearing zone 101029- October 29,2010 0=primary sample DB=duplicate sample LS = low spike RB = Rinseate Blank 7 Method Summary 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on October 29, 2010 and November 4, 2010. Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spike samples 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. 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 in Table 2, Table 3 and Table 4. Page 13 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 ' Table 2. 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 Ginger ETS-8-044.0 11/08/10 Agilent 1200 Betasil C18 (2.1 mm X 100 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5p 25 uL Applied Biosystems API 5000 Turbo Spray Turbo ion electrode Neqative Analyst 1.4.2 Table 3. Liquid Chromatography Conditions. Step Number 0 1 2 3 4 5 Total Time (min) 0 1.0 13.0 15.0 15.5 17.0 Flow Rate (fdJmin) 750 750 750 750 750 750 Percent A (2 mM ammonium acetate) 97.0 97.0 5.0 5.0 97.0 97.0 Percent B (Methanol) 3.0 3.0 95.0 95.0 3.0 3.0 Table 4. Mass Transitions. Analyte Mass Transition Q1/Q3 Internal Standard Mass Transition Q1/Q3 PFBS 299/80 299/99 f ' OJPFBS 303/84 PFHS 399/99 399/80 fO JP F H S 403/84 499/99 PFOS 499/80 fC JP FO S 507/80 499/130 [13CJPFOS surrogate 503/80 fC J P F O S 507/80 Dwell time was 50 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation. alytical Results 8.1 Calibration Samples were analyzed against a stable isotope matrix-matched internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into laboratory prepared synthetic groundwater containing calcium and magnesium. A Page 14 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS In Groundwater from Decatur, AL October 2010 total of eleven spiked standards ranging from 0.025 ng/mL to 10 ng/mL (nominal) analyzed. The 0.025 ng/mL curve point was disabled for PFOS to meet accuracy criteria. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. All analytes met the acceptance criteria of less than of equal to 5% relative standard deviation (RSD) for peak ratio and retention time criteria of less than or equal to 2% RSD was met for PFBS and PFOS. The area ratio for PFHS was 5.9%. A method deviation is filed with the raw data. 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 5. Table 5. L im it o f Q uantitation (LOQ). Analysis Date 11/08/10 PFBS LOQ, ng/mL 0.0250 PFHS LOQ, ng/mL 0.0250 PFOS LOQ, ng/mL 0.0400 8.4 Continuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All CCVs met method criteria of 100% 25%. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: method blanks, trip blanks and equipment rinseate blanks. Method blank results were reviewed and used to evaluate method performance to determine the LOQ for each analyte. Trip blanks reflect the shipping and sample collection conditons the sample bottles and samples experience. Equipment rinseate blanks are aqueous samples that reflect the efficiency of equipment cleaning in the field between different sample collections and are proof of no cross contamination of samples from the equipment. 8.6 Lab Control Spikes (LCSs) Lab control spikes were prepared and analyzed in triplicate at two levels. LCSs were prepared by spiking known amounts of the target analytes into 10 mL of laboratory prepared synthetic groundwater to produce the desired concentration. The spiked water samples were then 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 220%, were met for PFBS, PFHS, and linear PFOS. As the reference materials used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of linear and branched isomers, additional LCS samples of linear and branched PFOS were prepared at two concentrations to evaluate the potential for analytical bias. The linear and branched LCS at both levels did not meet method acceptance criteria with average Page 15 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 recoveries of 126% and 122%, respectively. All LCS results were used in the determination of method analytical uncertainty in section 8.7. The following calculations were used to generate data in Table 6 for laboratory control spikes: , r, ._ Calculated Concentration , , LCS Percent Recovery = ------------------------------------- * 100% Spike Concentration , LCS% RSD = standard deviation LCS replicates . 10Q% average LCS recovery Table 6. Laboratory C ontrol Spike Recovery. ETS-8-044.0 Analyzed 11/08/10 Lab ID Spiked Concentration (ng/mL) PFBS Calculated Concentration (ng/mL) %Recovery Spiked Concentration (ng/mL) LCS-101105-1 LCS-101105-2 LCS-101105-3 0.198 0.198 0.198 0.200 101 0A98 0.200 101 0.198 0.215 109 0.198 Average %RSD LCS-101105-4 LCS-101105-5 LCS-101105-6 1.98 1.98 .1.98 104% 4.5% 2.03 1.82 2.05 103 92.2 104 1.99 1.99 1.99 Average %RSD 100% 6.6% PFHS Calculated Concentration (ng/mL) 0.212 0.207 0.220 108% 2.8% 1.96 1.91 1.97 97.8% 1.7% %Recovery 107 105 111 98.6 95.9 98.8 ETS-8-044.0 Analyzed 11/08/10 PFOS (linear) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) XRecovery Lab ID LCS-101105-1 LCS-101105-2 LCS-101105-3 0.198 0.198 0.198 0.189 0.208 0.218 95.6 LCS-101105-7 105 LCS-101105-8 110 LCS-101105-9 Average %RSD LCS-101105-4 LCS-101105-5 LCS-101105-6 1.98 1.98 1.98 104% 7.1% 1.97 1.89 2.09 99.3 95.4 106 Average %RSD LCS-101105-10 LCS-101105-11 LCS-101105-12 Average %RSD 100% 5.3% Average %RSD PFOS (linear+ branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) XoRecovery 0.196 0.196 0.196 0.256 0.234 0.250 131 119 128 1.97 1.97 1.97 126% 5.0% 111 2.52 2.42 2.29 128 123 116 122% 4.9% (1) (1) Laboratory control sample average recovery did not meet method acceptance criteria of 100% 20%. Page 16 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 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%. Table 7. Analytical Uncertainty. Analyte PFBS PFHS PFOS Standard Deviation 8.06 7.99 10.7 Method Uncertainty 100%16% 100%16% 100%21% 8.8 Field Matrix Spikes (FMS) A field matrix spike sample was collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes were generated by adding a measured volume of field sample to a container spiked by the laboratory with PFBS (linear), PFHS (linear), and PFOS (linear) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. Table 8. Field Matrix Spike Levels. Sam pling Location All sampling locations PFBS, ng/mL 0.999 PFHS, ng/mL 1.00 PFOS, ng/mL 0.999 ,,FMS ,,Recovery = (-S-a--m- p--l-e--C--o-n--c-e-n--t-r-a-t-i-o--n--o--f--F-M---S-----A---v-e-r-a-g-e---C--o--n-c--e-n--tr-a--t-io--n--:--F-i-e--l-d--S-a--m- p--l-e-&---F--i-e-l-d--S--a-m--p--l-e-D---u--p.) *100% 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 17 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Table 9. DAL GW 602L 101029 3MLIMSID Description GLP10-01-01-10-024 DAL GW 602L0 101029 GLP10-01-01-10-025 DAL GW602L DB 101029 GLP10-01-01-10-026 DAL GW 602L LS 101029 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable (1) The sample/sample duplicate RPD was 220%. Table 10. DAL GW 602S 101029 3MUMSID Description GLP10-01-01-10-028 GLP10-01-01-10-029 GLP10-01-01-10-030 DAL GW 602S0 101029 DAL GW602S DB 101029 DAL GW602S LS 101029 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.0815 NA 0.329 0.0811 NA 0.252 1.02 94.0 1.33 %Recovery NA NA 104 0.0813ng/mL 0.49% 0.291 ng/mL 27% (1> PFOS Concentration (ng/mL) 0.712 0.776 1.81 %Recovery NA NA 107 0.744 ng/mL 8.6% PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.224 NA 0.123 0.253 NA 0.131 1.48 124 0.944 %Recovery NA NA 81.7 0.239 ng/mL 12% 0.127 ng/mL 6.3% PFOS Concentration (ng/mL) 0.648 0.772 1.49 %Recovery NA NA 78.1 0.710 ng/mL 17% Page 18 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS In Groundwater from Decatur, AL October 2010 Table 11. DAL GW 603L 101029 3MUMSID Description GLP10-01-01-10-034 DAL GW 603L0 101029 GLP10-01-01-10-035 DAL GW603L DB 101029 GLP10-01-01-10-036 DAL GW603L LS 101029 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable Table 12. DAL GW 603S 101028 3MUMSID Description GLP10-01-01-10-021 GLP10-01-01-10-022 DAL GW 603S0 101028 DALGW603S DB 101028 GLP10-01-01-10-023 DAL GW603S LS 101028 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable PFBS PFHS Concentration Concentration (ng/mL) XRecovery (ng/mL) 0.101 NA 0.101 0.122 NA 0.116 1.16 105 1.04 XRecovery NA NA 93.2 0.112 ng/mL 19% 0.109 ng/mL 14% PFOS Concentration (ng/mL) 0.105 0.0997 1.02 XRecovery NA NA 91.9 0.102 ng/mL 5.2% PFBS PFHS Concentration Concentration (ng/mL) XRecovery (ng/mL) 0.164 NA 0.124 0.152 NA 0.120 1.12 96.3 0.952 XRecovery NA NA 83.0 0.158 ng/mL 7.6% 0.122 ng/mL 3.3% PFOS Concentration (ng/mL) 0.212 0.227 0.997 XRecovery NA NA 77.8 0.220 ng/mL 6.8% Page 19 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS In Groundwater from Decatur, AL October 2010 Table 13. DAL GW 604L 101029 3M UNIS ID Description GLP10-01-01-10-037 GLP10-01-01-10-038 GLP10-01-01-10-039 DAL GW 604L0 101029 DAL GW 604LDB 101029 DAL GW604L LS 101029 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable Table 14. DAL GW 604S 101029 3MUMSID Description GLP10-01-01-10-040 GLP10-01-01-10-041 GLP10-01-01-10-042 DAL GW 604S0 101029 DALGW604S DB 101029 DAL GW604S LS 101029 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.255 NA 0.200 0.302 NA 0.229 1.27 99.2 1.29 %Recovery NA NA 108 0.279 ng/mL 17% 0.215 ng/mL 14% PFOS Concentration (ng/mL) 1.48 1.43 2.32 %Recovery NA NA 86.6 1.46 ng/mL 3.4% PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.324 NA 0.214 0.282 NA 0.233 1.31 101 1.07 %Recovery NA NA 84.7 0.303 ng/mL 14% 0.224 ng/mL 8.5% PFOS Concentration (ng/mL) 0.493 0.451 1.33 %Recovery NA NA 85.9 0.472 ng/mL 8.9% Page 20 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Table 15. DAL GW 605R 101029 3MUMSID Description GLP10-01-01-10-043 GLP10-01-01-10-044 GLP10-01-01-10-045 DAL GW 605R0 101029 DAL GW605R DB 101029 DAL GW605R LS 101029 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.105 NA 0.0671 0.132 NA 0.0650 1.14 102 0.931 %Recovery NA NA 86.5 0.119 ng/mL 23% m 0.0661 ng/mL 3.2% PFOS Concentration (ng/mL) <0.0400 0.0403 0.952 %Recovery NA NA 91.3 0.0403 ng/mL m NA = Not Applicable (1) The sample/sample duplicate RPD was 220%. (2) A RPD could not be calculated as one sample replicate was <LOQ. Table 16. DAL GW 605L 101029 3M UNIS ID Description GLP10-01-01-10-031 DAL GW 605L0 101029 GLP10-01-01-10-032 DAL GW605L DB 101029 GLP10-01-01-10-033 DALGW605L LS 101029 Average Concentration (ng/mL) XRPD/RSD NA = Not Applicable (1) The sampie/sample duplicate RPD was 220%. PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.407 NA 0.693 0.405 NA 0.551 1.53 113 . 1.89 %>Recovery NA NA 127 0.406 ng/mL 0.49% 0.622 ng/mL 23% m PFOS Concentration (ng/mL) 0.528 0.515 1.42 %Recovery NA NA 89.9 0.522 ng/mL 2.5% Page 21 of 57 GLP10-01 -02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Table 17. DAL GW 607R 101028 3MUMSID Description GLP10-01-01-10-004 GLP10-01-01-10-005 GLP10-01-01-10-006 DAL GW607RO 101028 DAL GW607R DB 101028 DAL GW607R LS 101028 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable Table 18. DAL GW 607L 101028 31/1LIMS ID Description GLP10-01-01-10-001 GLP10-01-01-10-002 DAL GW 607L0 101028 DALGW607L DB 101028 GLP10-01-01-10-003 DALGW607L LS 101028 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable (1) The sample/sample duplicate RPD was 220%. PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.0870 NA 0.0661 0.0869 NA 0.0753 1.16 107 1.11 %Recovery NA NA 104 0.0870ng/mL 0.12% 0.0707 ng/mL 13% PFOS Concentration (ng/mL) 0.0625 0.0597 1.02 %Recovery NA NA 96.0 0.0611 ng/mL 4.6% PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.0606 NA 0.0665 0.0623 NA 0.0980 1.12 106 1.04 %Recovery NA NA 95.8 0.0615 ng/mL 2.8% 0.0823 ng/mL 38%<1> PFOS Concentration (ng/mL) 0.0882 0.0957 1.06 %Recovery . NA NA 96.9 0.0920 ng/mL 8.2% Page 22 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Table 19. DAL GW 609R 101027 3MLIMSID Description GLP10-01-01-10-010 GLP10-01-01-10-011 GLP10-01-01-10-012 DAL GW 609R0 101027 DAL GW609R DB 101027 DAL GW609R LS 101027 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable (1) The sample/sample duplicate RPD was >20%. PFBS PFHS Concentration Concentration (ng/mL) YoRecovery (ng/mL) 0.446 NA 0.125 0.513 NA 0.182 1.71 123 1.06 YoRecovery NA NA 90.7 0.480 ng/mL 14% 0.154 ng/mL 3 r/o W PFOS Concentration (ng/mL) 0.132 0.196 1.09 YoRecovery NA NA 92.7 0.164 ng/mL 39% m Table 20. DAL GW 609L101027 3MUMSID Description GLP10-01-01-10-007 GLP10-01-01-10-008 DAL G W 609L0 101027 DAL GW 609LDB 101027 GLP10-01-01-10-009 DAL GW609L LS 101027 Average Concentration (ng/mL) YoRPD/RSD PFBS PFHS Concentration Concentration (ng/mL) YoRecovery (ng/mL) 0.270 NA 0.479 0.247 NA 0.474 1.36 110 1.56 YoRecovery . NA NA 108 0.259 ng/mL 8.9% 0.477 ng/mL 1.0% PFOS Concentration (ng/mL) 2.47 2.35 3.55 YoRecovery NA NA NC 2.41 ng/mL 5.0% (1> NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) The sampling location did not have an appropriate FMS to sufficiently evaluate PFOS recovery. Page 23 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Table 21. DAL GW 611R 101027 3M UNIS ID Description GLP10-01-01-10-013 GLP10-01-01-10-014 GLP10-01-01-10-015 DAL G W 611R0 101027 DAL GW 611R DB 101027 DAL GW611R LS 101027 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable (1) The sample/sample duplicate RPD was >20%. Table 22. DAL GW 611L 101027 3MLIMSID Description GLP10-01-01-10-016 DAL GW 611L0 101027 GLP10-01-01-10-017 DAL GW 611LDB 101027 GLP10-01-01-10-018 DAL GW 611L LS 101027 Average Concentration (ng/mL) %RPD/RSD NA = Not Applicable PFBS PFHS Concentration (ng/mL) 0.185 0.197 1.23 XRecovery NA NA 104 Concentration (ng/mL) 0.0333 0.0459 1.04 XRecovery NA NA 100 0.191 ng/mL 6.3% 0.0396 ng/mL 32% w PFOS Concentration (ng/mL) 0.559 0.601 1.60 %Recovery NA NA 102 0.580ng/mL 7.2% PFBS PFHS Concentration (ng/mL) 0.315 0.319 1.36 %Recovery NA NA 104 Concentration (ng/mL) 0.167 0.166 1.06 %Recovery NA NA 89.4 0.317 ng/mL 1.3% 0.167 ng/mL 0.60% PFOS Concentration (ng/mL) 0.957 0.909 1.85 %Recovery NA NA 91.8 0.933 ng/mL 5.1% Page 24 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Table 23. Trip Blank 3MUMSID GLP10-01-01-10-019 GLP10-01-01-10-020 Description TRIP BLANK SAMPLE TRIP BLANK FMS NA = Not Applicable Table 24. DAL GW 602S RB 101029 3M UNIS ID GLP10-01-01-10-027 NA = Not Applicable Description DALGW602S RB 101029 PFBS PFHS Concentration Concentration (ng/mL) %Recovery (ng/mL) <0.0250 NA <0.0250 1.05 105 0.932 %Recovery NA 93.2 PFOS Concentration (ng/mL) <0.0400 0.933 %Recovery NA 93.4 PFBS PFHS PFOS Concentration (ng/mL) <0.0250 Concentration Concentration (ng/mL) (ng/mL) <0.0250 <0.0400 Page 25 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for PFBS, PFHS, and PFOS. Analysis was successfully completed following 3M Environmental Laboratory method ETS-8-044.0 described herein. 11 Data/Sample Retention ' All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 12 Attachments Attachment A: Protocol Amendment 10 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 26 of 57 GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS In Groundwater from Decatur, AL October 2010 13 Signatures Cleston Lange, Ph.D., 3M Principal Analytical Investigator ------- -------------------------------------------------------- ^ William K. Reagen, Ph.D., 3M Environmental Laboratory Manager Date Page 27 of 57 Attachment A GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Analytical Protocol: GLP10-01-02 Amendment 10 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. 10 Amendment Date: October 19, 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 Off-Site Phase 3 New Monitoring Wells Page 1 of 7 Page 28 of 57 Attachment A GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Analytical Protocol: GLP10-01-02 Amendment 10 This amendment modifies the following portion of protocol: "Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program" Protocol reads: No changes to the wording of the protocol are required. A mend to read: No changes to the wording of the protocol are required. This amendment only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis of groundwater samples from Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Program for PFOS, PFHS and PFBS (GLP10-01-02). The anticipated sample collection will occur around the timeframe of October 25, 2010. The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-02-10 and reported as interim report GLP10-01-02-10, (reflecting study GLP10-01-02 and amendment -10). Reason: The reason for this amendment is to document the General Project Outline (GPO) which describes the anticipate groundwater sample collection event to be conducted for the 3M Decatur, AL facility. The GPO is four pages in length and included as attached to this amendment form. Page 2 of 7 Page 29 of 57 Attachment A GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Analytical Protocol: GLP10-01-02 Amendment 10 Amendment Approval Un. Gary Hohenstein, Sponsor Representative Cleston C. Lange, Principal Analytical Investigator Date / Z> ) d 7 Date Page 3 of 7 Page 30 of 57 Attachment A GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Analytical Protocol: GLP10-01-02 Amendment 10 Jiw i Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: From: cc: Date: Subject: 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 Ocotber 19,2010 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; GLP Interim Report 10 - Off-Site Phase 3 New Monitoring Wells 1 General Project Information C o n ta c ts Lab Request Number Six Digit Departm ent Num ber P roject SchedulefTest Dates 3M S ponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651)737-3570 a a hohenstein@ m m m .com 3M E nvironm ental Laboratory M anagem ent William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaaen@ m m m .com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 ccla n a e @ m m m .c o m Sam pling C oordinator Timothy Frinak Weston Solutions T im o th v .frin a k @ w e s to n s o lu tio n s .c o m Phone: (334>-332-9123 GLP10-01 -02-10 Dept #530711, Project #0022674449 Sampling scheduled for the week of October 25, 2010 All verbal and written correspondence will be directed to Gary Hohenstein. Page 4 of 7 Page 31 of 57 Attachment A GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS In Groundwater from Decatur, AL October 2010 Analytical Protocol: GLP10-01-02 Amendment 10 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze surface water and groundwater samples collected from twenty-five sampling locations for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) as part of the Avenue A Investigation. Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples from Decatur, AL will be collected by Weston Sotutions personnel the week of October 25, 2010. The 3M Environmental Laboratory will prepare the sample bottles with all required spikes to ensure that results for PFBS, PFHS, and PFOS are of a known precision and accuracy. The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP1001- 02- 10. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of October 25,2010. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Friday, October 22, 2010. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ Weston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 Page 5 of 7 Page 32 of 57 Attachment A GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Analytical Protocol: G L P 10-01-02 Amendment 10 4 Test Parameters The targeted limit of quantitation will be 0.025 ng/mL (ppb) for PFBS, PFHS, and PFOS. A total of seventeen sampling locations have been specified. See attachment A for a list of the sampling locations that will be collected for this sampling event. For each sampling location, a total of three sample bottles will be collected (sample, sample duplicate, and a 1 ng/mL field matrix spike). The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. Two sets of trip blanks consisting of reagent-grade water and a 1 ng/mL trip blank spike will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. All sample bottles will include the addition of 180 2-PFBS, 18Or PFHS, and 13C8-PFOS (internal standard) at a nominal concentration of 1 ng/mL. All sample bottles will also include the addition of 3C4-PFOS (surrogate spike) at a nominal concentration of 0.1 ng/mL. One additional bottle will be prepared to be used for the preparation of the equipment rinseate blank. A 500mL bottle of laboratory reagent water will be sent with the sample bottles to be used to generate the rinseate blank sample. A total of 56 sample bottles will be prepared. 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Alternately, samples may be analyzed by ETS 8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 100+30%. Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Where applicable, samples will be analyzed against an internal standard calibration curve. Each curve point will contain isotopically-labeled perfluorocarboxylic acids and perfluorosulfonic acids at a nominal concentration of 1 ng/mL. The calibration curve will be generated by taking the ratio of the standard peak area counts over the internal standard peak area counts to fit the data for each analyte. 6 Reporting Requirements For each sampling location, the report will contain the results for the sample, sample duplicate, and the field matrix spike. Trip blank and trip blank spikes will be reported for the sampling event as will any equipment/rinseate blanks prepared in the field. Laboratory control spikes of reagent water prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks of reagent water prepared at the time of sample extraction will be used to determine the method detection limit. For those sampling locations where the field matrix spike level was not appropriate, due to higher than expected analyte concentrations, a laboratory matrix spike may be prepared and will be included in the final report. Page 6 of 7 Page 33 of 57 Attachment A Attachment A GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 Analytical Protocol: G L P 1 0 -0 1 -0 2 Am endm ent 10 Bottle Request Phase 3 Investigation Off-site Phase 3 New Monitoring Wells 02181.129.108.0001 D A T E R E Q U E S T E D : 18 O cto b er 2010 O cto b er 2010 D A T E R E Q U IR E D : 25 This request addresses the bottle requirements for the following wells: 602R 602S 602L 603R 603S 603L 604R 604S 604L 605R 605L 607S 607L 609R 609L 611R 611L Total Wells: 17 Sample Summary No. of Samples 17 1 2 Sample Tvpe Groundwater Rinseate Sample Trip Blanks Comment Will need HPLC water Anticipate 1 per cooler Note: Some o f the wells have limited volume so the smaller the volume requirements the better. SHIPPING INFORMATION Please ship to the following address: Martin Smith \ Weston Field Office 3M Decatur Plant 1400 State Docks Road Decatur, AL 35601 256-552-6189 Page 7 of 7 Page 34 of 57 Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 10 Analysis for October 2010 itF S !0 water from Decatur' AL Printing Date: Monday, January 03, 2011 Page 35 of 57 Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 10 Analysis for October 2010 { r j ^ o ^ w a t e r from Decatur, AL Data worked up by STW Printing Time: 1:36:03 PM ' Printing Date: Monday, January 03, 2011 Page 1 of 1 Page 36 of 57 Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 10 Analysis for P F g S ^ H ^ j p f October 2010 water from Decatur, AL Data worked up by STW Printing Time: 1:36:21 PM Printing Date: Monday, January 03, 2011 Page 1 of 1 Page 37 of 57 Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 10 Analysis for P F g S ^ l ^ j p l October 2010 jrjg ro jj^ w a te r from Decatur, AL Data worked up by STW Printing Time: 1:35:20 PM Printing Date: Monday, January 03, 2011 Page 1 of 8 Page 38 of 57 *** Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 10 AnalVSS for PFI ^ W % a & Pf f l f o ^ S 0 water frm DeCatuf'A L October 2010 Printing Time: 1:35:21 PM Printing Date: Monday, January 03, 2011 Page 39 of 57 Ginger AG01330509 Attachment B ISample Name: "g101108a06r Sample ID: ` GLP10-01-02Peak Name: 'MPFBS(IS)" M asses): '303.0/84.0 amu" Comment 'D AL G W 61 1L0 101027" Annotation:" Sample Index: 63 Sample Type: Unknown Concentration: 0.975 ng/mL Calculated Cone: N/A Acq. Date: 11/9/2010 Acq. Time: 5:25: 14 AM Modified: No Proc. Algorithm: Inte U U i u a n - IC'A Min. Peak Height: 0.00 cps Min. Peak, width: 0.00 sec Smoothing Width: 0 " points RT Window. 30.0 sec Expected RT: 12.1 min Use Relative RT: No Int. Type: all Area: Height: Start Time End Time: GLP10-01-02; Interim Report 10 Analysis for October 2010 jr jg r o ^ w a te r from Decatur, AL ISample Nam e:'g101108a07(r Sample ID: 'Method Blank" Peak Name: 'M PFBS(IS)' Mass(es): *303.0/84.0 amu* Comment " 10 005-181' Annotation: " Sample Index: 70 Sample Type: Unknown Concentration: 0.975 ng/mL Calculated Cone: N/A Acq. Date: 11/9/2010 Acq. Time: 7:32:31 AM Modi tied: Proc. Algorithm: Min. Peak Height: Min. Teak. Width: elliO'0.00 cps 0.00 Smoothing Width: 0 pc-int. RT Window: 30.0 Expected RT Use Rei; i RT: No F ile :'g 1 0 1 1 0 8 a .w ifT Height: Start Time End Time: Vailey i: 12.1 2363 02 o 11.2 11.4 ISample Name:'g101108a019* Sample ID :'06008-191-6' Peak Name: 'MPFHS(IS)" Mass/es): '403.0/84.0 amu* Comment '1.0 ng/mL FC std in Synth. Water" Annotation: Sample Index: 1* Sample Type: Standard Concentration: 0.915ng/mL Calculated Cone: N/A Acq. Dace: 11/9/2010 Acq. Tima: 1:05:37 PM File: *g101106a.wifr Modified: No Proc. Algorithm: IntalliQuaicps Hin. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 0 RT Window: 30.0 ' ExpecRetie.d RT:: RT: N1o3.5 Int. Type : Retention ' Area : Height : Start Time End Tima: 599050 counts l.B9a*005 cps 13.5 min 13.8 min IZ O 1 Z 2 12.4 12.6 12.8 13.0 ISample Name: "g101108a030* Sample ID:'LCS-101105-4Peak ama: 'M P F H S flS r Mas*(e8): '403.0/84.0 amu" Comment *2ppb LCS* Annotation: " sample Index: 30 Sample Type: QC Concentration: 0.938 Calculated Cone : N/A Acq. Date: 11/9/2010 Acq. Tima: 7:25:44 PM Modi fied: No proc. Algorithm : InceliiQu an - IQA Mir.. Peak Heightc: 0.00 cps Min. Peak Width:: 0.00 sec Smoothinq Width : 0 points RT Window: 30.0 sec Expected RT: 13.6 min Use Relative RT : No Int. Type: Area: Haight; Start Time: End Time: Valley 13.6 min 692646 =ounts 2.S9e*00S cps 13.4 min 13.8 min 11.8 12.0 1Z2 12.4 12.6 1Z 8 13.0 Data worked up by STW Printing Time: 1:35:21 PM Printing Date: Monday, January 03, 2011 Page 3 of 8 13.2 13.4 13.6 13.8 14.0 14.2 14.4 Page 40 of 57 *** Ginger AG01330509 Attachment B (Sample Nam*:"g101108a039* Sample ID: "LCS-101105-' Peak Name: *MPFHS(IS)* M asses): *403.0/84.0 amu* Comment *2ppb LCS EOF* Annotation: ** Sample Index: 39 Sample Type: QC . Concentration: 0.940 ng/mL 2.2*5 Calculated Cone: N/A Acq. Date: 11/9/2010 2.1*5 Acq. Time: 10:09:10 PM 2.0*5 Modified: Yes Proc. Min. Algorithm: Int Peak Height:: e0 l. 0l0iC'uacnps- I0A 1.9*5 Min. Peak Width: Smoothing Width: 0 0.00 sec points 1.8*5 RT Window: 30.0 sec 1.7*5 Expected RT: 13. min Use Relative RT: No 1.6*5 Int. Type: Valley Retent ion Time: 13.6 min Area: 657053 counts Height: :?.21e*005 cps Start Time: 13.5 min End Time: 13.8 min 1.5*5 1.4*5 1.3*5 i 1.2*5 f 1.1*5 1 1.0*5' 9.0*4- 8.0*4 7.0*4 6.0*4 5.0*4- 4.0*4- 3.0*4- 2.0*4- 1.0*4- JSample Name: *g101108a070* Sample 10: 'Method Blank Peak Name: *MPFHS(1S)* Masses): *403.0/84.0 amu* Comment *10 005-181* Annotation: -- Sample Index: 70 Sample Type: Unknown Concentration: 0.545 ng/mL Calculated Cone: N/A Acq. Date: 11/9/2010 Acq. Time: 7:32:34 AM Modified: Proc. Algorithm: . Min. Peak Height: te0 l. 0li0Quai< Min. Peak width: 0.00 : Smoothing Width: RT Window: Expected RT: I Relativ RT: Height : Start Tim End Time: Data worked up by STW Printing Time: 1:35:22 PM Printing Date: Monday, January 03, 2011 GLP10-01 -02; Interim Report 10 Analysis for P F g S ^ H ^ d October 2010 jr jp r a ^ w a t e r from Decatur, AL rSample Name: *g101108a063* Sample ID: ' GLP10-01-02-10-016* Peak Name: *MPFHS(ISr Mae<ea): *403.0/84.0 amu* Com m ent'D AL G W 6 1 1 L 0 101027* Annotation:" Sample Index: 03 Sample ng/mt Fie: *0101108a.wrtT Modified: Ye? Proc. Algcrithm: Intellie u n - IA Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 Smoothing Width: 0 points RT Window: >0.0 sec Expected RT: 13.6 min Use Relative RT: no Int. Type: Valley Retention Time: 13.S min Area: 662 612 =c>unts Height: 2. 59e005 cps Start Time: 13.4 min End Time: 13.9 min Sample Name: *g101108a019* Sample ID: *08008-191-8* F ila :' Peak Nama: *PFBS* M asses): *299.0/99.0 amu,299.0/80.0 amu* ' ' FC std in Synth. Water* Annotation: ~ Standard 0.999 : 0.944 I 11/5/2010 4:05:37 PM Page 4 of 8 Page 41 o f 57 Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 10 Analysis for P f p g jr jg r o ^ w a t e r from Decatur, AL October 2010 PM Printing Date: Monday, January 03, 2011 Page 42 of 57 *** Ginger AG01330509 Attachment B 1Sample Name: *g101108a019* Sampte ID: *08008.191-8* Fite: *g101108a.wtfr Peak Name: *PFHS* M asses): *399.0/99.0 amu,399.0/80.0 amu* C om m ent"1.0ng/m LFC stdinSyntti,W ater* Annotation:" Sample Type: Standard Concentration: 1.00 ng/u Calculated Cone: 1.03 ng/n Ac.q. Date: 11/8/2010 Acq. Time: 1:05:37 pH Pros. Algorithm: . Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: Expected RT: Use Relati' RT: No Height: Start Tir End Time: valley ,e: 13. 1444595 c 5.0*5 4.8e5 4.6*5 4.4*5 4.2*5 4.0e5 3.8e5 3.6e5 3.4e5 3.2eS 3,0eS 2.8eS 2.6*5 2.4e5 2.2e5 2.0e5 1.8*5 1.6*5 1.4*5 1.2*5 1.0e5 8.0*4 6.0e4 4.0*4 2.0*4 12.6 128 ISampteNam *:` 0lO11O8aO39* Sample ID: "LCS-101105-10* Fto: *g101106a.wir Peak Nam*: *PFHS* M asses): *399.0/99.0 amu,399.0/80.0 amu* Comment *2ppb LCS ECF* Annotation: " Sample Index: 39 Sample Type: yC Concentration: 0.00 Calculated Cone: 0.113 Acq. Dace: 11/8/2010 Acq. Tima: 10:09:10 : Modified: RT Window: Expected RT: Yes 30.0 13.3 Height: Start Tim End Time: Data worked up by STW Printing Time: 1:35:24 PM Printing Date: Monday, January 03, 2011 132 13.4 13.6 13.6 14.0 14.2 14.4 GLP10-01-02; Interim Report 10 Analysis for P F g ^ H J ^ d October 2010 jr jg r o ^ w a t e r from Decatur, AL Sampte Nam*: *g101106*030" Sampte ID: LCS-101105-4* m Peak Nam*: *PFHS Mass/*): *399.0/99.0 amu,399.0/80.< 1 Comment *2ppb LCS' Annotation: ** Sample Index: 30 Sample Type: QC 1.59 ng/mL 9.5*51 Calculated Cone: 1.56 ng/mL Acq. Dace: 11/8/201 Acq. Time: 7:25:14 PM Modi fi e d : Proc. Algorithm: Min. Peak Height Min. Peak Width: Smoothing Width: RT Window: Expected RT: Nc IntelliO an - IQA 0.00 cps 0.00 sec 0 points 0.0 sec 13.6 min No 8.5*57.5*5- Int. Type: 7 a l 1ey Retention Time: 13.6 rain Area: 3137601 c unta Height: .53e*005 cps Start Time: 13.5 min End Time: 13.9 min 6.5*5- 6.0*5- 5.5*5 s. 5.0*5 4.5*5 4.0*5 3.5*5 3.0*5 2.5*5 2.0*5 1.5*5 1.0*5 5.0*4 0.0 126 12.8 13.0 ISample Nam*: *g101108*063* Sampte ID :` GLP10-01-02-10016* Peak Name: *PFHS* Mass(es): "399.0/99.0 amu,399.0/80.0 amu* Comment *OAL GW 611L 0 101027* Annotation: " Sample Index: Unknown tl/A 6.0*4 F ite : 'g 1 0 1 1 0 8 a .v w r Modified: RT Window: Expected RT: Use Relative RT: Yea 30.0 13.6 No Int. Type: Manual Retention Time: 13.5 275841 Height: i.36.004 Start T 13.3 End Tim' 13.7 cp3 min min 7.5*4 7.0*4 6.5*4 6.0*4 5.5*4 5.0*4 4.5*4 4.0*4 3.5*4 3.0*4 25*4 20*4 1.5*4 1.0*4 5000.0 0.0 Page 6 of Page 43 of 57 Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 10 Analysis for PFg, P g j r j g r o i j^ a t e r from Decatur, AL October 2010 Printing Date: Monday, January 03, 2011 Page 44 of 57 Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 10 Analysis for P F g j y ^ H l ^ d October 2010 jrjp jo ij^ w a te r from Decatur, AL Printing Date: Monday, January 03, 2011 Page 45 of 57 Attachment C DocuK5i$,!iKt-0na^ibiiaM>rtifocurreni! for 14 days from 01/03/2011 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 3M Environm ental Laboratory Method Method o f Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: Q ^ Approved By: William K. Reagen, Laboratory Manager O /g > Date ETS-8-044.0 Page 1 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 46 of 57 Attachment C DocusL^rt-im^/ifesirriRi^rtifocurreni, for 14 days from 01/03/201 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 1 Scope and Application This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in clean water samples. Water samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method is considered a p e rfo rm a n c e -b a s e d method. Data is considered acceptable as long as the defined QC elements are satisfied. Sample collection is not covered under this analytical procedure. 2 Method Summary Clean aqueous samples are analyzed by direct injection using LC/MS/MS. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered. This is a performance-based method. Method accuracy is determined for each sample set using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to each sample matrix. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. Fortification levels for field matrix spikes and for laboratory matrix spikes should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used to determine the statement of accuracy for analytical results. 3 Definitions 3.1 Calibration Standard A solution prepared by spiking a known volume of the Working Standard (WS) into a predetermined amount of ASTM Type I, HPLC grade water, or other suitable water, and analyzed according to this ' method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration. 3.2 Laboratory Duplicate Sample (LDS, or Lab Dup) A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures. 3.3 Field Blank (FB)/Trip Blank ASTM Type I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose of the FB is to determine if test substances or other interferences are present in the field environment. This sample is also referred to as a Trip Blank. ETS-8-044.0 Page 2 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 47 of 57 Attachment C D o cu i ^0ii^ite^iafi^itifo curre nt, for 14 days from 01/03/2011 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 3.4 Field Duplicate Sample (FDS, Field Dup) A sample collected in duplicate at the same time from the same location as the sample. The FDS is handled under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures. 3.5 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to the sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside of the sample container. The FMS should be spiked between approximately 50% and 10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes are added in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a study sample to help determine if the method is in control and whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At least one separate, un-spiked sample must be taken at the same time and place as each FMS. 3.7 Laboratory Control Sample (LCS) An aliquot of control matrix to which known quantities of the target analytes are added in the laboratory at the time of sample extraction. At least two levels are included, one generally at the low end of the calibration curve and one near the mid to upper range of the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared each day samples are extracted. 3.8 Laboratory Matrix Spike (LMS) A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous samples. 3.9 Laboratory Sample A portion or aliquot of a sample received from the field for testing. 3.10 Limit of Quantitation (LOQ) The lower limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix-dependent. The upper limit of quantitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. The highest standard in the calibration curve that meets method criteria is defined as the ULOQ. ETS-8-044.0 Page 3 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 48 of 57 Attachment C DocuxsttPiniMmesyiteeiiws^rtifocurrent, for 14 days from 01/03/2011 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 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 49 of 57 Attachment C Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to two solvents and equipped with a variable volume injector capable of injecting 5-100 pL connected to a tandem Mass Spectrometer (LC/MS/MS). I . Analytical balance capable of reading to 0.0001 g A device to collect raw data for peak integration and quantitation 15-mL and 50-mL disposable polypropylene centrifuge tubes. Gas tight syringes, 25pL, 50pL, 100pL, 250pL, 500pL, 1000pL. 1 ml. plastic HPLC autovial. Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 6.2 Chromatographic System Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm Analytical Column: Betasil C18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Time (min) 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate imL/minl 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak Area - quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. The previous information is intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met. ETS-8-044.0 Page 5 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 50 of 57 Attachment C DocuxsuemMmesyitoaiias^rtifocurrent, for 14 days from 01/03/2011 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: Analyte Transition Monitored PFBA 213 -169 PFPeA 263 ->219 PFHA 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 -> 219 PFDA 513 --469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 ->219 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 - 99 PFHS 399 --> 80 and 399 --> 99 PFOS 499 -> 80, 499 -> 99 and 499 -> 130 Multiple transitions for monitoring the analytes is an option, as summing multiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention time criteria are met to assure adequate specificity. The previous information is intended as a guide, alternate instruments and equipment may be used. 7 Reagents and Standards 7.1 Chemicals Water - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate - A.C.S. Reagent Grade 7.2 Standards Perfluorobutanoic Acid (PFBA - C4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (P F H A -C 6 acid); Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M Perfluorononanoic Acid (P F N A - C9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (PFDA - C10 acid); Oakwood Products, Inc Perfluoroundecanoic Acid (PFUnA-C11 acid); Oakwood Products, Inc Perfluorododecanoic Acid (P FD oA -C 12 acid); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 51 of 57 Attachment C Docuia3iii(i-0Tr8s2/itea-iKiii)rtif6curreni, for 14 days from 01703/2011 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 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 (c o rre c te d fo r p e rc e n t s a lt a n d p u rity ) and dilute to 100mL with methanol or other suitable solvent, in a 100mL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. molecular weight of anion salt correction factor = moclecular weight of salt 499 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 w orking standard--Add 0.5mL each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/mL mixed w orking standard--Add 1.25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/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 52 of 57 Attachment C Docus?iifdi-mi>e^iki8i|il)rtifoDurrent, for 14 days from 01/03/2011 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 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 of WS, ng/mL 125 125 125 125 250 250 250 250 5000 5000 5000 Volume of WS, fd. 10 15 20 30 20 50 100 200 25 50 100 Final Volume of Calibration Standard (m l of ASTM Type 1 Water, 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 1Water, 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 53 of 57 Attachment C DoeiMtri-0Tra ^ t o for 14 days from 01/03/2011 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 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 54 of 57 Attachment C ' Docura^?rt-ffMf ihirwdsiffirtifocurrent, for 14 days from 01/03/201 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 2010 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: Analyte found (ng/mL) = (Peak Area - Intercept) 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 55 of 57 Attachment C DocuststfPi^ima^itowaeisMifocurrent, for 14 days from 01/03/2011 Analysis for PFBS, PFHS, and PFOS in Groundwater from Decatur, AL October 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 56 of 57 MMW?ntial GLP10-01-02; Interim Report 10 Analysis for PFBS, PFHS, and PFOS In Groundwater from Decatur, AL October 2010 Record of D eviation/N onconform ance _____________________________________I. Identification___________________________________ Study / Project No. Date(s) of Occurrence: | Document Number: GLP10-01-02-10 11/8/10- g 101108a ____ ____ ________ [ETS-8-044.0______ Deviation type 0 SOP Equipment Procedure 0 Method (Check one) Protocol______ GPO_________________ Other:____________________ _____________________ II. Description (attach extra p a g e s as n e e d e d ) _________ Method Requirements: (1) System suitability area count RSD <5%, retention time RSD <2% (2) LCS average recovery of 100% 20%. (3) Sample/Sample Duplicate RPD <20%. A ctual p ro cedure /process:....................................................................................................................... (1j Area ratios were used in place of area counts since the calibration curve was generated using internal standard area ratios. The area ratio RSD for PFHS was just outside method acceptance criteria at 5.9%. (2) LCS average recovery for both sets of linear and branched PFOS were outside method acceptance criteria with average recoveries of 126% and 122%. (3) The RPD value for several sampling locations were >20% III. Actions Taken (such as amendment issued, SOP revision, etc.) Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1) System suitability - Other QC items were used to assess data accuracy for PFHS, which had area ratio RSDs outside method acceptance criteria - calibration curve point accuracy, curve fit criteria, CCV, and LCS and FMS recoveries, all meeting method acceptance criteria. 2) In general, the ECF LCS for PFOA and PFOS have been running 15-20% higher when quantitated using linear PFOA and PFOS. LCS recoveries <130% for ECF PFOA and PFOS are within FMS acceptance criteria of 100% 30% for ETS-8-044.0. All LCS were used in the determination of method uncertainty. 3) Sampling locations with RPD values >20% will be footnoted in the data tables. Actions: Halting of Work Client Notification Work Recall 0 Other: Deviations will be noted in final report. Project Lead/PAI A pproval: SjL^an W o lf ^ Study Director (if GLP): f O y b i X J l) S ponsor A pproval (for G LP protocol deviations): NA Technical Reviewer (optional): NA Withholding of Report Date: i f e / j e u M e: ife /u Date: NA Date: NA Laboratory Departm ent M anager Approval: Date: --------~ IV. Authorization to Resume Work Where halting of work occurred, resumption of work must first be approved by Laboratory Management Laboratory Departm ent M anager Approval: NA Date: NA Deviation N o .__________________ (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 57 of 57