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G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 GLP10-01-02: Interim Report 17 - Analysis of PFBS. PFHS. and PFOS in Groundwater Samples Collected from Decatur. AL. 1st Quarter 2011 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 St. Paul, MN 55144 Project Identification GLP10-01-02-17 Total Number of Pages 98 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. Testing Cert #2052.01 Page 1 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 This page has been reserved for specific country requirements. Page 2 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 GLP C o m p lia n c e S tatem ent Report Title: Interim Report 17 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected from Decatur, AL, 1st Quarter 2011 Study: 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. 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. Page 3 of 98 G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S , and P FO S In Groundwater 1st Quarter Sampling - 2011 Q uality A ssurance Statement Report Title: Interim Report 17 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected from Decatur, AL, 1st Quarter 2011 Study: 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. This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dates 6/15/2011 - 6/29/2011 Phase Data / Interim Report Date Reported to Testing Facility Management Study Director 7/16/2011 7/14/2011 Date Page 4 of 98 G L P 10-01-02; Interim Report 17 Analysis of P FBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table of C ontents GLP Compliance Statement.................................................................................................................. 3 Quality Assurance Statement................................................................................................................ 4 Table of Contents...................................................................................................................................5 List of Tables......................................................................................................................................... 6 1 Study Information............................................................................................................................ 8 2 Sum m ary........................................................................................................................................ 9 3 Introduction....................................................................................................................................11 4 Test & Control Substances...........................................................................................................11 5 Reference Substances................................................................................................................. 12 6 Test System ..................................................................................................................................13 7 Method Sum m ary......................................................................................................................... 14 7.1 M ethods........................................................................................................................ 14 7.2 Sample Collection..........................................................................................................14 7.3 Sample Preparation.......................................................................................................14 7.4 Analysis......................................................................................................................... 14 8 Analytical Resu Its.......................................................................................................................... 16 8.1 Calibration.......................................................... 16 8.2 System Suitability......................................................................................................... 17 8.3 Limit of Quantitation (LO Q )........................................................................................... 17 8.4 Continuing Calibration...................................................................................................17 8.5 Blanks............................................................................................................................ 17 8.6 Lab Control Spikes (LC Ss)........................................................................................... 18 8.7 Analytical Method Uncertainty...................................................................................... 22 8.8 Laboratory Matrix Spikes (LM S)................................................................................... 22 8.9 Field Matrix Spikes (FMS).............................................................................................22 Page 5 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 9 Data Summary and Discussion................................................................................................... 23 10 Conclusion........................................................... !....................................................................... 36 11 Data/Sample Retention............................................................................................................... 36 12 Attachm ents..................................................................................................................................36 13 Signatures.....................................................................................................................................37 List o f Ta bles Table 1. Summarized PFBS, PFHS, and PFOS Results (Decatur Groundw ater-Q 1 2011). ...10 Table 2. Instrument Parameters................................................................................................... 15 Table 3. Liquid Chromatography Conditions............................................................................... 15 Table 4. Mass Transitions........................... !............................................................................... 16 Table 5. Limit of Quantitation (LOQ)........................................................................................... 17 Table 6. Laboratory Control Spike Recovery...............................................................................19 Table 7. Analytical Uncertainty..................................................................................................... 22 Table 8. Field Matrix Spikes.........................................................................................................23 Table 9. GW 203LQ1 Y11 LF..................................................................................................... 25 Table 10. GW 220RQ1 Y11 LF.................................................................................................. 25 Table 11. GW 220LQ1 Y11 LF....................................................................................................26 Table 12. GW 222RQ1 Y11 LF.................................................................................................. 26 Table 13. GW 227RQ1 Y11 LF.................................................................................................. 27 Table 14. GW 227LQ1 Y11 LF................................................................................ 27 Table 15. GW 31OR Q1 Y11 C P .................................................................................................28 Table 16. GW 312RQ1 Y11 C P ..................................................................................................28 Table 17. GW 317LQ1 Y11 CP...................................................................................................29 Table 18. GW 324LQ1 Y11 CP...................................................................................................29 Table 19. GW 327RQ1 Y11 C P ................................................................................................. 30 Table 20. GW 328RQ1 Y11 C P ..................................................................................................30 Page 6 of 98 G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 21. GW 328LQ1 Y11 CP................................................................................................31 Table 22. GW 330R Q1 Y11 C P ................................................................................................31 Table 23. GW 330L Q1 Y11 ........................................................... 32 Table 24. GW 331S Q1 Y11........................................................................................................ 32 Table 25. GW 335SQ1 Y11 C P ......................................................................................... 33 Table 26. GW GRS04 Q1 Y11 CP..............................................................................................33 Table 27. Trip Blank 1 ................................................................................................................. 34 Table 28. Trip Blank 2 ................................................................................................................. 34 Table 29. GLP10-01-02-17 Equipment Rinseate B lank............................................................. 35 Table 30. GLP10-01-02-15 Soil Equipment Rinseate Blanks.................................................... 35 Page 7 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 !1 Study Information Sponsor 3M Company Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j.kesari@ westonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 St. Paul, MN 55144 Study Personnel W illiam K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clanae@mmm.com): phone (651)-733-9860 Susan Wolf, 3M Analyst Chelsie Grochow; analyst Jonathan Steege; analyst Study Dates Study Initiation: March 8,2010 Interim 17 Experimental Termination: May 18, 2011 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 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 2 Summary The 3M Environmental Laboratory received groundwater samples from wells located in Decatur, AL, representing eighteen (18) different sampling locations collected March 23 - April 1, 2011. A total of eighty-one sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate groundwater samples from each sampling location. Samples also included field matrix spike (FMS) samples for each location, two trip blanks containing Milli-QTM water and appropriate trip blank spikes, and one equipment rinseate blank. The equipment rinseate blanks did not have FMS samples prepared for determination of PFBS, PFHS or PFOS recovery. All groundwater samples for this project were logged under GLP10-01-02-17. In addition, four aqueous soil equipment rinseate blanks for GLP10-01-02-15 were analyzed and reported herein. The aqueous soil equipment rinseate blanks were collected on January 26 - 27,2011. As with the groundwater equipment rinseate blanks, the soil equipment blanks did not have FMS samples prepared for determination of PFBS, PFHS or PFOS recovery. The groundwater samples, trip and equipment rinseate blanks for GLP10-01-02-17 were received from Weston personnel on April 5, 2011. The aqueous soil equipment rinseate blanks for GLP10-01-02-15 were received from Weston personnel on February 2, 2011. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0. Many of the groundwater samples required dilution to attain PFBS, PFHS, and PFOS concentrations within the range of the curve, in some instances up to a 200-fold dilution were required. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. Equipment rinseate and the trip blanks were below the lower limit of quantitation (LLOQ), indicating adequate control of sample contamination during shipping and sample collections. The PFBS concentration results for all groundwaters ranged from 0.0246 ng/mL to 3020 ng/mL. The PFHS concentration results for all groundwaters ranged from 0.119 ng/mL to 5360 ng/mL. The PFOS concentration results for the reported groundwaters ranged from 0.250 ng/mL to 6010 ng/mL. The analytical uncertainties associated with the reported results are as follows: PFBS 100% 17%, PFHS 100% 17%, and PFOS 100% 22% . Page 9 of 98 G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 1. Summarized PFBS, PFHS, and PFOS Results (Decatur Groundwater - Q1 2011). Sampling Location GW203LQ1 Y11 LF GW220RQ1 Y11 LF GW220LQ1 Y11 LF GW 222R Q1 Y11 LF GW227RQ1 Y11 LF GW227LQ1 Y11 LF GW 31OR Q1 Y11 CP GW312RQ1 Y11 CP GW317LQ1 Y11 CP GW324LQ1 Y11 CP GW327RQ1 Y11 CP GW328RQ1 Y11 CP GW 328L Q1 Y11 CP GW330RQ1 Y11 CP GW330LQ1 Y11 CP GW 331S Q1 Y11 CP GW 335S Q1 Y11 CP GWGRS04Q1 Y11 CP Trip Blank (Milli-QTM Water) GLP10-01-02-17 Equipment Rinseate Blank GLP10-01-02-15; Four Aqueous Soil Equipment Rinseate Blanks PFBS Avg. Cone. (ng/mL) %RPD 105 2.9% 8.41 0.83% 11.5 2.6% 97.6 2.8% 19.6 24% <2> 292 4.1% 840 0.83% 1190 3.4% 0.0246 21% (2) 112 1.8% 93.3 2.7% 39.0 5.1% 71.9 3.3% 3020 1.7% (4> 545 17% 558 29% (2) 1080 3.7% (5) 2020 6.9% <0.0200 <0.0200 <0.0250 PFHS Avg. Cone. (ng/mL) %RPD 595 2.0% 34.3 4.7% 52.0 4.8% 607 2.8% 106 23% (2) 62.2 1.8% 485 8.0% 629 26% (2) 0.119 3.4% 111 5.4% 168 1.8% (3) . 63.1 5.1% 22.3 3.6% 259 1.5% 625 17% 292 15% 2030 2.5% (4) 5360 6.9% <0.0400 <0.0400 <0.0250 PFOS Avg. Cone. (ng/mL) %RPD 861 12 <1) 51.5 3.1% 83.5 11% 781 6.7% 740 23% <2) 363 1.4% 1020 14% 1010 34% <2) 0.250 15% 316 10% 617 8.4% 217 6.0% 1.33 14% 720 1.4% 223 9.0% 642 8.3% 6010 6.7% (4) n r (6) <0.500 <0.500 <0.0250 The analytical method uncertainties associated with the reported results are as follows: PFBS 100% 16%, PFHS 100% 18%, and PFOS 100% 2 1 % . (1) The analytical uncertainty for PFOS has been adjusted to 38% based on FM S recovery. (2) The RPD did not meet method acceptance criteria of 20%. (3) The analytical uncertainty for PFHS has been adjusted to 41 % based on FM S recovery. (4) Sampling location did not contain an appropriate spike level to assess recovery. (5) The analytical uncertainty for PFBS has been adjusted to 34% based on FMS recovery. (6) NR = Not Reportable. Recovery of the most appropriate FMS sample was <50%. See section 9 of the report for additional information. Page 10 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater . 1st Quarter Sampling - 2011 3 Introduction This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze ground water samples collected from various wells located in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on-site groundwater conditions. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and field spike samples. Each empty container was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear), PFHS (linear), and PFOS (linear) prior to being sent to the field for sample collection. See section 8.8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined- in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, trip blanks and equipment rinseate samples. Tables 9-27 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. G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 5 Reference Substances Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predominantly linear) Perfluorobutane sulfonate C 4F 9SO 3 Potassium Salt 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOS (linear) Perfluorooctane sulfonate C8F17SO 3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% PFHS (linear) Perfluorohexane sulfonate C6F13SO 3 Sodium Salt Wellington 4/2/2013 Frozen LPFHXSAM08 TCR08-0018 Crystalline 98% PFOS (linear + branched) Perfluorooctane sulfonate C8F1 7 S O 3 Potassium Salt CAS #2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% Page 12 of 98 GLP10-01-02; Interim Report 17 Analysis of PFBS, PFHS, and PFOS in Groundwater 1st Quarter Sampling - 2011 Reference Substance Chemical Name 13Ca-PFOS (linear) Sodium Perfluorooctanesulfonate Chemical Formula 13C8F17S 0 3'Na+ Identifier CAS # MPFC-C-0910 Source Wellington Expiration Date 09/28/2013 Storage Conditions Frozen Chemical Lot Number 092310 TCR Number TCR10-0048 Physical Description Liquid Purity 5 pg/mL<1) (1) Custom mixture of seven mass-labeled (13C) perfluoroalkylcarboxylic acids, two mass-labeled (13C ) perfluoroalkylsulfonates and one mass-labeled (,3C) perfluoro-1 -octanesulfonamide. The test system for this study are ground water samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. Sample Description Key Code. Example GW330L Q1 Y11 CP 1 String Number String Descriptor 1 Sample Type 2 Well Identifier 3 Well Level 4 Sampling Date 5 Sampling Location 6 Sample Type Example GW= Ground water Example: 330L R = Residuum shallow water-bearing zone L = Bedrock water-bearing zone S = Epikarst middle water-bearing zone Q1 Y11 = 1stquarter, 2011 CP = Chemical Plant FL = Former Landfill 0=primary sample 1=duplicate sample LS - low spike HS = high spike Page 13 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 7 Method Summery 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on October 1, 2010. Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with the sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. Samples that required dilution were prepared as follows: 1:5 dilutions were prepared by diluting 2mL sample with 8 mL of Milli Q water, 1:10 dilutions were prepared by diluting 1mL sample with 9 mL of Milli Q water, 1:20 dilutions were prepared by diluting 0.5mL sample with 9.5mL of Milli Q water, 1:50 dilutions were prepared by diluting 0.2mL sample with 9.8mL of Milli Q, and 1:100 dilutions were prepared by diluting 0.1 mL sample with 9.9mL of Milli Q water. 1:200 dilutions were prepared by diluting 0.05mL sample with 9.95mL of Milli Q water. Samples may also have been diluted further by varying the injection volume during analysis. Sampling locations GW 317L and GW 328L were prepared for PFOS by removing a 10 mL aliquot and adding an aliquot of a separate internal standard spiking solution (nominal concentration of 1 ng/mL). This same procedure was followed for the laboratory control samples. 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. 4/19/11 Analysis: All samples analyzed for PFBS, PFHS, and PFOS. 4/24/11 Analysis: Analyzed re-diluted sample set GW 222R Q1 Y11 LF for PFBS, PFHS, and PFOS. 5/12/11 Analysis: Analysis of GLP10-01-02-15 soil equipment rinseate blanks for PFBS, PFHS. 5/14/11 Analysis: Analysis of sampling location GW 317L Q1 Y11 CP and GW 328L Q1 Y11 for PFOS with internal standard. 5/16/11 Analysis: Analysis of GLP10-01-02-15 aqueous soil equipment rinseate blanks for PFOS. 5/17/11 Analysis: Analysis of re-diluted sample set GW GRS04 Q1 Y11 CP for PFOS with laboratory matrix spike. Page 14 of 98 G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 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 4/19/11 and 4/24/11 Agilent 1100 Prism RP (2.1 mm X 50 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5u 2 or 5 uL Applied Biosvstems API 5000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Table 3. Liquid Chromatography Conditions. ETS McCoy ETS-8-044.0 5/12/11,5/14/11,5/16/11,5/17/11 Agilent 1290 Prism RP (2.1 mm X 50 mm), 5 u Betasil C 18 (2.1 mm X 100 mm), 5u 10, 25 or 5 |iL Applied Biosystems API 5500 Turbo Spray Turbo ion electrode Negative Analyst 1.5.2 Step Number 0 1 2 3 4 5 0 1 2 3 4 5 Total Time (min) Flow Rate (fiL/min) PercentA (2 mM ammonium acetate) ETS-8-044.0 Analysis 4/19/11 and 4/24/11 0 300 90.0 1.0 300 90.0 11.0 13.5 14.0 300 300 300 10.0 10.0 90.0 17.0 300 90.0 ETS-8-044.0 Analysis 5/12/11,5/14/11,5/16/11, and 5/17/11 0 300 90.0 2.0 300 90.0 14.5 300 5.0 15.5 300 5.0 16.5 300 90.0 20.0 300 90.0 Percent B (Mediano!) 10.0 10.0 90.0 90.0 10.0 10.0 10.0 10.0 95.0 95.0 10.0 10.0 Page 15 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S In Groundwater 1st Quarter Sampling - 2011 Table 4. Mass Transitions. Analyte Reference Material Structure Mass Transition Q1/Q3 Internal Standard Mass Transition Q1/Q3 PFBS Linear 299/80 299/99 NA NA PFHS Linear 399/80 399/99 NA NA 499/80 PFOS Linear 499/99 ( l3CJPFOSn 507/80 499/130 Dwell time was 50 msec (4/19/11,4/24/11,5/14/11,5/16/11, and 5/17/11 analysis) or 20 msec (5/12/11 analysis) for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation. NA = Not Applicable (1) Internal standard was only used for the analysis of locations: G W 317L, G W 328L, and GLP10-01-02-15 soil equipment rinseate blanks for PFOS. 8 Analytical Results 8.1 Calibration 4/19/11,4/24/11,5/12/11, and 5/17/11 analysis: Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into Milli Q water. A total of fifteen spiked standards ranging from 0.020 ng/mL to 100 ng/mL were prepared, however, not all analytical runs included all fifteen standards. Low curve points were disabled to meet accuracy or method blank criteria. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS for each analytical batch. 5/14/11 analysis: Sampling locations GW 317L, GW 328L, and GLP10-01-02-15 soil equipment rinseate blanks for PFOS. Samples were analyzed against a matrix-matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and magnesium. The calibration standards contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of ten spiked standards ranging from 0.050 ng/mL to 25 ng/mL were analyzed for PFOS. A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. 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 PFOS. 5/16/11 analysis: Sampling locations GLP10-01-02-15 soil equipment rinseate blanks for PFOS. Samples were analyzed against a matrix-matched stable isotope internal standard calibration curve. Page 16 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and magnesium. The calibration standards contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of nine spiked standards ranging from 0.0250 ng/mL to 2.5 ng/mL were analyzed for PFOS. A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. 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 PFOS. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, and PFOS for each analytical batch. 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 LOQs associated with the sample analysis are listed in the table below. Table 5. Limit of Quantitation (LOQ). Analysis Date Dilution PFBS LOQ, ng/mL PFHS LOQ, ng/mL 4/19/11 1 0.0200 0.0400 5 0.100 0.200 10 0.200 0.400 20 0.400 0.800 50 1.00 2.00 100 2.00 4.00 4/24/11 20 0.400 5.00 50 1.00 12.5 5/12/11 1 0.0250 0.0250 5/14/11 1 NA NA 5/16/11 1 NA NA 5/17/11 200 NA NA NA = Not Applicable; analytical results for were not reported from the run. PFOS LOQ, ng/mL 0.500 2.50 5.00 10.0 25.0 50.0 5.00 12.5 NA 0.0500 0.0250 20 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 reported samples were bracketed by CCVs that met method criteria of 100% 25%. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: method procedural blanks, field/trip blanks, and equipment blanks. Method procedural blank results were reviewed and used to evaluate method performance and to determine the LOQ for each analyte. Page 17 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 8.6 Lab Control Spikes (LCSs) A minimum of two lab control spike levels were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into 10 mL of Milli Q water 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 <20%. 4/19/11 Analysis: Three levels of LCS were prepared and met method acceptance criteria for PFBS, PFHS, and linear PFOS. 4/24/11 Analysis: Three levels of LCS were prepared and met method acceptance criteria for PFBS. The low set of LCS samples were BLOQ for PFHS and PFOS, while the mid and high set of LCS samples met method acceptance criteria. 5/12/11 Analysis: Two levels of LCS were prepared and met method acceptance criteria for PFBS and PFHS. 5/14/11 Analysis: Three levels of LCS were prepared and met method acceptance criteria for linear PFOS. 5/16/11 Analysis: Two levels of LCS were prepared and met method acceptance criteria for PFOS. 5/17/11 Analysis: Two levels of LCS were prepared and met method acceptance criteria for PFOS. As the reference materials used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of both linear and branched isomers, additional LCS samples of PFOS (linear + branched) were prepared to evaluate the potential for analytical bias. 4/19/11 Analysis: Three levels of linear and branched PFOS LCS were prepared and met method acceptance criteria. 4/24/11 Analysis: Three levels of linear and branched PFOS LCS were prepared. The low set of LCS samples were BLOQ, while the mid and high set of LCS samples met method acceptance criteria, and met method acceptance criteria. 5/14/11 Analysis: Three levels of linear and branched PFOS LCS were prepared and met method acceptance criteria. 5/16/11 Analysis: Two levels of linear and branched PFOS LCS were prepared and met method acceptance criteria. 5/17/11 Analysis: Two levels of linear and branched PFOS LCS were prepared and met method acceptance criteria. The following calculations were used to generate data in Table 6 for laboratory control spikes. Calculated Concentration LCS Percent Recovery = 100% Spike Concentration standard deviation LCS replicates LCS% RSD = 100% average LCS recovery Page 18 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 Table 6. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 4/19/11 Lab ID L C S -1 10412-1 L C S -1 10412-2 L C S -1 10412-3 Average %RSD L C S -1 10412-4 L C S -1 10412-5 L C S -1 10412-6 Average %RSD L C S -1 10412-7 L C S -1 10412-8 L C S -1 10412-9 Average %RSD Spiked Concentration (ng/mL) 2.00 2.00 2.00 20.0 20.0 20.0 50.0 50.0 50.0 PFBS Calculated Concentration (ng/mL) 2.17 2.16 2.23 109% 1.4% 20.6 23.6 22.5 111% 6.8% 52.2 56.9 57.0 111% 5.2% %Recoverv 109 108 111 103 118 112 104 114 114 Spiked Concentration (ng/mL) 2.00 2.00 2.00 20.0 20.0 20.0 50.0 50.0 50.0 PFHS Calculated Concentration (ng/mL) 2.22 2.30 2.29 113% 1.8% 21.1 23.5 22.7 112% 5.4% 51.9 56.0 56.9 110% 4.8% %Recoverv 111 115 114 106 118 113 104 112 114 ETS-8-044.0 Analyzed 4/19/11 Lab ID L C S -1 10412-1 L C S -1 10412-2 L C S -1 10412-3 Average %RSD L C S -1 10412-4 L C S -1 10412-5 L C S -1 10412-6 Average %RSD L C S -1 10412-7 L C S -1 10412-8 L C S -1 10412-9 Average %RSD Spiked Concentration (ng/mL) 2.00 2.00 2.00 20.0 20.0 20.0 50.0 50.0 50.0 PFOS (lineai) Calculated Concentration (ng/mL) 2.21 2.51 2.10 114% 9.0% 21.7 24.3 23.0 115% 6.1% 52.7 56.7 57.7 111% 4.8% %Recoverv Lab ID 111 LC S -110412-10 125 LCS-110412-11 105 LCS-110412-12 Average %RSD 108 LCS-110412-13 122 LCS-110412-14 115 LCS-110412-15 Average %RSD 105 LCS-110412-16 113 LCS-110412-17 115 LCS-110412-9 Average %RSD PFOS (linear+ branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 2.02 2.14 106 2.02 2.02 2.03 2.31 107% 6.1% 101 114 20.2 20.2 20.2 21.8 23.3 22.3 108 115 110 111% 3.2% 50.5 50.5 50.5 61.5 60.0 52.7 122 119 104 115% 8.4% Page 19 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 6 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 4/24/11 Lab ID L C S -1 10422-1 L C S -1 10422-2 L C S -1 10422-3 Average %RSD L C S -1 10422-4 LCS-110422-5 L C S -1 10422-6 Average %RSD L C S -1 10422-7 L C S -1 10422-8 L C S -1 10422-9 Average %RSD Spiked Concentration (ng/mL) 0.200 0.200 0.200 2.00 2.00 2.00 20.0 20.0 20.0 PFBS Calculated Concentration <ng/mL) 0.189 . 0.200 0.231 103% 10% 1.91 2.12 2.23 105% 7.9% 19.6 21.5 23.4 107% 8.9% %Recoverv 94.3 99.8 115 95.6 106 112 97.9 107 117 Spiked Concentration (ng/mL) 0.200 0.200 0.200 2.00 2.00 2.00 20.0 20.0 20.0 PFHS Calculated Concentration (ng/mL) <0.250 <0.250 <0.250 NA'1' 1.82 2.23 2.01 101% 10% 17.6 18.9 20.6 95.3% 7.8% %Recoverv NA NA NA 91.1 112 101 88.2 94.7 103 ETS-8-044.0 Analyzed 4/24/11 Lab ID Spiked Concentration (ng/mL) PFOS (linear) Calculated Concentration (ng/mL) L C S -1 10422-1 0.200 <0.250 L C S -1 10422-2 L C S -1 10422-3 Average %RSD 0.200 0.200 <0.250 <0.250 NA'1 L C S -1 10422-4 L C S -1 10422-5 L C S -1 10422-6 Average %RSD L C S -1 10422-7 L C S -1 10422-8 L C S -1 10422-9 Average %RSD 2.00 2.00 2.00 20.0 20.0 20.0 1.75 1.97 1.95 94.5% 6.2% 20.5 23.7 24.1 114% 8.5% %Recovery Lab ID NA LCS-110422-10 NA LCS-110422-11 NA LCS-110422-12 Average %RSD 87.7 L C S -1 1 0 422-13 98.4 L C S -1 1 0 422-14 97.3 L C S -1 10422-15 Average %RSD 103 LCS-110422-16 118 LCS-110422-17 121 LC S -110422-18 Average %RSD PFOS (linear+ branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 0.202 <0.250 NA 0.202 0.202 <0.250 <0.250 NA'1' NA NA 2.02 2.02 2.02 20.2 20.2 20.2 1.84 1.82 1.69 88.1% 4.5% 21.0 22.1 21.9 107% 2.8% 90.8 89.9 83.5 104 110 108 (1) The sample result was BLOQ. A recovery could not be calculated. Page 20 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 6 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 5/12/11 Lab ID L C S -1 10509-1 L C S -1 10509-2 L C S -1 10509-3 Average %RSD L C S -1 10509-4 L C S -1 10509-5 L C S -1 10509-6 Average %RSD Spiked Concentration (ng/mL) 0.198 0.198 0.198 1.98 1.98 1.98 PFBS Calculated Concentration (ng/mL) 0.185 0.202 0.212 101% 6.9% 1.70 2.22 2.40 106% 17% `/Recovery 93.2 102 107 85.7 112 121 Spiked Concentration (ng/mL) 0.198 0.198 0.198 1.98 1.98 1.98 PFHS Calculated Concentration (ng/mL) 0.201 0.221 0.223 108% 5.6% 1.74 2.19 2.25 104% 13% `/Recovery 101 111 112 88.0 111 113 ETS-8-044.0 Analyzed 5/14/11 Lab ID L C S -1 10513-1 L C S -1 10513-2 L C S -1 10513-3 Average %RSD L C S -1 10513-4 L C S -1 10513-5 L C S -1 10513-6 Average %RSD L C S -1 10513-7 L C S -1 10513-8 L C S -1 10513-9 Average %RSD Spiked Concentration (ng/mL) 0.199 0.199 0.199 1.99 1.99 1.99 9.94 9.94 9.94 PFOS (linear) Calculated Concentration (ng/mL) 0.188 0.183 0.182 92.7% 1.8% 2.22 2.12 2.36 112% 5.0% 9.09 9.25 8.19 89.0% 6.4% !'Recovery Lab ID 94.6 L C S -1 10513-10 92.0 91.4 L C S -1 10513-11 L C S -1 10 513-12 Average %RSD 111 LC S -110513-13 107 LCS-110513-14 118 LCS-110513-15 Average %RSD 91.5 L C S -1 1051 3-1 6 93.0 L C S -1 10 513-17 82.4 L C S -1 10 513-18 Average %RSD PFOS (linear+ branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) `/Recovery 0.201 0.196 97.6 0.201 0.201 0.209 0.207 102% 3.4% 104 103 2.01 2.01 2.01 2.05 2.01 2.14 102 100 106 103% 3.0% 10.0 10.0 10.0 9.96 9.85 9.84 98.8% 0.67% 99.6 98.5 98.4 ETS-8-044.0 Analyzed 5/16/11 Lab ID Spiked Concentration (ng/mL) L C S -1 10509-1 0.198 L C S -1 10509-2 L C S -1 10509-3 Average %RSD 0.198 0.198 L C S -1 10509-4 L C S -1 10509-5 L C S -1 10509-6 Average %RSD 1.98 1.98 1.98 PFOS (linear) Calculated Concentration (ng/mL) 0.152 0.164 0.182 83.6% 9.1% 1.52 1.99 2.06 93.6% 16% %Recovery Lab ID 76.6 L C S -1 10509-10 82.6 91.7 L C S -1 10509-11 LCS-110509-12 Average %RSD 76.7 L C S -1 10 509-13 100 LCS-110509-14 104 LCS-110509-15 Average %RSD PFOS (linear+ branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 0.200 0.199 99.6 0.200 0.200 0.207 0.207 102% 1.9% 103 103 2.00 2.00 2.00 2.03 2.15 2.05 104% 3.1% 102 108 103 Page 21 of 98 GLP10-01-02; Interim Report 17 Analysis of PFBS, PFHS, and PFO S in Groundwater 1st Quarter Sampling - 2011 Table 6 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 5/17/11 Lab ID L C S -1 10517-1 LCS-110517-2 LCS-110517-3 Average %RSD LCS-110517-4 LCS-110517-5 LCS-110517-6 Average %RSD Spiked Concentration (ng/mL) 4.98 4.98 4.98 40.0 40.0 40.0 PFOS (lineari Calculated Concentration (ng/mL) 5.82 5.73 5.69 115% 1.3% 44.5 45.3 45.6 113% 1.4% %Recovery Lab ID 117 LCS-110517-7 115 LCS-110517-8 114 LCS-110517-9 Average %RSD 111 LC S-110517-10 113 LCS-110517-11 114 LCS-110517-12 Average %RSD PFOS (linear + branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 5.04 4.79 95.1 5.04 5.04 5.04 4.90 100 97.2 97.4% 2.5% 40.4 40.4 40.4 40.3 41.9 41.7 99.8 104 103 102% 2.1% 8.7 Analytical Method Uncertainty Analytical uncertainty Is based on historical LCS 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 LCS samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. A minimum of the 50 data points were used to generate the method uncertainty values. Table 7. A nalytical U ncertainty. Analyte PFBS PFHS PFOS Standard Deviation 8.72 8.43 11.0 Method Uncertainty 17% 17% 22% 8.8 Laboratory Matrix Spikes (LMS) Two laboratory matrix spikes were prepared for sample set GW GRS04 Q1 Y1 CP for PFOS. The high FMS at 5000 ng/mL was not meeting method acceptance criteria for PFOS, therefore, a 5000 ng/mL LMS sample was prepared on both the primary sample and the sample duplicate. It was noted at the time of sample preparation, that the primary sample for this sampling set contained significantly more sediment in the sample bottle as compared to the other sample bottles collected for this location. The color of the sample was similar to the color of dark tea and had a strong petroleum odor. The LMS sample was prepared by removing a 0.05 mL aliquot of both the primary sample and the sample duplicate, adding an aliquot of spiking solution, and adding laboratory reagent water for a final volume of 10 mL. The dilution factor for the LMS samples was 200x. The LMS samples met method acceptance criteria with recoveries for 106% and 107% respectively. 8.9 Field Matrix Spikes (FMS) Field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes were generated by adding a measured volume of field sample to a container spiked by the laboratory with PFBS (linear), PFHS (linear), and PFOS (linear) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike Page 22 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Q uarter S am plin g- 2011 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 Spikes. Sampling Location 317L 220R, 220L, 328L 203L, 222R, 227L, 227R, 31 OR, 324L, 327R, 330L(1), 331S and 335S GRS04, 312R, 330R|1> 328R Trip Blank Sets 1 and 2 Spike Level Low FMS High FM S Low FMS High FM S Low FMS High FM S Low FMS High FM S Low FMS High FM S Low FMS Mid FM S High FMS PFBS (ng/mL) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 PFHS (ng/mL) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 PFOS (ng/mL) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 (1) The sample collection bottles used to collect location G W 330R were intended for location G W 3 3 0 L . The sample collection bottles used to collect location G W 330L were Intended for location G W 330R. FMS Recovery - (amP*e Concentration o f FMS - Average Concentration:Field Sample & Field Sample Dup.) + 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 blank. 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. DAL GW 203L Q1 Y11 LF (Table 9) - The recovery of the HS for PFOS was 138%. Since this was the only appropriate spike level, the analytical uncertainty has been adjusted for PFOS to 38%. DAL GW 327R Q1 Y11 CP (Table 19) - The recovery of the LS for PFHS was 141 % and the recovery of the HS was 96.3%. Since the LS is the most appropriate spike level, the analytical uncertainty has been adjusted for PFHS to 41 %. DAL GW 330R Q1 Y11 CP (Table 22) - The wrong sample bottles were used to collect this sampling location. As a result, an appropriate field matrix spike was not available for PFBS. Page 23 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 DAL GW 335S Q1 Y11 CP (Table 25) - The recovery of the HS for PFBS was 134%. Since this was the only appropriate spike level, the analytical uncertainty has been adjusted for PFBS to 34%. An appropriate field matrix spike was not available for PFHS and PFOS. DALG W G RS04Q 1 Y1 CP (Table 26)-T h e sample set was initially analyzed on 4/19/11. The sample/sample duplicate RPD for PFOS did not meet method acceptance criteria at 50%, and the recovery of the HS for PFOS did not meet method acceptance criteria with a recovery 23.7%. The sample set was re-diluted and analyzed on 5/17/11. The sample/sample duplicate RPD for PFOS did not meet method acceptance criteria at 48%, and the HS for PFOS still outside method acceptance criteria with a recovery of 32.9%. The LMS samples prepared on the primary sample and sample duplicate did meet method acceptance criteria with recoveries of 106% and 107% respectively. However, due to both the RPD and FMS recovery not meeting method acceptance criteria for PFOS, a result for PFOS will not be reported for this sampling location. Page 24 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P F O S in Groundwater 1st Quarter Sampling - 2011 Table 9. GW 203L Q1 Y11 LF 3M UM SID Description GLP10-01-02-17-053 GLP10-01-02-17-054 GLP10-01-02-17-055 GLP10-01-02-17-056 GW 203L Q1 Y11 LF 0 GW 203L Q1 Y11 LF 1 GW203LQ1 Y11 LF LS GW203LQ1 Y11 LF HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 106 103 232 1300 NA NA 128 120 105 ng/mL 2.9% Concentration (ng/mL) XRecovety 601 589 689 1610 NA NA NC 102 595 ng/mL 2.0% Concentration (ng/mL) %Recovery 914 NA 808 NA 974 NC 2240 138 (1) 861 ng/mL 12% m NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 4/19/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for PFOS to 38%. Table 10. GW 220R Q1 Y11 LF 3M L IM S ID Description GLP10-01 -02-17-033 GLP10-01-02-17-034 GLP10-01-02-17-035 GLP10-01-02-17-036 GW220RQ1 Y11 LF 0 GW220RQ1 Y11 LF 1 GW220RQ1 Y11 LF LS GW220RQ1 Y11 LF HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) XRecovery 8.44 8.37 19.4 125 NA NA 110 117 8.41 ng/mL 0.83% Concentration (ng/mL) %Recovery 35.1 33.5 45.4 144 NA NA NC 110 34.3 ng/mL 4.7% Concentration (ng/mL) XRecovery 52.3 50.7 NA NA 61.5 134 NC 82.5 51.5 ng/mL 3.1% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 5x and analyzed 4/19/11. Page 25 of 98 G LP10-01-02; Interim Report 17 Analysis o f PFBS, PFHS, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 11. GW 220L Q1 Y11 LF 3M UNIS ID Description GLP10-01-02-17-037 GW220LQ1 Y11 LF 0 GLP10-01 -02-17-038 GW220LQ1 Y11 LF 1 GLP10-01-02-17-039 GW220LQ1 Y11 LF LS GLP10-01-02-17-040 GW220LQ1 Y11 LF HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration Concentration Concentration (ng/mL) YoRecovery (ng/mL) YoRecovery (ng/mL) YoRecovery 11.3 NA 50.7 NA 79.0 NA 11.6 NA 53.2 NA 87.9 NA 23.1 117 64.0 NC 92.2 NC 127 116 158 106 161 77.6 11.5 ng/mL 2.6% 52.0 ng/mL 4.8% 83.5 ng/mL 11% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 5x and analyzed 4/19/11. Table 12. GW 222R Q1 Y11 LF 3M UNIS ID Description GLP10-01-02-17-041 GW222RQ1 Y11 LF 0 GLP10-01-02-17-042 GW222RQ1 Y11 LF 1 GLP10-01-02-17-043 GW222RQ1 Y11 LF LS GLP10-01-02-17-044 GW222RQ1 Y11 LF HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 96.2 NA 98.9 NA 203 105 1150 105 97.6 ng/mL 2.8% Concentration (ng/mL) YoRecovery 615 NA 598 NA 859 NC 1540 93.4 607 ng/mL 2.8%, Concentration (ng/mL) YoRecovery 755 NA 807 NA 829 NC 1620 83.9 781 ng/mL 6.7% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x .with the exception of the HS which was diluted 50x, and analyzed 4/24/11. Page 26 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 Table 13. GW 227R Q1 Y11 LF 3M UM SID Description GLP10-01-02-17-029 GW227RQ1 Y11 LF 0 GLP10-01-02-17-030 GW227RQ1 Y11 LF 1 GLP10-01-02-17-031 GW227RQ1 Y11 LF LS GLP10-01-02-17-032 GW227RQ1 Y11 LF HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 21.9 NA 17.2 NA 131 111 1130 111 19.6 ng/mL 24%<1) Concentration (ng/mL) %Recovery 118 NA 93.6 NA 234 128 1190 108 106 ng/mL 23%(V Concentration (ng/mL) %Recovery 826 653 1000 1970 NA NA NC 123 740 ng/mL 23% <v NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 4/19/11. (1) The RPD did not meet method acceptance criteria of 20%, Table 14. GW 227L Q1 Y11 LF 3M UM SID Description GLP10-01 -02-17-025 GW227LQ1 Y11 LF 0 GLP10-01-02-17-026 GLP10-01 -02-17-027 GLP10-01 -02-17-028 GW227LQ1 Y11 LF 1 GW227LQ1 Y11 LF LS GW227LQ1 Y11 LF HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 286 NA 298 NA 389 NC 1280 98.8 292ng/mL 4.1% Concentration (ng/mL) %Recovery 61.6 NA 62.7 NA 165 103 1010 94.8 62.2 ng/mL 1.8% Concentration (ng/mL) %Recovery 365 NA 360 NA 477 NC 1190 82.8 363 ng/mL 1 1.4% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 4/19/11. Page 27 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFHS, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 15. GW 31OR Q1 Y11 CP 3M L IM S ID Description GLP10-01-02-17-021 GW310RQ1 Y11 CP0 GLP10-01-02-17-022 GLP10-01-02-17-023 GW310RQ1 Y11 CP 1 GW310RQ1 Y11 CP LS GLP10-01-02-17-024 GW310RQ1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 836 NA 843 982 1890 NA NC 105 840 ng/mL 0.83% Concentration (ng/mL) %Recovery 465 NA 504 NA 573 1570 NC 109 485 ng/mL 8.0% Concentration (ng/mL) %Recovery 943 1090 1050 1810 NA NA NC 79.4 1020 ng/mL 14% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 10Ox and analyzed on 4/19/11. Table 16. GW312RQ1 Y11 CP 3M UM SID Description GLP10-01-02-17-077 GW312RQ1 Y11 CP 0 GLP10-01-02-17-078 GW312RQ1 Y11 CP 1 GLP10-01-02-17-079 GW312RQ1 Y11 CP LS GLP10-01-02-17-080 GW312RQ1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery 1170 NA 1210 NA 2370 118 7050 117 1190 ng/mL 3.4% 710 NA 547 NA 1480 85.2 5330 94.0 629 ng/mL 26% <v 1180 NA 833 NA 1980 97.4 5770 95.3 1010 ng/mL 34% m NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 10Ox and analyzed 4/19/11. (1) The RPD did not meet method acceptance criteria of 20%. Page 28 of 98 G L P 10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 17. GW 317L Q1 Y11 CP 3MLIMS ID Description GLP10-01-02-17-017 GW317LQ1 Y11 CP 0 GLP10-01-02-17-018 GW317LQ1 Y11 CP 1 GLP10-01-02-17-019 GW317LQ1 Y11 CP LS GLP10-01-02-17-020 GW317LQ1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) XRecovery 0.0272 NA 0.0220 NA 1.15 113 10.8 108 0.0246 ng/mL 21%(1> Concentration (ng/mL) XRecovery 0.121 NA 0.117 NA 1.24 112 11.3 112 0.119 ng/mL3A% Concentration (ng/mL) %Recovery 0.268 NA 0.231 NA 1.33 8.77 108 85.2 0.250 ng/mL 15% NA = Not Applicable Results for PFBS and PFHS reported from 4/19/11 analysis. Results for PFOS reported from 5/14/11 analysis. (1) The RPD did not meet method acceptance criteria of 20%. Table 18. GW 324L Q1 Y11 CP 3M UM SID Description GLP10-01 -02-17-045 GLP10-01 -02-17-046 GLP10-01 -02-17-047 GLP10-01 -02-17-048 GW 324L Q1 Y11 CP 0 GW 324L Q1 Y11 CP 1 GW 324L Q1 Y11 CP LS GW 324L Q1 Y11 CP HS Average Concentration (ng/mL) %RPD . PFBS PFHS PFOS Concentration (ng/mL) %Recovery 113 NA 111 NA 236 124 1210 110 112 ng/mL 1.8% Concentration (ng/mL) %Recovery 114 NA 108 NA 226 115 1080 96.9 111 ng/mL 5.4% Concentration (ng/mL) %Recovery 332 299 414 1280 NA NA NC 96.5 316 ng/mL 10% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 4/19/11. Page 29 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 19. GW 327R Q1 Y11 CP 3M LIMS ID Description GLP10-01-02-17-073 GW327RQ1 Y11 CP 0 GLP10-01-02-17-074 GW327RQ1 Y11 CP 1 GLP10-01-02-17-075 GW327RQ1 Y11 CP LS GLP10-01-02-17-076 GW327RQ1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 92.0 NA 94.5 NA 216 123 1290 120 93.3 ng/mL 2.7% Concentration (ng/mL) %Recovery 169 166 308 1130 NA NA 141(1) 96.3 168 ng/mL 1.8% w Concentration (ng/mL) %Recovery 591 643 652 1480 NA NA NC 86.3 617 ng/mL 8.4% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 4/19/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for PFHS to 41 %. Table 20. GW 328R Q1 Y11 CP 3M L IM S ID Description GLP10-01-02-17-061 GLP10-01-02-17-062 GLP10-01-02-17-063 GLP10-01 -02-17-064 GW328R Q1 Y11 CP 0 GW328RQ1 Y11 CP 1 GW328RQ1 Y11 CP LS GW328RQ1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) XRecovery 38.0 NA 40.0 152 612 NA 113 115 39.0 ng/mL 5.1% Concentration (ng/mL) %Recovery 64.7 NA 61.5 161 NA 97.9 516 90.6 63.1 ng/mL 5.1% Concentration (ng/mL) %Recovery 223 NA 210 NA 323 NC 677 92.1 217 ng/mL 6.0% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Sample, sample duplicate, and LS diluted 10x, HS diluted 20x, and analyzed 4/19/11. Page 30 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 21. GW 328L Q1 Y11 CP 3M UM SID Description GLP10-01-02-17-057 GW 328L Q1 Y11 CP 0 GLP10-01-02-17-058 GW328LQ1 Y11 CP 1 GLP10-01-02-17-059 GW 328L Q1 Y11 CP LS GLP10-01-02-17-060 GW 328L Q1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 73.1 70.7 82.7 189 NA NA NC 117 71.9 ng/mL 3.3% Concentration (ng/mL) %Recovery 22.7 NA 21.9 NA 32.4 NC 123 101 22.3 ng/mL 3.6% Concentration (ng/mL) %Recovery 1.42 NA 1.24 NA 9.38 80.5 N A <1) NA (1) 1.33 ng/mL 14% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 10x and analyzed for PFBS and PFHS on 4/19/11. Results for PFOS reported from undiluted samples analyzed on 5/14/11. (1) Sample was not analyzed since the spike level was not expected to be appropriate as compared to the sample concentration. Table 22. GW 330R Q1 Y11 CP 3M L IM S ID Description GLP10-01 -02-17-009 GW330RQ1 Y11 CP 0 GLP10-01-02-17-010 GW330RQ1 Y11 CP 1 GLP10-01-02-17-011 GW330RQ1 Y11 CP LS GLP10-01-02-17-012 GW330RQ1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery 2990 NA 3040 NA 3130 NC 4130 NC 3020 ng/mL 1.7%(V 257 NA 261 NA 383 NC 1390 113 259 ng/mL 1.5% 725 NA 715 NA 771 NC 1790 107 720 ng/mL 1.4% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x, with the exception of the HS sample which was diluted 100X, and analyzed on 4/19/11. (1) Samples were coDected in bottles intended for G W 330L, which contained FMS samples at 100 ng/mL and 1000 ng/mL. Bottles intended for G W 330R contained FMS samples at 1000 ng/mL and 5000 ng/mL. As a result, an appropriate field matrix spike was not available for PFBS. Page 31 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 23. GW330LQ1 Y11 3M UM SID Description GLP10-01-02-17-013 GLP10-01-02-17-014 GLP10-01-02-17-015 GLP10-01-02-17-016 GW 330L Q1 Y11 CP 0 GW 330L Q1 Y11 CP 1 GW 330L Q1 Y11 CP LS GW 330L Q1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery 590 NA 499 NA 1670 113 6290 115 545 ng/mL ir/o 677 NA 572 NA 1810 119 6630 120 625 ng/mL 17% 233 NA 213 NA 1100 87.7 5270 101 223 ng/mL 9.0% NA = Not Applicable Samples diluted 20x, with the exception of the H S sample, which was injected at a volume to simulate a dilution of 125X, and analyzed on 4/19/11. Samples were collected in bottles intended for G W 330R, which contained FM S samples at 1000 ng/mL and 500 ng/mL. Bottles intended for G W 330L contained FMS samples at 100 ng/mL and 1000 ng/mL Table 24. GW331SQ1 Y11 3M UM SID Description GLP10-01-02-17-069 GW 331S Q1 Y11 CP 0 GLP10-01 -02-17-070 GW 331S Q1 Y11 CP 1 GLP10-01-02-17-071 GW 331S Q1 Y11 CP LS GLP10-01-02-17-072 GW 331S Q1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 640 NA 476 NA 614 NC 1570 101 558 ng/mL 29% m Concentration (ng/mL) %Recovery 314 NA 269 367 1160 NA NC 86.9 292 ng/mL 15% Concentration (ng/mL) %Recovery 668 615 714 1530 NA NA NC 88.9 642 ng/mL 8.3% NA = Not Applicable NO = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed on 4/19/11. (1) The RPD did not meet method acceptance criteria of 20%. Page 32 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 25. GW 335S Q1 Y11 CP 3M LIMS ID Description GLP10-01-02-17-049 GW 335S Q1 Y11 CP 0 GLP10-01-02-17-050 GW 335S Q1 Y11 CP 1 GLP10-01-02-17-051 GW 335S Q1 Y11 CP LS GLP10-01-02-17-052 GW 335S Q1 Y11 CP HS Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 1100 1060 1220 2420 NA NA NC 134 (1) 1080 ng/mL 3.7% Concentration (ng/mL) XRecovery 2050 NA 2000 NA 2130 NC 3310 NC 2030 ng/mL i 2.5% P) Concentration (ng/mL) %Recovery 5810 6210 5870 NA NA NC 7690 NC 6010 ng/mL 6.7% p> NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x for PFBS and PFHS, while samples were injected at a volume to simulate a dilution of 125x for PFOS and analyzed on 4/19/11. (1) Field matrix spike did not meet method acceptance criteria. . (2) The analytical uncertainty has been adjusted for PFBS to 34%. (3) An appropriate spike level was not available to assess accuracy for PFHS and PFOS. Table 26. GW GRS04 Q1 Y11 CP PFBS PFHS PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery GLP10-01-02-17-065 GW GRS04 Q1 Y11 CP 0 2090 NA GLP10-01-02-17-066 GLP10-01-02-17-067 GLP10-01-02-17-068 GW GRS04 Q1 Y11 CP 1 GW GRS04 Q1 Y11 CP LS GWGRS04Q1 Y11 CP HS 1950 3290 8310 NA NC 126 Average Concentration (ng/mL) %RPD 2020 ng/mL 6.9% Concentration (ng/mL) %Recovery 5540 NA 5170 NA 6510 NC 11800 129 5360 ng/mL 6.9% Concentration (ng/mL) %Recovery Not Reported Not Reported m NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 10Ox for PFBS and PFHS and analyzed on 4/19/11. Samples diluted 200x for PFOS and analyzed on 5/17/11. (1) Both the RPD and FM S recovery did not meet method acceptance criteria for PFOS. A result for PFOS will not be reported for this sampling location. S ee discussion in section 9 of the report for additional information. Page 33 of 98 G L P 10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 27. Trip Blank 1 3M UM SID GLP10-01-02-17-001 GLP10-01-02-17-002 GLP10-01-02-17-003 GLP10-01-02-17-004 Description Trip Blank 1 Sample Trip Blank 1 Low Trip Blank 1 Mid Trip Blank 1 High PFBS PFHS PFOS Concentration (ng/mL) <0.0200 10.5 112 1060 %Recovery NA 105 112 106 Concentration (ng/mL) <0.0400 11.1 116 1110 %Recovery NA 111 116 111 Concentration (ng/mL) <0.500 10.9 103 945 %Recovery NA 109 103 94.5 NA = Not Applicable FM S Mid diluted 10x, FMS High diluted 50x, and analyzed on 4/19/11. Table 28. Trip Blank 2 3M LIMS ID GLP10-01-02-17-005 GLP10-01-02-17-006 GLP10-01-02-17-007 GLP10-01 -02-17-008 Description Trip Blank 2 Sample Trip Blank 2 Low Trip Blank 2 Mid Trip Blank 2 High PFBS PFHS PFOS Concentration (ng/mL) <0.0200 10.4 105 1050 XRecovery NA 104 105 105 Concentration (ng/mL) <0.0400 10.8 108 1120 "/Recovery NA 108 108 112 Concentration (ng/mL) <0.500 11.0 88.2 962 %Recovery NA 110 88.2 96.2 NA = Not Applicable FMS Mid diluted 10x, FM S High diluted 50x, and analyzed on 4/19/11. Page 34 of 98 G LP 10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Table 29. GLP10-01-02-17 Equipment Rinseate Blank 3M LIMS ID Description GLP10-01-02-17-081 Equipment Blank GRS04 PFBS PFHS PFOS Concentration Concentration Concentration (ng/mL) (ng/mL) (ng/mL) <0.0200 <0.0400 <0.500 Sample was analyzed on 4/19/11. Table 30. GLP10-01-02-15 Soil Equipment Rinseate Blanks 3M L IM S ID GLP10-01 -02-15-013 GLP10-01-02-15-017 GLP10-01-02-15-019 GLP10-01-02-15-078 Description DAL SS SS15RB DAL SS SS18RB DAL SS SS10RB DAL SS SS26 RB Samples analyzed for PFBS and PFHS on 5/12/11. Samples analyzed for PFOS on 5/16/11. PFBS PFHS PFOS Concentration (ng/mL) <0.0250 <0.0250 <0.0250 <0.0250 Concentration (ng/mL) <0.0250 <0.0250 <0.0250 <0.0250 Concentration (ng/mL) <0.0250 <0.0250 <0.0250 <0.0250 Page 35 of 98 G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 10 Conclusion Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for PFBS, PFHS, and PFOS. Analysis was successfully completed following 3M Environmental Laboratory method ETS-8-044.0 described herein. 11 Cata/Sampie Retention All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 12 Afflacjtim&nts Attachment A: Protocol Amendment 17 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 36 of 98 113 Signatures G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 William K. Reagen, Ph.D., 3M Environmental Laboratory Department Manager Date Page 37 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Attachment A: Protocol A mendment Page 38 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Analytical Protocol: G L P 1 0 -0 1 -0 2 Amendment 17 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. 17 Amendment Date: March 14, 2011 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 Decatur 1st Quarter Groundwater Sampling Page 1 of 7 Page 39 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Analytical Protocol: G L P lO -0 1 -0 2 Am endm ent 17 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 o f the protocol are required. A mend to read: No changes to the wording o f the protocol are required. This am endm ent only addresses and documents the addition o f the General Project Outline (GPO) fo r the collection and analysis o f 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 sam ple collection w ill occur around the tim efram e o f the week o f March 21, 2011. The groundwater samples for this sampling event w ill be entered into the 3M Environmental Laboratory UM S as project GLP10-01-01-17 and reported as interim report GLP10-01-02-17, (reflecting study GLP10-01-02 and am endm ent-17). Reason: The reason for this amendment is to docum ent the General Project O utline (GPO) which describes the anticipate groundwater sample collection event to be conducted fo r 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 40 of 98 Analysis of' Amendment Approval 1st Quarter ! It 17 Cleston C. Lange, Principal Analytical Investigator Date Page 41 of 98 G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Analytical Protocol: G L P f0 -0 1 -0 2 Amendment 17 vi L Environmental Health & Safety Operations, Environmental Laboratory C-cnsrnj Oist'ine To: F rom : cc: Date: Subject: Gary Hohenstein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Cleston Lange, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions Charles Young, Weston Solutions March 14,2011 Analysis o f Perfluorooctane Sulfonate (PFOS), Perfiuorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sedim ent fo r the 3M Decatur Phase 3 Site-Related M onitoring Program; GLP Interim Report 0 9 - Decatur 1st Q uarter 2-11 Groundwater Sampling 1 General Project Information C o n ta c ts Lab Request Number Six Digit Departm ent Num ber Project Schedule/Test Dates 3M Sponsor Representative Gary Hohenstein 3M EHS Operations 3 M Building 2 2 4-5W -0 3 Saint Paul, MN 55144-1000 Phone: (651)737-3570 aahohensteiniffimmm.com 3M Environm ental Laboratory Managem ent William K. Reagen 3M EHS Opns, Environmental Laboratory 2 6 0 -5 N -1 7 651 733-9739 w krea aen fflm m m .c om Principal A nalytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 2 6 0 -5 N -1 7 651 733-9860 c c lan a efflm m m .co m Sam pling C oordinator Timothy Frinak W eston Solutions Timothv.frinakfflwestonsolutions.com Phone: (334)-332-9123 G L P 1 0-01-0 2-1 7 Dept #530711, Project #0022674449 Sampling scheduled for the w eek of March 21 ,201 1 A ll verbal an d written correspondence will b e directed to G a ry H ohenstein. . Page 4 of 7 Page 42 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Analytical Protocol: G L P W -0 1 -0 2 Am endm ent 17 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) w ill receive and analyze groundwater samples collected from seventeen groundwater w ells for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS). Analyses w ill be conducted under the GLP requirem ents o f EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater sam ples from Decatur, AL w ill be collected by W eston Solutions personnel the week of March 21,2011. The 3M Environm ental Laboratory w ill prepare the sample bottles with ail required spikes to ensure that results fo r PFBS, PFHS, and PFOS are of a known precision and accuracy. The final report w ill be subm itted to Gary Hohenstein and Jai Kesari upon com pletion under interim report GLP10-01-0217. 3 Project Schedule Sample collection bottles will be prepared by the 3M Environmental Laboratory. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival by Friday, March 18,2011. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ W eston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 4 Test Parameters The targeted lim it of quantitation will be 0.025 ng/m L (ppb) for PFBS, PFHS, and PFOS. A total of seventeen sampling locations have been specified. For each sampling location, four sample bottles will be collected (sample, sample duplicate, low field matrix spike, and high field matrix spike). The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. Four sets of trip blank spikes consisting of reagent-grade water, as well as an additional bottle to be used for the preparation o f the equipment rinseate blanks, w ill be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. Results from GLP10-01-02-02 and GLP10-01-02-09 were used to determine the field matrix spike levels for GLP10-0101-17 listed in Table 1. Table 1. S am pling L o ca tio n s and F ield M atrix S pike levels. Well No. 317L 220R, 220L, 328L 203L, 222R, 227L, 227R, 31OR, 324L, 327R, 330L, 331 S, 335S GRS04, 312R, 330R 328R Trip Blank Sets 1 and 2 Sample Level Low High Low High Low High Low High Low High Low Mid High Spike Cone. (ng/mL) 1 10 10 100 100 1000 1000 5000 100 500 10 100 1000 Page 5 of 7 Page 43 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sam pling - 2011 Analytical Protocol: G L P W -U 1 -0 2 Am endm ent 17 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Due to previous data for these sampling locations (GLP10-01-02-02 and GLP10-01-02-09), samples GLP10-01 -02-17 will most likely require dilution. Samples requiring dilution will be prepared in Milli-Q water prior to analysis by ETS-8-044.0. The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 10030%. Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Alternately, samples may be analyzed by ETS 8-110.1 "Analysis of Fluorochemicals in Extracts Using HPLCElectrospray-Mass Spectrometry-Mass Spectrometry" as an analytical reference for the sample locations analyzed by direct on-column injection analysis of samples diluted with methanol as opposed to Milli-Q water. Calibration curves used for both ETS-8-044.0 and ETS-8-110.1 will be constructed using the linear isomer of PFOS only, from nominal concentrations of 0.02 ng/mL -1 0 0 ng/mL. Due to the expected concentration of linear + branched PFOS in the samples, there may be the potential for analytical bias due to quantitating linear and branched isomers o f PFOS against a predominately linear reference standard for PFOS at the higher end of the calibration curve. Laboratory control samples (LCS) o f linear + branched PFOS w ill be prepared at three concentrations to evaluate the potential for analytical bias. LCS with average recoveries greater than 100%30%may suggest analytical bias. If the recovery of the linear + branched LCS is greater than 100%30% it may be necessary to quantitate PFOS by processing the linear and branched isomers separately and summing the calculated concentrations together to generate the final PFOS concentration. This may be done to help minimize any potential analytical bias due to quantitating linear and branched isomers of PFOS against a predominately linear reference standard for PFOS. 6 Reporting Requirements For each sampling location, the report w ill contain the results for the sample, sample duplicate, and the field matrix spikes. Trip blank sets w ill be reported for the sampling event as will any equipment blanks prepared in the field. Laboratory control spikes of reagent water prepared at the time o f sample extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks o f reagent water prepared at the time of sample extraction will be used to determine the method detection limit. Any laboratory matrix spikes that may be prepared will also be included in the final report 7 Email Correspondence Attachment A: Sampling Bottle Request Page 6 of 7 Page 44 of 98 G LP10-01-02; Interim Report 17 Analysis o f PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 A nalytical Protocol: G L P 1 0 -0 1 -0 2 Amendment 17 203L 220R 220L 222R 227R 227L Decatur FC Sample Locations (Q 12011} Confirmed Samples Potential Samples (See Note) 310R 335S RW312R 317L GRS04 RW327R 324L RW331S 328R 328L 330R 330L Total Num ber o f Samples: Rinsate Samples: Trip Blanks 18 1 W ater Needed: Yes 2 NOTE: G roundw ater samples w ill be collected from the recovery w ells if th e system is operating at the tim e o f the sam pling event. We are expected to begin sam pling activities the week o f 21 March Page 7 of 7 Page 45 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Attachm ent B: R epresentative Sa m ple C hrom atogram s and Calibration C urve(s ) Page 46 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFHS, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Printing Date: Monday, July 18, 2011 Page 47 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Printing Date: Monday, July 18, 2011 Page 48 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Page 49 of 98 Ginger AG01330509 Sample Name: ag110419b016* Sample ID:-10007-27-8* F*e:'g110419b.wtfT Peak Name: TFBS* Masses): "299.0/99.0amu,299.0/80.0amu' Comment: '1.0ngftnLFC StdInM B Q water* Annotation: Sample Index: 16 Sample Type: Standard Concentration: Calculated Cone: 0.993 4/19/201 Acq. S:01: 04 Hodlfied: Proc. Algorithm: Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: Expected RT: Use Relative RT: Int. Type: Manual Retention Time: 12.0 Area: 29S559 Height: Start Time End Time: I Sample Name: gl10418634' Sample MJ:T.CS-110412-10" Fie: 'gt104fSfc.wtT Peak Name: "PCBS* Masses): *299.0199.0amu,299.0/80.0amu* Comment *2ppb L C S E C r Annotation:** Sample Index: Sample Type: Concentration 0.00 ng/ral. Calculated Coi 0.0243 ng/mL Aeq. Date: Acq. Time : 1/01: 92/42:02131 PM Modified: No Proc. Algorithm: IntelliQuan - IQA Min. Peak Height: 0.00 cps Kin. Peak width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 sec Expected RT: Ose I i RT: No Int. Type: Retention Time: Area; Height: Data printed by STW Printing Time: 9:43:21 AM G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Page 50 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Data printed by STW Printing Time: 9:43:21 AM Page 2 of 13 Page 51 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis o f PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Data printed by STW Printing Time: 9:43:21 AM Page 3 of 13 Page 52 of 98 Ginger AG01330509 Printing Time: 9:43:21 AM G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Page 53 of 98 Ginger AG01330509 I Sample Name: *g110418b192* Sample ID: 'GLP10-01-02-17-077* Peak Name: *PFBS* M asses): *299.^99.0 amu,299.0/80.0 arm * Comment "GW 312R Q1 Y11 CP 0 (100X)* Annotation:" Sample Index: 192 Sample Type: Unknown Concentration: N/A Calculated Cone: 1170. r Acq. Date: 4/21/2011 Aeq. Time: 9:47:23PM File: `g110419b.wHT Modified: Yea Proc. Algorithm: IntelliQuan Min. Peak Height: 0.00 c[ Min. Peak Hidth: 0.00 sc Smoothing Hidth: 0 poi R? Window: 30.0 sc Expected RT: 12.1 mi Use Relative RT: Ho Height: Start Time: End Time: I Sample Name:*g11041Sb031* San*telD :TC $-110412Peak Name: "PFHS* M asses): "399.0/99.0 ----------- Comment *2ppb LCS* Annotation:" Sample Index: 31 Sample Type: Qc Concentration: 2.00 ng/raL Calculated Cone: 2.22 ng/raL Acq. Date: 4/19/2011 Acq. Tine: 9:30:32 PM Modified: No Proc. Algorithn: IntelliQuan - IQA Min. Peak Height: 0 .0 0 cps Min. Peak Hidth: 0.00 sec Smoothing Width: 0 points RT Window: Expected RT: Use Relative RT: 30.0 13.2 No sec min Height : Start Tine End Time: Valley ae: 13.1 1253265 cc 315000. < 13.0 F ie: 'g110419b.wtfT Data printed by STW Printing Time: 9:43:21 AM G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Page 5 of 13 Page 54 of 98 Ginger AG01330509 I Sample Name:*g110419bC3r Sample ID: \C S-110412-4' File: *g110419b.wff Peak Nam#: PFHS" M asses): *399dV99.0 amu.399.0/80.0 amu* Comment *20pf)b LCS* Annotation: ~ Sample Index: Sample Type: Concentration: Calculated Acq. Date: Acq. Tine: Modified: Proc. Algorithm: Peak Height: 0.00 \ Width: 0.00 Smoothing width: 0 RT Window: 30.0 Expected RT: 13.2 Relative RT : No G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Data printed by STW Printing Time: 9:43:21 AM Page 6 of 13 Page 55 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFHS, and P FO S In Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Data printed by STW Printing Time: 9:43:21 AM Page 7 of 13 Page 56 of 98 Ginger AG01330509 Printing Time: 9:43:21 AM G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb I Sample Name: g110419b150` Sample ID: ` GLP10-01-02-17-053` I Peak Name: TPHS* Mass(e): *399.0/99.0 amu,399.0/80.0 amu* I Comment*GW23LQ1 Y11 LFO (20Xy Annotation:" Sample Index: 150 Sample Type: Unknown Concentration: M/A Calculated Cone: 601. ng/mL Date: 4/21/2011 . Time: 9:11:16 AM Ftte:` g110419b.wrfr ified: Ho Proc. Algorithm: IntelllQuan - IQ1 Min. peak Height: 0.00 cps lin. Peak Width: 0.00 sec moothing Width: 0 points RT Window: 30.0 sec Expected RT: 13.2 min Use Relative RT: Mo t. Type: Valley Retention Time: 13.2 min Area: 15403694 counts Height: 3000000. cps Start Time: 13.0 min End Time: 13.7 min Sample Name:`fl110419b178* Sample ID: *GlP1<M)1-02-17-069` Peak Name: ` PFHS* Mass(as): ` 399.0/99.0 amu.399.0/80.0 amu' Comment"GW331SQ1 Y11 CP0{50X)* Annotation:" Sample Index: 178 Sample Type: Unknown Concentration: H/A Calculated Cone: 314. ng/mL Acq. Date: 4/21/2011 Acq. Time: 5:35:25 PM FUe:*g110419b.wfT Modified: Mo Proc. Algorithm: IntelllQuan - IQJ Min. Peak Height: 0.00 cps Width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 1 RT: 13.2 s Relativ RT: 3491623 c; 696000. c 12.9 13.6 Page 8 of 13 Page 57 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P F O S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Data printed by STW Printing Time: 9:43:21 AM Page 9 of 13 Page 58 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFHS, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Data printed by STW Printing Time: 9:43:22 AM Page 10 of 13 Page 59 of 98 Ginger AG01330509 I SampleNanM:*g1 104196075* SampleIO:*GLP1<K)1-02-17-009` FUe:*g110419b.wifr Peak Name: *PFOS* Masses): *499.0/99.0 amu,499.0/80.0 amu.499.0/130.0 amu* Comment*GW330RQ1 Y11 C P0 (50Xf Annotation:" Sample Index: IS Sample Type: Unknown Concentration: N/A Calculated Cone: 725. ng/mL Acq. Date: 4/20/2011 Acq. Time: 10:41:14 AH Modified: Yes Proc. Algorithm: I IHQuan - MQII Noise Percentage: 50 Base. Sub. Window: Peak-Split, factor: 2 Report Largest Peak: No Min. Peak Height: 0.C Min. Peak Width: 0.< Smoothing width: 0 RT Window: 30.0 Expected RT: 13.9 Use Relative RT: No Int. Type: Manual Retention Time: 13.9 Area: 11625337 c Height: 1600000. Start Tin 13.5 End Time: 14.3 I Sample Name: *g1 104196094' Sample ID: ` GLP10-01-02-17-021' FUe:*gl104196.wW Peak Name: TFOS* Masses): *499.0/99.0 amu.499.0/80.0 emu,499.0/130.0 amu* Comment*GW310RQ1 Y11 CP0{100X)* Annotation:" Sample Index: 94 Sample Type: Unknown Concentration: N/A Calculated Cone: 943. ng/mL Acq. Date: 4/20/2011 Acq. Time: 4:23:15 PM e.5e5 Modified: Yes Proc. Algorithm: IntelliQuan - Noise Percentage: 50 Base. Sub. Window: 1.00 mJ Peak-Split. Factor: 2 Report Largest Peak: No Min. Peak Height: 0.00 c Min. Peak Width: 0.00 : Smoothing Width: 0 RT Window: 30.0 sec Expected RT: 13.9 min Use Relative RT: No Int. Type: Retention t Area: Height: Start Time: End Time: Manual se: 13.9 7707027 cc 913000. c 13.5 Data printed by STW Printing Time: 9:43:22 AM 15.17,15.26 13.0 13.5 14.0 14.5 15.0 15.5 16.0 1339 1388 1438 1488 1537 1587 ....- - G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb I Sample Name: 'g110419b089' Sangla ID: 'GLP10-01-02-17-Oir F#: 'fl110419b.wtfr I Peak Name; 'PFOS" Masses): ,499.CW9.Oarmj.499.0O.Oamu,499.0/130.0amu* I Comment'GW317LQ1Y11 CP O' Amotatton:** Sample Index: 89 Sample Type: Unknown Concentration : tl/A Calculated Cone: 0.222 ng/mL Acq. Date: 4/20/2011 Acq. Tine: 2:53:14 PH Modified: Yes c. Algorithm: intelllQuan - MQII Noise Percentage: 50 e. Sub. Hindou: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: No in. Peak Height: 0.00 cps in. Peak Width: 0.00 sec Smoothing Width: 0 point Window: 30.0 sec Expected RT: 13.9 in Relative RT: No Int. Typ: Manual Retention Time: 13.9 min Area: 232083 counts Height: 32300. cps Start Time: 13.6 min End Time: 14.1 min ISample Name: 'g l 104190103* Sample IO;'GLP10-01-02-17-025' FHe:`g110419b.wifT Peek Name: -PROS' Masses); '499.0/99.0 amu.499.0/30.0 amu.499.0/130.0 amu* Comment 'GW227LQ1 Y11 LF0(20X)* ` - Sample Index: 103 Sample Type: Unknown Concentration: H/A Calculated Cone: 365. ng/nL Acq. Date: 4/20/2011 . Time : 7 :04 :56 PM Modified: Yes Proc. Algorithm: IntelllQuan - MQII se Percentage: 50 e. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: No . Peak Height: 0.00 cps . Peak Width: 0.00 sec Smoothing Width: 0 point RT Window: 30.0 sec Expected RT: 13.9 min Use Relative RT: Ho . Type: Manual Page 11 of 13 Page 60 of 98 Ginger AG01330509 Printing Time: 9:43:22 AM G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Page 61 of 98 *** Ginger AG01330509 G LP10-01 -02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0419b.rdb Data printed by STW Printing Time: 9:43:22 AM Page 13 of 13 Page 62 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0424b.rdb Printing Date: Monday, July 18, 2011 Page 63 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of P FBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0424b.rdb Printing Date: Monday, July 18, 2011 Page 64 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0424b.rdb Printing Date: Monday, July 18, 2011 Page 65 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0424b.rdb Printing Time: 9:53:33 AM Printing Date: Monday, July 18 2011 Page 66 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0424b.rdb Printing Date: Monday, July 18, 2011 Page 67 of 98 Ginger AG01330509 Sample Name: *g110424b027* Sample ID : "Method Blank* F le: *g110424b.wtfr Peak Name: "PFHS* M astes): ' 399.0/99.0 amu.399.0/80.0 * Comment:*TN11-0156 MB Q W aisf Annotation: Sample Sample Type: Concentration: Calculated Coi Acq. Date: Proc. Algorithm: I Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: Expected RT: Use Relative RT: Height : Start 1 End Tin 11.0 1091 11.5 1141 I Sample Name: *g ii04a4b042* Sample ID: tLCS-110422-13` F ile :`g110424b.wifr Peak Name: 'P FH S ' M asses): *399.0/99.0 amu,399.0/30JDamu' Comment: *2ppb LCS EOF Annotation: " Sample Index: 42 Sample Type: QC 1.3*4 Concentration: Calculated Cone: 0.00 <0 ng/mL 1.3e4 Acq. Date: Acq. Time: 4/25/2011 8:40:02 AM 1.2*4 Modified: Yea 1.2e4 Pioc. Algorithm: IntelliQuan - IQA Min. Peak Height: 0.00 cps 1.1*4 Min. Peak Width: 0.00 sec 1.1e4 Smoothing Width: 0 points RT Window: 30.0 sec 1.0*4 Expected RT: 13.2 min Use Relative RT: No 12.0 1190 13.2 min 59452 counts 12900. cps 13.0 min 7500.0 7000.0 6500.0 I 6000.0 E - 5500.0 5000.0 4500.0 4000/3 3500.0 3000.0 2500.0 2000.0 1500.0 1000.0 500.0 12.5 1240 13.0 13.5 1269 1339 Time, min 14.0 1368 14.5 1438 Data printed by STW Printing Time: 9:53:33 AM Printing Date: Monday, July 18, 2011 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name gll0424b.rdb Page 3 of 6 Page 68 of 98 *** Ginger AG01330509 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Smpling - 2011 Results Name: gll0424b.rdb Printing Date: Monday, July 18, 2011 Page 69 of 98 Ginger AG01330509 I Sampte Nam*: `g110424034' Sample ID: TC&-110422-4* F la: 'g1104246.\Mtr Peak Kam: "PfO S* Masses}: '499.0/99.0 amu,499.0/80.0 amu,499.0/130.0 amu* Comment: *2ppb LCS* Annotation: " Sample Index: 34 Sample Type: qc Acq. Tine: :16:26 AH Hodifled: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: SO Base. Sub. Window: 1.00 min Peak-Split. Factor: 0 Report Largest Peak Height: Kin. Peak w id th : cps Smoothing w id th : RT Window: Expected RT: Use Relative RT: Height : Start Tima: End Time: Valley ie: 13.9 1369391 co 324000. c 13.9 I Sample Name: g110424b045` Sample ID: T.CS-110422-7* F le:'g110424b.w tr Peak Kama: *PFOS` Mass(es): `499.0/99.0 ai u.499.0/30.0 amu,499.0/130.0 ai Comment: *20ppb LCS* Annotation: " Sample Index: 45 Sample Type: QC Concentration: 20.0 ng/mL Calculated Cone: 20.5 ng/mL Acq. Date: 4/25/2011 Acq. Tine: 9:34:04 AH Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 0 Report Largest Peak: No Min. Peak Height: 0.00 cps Min. Peak width: 0.00 sec Smoothing Width; 0 point RT Window: 30.0 sec Expected RT: 14.0 min Use Relative RT: No Int. Type: Retention T Area: Height: Start Time: End Tima: Manual ie: 13.9 14678095 3410000. c Data printed by STW Printing Time: 9:53:33 AM Printing Date: Monday, July 18, G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0424b.rdb Page 5 of 6 Page 70 of 98 Ginger AG01330509 Printing Time: 9:53:33 AM Printing Date: Monday, July 18, 2011 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: gll0424b.rdb Page 6 of 6 Page 71 of 98 *ETS-McCoy G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0512a.rdb Printing Date: Monday, July 18, 2011 Page 72 of 98 *ETS-McCoy G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0512a.rdb Data printed by STW Printing Time: 10:09:54 AM Printing Date: Monday, July 18, 2011 Page 1 of 1 Page 73 of 98 *ETS-McCoy G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0512a.rdb I Sample Name: *mc1l0512o013* Sample ID: *10007-51-06* FBe: *roc1l0512a.w tr Peak Name:*PFBS* Mashas): *299.00080.000 0a.299.00a09.000 D a' Comment:*0.25 ng/mL. FC std in Synth. W ater" Am wtntion:" Sample Index: 13 Sample Type: Standard Concentration: 0.250 ng/mL Calculated Cone: 0.250 ng/mL Acq. Date: 5/12/2011 1 Acq. Time: 1:27:52 PH Modified: No Proc. Algorithm: IntelliQuan - IQA II Min. peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 0 RT Window: 30.0 Expected RT: 10.0 Use Relative RT: No cps sec points sec min Valley : 10.6 min 63874 counts 1 .48e+004 cps 10.5 min 10.8 min 1.3e4 1 1 8000.0 1 7000.0 H 6000.0 SampiaName: *mc110512a021* Sarrpte7D:*GLP10-Q1-02.1$-013' T3e^mc7To512a.wtfT Peak Name: *PFBS* M asses):TaS.aXVBO.OOO Da,299.000.^9.000 Da* Comment *DAL SS SS15 RB* Annotation:** Sample Index: 21 Sample Type: Unknown Concentration: N/A Calculated Cone: <0 Acq. Date: 5/12/2011 Acq. Time: 4:12:51 PM Kodifled: No Proc. Algorithm: IntelliQuan Hin. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 polr RT Window: 30.0sec Expected RT: 10.6 rair Use Relative RT: No Int. Type: Retention Time: Height: Start Time: I 6000.0 4000.0 3000.0 2000.0 1000.0 3.72 12.72 0.0 I<lMi 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 I Sample Name: *mc110512a020* Sample ID: '11002-76* Fle:*mc110512a.wtff* Peak Name:*PFBS' Mass(es): *299.000/80.000 Da.299.000/99.000 Da* Comment:"Method blank* Annotation: " Sample Index: 20 Sample Type: Unknown Concentration: N/A Calculated Cone: <0 Acq. Date: 5/12/2011 1400- Acq. Time: 3:52:15 PH Modified: No Proc. Algorithm: IntelliQuan - IQA II Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing width: 0 points RT Window: Expected RT: 30.0 see 10.6 min Use Relative RT: No Int. Type: Base To Base Retention Time: 10.7 min Area: S51 counts Height: 6.03e*002 cps Start Time: 10.7 min End Time: 10.7 min I Sample Name: *mc110512a028* Sample ID : TCS-110509-1* Peak Name: ` PFBS* Mass(ea): *299.000/80.000 Oa.2T.......... Comment *0.2ppb LCS* Annotation: ** Sample Index: 28 Sample Type: QC 1.15e4 Concentration: 0.198 ng/mL Calculated Cone: 0.165 ng/mL 1.10e4 Acq. Date: 5/12/2011 Acq. Time: 6:37:13 PM 1.05e4 Modified: Proc. Algorithm: IntelliQuan - IQA I Min. Peak Height: 0.00 cps Min. Peak width; Smoothing Width: RT Window: Expected RT: Use Relative RT: 1.00e4 9500.00 9000.00 8500.00 8000.00 FUa:*mc110512a.wifT 7500.00 Height: Start Time: End Time: 7000.00 6500.00 ^ 6000.00 I 5500.00 E " 5000.00 4500.00 4000.00 3500.00 3000.00 2500.00 2000.00 1500.00 1000.00 500.00 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 0.00 Data printed by STW Printing Time: 10:12:53 AM Printing Date: Monday, July 18, 2011 Page 1 of 3 JjBSajTjiE-- Page 74 of 98 *ETS-McCoy ISample Nam: *mc110512a034* Sample ID: TC S4105094* Fila: *mc110512a.wifr Peak Nam: *PFBS* M s(m ): *299.000/80.000 Da.299.000/99.000 Da* SamCpolmemIenndt:e*2xp:pb LCS* 34Annotation: *r Sample Type: QC Concentration: ng/mL 9.5e4 Calculated Cone: 1.70 Acq. Date: 5/12/201: Acq. Time: B:40 :S9 PM Modified: Wo Proc. Algorithm' IntelliQuan - IQA I Min. Peak Height : 0.00 cps Min. Peak width. 0.00 Smoothing Width 0 poi. RT Window: 30.0 Expected RT; 10.6 min Use Relative RT No 64 6.0*4 7.5e4 7.0*4 Int. Type: Valley Retention Time: 10.6 min Area: 13166 counts Height: 9. S0e+004 Start Time: 10.5 min End Time: 10.9 min 6.5*4 6.0*4 5.5*4 5 S k 4.5*4 E 4.0*4 3.5*4 3.0*4 2.5*4 2.0*4 1.5*4 1.0*4 5000.0 8.5 9.0 I Sample Name: *mc110512a021` Sample ID: ` GLP10-01-02-15-013* FUe: *m e1105t2a.wifl* Peak Nam: *PFHS* M asses): *399.000/80X300 Oa,399.00(V99.000 Da" Comment: "DAL SS SSI5 RB* Annotation: ** Sample Index: 21 Sample Type: Unknown Concentration: n /A Calculated Cone: < 0 Acq. Date: 5/12/2011 Acq. Time: 4:12:51PM Modified: Ho Proc. Algorithm: IntelliQuan - iqj Min. Peak Height: 0.00 cps Min. Peak Nldth: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 sec Expected RT: 12.S min Use Relative RT: Ho Int. Type: Retention Time: Height: Start Time: End Time: Base To Base 12.6 min 1.02e+002 cps Data printed by STW Printing Time: 10:12:53 AM Printing Date: Monday, July 18, 2011 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P F O S in Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0512a.rdb Semple Name: *mc110512*313* Semple I0 : "10007-51-06* Fe:*m c110512a.wtr Peak Nam: *PFHS* Mssa(*s): *399.000/80.000 Da,399.000/99.000 Da* m Comment *0.25 . . FC std in Synth.Water* Annotation: " Sample Index: Sample Type: Concentration: Calculated Cone: 1.1S4 Acq. Date: Acq. Time: 1.10*4 1.0S4 Proc. Algorithm: IntelliQuan - Min. Peak Height: 0.00 cp: Min. Peak Width: 0.00 sec Smoothing Width: 0 poir RT Window: 30.0 sec icted RT 12.6 mir Relativ 1.00*4 9500.00 9000.00 6500.00 6000.00 7500.00 Height: Start Time: End Time: 7000.00 8 6500.00 ^ 6000.00 s 5500.00 E 5000.00 4500.00 4000.00 3500.00 3000.00 2500.00 2000.00 1500X10 1000.00 500X30 0.00 I Sample Name: *mc1105l2a020* Sample ID: *11002-76* Fae:*m c110Sl2a.wttr Peak Name: 'PFHS* Mass(es): *399.000/80.000 Da,399.000/99.000 Da* Comment "Method blank* Annotation: ** Sample Index: 20 Sample Type: Unknown Concentration: M/A Calculated Cone: <0 Acq. Date: 5/12/2011 Acq. Time: 3:52:15 PM Modified: Ho Proc. Algorithm: IntelliQuan - IQA II Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing width: 0 points RT Window: 30.0 sec Expected RT: 12.6 min Use Relative RT: Ho rpe: Base To Base Page 2 of 3 Page 75 of 98 *ETS-McCoy G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0512a.rdb Printing Date: Monday, July 18, 2011 Page 76 of 98 *ETS-McCoy mc110514b.rdb (PFOS): "Quadratic" Regression ("1 / x" weighting): y = 0.0025 xA2 + 1.27 x + 0.0126 (r = 0.9999) G L P 10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0514b.rdb ___________________________________________________________________________________ Analyte Cone. / IS Cone._________________________ Data printed by STW Printing Time: 10:15:01 AM Page 1 of 1 Printing Date: Monday, July 18, 2011 Page 77 of 98 *ETS-McCoy G L P 10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0514b.rdb Data printed by STW Printing Time: 10:16:22 AM Printing Date: Monday, July 18 2011 Page 1 of 4 Page 78 of 98 ETS-McCoy Data printed by STW Printing Time: 10:16:22 AM Printing Date: Monday, July 18, 2011 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFHS, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name mcll0514b.rdb Page 2 of 4 Page 79 of 98 *ETS-McCoy G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0514b.rdb Printing Time: 10:16:22 AM Printing Date: Monday, July 18, 2011 Page 80 of 98 ETS-McCoy Data printed by STW Printing Time: 10:16:22 AM Printing Date: Monday, July 18, 2011 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0514b.rdb Page 4 of 4 P age 81 of 98 *ETS-McCoy G L P 10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0517a.rdb Printing Date: Monday, July 18, 2011 Page 82 of 98 ETS-McCoy Data printed by STW Printing Time: 10:20:21 AM Printing Date: Monday, July 18, 2011 G LP10-01-02; Interim Report 17 Analysis o f PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0517a.rdb Page 83 of 98 ETS-McCoy Printing Time: 10:20:21 AM Printing Date: Monday, July 18, 2011 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 Results Name: mcll0517a.rdb Page 2 of 2 Page 84 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Attachm ent C: A nalytical M ethod Page 85 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 3M Environmental Laboratory Method Method o f Analysis for the Determination o f Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: q L j ^ ~ j Approved By: W illiam K. Reagen, Laboratory Manager Date ETS-8-044.0 Page 1 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 86 of 98 G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 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), PerfluoroundecanoicAcid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in clean water samples. W ater samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method is considered a 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 87 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 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 88 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 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 fam iliar with the laboratory equipment and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or operator manual for additional information and cautions. 5 Interferences During sample preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks. ETS-8-044.0 Page 4 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 89 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S , and P FO S in Groundwater 1st Quarter Sampling - 2011 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 m l. plastic HPLC autovial. Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 6.2 Chromatographic System Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm Analytical Column: Betasil C 18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Time (min) 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (m L/m in) 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak Area - quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. The previous inform ation is intended as a guide; alternate conditions and equipm ent 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 90 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: A n a lyte Transition Monitored PFBA 213 -> 169 PFPeA 263 ->219 PFHA 3 1 3 -> 2 6 9 and 313 -> 1 1 9 PFHpA 363 -> 319, 363 -> 169 and 363 -> 119 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 2 1 9 PFDA 513 -> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 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 M ultiple transitions for m onitoring the analytes is an option, as summing m ultiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention tim e criteria are met to assure adequate specificity. The previous information is intended as a guide, alternate Instruments and equipment may be used. 7 Reagents and Standards 7.1 Chemicals W ater - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium A cetate-A .C .S . Reagent Grade 7.2 Standards Perfluorobutanoic Acid (P F B A -C 4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (PFHA - C6 acid); Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M PerfluorononanoicAcid (PFNA - C9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (P F D A -C 10acid); Oakwood Products, Inc PerfluoroundecanoicAcid (PFU nA-C 11 acid); Oakwood Products, Inc PerfluorododecanoicAcid (P F D 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 o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a ly s is Page 91 of 98 G LP10-01-02; Interim Report 17 Analysis of P FBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 The previous inform ation is intended as a guide. Reagents and standards from alternate sources may be used. 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)--Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/m L ta rg e t 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 10OmL with methanol or other suitable solvent, in a 10OmL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. m olecular weight of anion salt correction factor = m oclecular weight of salt PFOS (K +)salt correction factor = ------= 0.9275 538 10 mg CsF^SOs'K* with purity 90% = 8.35mg C8F i7S03" (10 mg*0.90*0.9275=8.35 mg) 5 pg/m L (5000 ng/m L) m ixed w orking standard--Add 0.5mL each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/m L m ixed w orking standard--Add 1 25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/m L m ixed standard--Add 625pL of the 5 pg/mL-mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage C onditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. ETS-8-044.0 Page 7 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 92 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, PFH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 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 Volume o f WS, pL Final Volume of Calibration Standard (mL of ASTM Type 1Water, or other suitable water) Final Concentration of Calibration Standard, ng/mL (ppb) in ASTM Type 1Water, or other suitable water 125 125 125 125 250 250 250 250 5000 5000 5000 10 15 20 30 20 50 100 200 25 50 100 50 50 50 50 50 50 50 50 50 50 50 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 93 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 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 94 of 98 G L P 10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S In Groundwater 1st Quarter Sampling - 2011 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: (Peak Area - Intercept) Analyte found (ng/mL) = xDF Slope DF = factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. Recovery - anaWe f und (ng/mL) - Average analyte found in sample (ng/mL) Analyte added (ng/mL) 12 Method Performance Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report. 12.1 System Suitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of <5% and a retention time RSD of 2% to be compliant. 12.2 Quantitation C alibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Perform ance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 95 of 98 G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter S am plin g- 2011 D em onstration o f S pecificity: Specificity is demonstrated by chromatographic retention time (within 4 % of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions R e vision Number Summary o f 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 96 of 98 Attachment D: D eviation(s) G LP10-01-02; Interim Report 17 Analysis of PFBS, P FH S, and P FO S in Groundwater 1st Quarter Sampling - 2011 Page 97 of 98 Rec o r d of d evia tio n /N G LP10-01-02; Interim Report 17 1. Identification Study / Project No. GLP10-01-02-17 Date(s) o f Occurrence: g11419b Document Num ber E T S -8 -0 4 4 .0 Deviation type (Check one) SOP Protoco Equipm ent Procedure Method GPO Other: II. Description (attach e xtra p a g e s a s n e e d e d ) Method Requirements: 1. RPD values 520% (section 10.3). 2. FMS recovery within 30% (section 10.6). Actual procedure/process: 1. The following sampling locations had sample/sample duplicate RPDs outside method acceptance criteria; DAL GW 227R: PFBS (24%), PFHS (23%), PFOS (23%), DAL GW 312R: PFHS (26%) and PFOS (34%), and DAL GW 331S; PFBS (29%). 2. The following sampling locations had FMS samples outside method acceptance criteria; DAL GW 203L HS for PFOS (138%), DAL GW 335S HS for PFBS (134%), DAL GW GRS04 HS for PFOS (<50%), and DAL GW 327R LS for PFHS (141%). III. Actions Taken ____________________________(such as amendment issued, SOP revision, etc.)__________________________ Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1. Sampling locations with RPD values outside method acceptance criteria will be flagged in the report. 2. Sampling locations with FMS recoveries outside method acceptance criteria will be flagged In the report and the analytical uncertainty adjusted for PFOS for DAL GW 203L, PFBS for DAL GW 335S, and PFHS for DAL GW 327R. No PFOS results will be reported for DAL GW GRS04 since the recovery of the HS was <50%. Actions: Halting o f W ork C lient Notification W ork Recall W ithholding o f Report 0 Other: Deviations will be noted in final report. Project Lead/PAI Approval: p Study Director (if GLP): Sponsor Approval (for GLP protocol deviations): NA Technical Reviewer (optional): NA Date: , , ~>M n Date:?/i4fK Date: NA Date: NA Laboratory Department Manager Approval: Date: . _____-- ------------------ ----------- ---------------------------------------- 7/W /7 IV. Authorization to Resume Work _____ Where halting of work occurred, resumption of work must first be approved by Laboratory Management Laboratory Department Manager Approval: NA Date: NA Deviation N o .______________ (assigned by Study Director or Team Leader at the end of study or project) ETS-4-008.7 Page 1 of 1 Documentation o f Deviations and Control o f Nonconform ing Testing Page 98 of 98