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GLP10-01-02; Interim Report 29 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at Off-Site Wells in Decatur, AL in March/April 2012 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 P hone:610-701-3761 Author Susan W olf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 St. Paul, MN 55144 Project Identification GLP10-01-02-29 Total Number of Pages 148 The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Testing Certificate # 2052.01. Testing that complies with this International Standard also meets principles of ISO 9001:2000. Testing Cert #2052.01 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 This page has been reserved for specific country requirements. Page 2 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS In Groundwater Off-Site Wells In Decatur, AL - March/April 2012 GLP Compliance Statement Report Title: GLP10-01-02; Interim Report 29 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at Off-Site Wells in Decatur, AL in March/April 2012. 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. Date Page 3 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells In Decatur, AL - March/April 2012 Quality Assurance Statement Report Title: GLP10-01-02; Interim Report 29 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at Off-Site Wells in Decatur, AL in March/April 2012. 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 4/30/12 Phase Data and Report Date Reported to Testing Facility Management Study Director 5/4/12 5/4/12 Ou*__) QAU Representative ^ ___________________ d .? //z Date Page 4 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table of Contents GLP Compliance Statement.......................................................................................................................3 Quality Assurance Statement.....................................................................................................................4 Table of Contents........................................................................................................................................5 List of T a b le s...............................................................................................................................................6 1 Study Information.................................................................................................................................8 2 Sum m ary..............................................................................................................................................9 3 Introduction......................................................................................................................................... 11 4 Test & Control Substances...............................................................................................................11 5 Reference Substances......................................................................................................................12 6 Test S ystem ....................................................................................................................................... 13 7 Method S um m ary..............................................................................................................................14 7.1 M ethods.............................................................................................................................14 7.2 Sample Collection..............................................................................................................14 7.3 Sample Preparation...........................................................................................................14 7.4 Analysis..............................................................................................................................14 8 Analytical Results............................................................................................................................... 15 8.1 Calibration ..........................................................................................................................15 8.2 System Suitability ..............................................................................................................16 8.3 Limit of Quantitation (LO Q )...............................................................................................16 8.4 Continuing Calibration.......................................................................................................16 8.5 Blanks................................................................................................................................. 16 8.6 Lab Control Spikes (LC Ss)...............................................................................................16 8.7 Analytical Method Uncertainty......................................................................................... 20 8.9 Field Matrix Spikes (FMS)..................................................................................................20 Page 5 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 9 Data Summary and Discussion....................................................................................................... 21 10 Conclusion..........................................................................................................................................34 11 Data/Sample Retention..................................................................................................................... 34 12 Attachm ents.......................................................................................................................................34 13 Signatures..........................................................................................................................................35 List of Tables Table 1. Summarized PFBS, PFHS, and PFOS Results (Off-Site Wells, March/April 2012)........ 10 Table 2. Sample Description Key Code............................................................................................. 13 Table 3. Instrument Parameters......................................................................................................... 14 Table 4. Liquid Chromatography Conditions......................................................................................15 Table 5. Mass Transitions................................................................................................................... 15 Table 6. Limit of Quantitation (LOQ)...................................................................................................16 Table 7. Laboratory Control Spike Recovery..................................................................................... 18 Table 8. Analytical Uncertainty............................................................................................................20 Table 9. Field Matrix Spike Levels......................................................................................................20 Table 10. DAL GW 602S 120330.......................................................................................................22 Table 11. DAL GW 602L 120330........................................................................................................22 Table 12. DAL GW 603S 120330.......................................................................................................23 Table 13. DAL GW 603L 120330........................................................................................................23 Table 14. DAL GW 604R 120330.......................................................................................................24 Table 15. DAL GW 604S 120330.......................................................................................................24 Table 16. DAL GW 604L 120403........................................................................................................25 Table 17. DAL GW 605R 120404.......................................................................................................25 Table 18. DAL GW 605L 120404........................................................................................................26 Table 19. DAL GW 607R 120403.......................................................................................................26 Table 20. DAL GW 607L 120403........................................................................................................27 Page 6 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 21. DAL GW 609R 120330......................................................................................................27 Table 22. DAL GW 609L 120330.......................................................................................................28 Table 23. DAL GW 610R 120404......................................................................................................28 Table 24. DAL GW 610L 120404.......................................................................................................29 Table 25. DAL GW 611R 120404......................................................................................................29 Table 26. DAL GW 611L 120404.......................................................................................................30 Table 27. DAL GW MW121 120405..................................................................................................30 Table 28. DAL GW MW47 120405....................................................................................................31 Table 29. DAL GW MW13S 120404..................................................................................................31 Table 30. DAL GW MW13I 120404...................................................................................................32 Table 31. DAL GW MW13B 120404..................................................................................................32 Table 32. Rinseate Blanks.................................................................................................................. 33 Table 33. Trip Blank............................................................................................................................ 33 Page 7 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 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 William K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clange@mmm.com) ; phone (651)-733-9860 Susan Wolf, 3M Analyst Chelsie Grochow, Analyst Kevin Eich, Analyst Kelly Ukes, Analyst Study Dates Study Initiation: March 8, 2010 Interim 29 Experimental Termination: April 26, 2012 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 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 2 Summary The 3M Environmental Laboratory prepared sample containers for twenty-four existing off-site wells in Decatur, AL. Samples were collected March 30, 2010 - April 5, 2012. O f the seventy-six sample containers prepared, seventy groundwater sample bottles were received at the 3M Environmental Laboratory for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS), and perfluorooctane sulfonate (PFOS) analysis from Weston personnel on April 9, 2012. Sampling locations DAL GW 602R and DAL GW 603R were not sampled. All samples were logged into the laboratory information management system (LIMS) under project GLP10-01-02-29. For each sampling location, a field sample, field duplicate sample and field matrix spike (FMS) sample were collected. Samples also included a trip blank containing Milli-QTM water and an appropriate trip blank spike. Two equipment rinseate blanks were also collected. The equipment rinseate blanks did not have FMS samples prepared for determination of recovery. All sample bottles were fortified with internal standard 13C8-PFOS and surrogate recovery standard 13C4-PFOS prior to sample collection. All of the samples were prepared and analyzed for PFBS, PFHS, PFOS and the surrogate recovery standard 13C4-PFOS, following 3M Environmental Laboratory Method ETS-8-044.1. Where applicable, samples were analyzed against an internal standard calibration curve. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The trip blank and equipment blanks were below the lower limit of quantitation (LLOQ) for all analytes, indicating adequate control of sample contamination during shipping and sample collections. The analytical method uncertainties for samples analyzed by internal calibration are: PFBS + 13%, PFHS + 14% and PFOS + 18%. Due to a sample container preparation error, the internal standard was inadvertently not added to the field sample duplicate and FMS sample bottles for location DAL GW 602S. As a result, this sampling location was analyzed by external calibration with analytical method uncertainties estimated at: PFBS + 15%, PFHS + 13% and PFOS + 38%. Page 9 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 1. Summarized PFBS, PFHS, and PFOS Results (Off-Site Wells, March/April 2012) (1) Sampling Location DAL GW 602S 120330 DAL GW 602L 120330 DAL GW 603S 120330 DAL GW 603L 120330 DAL GW 604R 120330 DAL GW 604S 120330 DAL GW 604L 120403 DAL GW 605R 120404 DAL GW 605L 120404 DAL GW 607R 120403 DAL GW 607L 120403 DAL GW 609R 120330 DAL GW 609L 120330 DAL GW 610R 120404 DAL GW 610L 120404 DAL GW 611R 120404 DAL GW 611L 120404 DAL GW MW121 120405 DAL GW MW47 120405 DAL GW MW13S 120404 DAL GW MW13I 120404 DAL GW MW13B 120404 Trip Blanks (Milli-QTM Water) GLP10-01-01-30 Equipment rinseate blanks: DAL GW 604L and DAL GW 607R PFBS Avg. Conc. (ng/mL) RPD 0.288 0.35% (2) 0.0699 6.3% 0.177 6.8% 0.0946 6.7% 0.310 2.3% 0.340 1.2% 0.449 6.5% 0.134 17% 0.0988 19% 0.187 15% 0.180 14% 0.433 0.69% 0.348 15% 0.0543 0.74% 0.131 2.3% 0.295 1.7% 0.261 6.9% <0.0250 0.174 1.1% 0.0831 3.9% 0.0682 2.5% 0.0803 2.7% <0.0250 PFHS Avg. Conc. (ng/mL) RPD 0.182 2.8% (2) 0.252 7.1% 0.119 20% 0.108 5.6% 0.184 10% 0.229 4.4% 0.227 6.2% 0.115 7.0% 0.203 8.9% 0.192 8.3% 0.220 6.4% 0.0947 2.2% 0.169 33% (3) 0.0756 8.2% 0.136 5.2% 0.128 5.5% 0.140 1.4% <0.0250 0.113 17% 0.0404 5.4% 0.0457 0.0% 0.0521 5.0% <0.0250 PFOS Avg. Conc. (ng/mL) RPD 0.468 9.6% (2) 0.544 13% 0.417 12% 0.0905 3.9% 1.12 8.9% 0.478 0.63% 0.811 5.4% 0.0532 29% (3) 0.213 16% 0.274 0.37% 0.322 12% 0.162 9.3% 0.569 2.6% 0.275 4.4% 0.646 0.62% 0.650 2.5% 0.458 6.3% 0.0307 (4) 0.166 14% <0.0232 <0.0232 0.0376 49% (3) <0.0232 <0.0250 <0.0250 <0.0232 Locations DAL G W 602R and DAL G W 603R were not sampled. (1) All samples w ere analyzed using internal calibration unless otherwise noted. The analytical method uncertainties associated with the reported results using internal calibration are: PFBS 13%, PFHS 14%, and PFOS 18%. (2) Samples for location DAL G W 602S were analyzed using external calibration. The analytical method uncertainties associated with the reported results using external calibration are: PFBS 15%, PFHS 13%, and PFOS 38%. (3) Sample/sample duplicate RPD did not meet acceptance criteria of <20%. (4) A sam ple/sam ple duplicate RPD could not be determined due to the primary sample being not reportable. Page 10 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 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 twenty-two locations at off-site wells in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize regional 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 one field matrix spike sample. 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 isomer), PFHS (linear isomer), and PFOS (linear and branched isomers) prior to being sent to the field for sample collection. All sample bottles included the addition of 18O2-PFBS, 13C3-PFHS, and 13C8-PFOS (internal standard) at a nominal concentration of 1 ng/mL. All sample bottles also included the addition of 13C4-PFOS (surrogate recovery standard) at a nominal concentration of 0.1 ng/mL. See section 8.8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds In Water by LC/MS/MS; Direct Injection Analysis". The use of internal standards was used to aid in the data quality objectives. Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate surface water samples collected and the trip blank sample. Tables 10-33 summarize the individual sample results and the associated field matrix spike recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report 4 Test & Control Substances There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. Page 11 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 5 Reference Substances The analytical reference substances used for this study are listed below. Reference Substance Chemical Name Chemical Formula Identifier Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (pre do m ina ntly linear) Potassium Perfluorobutane sulfonate C4FgSO3-K+ NA Target Analyte Reference Standard 3M 01/10/2017 Frozen 41-2600-8442-5 TCR-121 W hite Powder 96.7% 18o 2-p f b s [18 2]-Ammonium Perfluorobutanesulfonate C4F9S[18O2]O-NH4+ NA Internal Standard RTI International 03/09/2015 Frozen 11546-107-2 TCR-1044, TCR-1040 Liquid >99% Reference Substance Chemical Name Chemical Formula Identifier Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFHS (L in e a r) Sodium Perfluorohexane sulfonate C 6F 13SO3 Na L-PFHXS Target Analyte Reference Standard W elling to n 03/25/2018 Frozen LPFHxSAM08 TCR08-0018 Crystalline 100% 13C3- PFHS Sodium Perfluorohexanesulfonate 13C312C3F13SO3-Na+ MPFC-C-0112 Internal Standard W elling to n 01/24/2015 Frozen MPFC-C-0112 TCR12-0004 Liquid NA (1) (1) Compound is part of a custom mixture of mass-labeled perfluorinated compounds at a concentration of 5.0 pg/mL. Page 12 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 R eference S u b s ta n c e Chemical Name Chemical Formula Identifier Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOS (Linear + Branched) Potassium Perfluorooctane sulfonate C aF17SO3-K+ Br-PFOSK Target Analyte Reference Standard W ellington 03/17/2014; 12/01/2014 Frozen brPFOSK0708; brP F O S K 1111 TCR11-0010; TCR11-0041 Liquid 99.9% PFOS (Linear + Branched) Potassium Perfluorooctane sulfonate C 8F 17S O 3-K+ CAS # 2795-39-3 FMS Reference Standard Sigma Aldrich 02/04/2014 A m b ie n t 1424328V TCR11-0028 W hite Powder 99.7% 13c 4-p f o s Sodium Perfluorooctane sulfonate 13C412C4F17SO3-N a + MPFOS Surrogate Recovery Standard W ellington 09/08/2013 Frozen MPFOS0910 TCR10-0044 Liquid >98% 13c 8-p f o s Sodium Perfluorooctane sulfonate 13C8F17SO3-Na+ MPFC-C-0112 Internal Standard W elling to n 01/24/2015 Frozen MPFC-C-0112 TCR12-0004 Liquid NA (1) (1) Compound is part of a custom mixture of mass-labeled perfluorinated compounds at a concentration of 5.0 pg/mL. 6 Test System The test systems for this study are groundwater samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. Table 2. Sample Description Key Code. String Number Example 1 2 3 4 5 6 String Descriptor DAL-GW-602S-0-120330 Sample Location Sample Type Well Identifier Well Level Sample Type Sampling Date Example DAL= Decatur, Alabama GW= Ground Water Example: 602S R = Residuum shallow water-bearing zone L = Bedrock water-bearing zone S = Epikarst middle water-bearing zone 120330- March 30, 2012 0=primary sample DB=duplicate sample FMS = Held Matrix Spike Page 13 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 7 Method Summary 7.1 Method Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles associated with GLP10-01-02-29 were returned to the laboratory at ambient conditions on April 9, 2012. 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. During the preparation of the laboratory control samples, an aliquot of a separate internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The samples bottles were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below in Table 3, Table 4 and Table 5. Table 3. Instrument Parameters. Instrument Name Analytical Method Followed Analysis Date Liquid Chromatograph Guard column Analytical column Injection Volum e Mass Spectrometer Ion Source Electrode Polarity Software ETS Buster ETS-8-044.1 4/23/12 Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5u Betasil C18 (4.6 mm X 100 mm), 5^ 50 ixL Applied Biosystems API 4000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Page 14 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 4. Liquid Chromatography Conditions. Step Number 0 1 2 3 4 5 Total Time (min) 0.0 2.0 14.5 15.5 16.5 20.0 Flow Rate (fL/min) Percent A (2 m M ammonium acetate) ETS-8-044.1 750 97.0 750 97.0 750 5.0 750 5.0 750 97.0 750 97.0 Percent B (methanol) 3.0 3.0 95.0 95.0 3.0 3.0 Table 5. Mass Transitions. Analyte PFBS PFHS PFOS f 3C]-PFOS Mass Transition Q1/Q3 299/80 299/99 399/80 399/99 499/80 499/99 499/130 503/80 Reference Material Structure Linear Linear Linear + Branched Linear Internal Standard f 8O2]-PFBS d C j-P F H S [ 3C]-PFOS f 3C]-PFOS Mass Transition Q1/Q3 303/84 402/99 507/80 507/80 Dwell time was 50 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation. 8 Analytical Results 8.1 Calibration 8.1.1 Internal standard calibration: Samples were analyzed using a stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into laboratory-prepared synthetic groundwater containing calcium and magnesium. A separate internal standard spiking solution was prepared and an aliquot was added at the same level to all calibration standards and laboratory control samples at a nominal concentration of 1 ng/mL. A calibration curve ranging from approximately 0.025 ng/mL to 25 ng/mL (0.025 ng/mL to 10 ng/mL for 13C4-PFOS surrogate) was prepared. A quadratic, 1/x weighted, calibration curve of the standard peak area/peak area ratios 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 ratios and the resultant calibration curve confirmed accuracy of each curve point. The PFOS reference standard used to prepare the calibration standards consisted of both linear and branched isomers. Page 15 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 8.1.2 External standard calibration for sampling location DAL GW 602S: See 8.1.1 for the preparation of the calibration curve. For external standard calibration, a quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. For both internal standard and external standard calibration, 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, PFOS, and 13C4-PFOS. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of each 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, PFOS, and 13C4-PFOS. 8.3 Limit of Quantitation (LOQ) The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts or area ratio are at least twice those of the appropriate blanks. The LOQ for all analytes can be found in Table 6. Table 6. Limit of Quantitation (LOQ). Analysis Date PFBS LOQ, ng/mL PFHS LOQ, ng/mL 4/23/12 (1) 0.0250 0.0250 (1) Internal and external calibration analysis. PFOS LOQ, ng/mL 0.0232 8.4 Continuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All CCVs met method criteria of 100% 25% for all analytes except for a CCV for 13C4-PFOS using external calibraiton, which had a recovery of 71.8%. Samples bracketed by this CCV included the LCS samples and results for sampling location DAL GW 602S. A method deviation is included in Attachment D. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: procedural blanks, trip blanks, and equipment rinseate blanks. Procedural blank results were reviewed and used to evaluate method performance and to determine the LOQ. Trip blanks reflect the shipping and sample collection conditons the sample bottles and samples experience. Equipment rinseate blanks are aqueous samples that reflect the efficiency of equipment cleaning in the field between different sample collections to ensure no cross contamination of samples from the equipment. 8.6 Lab Control Spikes (LCSs) Low, mid, and high lab control spikes were prepared for the target analytes and analyzed in triplicate, while only low and high lab control spikes were prepared for the 13C4-PFOS surrogate. LCSs were prepared by spiking known amounts of the analyte into synthetic groundwater to produce the desired concentration. The spiked water samples were then prepared and analyzed in the same manner as the samples. The method acceptance criteria, average of LCS at each level should be within 100% 20% Page 16 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 with an RSD <20%, was met for all analytes except for the mid level LCSs for PFOS and 13C4-PFOS using external standard calibration, which had a average recovery of 122% for both PFOS and 13C4PFOS. All LCS samples were used in the determination of the analytical method uncertainty in section 8.7. A method deviation is included in Attachment D. The following calculations were used to generate data in Table 7 for laboratory control spikes. LCS Percent Recovery -C--a--l-c-u--l-a--t-e-d---C--o--n--c-e--n--t-r-a--t-io--n- **1.00% Spike Concentration LCS% RSD = standard deviation LCS replicates * 100% average LCS recovery Page 17 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 7. Laboratory Control Spike Recovery. ETS-8-044.1 Analyzed 4/23/12 Internal Standard Calibration PFBS Lab ID Spiked Concentration (n g /m L ) Calculated Concentration (n g /m L ) %Recovery Spiked Concentration (n g /m L ) LCS-120416-1 LCS-120416-2 LCS-120416-3 0.198 0.198 0.198 0.203 102 0.198 0.216 109 0.198 0.222 112 0.198 Average %RSD 108% 4.8% LCS-120416-4 LCS-120416-5 LCS-120416-6 1.98 1.98 1.98 2.13 108 1.98 2.16 109 1.98 2.10 106 1.98 Average %RSD 108% 1.4% LCS-120416-7 LCS-120416-8 LCS-120416-9 9.94 9.94 9.94 9.83 9.58 9.41 98.9 96.4 94.7 9.92 9.92 9.92 Average %RSD 96.7% 2.2% PFHS Calculated Concentration (n g /m L ) 0.201 0.210 0.215 105% 2.9% 2.10 2.30 2.21 111% 4.5% 10.0 9.16 9.39 96.0% 4.7% %Recovery 102 106 108 106 116 112 101 92.3 94.7 ETS-8-044.1 Analyzed 4/23/12 Internal Standard Calibration Lab ID PFOS (Linear + Branched) 13C4-P F O S surrogate Spiked Concentration (n g /m L ) Calculated Concentration (n g /m L ) %Recovery Spiked Concentration (n g /m L ) Calculated Concentration (n g /m L ) %Recovery LCS-120416-1 LCS-120416-2 LCS-120416-3 0.184 0.184 0.184 0.179 0.198 0.199 97.3 107 108 0.189 0.189 0.189 0.202 0.199 0.193 107 105 102 Average %RSD LCS-120416-4 LCS-120416-5 LCS-120416-6 1.84 1.84 1.84 104% 5.7% 1.84 1.91 1.95 99.8 104 106 105% 2.4% 1.89 1.91 1.89 1.99 1.89 2.01 101 105 106 Average %RSD 103% 3.1% 104% 2.5% LCS-120416-7 LCS-120416-8 LCS-120416-9 9.22 9.22 9.22 9.16 8.78 8.59 99.3 95.3 93.2 NA NA NA NA NA NA NA NA NA Average %RSD 95.9% 3.2% NA NA = Not Applicable (1) LCS did not meet acceptance criteria of 100 20%. Page 18 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 7 Continued. Laboratory Control Spike Recovery. ETS-8-044.1 Analyzed 4/23/12 External Standard Calibration Lab ID PFBS Spiked Concentration (n g /m L ) Calculated Concentration (n g /m L ) %Recovery Spiked Concentration (n g /m L ) PFHS Calculated Concentration (n g /m L ) LCS-120416-1 LCS-120416-2 LCS-120416-3 Average %RSD 0.198 0.198 0.198 0.184 0.190 0.196 95.9% 3.2% 92.7 96.1 98.9 0.198 0.198 0.198 0.188 0.203 0.203 99.6% 4.2% LCS-120416-4 LCS-120416-5 LCS-120416-6 Average %RSD LCS-120416-7 LCS-120416-8 LCS-120416-9 Average %RSD 1.98 1.98 1.98 9.94 9.94 9.94 1.91 1.88 1.92 96.1% 1.1% 8.77 8.25 8.02 84.0% 4.6% 96.2 95.0 97.1 88.2 83.0 80.7 1.98 1.98 1.98 9.92 9.92 9.92 2.06 2.04 2.04 103% 0.56% 8.98 8.68 8.83 89.0% 1.7% %Recovery 94.8 102 102 104 103 103 90.6 87.5 89.0 ETS-8-044.1 Analyzed 4/23/12 External Standard Calibration PFOS (Linear + Branched) 13C4-P F O S surrogate Lab ID Spiked Concentration (n g /m L ) Calculated Concentration (n g /m L ) %Recovery Spiked Concentration (n g /m L ) Calculated Concentration (n g /m L ) %Recovery LCS-120416-1 LCS-120416-2 0.184 0.184 0.224 122 0.189 0.200 109 0.189 0.256 0.205 135 108 LCS-120416-3 0.184 0.178 96.5 0.189 0.175 92.7 Average %RSD 109% 12% 112% 19% LCS-120416-4 LCS-120416-5 LCS-120416-6 Average %RSD LCS-120416-7 LCS-120416-8 LCS-120416-9 Average %RSD 1.84 1.84 1.84 9.22 9.22 9.22 2.55 2.03 2.14 122% 13% (1) 11.8 9.40 10.9 116% 11% 139 110 116 128 102 118 1.89 1.89 1.89 NA NA NA 2.65 2.07 2.17 122% 13% (1) NA NA NA NA 140 110 115 NA NA NA NA = Not Applicable (1) LCS did not meet acceptance criteria of 100 20%. Page 19 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 8.7 Analytical Method Uncertainty Analytical method uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. While the mid set of LCS samples for PFOS by external standard calibration had a recovery of 122%, this value was within the analytical method uncertainty for PFOS by external standard calibration as determined by ETS-12-012.2. Table 8. Analytical Uncertainty. Analyte PFBS PFHS PFOS PFBS PFHS PFOS Calibration Internal Internal Internal External External External Standard Deviation 6.42 7.00 9.10 7.59 6.60 18.8 Method Uncertainty 13% 14% 18% 15% 13% 38% 8.8 Field Matrix Spikes (FMS) Low, mid, and high field matrix spikes (FMS) 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 + branched) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. Table 9. Field Matrix Spike Levels. Sampling Location 602S, 603S, 603L, 604R, 604S, 604L, 605R, 605L, 607R, 607L, 609R, 610R, 611R, 611L, MW121, MW47, MW13S, MW13I, and MW13B, Trip Blank 602L, 609L, and 610L PFBS, ng/mL 1.01 2.01 PFHS, ng/mL 0.998 2.00 PFOS, ng/mL 0.998 2.00 ( Sam ple Concentration o f FMS - Average C o nce ntration: Field Sam ple & Field Sam ple Dup.) FMS Recovery = --------- --------------------------------------------------------------------------------------------------------------------------------- * 100% Spike Concentraton Page 20 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 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 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 MW121 120405; When quantitated by internal standard calibration, the calculated concentration for the primary sample, based on the analyte/IS area ratio, was within the calibration range. However the actual peak area counts for the primary sample for PFOS were less than the peak area counts for the PFOS LOQ standard. Therefore, a sample result for PFOS will not be reported for the primary sample. Page 21 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 10. DAL GW 602S 120330 3M LIMS ID Description GLP10-01-02-29-004 DAL-GW-602S-0-120330 GLP10-01 -02-29-005 DAL-GW-602S-DB-120330 GLP10-01-02-29-006 DAL-GW-602S-FMS-120330 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.287 NA 0.288 1.20 NA 90.3 0.288 ng/m L 0.35% Concentration (n g /m L ) %Recovery 0.179 0.184 1.14 NA NA 96.0 0.182 ng/m L 2.8% Concentration (n g /m L ) %Recovery 0.490 0.445 1.32 NA NA 85.4 0.468 ng/m L 9.6% 13C4-PFOS %Recovery 116 102 93.4 104% 11% NA = Not Applicable All samples were quantitated by external standard calibration. Table 11. DAL GW 602L 120330 3M LIMS ID Description GLP10-01 -02-29-007 DAL-GW-602L-0-120330 GLP10-01 -02-29-008 DAL-GW-602L-DB-120330 GLP10-01 -02-29-009 DAL-GW-602L-FMS-120330 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.0721 0.0677 1.94 NA NA 93.0 0.0699 ng/m L 6.3% Concentration (n g /m L ) %Recovery 0.261 0.243 2.36 NA NA 105 0.252 ng/m L 7.1% Concentration (n g /m L ) %Recovery 0.579 0.508 2.63 NA NA 104 0.544 ng/mL 13% %Recovery 94.5 84.9 97.7 92.4% 7.2% NA = Not Applicable All samples were quantitated by internal standard calibration. Page 22 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 12. DAL GW 603S 120330 3M LIMS ID Description GLP10-01 -02-29-013 DAL-GW-603S-0-120330 GLP10-01 -02-29-014 DAL-GW-603S-DB-120330 GLP10-01 -02-29-015 DAL-GW-603S-FMS-120330 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.183 0.171 1.36 NA NA 117 0.177 ng/m L 6.8% Concentration (n g /m L ) %Recovery 0.131 NA 0.107 1.33 NA 121 0.119 ng/mL 20% Concentration (n g /m L ) %Recovery 0.443 0.391 1.56 NA NA 115 0.417 ng/mL 12% 13C4-PFOS %Recovery 110 115 104 110% 5.2% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 13. DAL GW 603L 120330 3M LIMS ID Description GLP10-01 -02-29-016 DAL-GW-603L-0-120330 GLP10-01 -02-29-017 DAL-GW-603L-DB-120330 GLP10-01 -02-29-018 DAL-GW-603L-FMS-120330 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.0977 0.0914 0.955 NA NA 85.2 0.0946 ng/m L 6.7% Concentration (n g /m L ) %Recovery 0.105 0.111 1.01 NA NA 90.4 0.108 ng/m L 5.6% Concentration (n g /m L ) %Recovery 0.0922 0.0887 0.962 NA NA 87.3 0.0905 ng/m L 3.9% %Recovery 96.5 102 85.9 94.7% 8.6% NA = Not Applicable All samples were quantitated by internal standard calibration. Page 23 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 14. DAL GW 604R 120330 3M LIMS ID Description GLP10-01 -02-29-019 DAL-GW-604R-0-120330 GLP10-01-02-29-020 DAL-GW-604R-DB-120330 GLP10-01 -02-29-021 DAL-GW -604R-FMS-120330 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.306 0.313 1.360 NA NA 104 0.310 ng/m L 2.3% Concentration (n g /m L ) %Recovery 0.193 NA 0.174 1.28 NA 110 0.184 ng/mL 10% Concentration (n g /m L ) %Recovery 1.17 1.07 2.16 NA NA 104 1.12 ng/m L 8.9% 13C4-PFOS %Recovery 101 103 106 103% 2.1% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 15. DAL GW 604S 120330 3M LIMS ID Description GLP10-01-02-29-022 DAL-GW-604S-0-120330 GLP10-01-02-29-023 DAL-GW-604S-DB-120330 GLP10-01-02-29-024 DAL-GW-604S-FMS-120330 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.338 0.342 1.40 NA NA 105 0.340 ng/m L 1.2% Concentration (n g /m L ) %Recovery 0.224 0.234 1.28 NA NA 105 0.229 ng/m L 4.4% Concentration (n g /m L ) %Recovery 0.476 0.479 1.56 NA NA 108 0.478 ng/m L 0.63% %Recovery 96.0 103 104 101% 4.2% NA = Not Applicable All samples were quantitated by internal standard calibration. Page 24 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 16. DAL GW 604L 120403 3M LIMS ID Description GLP10-01-02-29-025 DAL-GW-604L-0-120403 GLP10-01-02-29-026 DAL-GW-604L-DB-120403 GLP10-01-02-29-027 DAL-GW-604L-FMS-120403 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.434 NA 0.463 1.47 NA 101 0.449 ng/m L 6.5% Concentration (n g /m L ) %Recovery 0.234 0.220 1.29 NA NA 107 0.227 ng/m L 6.2% Concentration (n g /m L ) %Recovery 0.833 0.789 1.95 NA NA 114 0.811 ng/m L 5.4% 13C4-PFOS %Recovery 102 103 99.9 102% 1.5% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 17. DAL GW 605R 120404 3M LIMS ID Description GLP10-01-02-29-028 DAL-GW-605R-0-120404 GLP10-01-02-29-029 DAL-GW-605R-DB-120404 GLP10-01 -02-29-030 DAL-GW-605R-FMS-120404 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.145 0.122 0.951 NA NA 80.9 0.134 ng/mL 17% Concentration (n g /m L ) %Recovery 0.119 0.111 0.984 NA NA 87.1 0.115 ng/m L 7.0% Concentration (n g /m L ) %Recovery 0.0608 0.0456 0.930 NA NA 87.9 0.0532 ng/mL 2 9 % 1 %Recovery 84.6 95.0 86.8 88.8% 6.1% NA = Not Applicable All samples were quantitated by internal standard calibration. (1) Sample/sample duplicate RPD did not meet acceptance criteria <20%. Page 25 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 18. DAL GW 605L 120404 3M LIMS ID Description GLP10-01 -02-29-031 DAL-GW-605L-0-120404 GLP10-01-02-29-032 DAL-GW-605L-DB-120404 GLP10-01 -02-29-033 DAL-GW-605L-FMS-120404 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.108 0.0896 1.19 NA NA 108 0.0988 ng/m L 19% Concentration (n g /m L ) %Recovery 0.212 NA 0.194 NA 1.26 106 0.203 ng/m L 8.9% Concentration (n g /m L ) %Recovery 0.230 NA 0.195 1.23 NA 102 0.213 ng/mL 16% %Recovery 98.7 88.0 101 95.9% 7.3% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 19. DAL GW 607R 120403 3M LIMS ID Description GLP10-01-02-29-034 DAL-GW-607R-0-120403 GLP10-01 -02-29-035 DAL-GW-607R-DB-120403 GLP10-01-02-29-036 DAL-GW-607R-FMS-120403 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.201 NA 0.173 1.11 NA 91.4 0.187 ng/mL 15% Concentration (n g /m L ) %Recovery 0.200 NA 0.184 1.31 NA 112 0.192 ng/m L 8.3% Concentration (n g /m L ) %Recovery 0.274 NA 0.273 1.28 NA 101 0.274 ng/m L 0.37% 13C4-PFOS %Recovery 96.0 110 100 102% 7.0% NA = Not Applicable All samples were quantitated by internal standard calibration. Page 26 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 20. DAL GW 607L 120403 3M LIMS ID Description GLP10-01 -02-29-037 DAL-GW-607L-0-120403 GLP10-01 -02-29-038 DAL-GW-607L-DB-120403 GLP10-01 -02-29-039 DAL-GW-607L-FMS-120403 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.192 NA 0.167 1.19 NA 100 0.180 ng/mL 14% Concentration (n g /m L ) %Recovery 0.227 NA 0.213 1.24 NA 102 0.220 ng/m L 6.4% Concentration (n g /m L ) %Recovery 0.302 NA 0.341 1.42 NA 110 0.322 ng/mL 12% 13C4-PFOS %Recovery 96.0 105 101 100% 4.3% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 21. DAL GW 609R 120330 3M LIMS ID Description GLP10-01-02-29-040 DAL-GW-609R-0-120330 GLP10-01 -02-29-041 DAL-GW -609R-DB-120330 GLP10-01-02-29-042 DAL-GW-609R-FMS-120330 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.431 0.434 1.38 NA NA 93.8 0.433 ng/m L 0.69% Concentration (n g /m L ) %Recovery 0.0936 0.0957 1.13 NA NA 104 0.0947 ng/m L 2.2% Concentration (n g /m L ) %Recovery 0.169 0.154 1.14 NA NA 98.0 0.162 ng/m L 9.3% %Recovery 94.7 92.1 101 95.8% 4.6% NA = Not Applicable All samples were quantitated by internal standard calibration. Page 27 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 22. DAL GW 609L 120330 3M LIMS ID Description GLP10-01-02-29-043 DAL-GW-609L-0-120330 GLP10-01-02-29-044 DAL-GW-609L-DB-120330 GLP10-01-02-29-045 DAL-GW-609L-FMS-120330 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.373 0.322 2.16 NA NA 90.2 0.348 ng/mL 15% Concentration (n g /m L ) %Recovery 0.196 0.141 2.23 NA NA 103 0.169 ng/m L 3 3 % (1) Concentration (n g /m L ) %Recovery 0.576 0.561 2.47 NA NA 95.1 0.569 ng/m L 2.6% 13C4-PFOS %Recovery 100 114 97.0 104% 8.8% NA = Not Applicable All samples were quantitated by internal standard calibration. (1) Sample/sample duplicate RPD did not meet acceptance criteria of <20%. Table 23. DAL GW 610R 120404 3M LIMS ID Description GLP10-01-02-29-046 DAL-GW-610R-0-120404 GLP10-01-02-29-047 DAL-GW-610R-DB-120404 GLP10-01-02-29-048 DAL-GW-610R-FMS-120404 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.0545 NA 0.0541 NA 1.09 103 0.0543 ng/m L 0.74% Concentration (n g /m L ) %Recovery 0.0787 NA 0.0725 NA 1.13 106 0.0756 ng/m L 8.2% Concentration (n g /m L ) %Recovery 0.269 0.281 1.28 NA NA 101 0.275 ng/m L 4.4% %Recovery 99.8 89.2 90.0 93.0% 6.3% NA = Not Applicable All samples were quantitated by internal standard calibration. Page 28 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 24. DAL GW 610L 120404 3M LIMS ID Description GLP10-01-02-29-049 DAL-GW-610L-0-120404 GLP10-01 -02-29-050 DAL-GW-610L-DB-120404 GLP10-01 -02-29-051 DAL-GW -610L-FMS-120404 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.132 NA 0.129 2.11 NA 98.5 0.131 ng/m L 2.3% Concentration (n g /m L ) %Recovery 0.139 NA 0.132 2.15 NA 101 0.136 ng/m L 5.2% Concentration (n g /m L ) %Recovery 0.644 0.648 2.77 NA NA 106 0.646 ng/m L 0.62% %Recovery 93.2 95.7 100 96.4% 3.8% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 25. DAL GW 611R 120404 3M LIMS ID Description GLP10-01-02-29-052 DAL-GW-611R-0-120404 GLP10-01 -02-29-053 DAL-GW-611R-DB-120404 GLP10-01-02-29-054 DAL-GW-611R-FMS-120404 Average Concentration (ng/mL) % RPD/RSd PFBS PFHS PFOS 13C4-PFOS Concentration (n g /m L ) %Recovery 0.297 0.292 1.35 NA NA 105 0.295 ng/m L 1.7% Concentration (n g /m L ) %Recovery 0.131 0.124 1.19 NA NA 106 0.128 ng/m L 5.5% Concentration (n g /m L ) %Recovery 0.642 0.658 1.74 NA NA 109 0.650 ng/m L 2.5% %Recovery 91.2 92.1 104 95.7% 7.3% NA = Not Applicable All samples were quantitated by internal standard calibration. Page 29 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 26. DAL GW 611L 120404 3M LIMS ID Description G LP 10-01-02-29-055 DAL-GW -611L-0-120404 GLP10-01-02-29-056 DAL-GW-611L-DB-120404 GLP10-01 -02-29-057 DAL-GW-611L-FMS-120404 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.270 0.252 1.35 NA NA 108 0.261 ng/m L 6.9% Concentration (n g /m L ) %Recovery 0.141 NA 0.139 1.24 NA 110 0.140 ng/m L 1.4% Concentration (n g /m L ) %Recovery 0.472 0.443 1.55 NA NA 109 0.458 ng/m L 6.3% 13C4-PFOS %Recovery 94.0 108 108 103% 7.7% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 27. DAL GW MW121 120405 PFBS PFHS PFOS 13C4-PFOS 3M LIMS ID Description Concentration (n g /m L ) %Recovery GLP10-01 -02-29-058 DAL-GW-MW121 -0-120405 GLP10-01 -02-29-059 DAL-GW-MW121 -DB-120405 GLP10-01-02-29-060 DAL-GW-MW121-FMS-120405 <0.0250 <0.0250 0.972 NA NA 96.2 Average Concentration (ng/mL) %RPD/RSD <0.0250 ng/mL Concentration (n g /m L ) %Recovery <0.0250 <0.0250 0.969 NA NA 97.1 <0.0250 ng/mL Concentration (n g /m L ) %Recovery NR (1) 0.0307 0.912 NA NA 88.3 0.0307 n g /m L (2) %Recovery 107 100 83.9 97.0% 12% NA = Not Applicable All samples were quantitated by internal standard calibration. (1) NR = Not reportable; while the peak area ratio was within the calibration range, the actual sample peak area counts for PFOS were less than the area counts for the PFOS LOQ standard. (2) Sample/sample duplicate RPD could not be determined due to the primary sample being not reportable. Page 30 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 28. DAL GW MW47 120405 PFBS PFHS PFOS 13C4-PFOS 3M LIMS ID Description GLP10-01 -02-29-061 DAL-GW -MW47-0-120405 GLP10-01-02-29-062 DAL-GW-MW47-DB-120405 GLP10-01-02-29-063 DAL-GW-MW47-FMS-120405 Average Concentration (ng/mL) %RPD/RSD Concentration (n g /m L ) %Recovery 0.173 0.175 1.09 NA NA 90.7 0.174 ng/m L 1.1% Concentration (n g /m L ) %Recovery 0.122 NA 0.103 1.01 NA 89.9 0.113 ng/mL 17% Concentration (n g /m L ) %Recovery 0.178 0.154 1.06 NA NA 89.6 0.166 ng/mL 14% %Recovery 99.3 85.0 94.1 92.8% 7.8% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 29. DAL GW MW13S 120404 PFBS PFHS PFOS 13C4-PFOS 3M LIMS ID Description Concentration (n g /m L ) %Recovery GLP10-01-02-29-064 DAL-GW-MW13S-0-120404 GLP10-01-02-29-065 DAL-GW-MW13S-DB-120404 GLP10-01-02-29-066 DAL-GW-MW13S-FMS-120404 0.0847 0.0815 1.13 NA NA 104 Average Concentration (ng/mL) %RPD/RSD 0.0831 ng/m L 3.9% Concentration (n g /m L ) %Recovery 0.0415 NA 0.0393 1.11 NA 107 0.0404 ng/m L 5.4% Concentration (n g /m L ) %Recovery <0.0232 NA <0.0232 1.02 NA 102 <0.0232 ng/mL %Recovery 94.1 96.1 106 98.6% 6.2% NA = Not Applicable All samples were quantitated by internal standard calibration. Page 31 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 30. DAL GW MW13I 120404 PFBS PFHS PFOS 13C4-PFOS 3M LIMS ID Description Concentration (n g /m L ) %Recovery GLP10-01-02-29-067 DAL-GW-MW13I-0-120404 0.0673 NA GLP10-01-02-29-068 DAL-GW-MW13I-DB-120404 GLP10-01-02-29-069 DAL-GW-MW13I-FMS-120404 0.0690 1.10 NA 102 Average Concentration (ng/mL) %RPD/RSD 0.0682 ng/m L 2.5% Concentration (n g /m L ) %Recovery 0.0457 0.0457 1.08 NA NA 104 0.0457 ng/m L 0.0% Concentration (n g /m L ) %Recovery <0.0232 <0.0232 1.07 NA NA 107 <0.0232 ng/mL %Recovery 97.9 89.6 99.8 95.8% 5.6% NA = Not Applicable All samples were quantitated by internal standard calibration. Table 31. DAL GW MW13B 120404 PFBS PFHS PFOS 13C4-PFOS 3M LIMS ID Description Concentration (n g /m L ) %Recovery GLP10-01 -02-29-070 DAL-GW -MW13B-0-120404 GLP10-01 -02-29-071 DAL-GW -MW13B-DB-120404 GLP10-01 -02-29-072 DAL-GW-MW13B-FMS-120404 0.0814 0.0792 0.988 NA NA 89.9 Average Concentration (ng/mL) %RPD/RSD 0.0803 ng/m L 2.7% Concentration (n g /m L ) %Recovery 0.0534 NA 0.0508 1.01 NA 96.0 0.0521 ng/m L 5.0% Concentration (n g /m L ) %Recovery 0.0283 NA 0.0469 1.04 NA 100 0.0376 ng/mL 4 9 % 1 %Recovery 96.0 109 97.2 101% 7.0% NA = Not Applicable All samples were quantitated by internal standard calibration. (1) Sample/sample duplicate RPD did not meet acceptance criteria <20%. Page 32 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 32. Rinseate Blanks 3M LIMS ID Description GLP10-01 -02-29-073 DAL-GW-604L-RB-120403 GLP10-01 -02-29-074 DAL-GW-607R-RB-120403 PFBS PFHS PFOS Concentration (n g /m L ) <0.0250 <0.0250 %Recovery NA NA Concentration (n g /m L ) <0.0250 <0.0250 %Recovery NA NA Concentration (n g /m L ) <0.0232 <0.0232 %Recovery NA NA 13C4-PFOS %Recovery 97.7 101 NA = Not Applicable All samples were quantitated by internal standard calibration. Table 33. Trip Blank PFBS PFHS PFOS 3M LIMS ID Description Concentration (n g /m L ) GLP10-01 -02-29-075 DAL-GW-TRIP01 -0-120316 GLP10-01 -02-29-076 DAL-GW-TRIP01 -FMS-120316 <0.0250 1.04 %Recovery NA 103 Concentration (n g /m L ) <0.0250 1.04 %Recovery NA 104 Concentration (n g /m L ) <0.0232 0.973 %Recovery NA 97.5 13C4-PFOS %Recovery 94.8 104 NA = Not Applicable All samples were quantitated by internal standard calibration. Page 33 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 10 Conclusion Laboratory control spikes and field m atrix spikes w ere used to determ in e the analytical m ethod accuracy and precision fo r PFBS, PFH S , and PFO S . A nalysis w as successfully com pleted follow ing 3M E nvironm ental Laboratory m ethod ETS-8-044.1 described herein. 11 Data/Sample Retention A ll rem aining sa m p le s and associated project data (ha rdco py and electronic) w ill be archived according to 3M E nvironm ental Laboratory standard operating procedures. 12 Attachments A tta ch m e n t A: P rotocol A m e n d m e n t 29 (G eneral P roject O utline) and P rotocol A m e n d m e n t 33 (S am pling Locations N ot C ollected) A tta chm e nt B: R e presentative C h rom ato gram s and C alibration C urves A tta chm e nt C: A nalytical M ethod-E TS -8-044.1 A tta chm e nt D : M ethod D eviation Page 34 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 13 Signatures Cleston Lange, Ph.D., 3M Principal Analytical Investigator 57W -Z2- Date William K. Reagen, Ph.D., 3M Environmental Laboratory Department Manager Date Page 35 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Attachment A: Protocol A mendments Page 36 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 A nalytical Protocol: GLP10-01-02 Am endm ent 29 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. 29 Amendment Date: March 16, 2012 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP10-01-02 Sampling Event Off-Site Wells Page 1 of 6 Page 37 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2Q12 Analytical Protocol: GLP10-01-02 Am endm ent 29 This amendment modifies the following portion of protocol: "Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program" Protocol reads: No changes to the wording of the protocol are required. Amend to read: No changes to the wording of the protocol are required. This amendment only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis of groundwater samples as part o f the 3M Decatur Phase 3 Program for PFOS, PFHS and PFBS (GLP10-01-02). The anticipated sample collection will occur around the timeframe of the week of March19, 2012. The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-02-29 and reported as interim report GLP10-01-02-29, (reflecting study GLP10-01-02 and amendment -29). Reason: The reason for this am endm ent is to document the General Project Outline (GPO) which describes the anticipate groundwater sample collection event for twenty-four off-site wells near the 3M Decatur facility. The GPO is three pages in length and included as attached to this amendment form. Page 2 of 6 Page 38 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 A nalytical Protocol: GLP10-01-02 Am endm ent 29 Amendment Approval William Reagen,JEHS Opns Environmental Lab Management Jaisimha Kesari P.E., DEE, Study Director Date zfceh'Z' Dat Page 3 of 6 Page 39 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Analytical Protocol: GLP10-01-02 Amendment 29 3 M Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: From: cc: Date: Subject: Gary Hohenstein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Cleston Langey, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions March 16, 2012 Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 29 -O ff-S ite Wells 1 General Project Information Contacts Lab Request Number Six Digit D epartm ent N um ber Project Schedule/Test Dates 3M Sponsor R epresentative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 aahohenstein@mmm.com 3M Environm ental Laboratory M anagem ent William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaaen@mmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cclanae@mmm.com Sam pling Coordinator Timothy Frinak Weston Solutions T lm o th v.frin a k@ w e sto n so lu tio n s.co m Phone: (334)-332-9123 G LP 10-01-02-29 Dept #530711, Project #0022674449 Sampling scheduled for the week of March 19, 2012 A ll verbal and written correspondence will be directed to G ary Hohenstein. Page 4 of 6 Page 40 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 A nalytical Protocol: GLP10-01-02 Amendment 29 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze groundwater samples collected from two sampling locations for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) from existing wells located on the BP property. Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples will be collected by Weston Solutions personnel the w eek of March 19. 2012. The 3M Environmental Laboratory will prepare the sample bottles with all required spikes to ensure that results for PFBS, PFHS, and PFOS are of a known precision and accuracy. The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP10-01-02-29. 3 Project Schedule _________ Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of March 19, 2012. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Monday, March 19, 2012. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ Weston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 4 Test Parameters The targeted limit of quantitation will be 0.025 ng/mL (ppb) for PFBS, PFHS, and PFOS. Twenty-four sampling locations have been specified. For each sampling location, a total of three sample bottles will be collected (sample, sample duplicate and field matrix spike). The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. One set of trip blanks consisting of reagent-grade water as well as a trip blank spike will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. All sample bottles will include the addition of 180 2-PFBS, 180 2-PFHS, and T3C8-PFOS (internal standard) at a nominal concentration of 1 ng/mL. All sample bottles will also include the addition of 13C4-PFOS (surrogate spike) at a nominal concentration of 0.1 ng/mL. Two additional bottles will be prepared to be used for the preparation of the equipment rinseate blanks. A 1-L bottle of laboratory reagent water will be sent with the sample bottles to be used to generate the rinseate blank sample. The table below lists the matrix spike levels that will be prepared. W ell No. Spike Cone. (ng/mL) 602R, 602S, 603R, 603S, 603L, 604R, 604S, 604L, 605R, 605L, 607R, 607L, 609R, 610R, 611R, 611L, MW121, MW47, MW13S, MW13I, and MW13B 1.0 602L, 609L, and 610L Trip Blank 2.0 1.0 Page 5 of 6 Page 41 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 A nalytical Protocol: GLP10-01-02 Amendment 29 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds In Water by LC/MS/MS; Direct Injection Analysis". The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 10030%. Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Where applicable, samples will be analyzed against an internal standard calibration curve. Each curve point will contain isotopically-labeled perfiuorocarboxylic acids and perfluorosulfonic acids at a nominal concentration of 1 ng/mL. The calibration curve will be generated by taking the ratio of the standard peak area counts over the internal standard peak area counts to fit the data for each analyte. 6 Reporting Requirements For each sampling location, the report will contain the results for the sample, sample duplicate, and field matrix spike. Trip blank and trip blank spike will be reported for the sampling event as will any equipment/rinseate blanks prepared in the field. Laboratory control spikes of reagent water prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks of reagent water prepared at the time of sample extraction will be used to determine the method detection limit. Page 6 of 6 Page 42 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Analytical Protocol: GLP10-01-02 Amendment 33 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. 33 Amendment Date: May 1, 2012 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 Page 1 of 3 Page 43 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site W l S i n P e W o A L - M a o h ftp 202 Amendment 33 This amendment modifies the following portion of protocol: "Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program" Protocol reads: No changes to the wording of the protocol are required. Amend to read: No changes to the wording of the protocol are required. This amendment only addresses and documents sampling locations that were not collected as specified in previous protocol amendments that were written to address a groundwater sampling event. The following protocol amendments addressed a groundwater sampling event for which not all the specified locations were collected: Protocol Amendment GLP10-01-02-07. Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) at Decatur, AL in June/July 2010. Sampling locations 136R, 137R and 138R specified in the protocol amendment were not collected due to the well being dry at the time of sample collection. Protocol Amendment GLP10-01-02-18. Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) at Decatur, AL in June 2011. Sampling locations 136R and 137R specified in the protocol amendment were not collected due to the well being dry at the time of sample collection. Protocol Amendment GLP10-01-02-24. Analysis o f PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) at Decatur, AL, in December 2011. Sampling locations 136R and 137R specified in the protocol amendment were not collected due to the well being dry at the time of sample collection. Sampling locations CW26C and CW26L were not sampled. Protocol Amendment GLP10-01-02-26. Analysis of PFBS, PFHS, and PFOS in Surface W ater Samples Collected at Bert Jeffries Landfill in Decatur, AL in February 2012. Per instructions from the Sponsor Representative, no surface water samples were to be collected from the previously planned WT01 and the ET05 locations. Protocol Amendment GLP10-01-02-28. Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) at Decatur, AL, in March/April 2012. Sampling locations 136R, 137R, 138R, CW26C, and CW26L specified in the protocol amendment were not sampled. Protocol Amendment GLP10-01-02-29. Analysis of PFBS, PFHS, and PFOS in Ground Water Samples Collected at Off-Site Wells in Decatur, AL in March 2012. Sampling locations 602R and 603R specified in the protocol amendment were not sampled. Reason: The reason for this amendment is to document sampling locations that were not collected as specified in above mentioned protocol amendments. Page 2 of 3 Page 44 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Analytical Protocol: GLP10-01-02 Amendment 33 Amendment Approval Page 3 of 3 Page 45 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Attachment B: Representative Sa m ple Chrom atograms and Calibration Curve(s) Page 46 of 148 Workstation: ETSBUSTER GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 2:06:53 PM P r i nting Date: Thu rsday, Ap r i l 26, 2012 Page 47 of 148 Workstation: ETSBUSTER GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 2:06:40 PM P r i nting Date: Thu rsday, Ap r i l 26, 2012 Page 48 of 148 Workstation: ETSBUSTER GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 2:06:15 PM P r i nting Date: Thu rsday, Ap r i l 26, 2012 Page 49 of 148 Workstation: ETSBUSTER GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 2:06:24 PM P r i nting Date: Thu rsday, Ap r i l 26, 2012 Page 50 of 148 *** B u ster J2930203 I Sample Name: "b120423a017" Sample ID "11012-62-8" File "b120423aw Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "1.0 ng/mL FC std in Synth. Water" Annotation: "" Sample Index: 17 Sample Type: Standard 0.975 ng/mL 1.00e5 N/A 23/2012 Time: 7:37:05 PM 9.50e4 Proc. Algorithm: IntelliQi Noise Percentage: 50 min 9.00e4 8.50e4 Report Largest teak: Ye< Min. Peak Height: 0.I cps Min. Peak Width: 0. I Smoothing Width: 3 points RT Window: 30.0 Expected RT: 15.1 min 8.00e4 7.50e4 7.00e4 6.50e4 Retend Valley 15.1 min 361554 c< cps 15.0 min 15.7 min 6.00e4 5.50e4 00e4 54 . 4.50e4 4.00e4 3.50e4 3.00e4 2.50e4 2.00e4 1.50e4 1.00e4 5000.00 0.00 13.0 I Sample Name: "b120423a026" Sample ID: "LCS-120416-1" File: "b120423a.w Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "0.2ppb LCS" Annotation: "" Sample Index: N/A Date: 26 Sample Type: 0.966 ng/m 4/23/2012 QC 1.05e5 1.00e5 Time: 10:50:29 PM 9.50e4 Proc. Algorithm: Intel Noise Percentage: Base. Sub. .00 min 9.00e4 8.50e4 Report Largest Peak: Min. Peak Height: Min. Peak Width: Smoothing Width: Yes 0.00 0.00 3 cps points 8.00e4 7.50e4 RT Window: Expected RT: Use Relative RT: 30.0 15.1 No r R/tenTypt Valley : 15.1 359640 c 15.0 15.3 min cps min min 7.00e4 6.50e4 6.00e4 5.50e4 5.00e4 4.50e4 4.00e4 3.50e4 3.00e4 2.50e4 2.00e4 1.50e4 1.00e4 5000.00 0.00 Data printed by STW Printing Time: 1:19:13 PM P r i nting Date: Tuesday, M a y 08, 2012 15.12 1 4 ^ 145 35.0 ' ' 35.5 ' 6 ' 0 ' 16.5 _____________________ Time, min__________________________ 17.0 15.12 ' 4 .0 ' 14r^ _ ~ ~ 1 5 t ^ ' 35.5 T'me. min 'W GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab ISample Name: "b120423a024" Sample ID: "12001-160" File "b120423aw Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" t: "Method Blank" Annotation: "" : 0.975 ng/mL Calculated Conc: N/A Acq. Date: 4/23/2012 Acq. Time: 10:07:34 PM Modi Proc jorithm: IntelliQuan - MQII 50 1.00 min Width: Smoothing Width: .00 cps .00 sec points Expected RT: Use Relative RT: min :nt. Type : End Valley 389935 1.1 15.0 min cps min 1.00e5: 9.50e4 9.00e4 8.50e4 8.00e4 7.50e4 7.00e4 6.50e4 6.00e4 5.50e4 5.00e4 4.50e4 4.00e4 3.50e4 3.00e4 2.50e4 2.00e4 1.50e4 1.00e4 5000.00: 0.00 13.0 135 I Sample Name: "b120423a029" Sample ID: "LCS-120416-4" File: "b120423a.wiff" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "2ppb LCS" Annotation: "" 29 ng/mL N/A 2012 :49 PM 1.00e5: Proc. Algorithm: IntelliQuan - MQII 50 1.00 min cps 0 points min 9.50e4 9.00e4 8.50e4 8.00e4 7.50e4 7.00e4 :nt. Tioe: Valley min cps min min 6.50e4 6.00e4 5.50e4 5.00e4 4.50e4 4.00e4 3.50e4 3.00e4 2.50e4 2.00e4 1.50e4 1.00e4 5000.00: 0.00 13.0 Page 1 of 62 15.12 14"5_ 15.0 ' ' 15.5_ ' 1 6 ^ ' ' 16.5 ' _ 17.0 ' ' 37.5 Time, min 15.0 ' ' 3 s 5 _ Time. min 36.0 ' _ 16r 5 ' 3 T 0 17.5" Page 51 of 148 *** B u ster J2930203 I Sample Name: "b120423a032" Sample ID: "LCS-120416-71 Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 am Comment: "10ppb LCS" Annotation: "" Sample Index: 32 Sample Type QC Concentration 0.969 ng/mL Calculated Co: N/A 4/24/2012 12:59:13 AM Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0. Min. Peak Width: 0. Smoothing Width: 3 RT Window: 30.0 Expected RT: 15.1 Use Relative RT: No Retention 303348 co 8.43e+004 15. 0 15.3 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a041" Sample ID: "GLP10-01-02-29-007" I Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" J Comment: "DAL-GW-602L-0-" Annotation: "" Sample Index: 41 Sample Type: Unknown Concentration: 0. 975 ng/mL Calculated Coni N/A 4/24/2012 4:12:36 AM File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1. 00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 15.1 mi Use Relative RT: No Int. Type: Valley Retention Time: 15.1 mi Area: 355932 count 1.01e+005 15.0 15.5 15.11 5000.0 0.0 13.C 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17C 175 Time, min Sample Name: "b120423a044" Sample ID: "GLP10-01-02-29-013" File: "b120423a.wiff" Sample Name: "b120423a046" Sample ID: "GLP10-01-02-29-015" File: "b120423a.wiff" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" I Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "DAL-GW-603S-0-" Annotation: "" Comment: "DAL-GW-603S-FMS-" Annotation: "" Sample Index: 44 Sample Index: 46 Sample Type: Concentration: Unknown 0.975 15.10 Sample Type: Concentration: Unknown 0.975 ng/mL Calculated Corn N/A Calculated Con N/A Acq. Date: 4/24/2012 4/24/2012 Acq. Time: 5:16:57 AM 5:59:52 AM Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height Min. Peak Width: Smoothing Width: RT Window: 30.0 Expected RT: 15.1 Use Relative RT: No Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: .00 Peak-Split. Factor Report Largest Pea Min. Peak Width: Smoothing Width: RT Window: Expected RT: Use Relative RT: .00 3 30.0 15.1 No Retention 286956 counts 8.96e+004 cps 15.0 min 15.4 min Valley : 15.1 315826 co 8. 99e+00 4 15.0 15.2 lime, mir 15.10 Data printed by STW Printing Time: 1:19:14 PM P r i nting Date: Tuesday, M a y 08, 2012 Time, mir Page 2 of 62 Time, mir Page 52 of 148 *** B u ster J2930203 I Sample Name: "b120423a050" Sample ID "GLP10-01-02-29-016" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "DAL-GW-603L-0-" Annotation: "" Sample Index: 50 Sample Type: Unknown 0.975 ng/mL 1.00e5 N/A '24/2012 Time: 7:25:51 AM 9.50e4 Proc. Algorithm: IntelliQi Noise Percentage: 50 min 9.00e4 8.50e4 Report Largest teak: Yes Min. Peak Height: 0.I cps Min. Peak Width: 0. I Smoothing Width: 3 points RT Window: 30.0 Expected RT: 15.1 min 8.00e4 7.50e4 7.00e4 6.50e4 File "b120423aw,ff" Valley 15.1 367662 c< 15.0 15.5 min cps min min 6.00e4 5.50e4 00e4 54 . 4.50e4 4.00e4 3.50e4 3.00e4 2.50e4 2.00e4 1.50e4 1.00e4 5000.00 0.00 13.C I Sample Name: "b120423a056" Sample ID: "GLP10-01-02-29-022" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "DAL-GW-604S-0-" Annotation: "" Sample Index: 56 Sample Type: Unknow1n.00e5 0.975 ng/m N/A Date: 49/:2344/2012 9.50e4 File: "b120423a.wiff" 9.00e4 Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 15.1 min Use Relative RT: No 8.50e4 8.00e4 7.50e4 7.00e4 6.50e4 RetenTypn: Valley : 15.1 363836 c 1.01e+005 15.0 15.4 min cps min min 6.00e4 5.50e4 5.00e4 4.50e4 4.00e4 3.50e4 3.00e4 2.50e4 2.00e4 1.50e4 1.00e4 5000.00 0.00 "mI- Data printed by STW Printing Time: 1:19:14 PM P r i nting Date: Tuesday, M a y 08, 2012 114.5 ' ' 5.0 ' ' 1 5 "^ ' 16.0 * _16'5_ ___________ Time, min__________________________ 15.09 14r^ ' ' 15.0 ' ' 15-5 _ i6 .0 _ - '1 6 .5 Time, min GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a053" Sample ID: "GLP10-01-02-29-019" I Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" t: "DAL-GW-604R-0-" Annotation: "" 53 File: "b120423a.wiff" 0. 975 ng/mL N/A 4/24/2012 8:30:16 AM 8.5e4 8.0e4 Proc. Algorithm: IntelliQuan - MQII 50 1.00 min 7.5e4 7.0e4 Width: Smoothing Width: Expected RT: Use Relative RT: 30.0 00 cps 00 points min 6.5e4 6.0e4 5.5e4 nt. Tyoe: End Valley 15.1 344061 c 8.52e+004 15.0 15.5 min cps min min cps 5.0e4 14.5e4 4.0e4 3.5e4 3.0e4 2.5e4 2.0e4 1 5e4 1 0e4 5000.0: 0.0 13.0 13.5 Sample Name: "b120423a062" Sample ID: "GLP10-01-02-29-025" File: "b120423a.w Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "DAL-GW-604L-0-" Annotation: "" Calculated Acq Acq 0.975 n N/A 4/24/2012 11:43:37 AM Proc. Algorithm: IntelliQuan - MQII 50 1.00 min cps 0 points min nt. Tyoe: Valley : 15.1 353546 c 9.60e+004 15.0 min cps min min 9.5e4 9.0e4 8.5e4 8.0e4 7.5e4 7.0e4 6.5e4 6.0e4 5.5e4 5.0e4 4.5e4 4.0e4 3.5e4 3.0e4 2.5e4 2.0e4 1 5e4 1 0e4 5000.0 0.0 13.0 Page 3 of 62 15.09 14.5 ' ' 15.o ' 15.5 Time, min ' 16.0 16.5 37.0 ' " 177-5' "14.5 15.0 ' ' 15.5 Time, min ' 16r 0 16.5 _ 17.0 It" Page 53 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 54 of 148 Intensity, cps Intensity, cps *** B u ster J2930203 I Sample Name: "b120423a077" Sample ID: "GLP10-01-02-29-037" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "DAL-GW-607L-0-" Annotation: "" SSaammppllee ITnypdee:x: Unknown Concentration: 0 .975 Calculated Coni N/A 4/24/2012 5:05:50 PM File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height Min. Peak Width: 0.00 Smoothing Width: RT Window: 30.0 Expected RT: 15.1 Use Relative RT: Retention 339557 co 9.06e+004 15.0 15.4 15.08 Sample Name: "b120423a080" Sample ID: "GLP10-01-02-29-040" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu Comment: "DAL-GW-609R-0-" Annotation: "" Sample Index: Sample Type: Concentration: Calculated Conc: Acq. Date: Acq. Time: 80 Unknown 0.975 ng/mL N/A 4/24/2012 6:10:23 PM 1.15e5 1.10e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min 1.05e5 1.00e5 9.50e4 Peak-Split. Factor: Report Largest Peak: Min. Peak Height: Min. Peak Width: Smoothing Width: 2 Yes 0.00 0.00 cps sec 9.00e4 8.50e4 RT Window: Expected RT: Use Relative RT: 30.0 15.1 No sec min 7.50e4 Valley 7.00e4 Retention Time: 15.1 min Area: Height: 389732 counts L.16e+005 cps Start Time: End Time: 15.0 min 15.3 min File: "b120423a.wiff" 4.50e4 4.00e4 3.50e4 3.00e4 2.50e4 2.00e4 1.50e4 1.00e4 5000.00 0.00 Data printed by STW Printing Time: 1:19:14 PM P r i nting Date: Tuesday, M a y 08, 2012 l ime, min GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Sample Name: "b120423a079" Sample ID: "GLP10-01-02-29-039 Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 Comment: "DAL-GW-607L-FMS-" Annotation: "" Sample Index: 79 Sample Type: Unknown Concentration: 0.975 ng/mL Calculated Corn N/A 4/24/2012 9.0e4 5:48:48 PM Modified: Yes 8.5e4 Proc. Algorithm: IntelliQuan Noise Percentage: 50 8.0e4 Base. Sub. Window: 1. 00 Peak-Split. Factor: 2 7.5e4 Report Largest Peak: Yes Min. Peak Height: 0.00 7.0e4 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se 6.5e4 Expected RT: Use Relative RT: 15.1 No mi 6.0e4 Retention Time 345574 co 9.41e+004 15.0 15.3 5.5e4 5.0e4 4.5e4 4.0e4 3.5e4 3.0e4 2.5e4 2.0e4 1 5e4 1 0e4 5000.0 0.0 13.0 13.5 14.0 Sample Name: "b120423a086" Sample ID: "GLP10-01-02-29-043" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 Comment: "DAL-GW-609L-0-" Annotation: "" Sample Index: 86 Sample Type: Unknown Concentration: Calculated Conc: 0.975 N/A ng/mL 8.5e4 Acq. Date: 4/24/2012 Acq. Time: 8:19:24 PM 8.0e4 File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1. 00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 s Expected RT: 15.1 m Use Relative RT: 7.5e4 7.0e4 6.5e4 6.0e4 5.5e4 Int. Type: Valley Retention Time: 15.1 m Height: Start Time: End Time: 1i.66e+004 cps 15.0 m 15.6 m 5.0e4 4.5e4 4.0e4 14.5 15.0 15.5 16.0 16.5 Time, min 17.0 17.5 3.5e4 3.0e4 2.5e4 2.0e4 1 5e4 1 0e4 5000.0 0.0 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 Time, min Page 5 of 62 Page 55 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 56 of 148 *** B u ster J2930203 I Sample Name: "b120423a101" Sample ID: "GLP10-01-02-29-055" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" Comment: "DAL-GW-611L-0-" Annotation: "" Sample Index: 101 Sample Type: Unknown Concentration: 0.975 ng/mL Calculated Conc: N/A Acq. Date: 4/25/2012 Acq. Time: 1:42:13 AM File: "b120423a.wiff' Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: Expected RT: Use Relative RT: Retention 363803 co 9.96e+004 15. 0 15.5 1508 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a105" Sample ID: "GLP10-01-02-29-059" I Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu" J Comment: "DAL-GW-MW121-DB-" Annotation: "" Sample Index: 105 Sample Type: Unknown Concentration: 0. 975 ng/mL Calculated Coni N/A 4/25/2012 3:08:14 AM File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width RT Window: 30.0 Expected RT: 15.1 Use Relative RT: No Int. Type: Valley Retention Time: 15.1 Area: 371078 cc Height: 1.03e+005 Start Time: 15.0 End Time: 15.4 15.09 Sample Name: "b120423a110" Sample ID: "GLP10-01-02-29-061" Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 amu Comment: "DAL-GW-MW47-0-" Annotation: "" Sample Index: 110 Sample Type: Unknown Concentration: 0 .841 Calculated Con N/A Acq. Date : Acq. Time : 4/25/2012 4:55:49 AM 6.5e4 File: "b120423a.wiff' Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 15.1 min Use Relative RT: No 6.0e4 5.5e4 5.0e4 4.5e4 Retention 293746 co 6.87e+004 15.0 15.5 4.0e4 3.5e4 3.0e4 2.5e4 I ime, mir Sample Name: "b120423a113" Sample ID: "GLP10-01-02-29-064 Peak Name: "13C3PFHS-IS(IS)" Mass(es): "402.0/99.0 Comment: "DAL-GW-MW13S-0-" Annotation: "" Sample Index: 113 Sample Type: Unknown Concentration: Calculated Conc: 0.975 N/A ng/mL 1.00e5 Acq' Time: 4/25/2012 6:00:10 AM 9.50e4 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1. 00 min Peak-Split. Factor: 2 Report Largest Peak: Yes 0.00 Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 s Expected RT: 15.1 m Use Relative RT: 9.00e4 8.50e4 8.00e4 7.50e4 7.00e4 6.50e4 Int. Type: Base To Bas Retention Time: 15.1 m Area: 358081 coun L. 01e+005 cps Start Time: 15.0 m End Time: 16.0 m 6.00e4 Intensity, cps 4.00e4 3.50e4 lime, mir 2.0e4 3.00e4 2.50e4 2.00e4 1.50e4 5000.0 1.00e4 5000.00 0.0 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 Time, min Data printed by STW Printing Time: 1:19:14 PM P r i nting Date: Tuesday, M a y 08, 2012 0.00 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 Time, min Page 7 of 62 Page 57 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 58 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 9 of 62 Page 59 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 60 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 11 of 62 Page 61 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 12 of 62 Page 62 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 13 of 62 Page 63 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 14 of 62 Page 64 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 15 of 62 Page 65 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 16 of 62 Page 66 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 17 of 62 Page 67 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date: Tuesday, M a y 08, 2012 Page 18 of 62 Page 68 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 1:19:14 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 69 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:14 PM P r i nting Date: Tuesday, M a y 08, 2012 Page 20 of 62 Page 70 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 71 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date: Tuesday, M a y 08, 2012 Page 22 of 62 Page 72 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 73 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 74 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date: Tuesday, M a y 08, 2012 Page 25 of 62 Page 75 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date: Tuesday, M a y 08, 2012 Page 26 of 62 Page 76 of 148 *** B u ster J2930203 I Sample Name: "b120423a128" Sample ID: "GLP10-01-02-29-076" Peak Name: "13C8PFOS-IS(IS)" Mass(es): "507.0/80.0 amu" Comment: "DAL-GW-TRIP01-FMS-" Annotation: "" SSaammppllee ITnypdee:x: Unknown Concentration: 0 .960 Calculated Coni N/A 3.2e5 4/25/2012 11:22:33 A 3.0e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 1 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 16.1 min Use Relative RT: No Int. Type: Valley Retention Time: 16.0 Area: 1180610 counts Height: 3.28e+005 cps Start Time: 15.9 min End Time: 16.3 min minu ; 2.8e5 2.6e5 2.4e5 2.2e5 2.0e5 File: "b120423a.wiff" 16.00 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Sample Name: "b120423a01/" Sample ID: "11012-62-8" File: "b120423a.wiff Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "1.0 ng/mL FC std in Synth. Water" Annotation: 1 Sample Index: 17 Sample Type: Standard Concentration: 0.945 ng/mL Calculated Corn N/A 4/23/2012 7:37:05 PM Modified: No Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mi Use Relative RT: No Int. Type: Valley Retention Time: 13.6 mi Area: 1822166 count Height: 4.98e+005 cp Start Time: 13.5 mi 13.60 8.0e4 6.0e4 4.0e4 2.0e4 0.0 ISample Name: "b120423a024" Sample ID: "12001-160" File: "b120423a.wiff" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" SamCpolmemeInntd: e"xM:ethod Blan2k4" Annotation: "" Sample Type: Unknown Concentration: Calculated Corn 0.945 n< N/A 5.0e5 Acq. Date : Acq. Time : 4/23/2012 10:07:34 PM 4.8e5 4.6e5 Modified: No Proc. Algorithm: IntelliQuan - MQII 4.4e5 Noise Percentage: Base. Sub. Window: 50 1.00 min 4.2e5 Peak-Split. Factor: 2 4.0e5 Report Largest Peak: Yes Min. Peak Height: 0 3.8e5 Min. Peak Width: Smoothing Width: 0 3 3.6e5 RT Window: Expected RT: Use Relative RT: 30.0 13.6 No 3.4e5 3.2e5 Retention e: 13.6 1846579 co 5.06e+005 13.5 14.5 3.0e5 2.8e5 2.6e5 2.4e5 2.2e5 2.0e5 13.61 I I Sample Name: "b120423a026" Sample ID: "LCS-120416. Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 a Comment: "0.2ppb LCS" Annotation: "" Sample Index: 26 Sample Type: QC Concentration: 0.937 ng/mL Calculated Conc: N/A Acq. Date: 4/23/2012 4.4e5- Acq. Time: 10:50:29 PM 4.2e5 File: "b120423a.wiff" Modified: No Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mi Use Relative RT: No Int. Type: Valley Retention Time: 13.6 mi Area: 1679916 count Height: 4.55e+005 cp Start Time: 13.5 mi End Time: 13.8 mi 4.0e53.8e5 3.6e53.4e5 3.2e5 3.0e52.8e5 2.6e52.4e5 2.2e5 2.0e5- 1 8e5 lime, mir 1361 1 6e5- 1 4e5 1 2e5 1 0e5- 8.0e4 6.0e4 4.0e4 2.0e4 0.0 Data printed by STW Printing Time: 1:19:15 PM 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min 8.0e4 6.0e4 4.0e4 2.0e4 0.0-11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Page 27 of 62 P r i nting Date: Tuesday, M a y 08, 2012 Page 77 of 148 *** B u ster J2930203 I Sample Name: "b120423a029" Sample ID: "LCS-120416-4" File: "b120423a.wiff" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "2ppb LCS" Annotation: "" SSaammppllee ITnypdee:x: QC Concentration: 0 .937 Calculated Coni N/A 4/23/2012 11:54:49 Pt Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 13.6 min Use Relative RT: No Int. Type: Valley Retention Time: 13.6 min Area: 1605602 counts Height: 4.40e+005 cps Start Time: 13.5 min End Time: 14.3 min > ISample Name: "b120423a041" Sample ID: "GLP10-01-02-29-0071 Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu Comment: "DAL-GW-602L-0-" Annotation: "" Sample Index: 41 Sample Type: Unknown Concentration: 0.945 ng/mL Calculated Conc: N/A 4.6e5 Acq. Date: Acq. Time: 4/24/2012 4:12:36 AM 4.4e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 13.6 min Use Relative RT: No 4.2e5 4.0e5 3.8e5 3.6e5 3.4e5 3.2e5 3.0e5 Int. Type: Valley Retention Time: 13.6 min Area: 1719510 counts Height: 1.72e+005 cps Start Time: 13.5 min End Time: 13.9 min 2.8e5 ntensity, cps 2.0e5 1.8e5 1.6e5 1.4e5 1.2e5 1.0e5 8.0e4 6.0e4 4.0e4 2.0e4 0.0 Data printed by STW Printing Time: 1:19:15 PM P r i nting Date: Tuesday, M a y 08, 2012 l ime, mir GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a032" Sample ID: "LCS-120416-7" File: "b120423a.wiff" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "10ppb LCS" Annotation: " Sample Index: 32 Sample Type: Concentration: QC 0.939 ng/mL Calculated Corn N/A 4/24/2012 3.6e5- 12:59:13 A Modified: No 3.4e5- Proc. Algorithm: IntelliQuan Noise Percentage: 50 3.2e5- Base. Sub. Window: 1.00 Peak-Split. Factor: 2 3.0e5- Report Largest Peak: Yes Min. Peak Height: Min. Peak Width: 0.00 0.00 2.8e5- Smoothing Width: RT Window: 3 30.0 se 2.6e5- Expected RT: Use Relative RT: 13.6 mi No 2.4e5- Int. Type: Valley Retention Time: 13.6 mi Area: 1457678 count Height: 3.78e+005 cp Start Time: 13.5 mi 2.2e52.0e51 8e5- 13.60 1 6e5- 1 4e5- 1 2e5- 1 0e5- 8.0e4- 6.0e4- 4.0e4- 2.0e4- 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min I Sample Name: "b120423a044" Sample ID: "GLP10-01-02-29-013" File: "b120423a.wiff Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-603S-0-" Annotation: "" Sample Index: Sample Type: 44 Unknown 13.60 Concentration: 0.945 ng/mL Calculated Conc: N/A Acq. Date: 4/24/2012 Acq. Time: 5 :16:57 AM Modified: Yes Proc. Algorithm: IntelliQuan - MQ Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 s Expected RT: 13.6 m Use Relative RT: No Int. Type: Valley Retention Time: 13.6 m Area: 152:9.52766e+005councps Page 28 of 62 Time, min Page 78 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a046" Sample ID: "GLP10-01-02-29-0151 Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu' Comment: "DAL-GW-603S-FMS-" Annotation: Sample Index: 46 Sample Type: Unknown Concentration: 0.945 Calculated Conc: N/A ng/mL 3.8e5 Acq. Date: Acq. Time: 4/24/2012 5:59:52 AM 3.6e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.0i Min. Peak Width: 0.0i Smoothing Width: 3 RT Window: 30.0 Expected RT: 13.6 Use Relative RT: No 3.4e5 3.2e5 3.0e5 2.8e5 2.6e5 2.4e5 Int. Type: Valley Retention Time: 13.6 Area: 1469746 coi Height: 3.85e+005 Start Time: 13.4 End Time: 13.9 2.2e5 2.0e5 I Sample Name: "b120423a050" Sample ID: "GLP10-01-02-29-016" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" J Comment: "DAL-GW-603L-0-" Annotation: "" Sample Index: 50 Sample Type: Unknown Concentration: Calculated Coni 0. 945 N/A ng/mL 4.4e5- 4/24/2012 7:25:51 AM 4.2e5- Modified: Yes Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mi Use Relative RT: No 4.0e53.8e53.6e5 3.4e5 3.2e53.0e52.8e5- File: "b120423a.wiff" Int. Type: Valley Retention Time: 13.6 mi Area: 1733753 count Height: 4.47e+005 cp Start Time: 13.5 mi 2.6e5 2.4e5 2.2e5- 2.0e5- 13.59 1 8e5- 1 6e5 1 4e5 1 2e5 8.0e4 6.0e4 4.0e4 2.0e4 1 0e58.0e46.0e4 4.0e4 2.0e4- 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Time, min Sample Name: "b120423a053" Sample ID: "GLP10-01-02-29-019 Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu Comment: "DAL-GW-604R-0-" Annotation: "" Sample Index: 53 I Sample Name: "b120423a056" Sample ID: MGLP10-01-02-29-022M File: "b120423a.wiff" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-604S-0-" Annotation: "" Sample Type: Unknown Concentration: 0.945 Calculated Conc: N/A ng/mL 4.0e5 Sample Index: Sample Type: Concentration: 56 Unknown 0.945 ng/mL 4.2e5- 13.59 Acq. Date: Acq. Time: 4/24/2012 8:30:16 AM 3.8e5 Calculated Conc: N/A Acq. Date: 4/24/2012 4.0e5- Modified: Yes 3.6e5 Acq. Time: Modified: 9:34:42 AM Yes 3.8e5- Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 13.6 min Use Relative RT: No Retention Time: 13.6 min Area: 1610054 counts Height: 1.03e+005 cps Start Time: 13.5 min End Time: 14.0 min Intensity, cps 3.4e5 3.2e5 3.0e5 2.8e5 2.6e5 2.4e5 2.2e5 2.0e5 1.8e5 Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mi Use Relative RT: No Int. Type: Valley Retention Time: 13.6 mi Area: 1648330 count Height: 4.22e+005 cp Start Time: 13.5 mi 3.6e53.4e53.2e53.0e52.8e52.6e52.4e52.2e52.0e51 8e5- 1.6e5 1 6e5- 1.4e5 1 4e5- 1.2e5 1 2e5- 1.0e5 1 0e5- 8.0e4 8.0e4- 6.0e4 6.0e4- 4.0e4 4.0e4- 2.0e4 2.0e4- 0.0 Data printed by STW Printing Time: 1:19:15 PM 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min 0.0-11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Page 29 of 62 P r i nting Date: Tuesday, M a y 08, 2012 Page 79 of 148 *** B u ster J2930203 I Sample Name: "b120423a062" Sample ID: "GLP10-01-02-29-025" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-604L-0-" Annotation: "" Sample Index: 62 Sample Type: Unknown Concentration: 0.945 ng/mL Calculated Conc: N/A Acq. Date: 4/24/2012 Acq. Time: 11:43:37 AM File: "b120423a.wiff' Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.0i Min. Peak Width: 0.0i Smoothing Width: 3 RT Window: 30.0 Expected RT: 13.6 Use Relative RT: No Int. Type: Valley Retention Time: 13.6 Area: 1579439 co Height: 4.19e+005 Start Time: 13.4 End Time: 13.9 1357 ISample Name: "b120423a065" Sample ID: "GLP10-01-02-29-028" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" SamCpolmemeInntd: e"xD:AL-GW-60655R-0-" Annotation: "" Sample Type: Unknown Concentration: 0.945 n Calculated Corn N/A Acq. Date : 4/24/2012 Acq. Time : 12:48:03 PM File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height Min. Peak Width: Smoothing Width: RT Window: 30.0 Expected RT: 13.6 Use Relative RT: No Retention Valley 13.6 1625694 counts 4.14e+005 cps 13.5 min I ime, mir 13.58 Data printed by STW Printing Time: 1:19:15 PM P r i nting Date: Tuesday, M a y 08, 2012 Time, mm GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a064" Sample ID: "GLP10-01-02-29-027" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" J Comment: "DAL-GW-604L-FMS-" Annotation: "" Sample Index: 64 Sample Type: Unknown Concentration: 0. 945 ng/mL Calculated Coni N/A 4/24/2012 12:26:32 Pt File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mi Use Relative RT: No Int. Type: Valley Retention Time: 13.6 mi Area: 1614820 count Height: 4.00e+005 cp Start Time: 13.4 mi End Time: 13.8 mi 13.59 I Sample Name: "b120423a068" Sample ID: "GLP10-01-02-29-031" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-605L-0-" Annotation: "" Sample Index: 68 Sample Type: Unknown 4.6e5- Concentration: 0.945 ng/mL Calculated Conc: N/A 4.4e5 Acq. Date: 4/24/2012 Acq. Time: 1:52:27 PM 4.2e5 Modified: Yes Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mi Use Relative RT: No Int. Type: Valley Retention Time: 13.6 mi Area: 1813666 count Height: 60e+005 13.4 13.9 4.0e53.8e5 3.6e5 3.4e5 3.2e5 3.0e52.8e5 2.6e5 2.4e5 2.2e5 2.0e5- File: "b120423a.wiff" lime, mir 13.57 1 8e5 1 6e5 1 4e5 1 2e5 1 0e5- 8.0e4 6.0e4 4.0e4 2.0e4 0.0-11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Page 30 of 62 Page 80 of 148 *** B u ster J2930203 ISample Name: "b120423a074" Sample ID: "GLP10-01-02-29-034" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" SamCpolmemeInntd: e"xD:AL-GW-607R-0-" Annotation: "" Sample Type: Unknown Concentration: 0 .945 Calculated Coni N/A 4/24/2012 4:01:21 PM File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 13.6 min Use Relative RT: No Int. Type: Valley Retention Time: 13.6 min Area: 1747826 counts Height: 4.69e+005 cps > End Time: 14.0 min 1356 ISample Name: "b120423a079" Sample ID: "GLP10-01-02-29-039" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-607L-FMS- " Annotation: "" Sample Index: 79 Sample Type: Unknown Concentration: 0.945 Calculated Corn N/A Acq. Date: 4/24/2012 Acq. Time: 5:48:48 PM File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0. Min. Peak Width: 0. Smoothing Width: 3 RT Window: 30.0 Expected RT: 13.6 Use Relative RT: No Retention Valley 13.6 1773995 co 4.43e+005 13. 4 13.7 l ime, mir 1358 Data printed by STW Printing Time: 1:19:15 PM P r i nting Date: Tuesday, M a y 08, 2012 Time, min GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Sample Name: "b120423a077" Sample ID: "GLP10-01-02-29-037" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-607L-0-" Annotation: "" Sample Index: 77 Sample Type: Unknown Concentration: Calculated Con 0.945 N/A ng/mL 4.4e5- 4/24/2012 5:05:50 PM 4.2e5 Modified: Yes Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1. 00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mi Use Relative RT: No 4.0e53.8e53.6e5 3.4e5 3.2e53.0e52.8e5- File: "b120423a.wiff" 1356 Int. Type: Valley Retention Time: 13.6 mi Area: 1743081 count 4.47e+005 2.6e5 2.4e5 2.2e5- 2.0e5- 1 8e5- 1 6e5 1 4e5 1 2e5 1 0e5- 8.0e4- 6.0e4- 4.0e4 2.0e4- 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min I Sample Name: "b120423a080" Sample ID: 'GLP10-01-02-29-040M File: "b120423a.wiff' Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-609R-0-" Annotation: "" Sample Index: Sample Type: 80 Unknown 1358 Concentration: 0.945 ng/mL Calculated Conc: N/A Acq. Date: 4/24/2012 Acq. Time: 6:10:23 PM Modified: Yes Proc. Algorithm: IntelliQuan - MQ Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 s Expected RT: 13.6 m Use Relative RT: No Int. Type: Valley Retention Time: 13.6 m Area: 173:8.26645e+00c5ouncps Page 31 of 62 Time, min Page 81 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab ISample Name: "b120423a086" Sample ID: "GLP10-01-02-29-043" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu' SamCpolmemeInntd: e"xD:AL-GW-60896L-0-" Annotation: "" Sample Type: Unknown Concentration: 0.945 ng/mL Calculated Conc: N/A 4/24/2012 4.2e5- Acq. Time: 8:19:24 PM 4.0e5- File: "b120423a.wiff' Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 13.6 min Use Relative RT: No Valley Retention Time: 13.6 min 3.6e53.4e53.2e53.0e52.8e52.6e5- Height: Start Time: End Time: .35e+005 cps 13.4 min 13.8 min Sample Name: "b120423a089" Sample ID: "GLP10-01-02-29-046" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" J Comment: "DAL-GW-610R-0-" Annotation: "" Sample Index: 89 Sample Type: Unknown Concentration: Calculated Coni 0. 945 N/A ng/mL 4.8e5- 4/24/2012 4.6e5- 9:23:58 PM 4.4e5- Modified: Yes Proc. Algorithm: IntelliQuan 4.2e5- Noise Percentage: 50 Base. Sub. Window: 1. 00 4.0e5- Peak-Split. Factor: 2 Report Largest Peak: Yes 3.8e5- Min. Peak Height: Min. Peak Width: Smoothing Width: 0.00 0.00 3 3.6e53.4e5- RT Window: Expected RT: 30.0 se 13.6 mi 3.2e5- Use Relative RT: No 3.0e5- File: "b120423a.wiff" Int. Type: Valley Retention Time: 13.6 mi Area: 1897558 count Height: 4. 84e+005 13.4 13.9 2.8e52.6e52.4e52.2e5- 13.57 Intensity, cps 1.8e5- 2.0e5- 1.6e5- 1 8e5- 1.4e51.2e51.0e58.0e46.0e44.0e42.0e4- 1 6e51 4e51 2e51 0e58.0e46.0e44.0e42.0e4- 0.011.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Time, min Sample Name: "b120423a092" Sample ID: "GLP10-01-02-29-049 Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu Comment: "DAL-GW-610L-0-" Annotation: "" Sample Index: 92 I Sample Name: "b120423a094" Sample ID: "GLP10-01-02-29-051" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-610L-FMS-" Annotation: "" File: "b120423a.wiff Sample Type: Concentration: Unknown 0.945 n< Sample Index: Sample Type: 94 Unknown 13.57 Calculated Corn N/A Acq. Date: 4/24/2012 4.4e5 Concentration: Calculated Conc: 0.945 ng/mL N/A Acq. Time: 10:28:29 PM 4.2e5 Acq. Date: Acq. Time: 4/24/2012 11:11:35 PM Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height Min. Peak Width: Smoothing Width: RT Window: 30.0 Expected RT: 13. 6 Use Relative RT: No 4.0e5 3.8e5 3.6e5 3.4e5 3.2e5 3.0e5 2.8e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQ Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 s Expected RT: 13.6 m Use Relative RT: No Retention Valley 13.6 1746274 counts 4.54e+005 cps 13.4 min 14.0 min 2.6e5 2.4e5 2.2e5 Int. Type: Base To Bas Retention Time: 13.6 m Area: 1746530 coun Height: 4.37e+005 c 2.0e5 8.0e4 6.0e4 4.0e4 2.0e4 0.0 Data printed by STW Printing Time: 1:19:15 PM 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min P r i nting Date: Tuesday, M a y 08, 2012 Page 32 of 62 Time, min Page 82 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a098" Sample ID: "GLP10-01-02-29-052" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu' Comment: "DAL-GW-611R-0-" Annotation: Sample Index: 98 Sample Type: Unknown Concentration: 0.945 ng/mL 4.4e5 Calculated Conc: N/A 4.2e5 Acq. Date: 4/25/2012 Acq. Time : 12:37:38 AM 4.0e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII 3.8e5 Noise Percentage: Base. Sub. Window: 50 1.00 min 3.6e5 Peak-Split. Factor: 2 Report Largest Peak: Yes 3.4e5 Min. Peak Height: Min. Peak Width: 0.00 cps 0.00 sec 3.2e5 Smoothing Width: RT Window: 3 points 30.0 sec 3.0e5 Expected RT: Use Relative RT: 13.6 min No 2.8e5 File: "b120423a.wiff' Int. Type: Valley Retention Time: 13.6 min Area: 1806004 counts Height: 4.40e+005 cps Start Time: 13.4 min End Time: 13.9 2.6e5 E ; mina 2.4e5 2.2e5 2.0e5 I Sample Name: "b120423a101" Sample ID: "GLP10-01-02-29-055" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" J Comment: "DAL-GW-611L-0-" Annotation: "" Sample Index: 101 Sample Type: Unknown Concentration: 0. 945 ng/mL Calculated Coni N/A 4/25/2012 4.2e5- 1:42:13 AM 4.0e5- Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 Expected RT: 13.6 1 Use Relative RT: No 3.8e53.6e53.4e53.2e53.0e52.8e5- Int. Type: Valley Retention Time: 13.6 Area: 1772134 coui 4.36e+005 2.6e52.4e52.2e5- File: "b120423a.wiff" 2.0e5- 1357 1 8e5- 1 6e5- 1 4e5- 1 2e5- 1 0e5- 8.0e4 8.0e4- 6.0e4 6.0e4- 4.0e4 4.0e4- 2.0e4 2.0e4- 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Time, min I Sample Name: "b120423a105" Sample ID: "GLP10-01-02-29-059" File: "b120423a.wiff" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" I Sample Name: "b 120423a110" Sample ID: "GLP10-01-02-29-061" File: "b120423a.wiff" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-MW121-DB-" Annotation: "" Comment: "DAL-GW-MW47-0-" Annotation: "" Sample Index: 105 CSoanmcpelnetrTaytpieo:n: Unk0n.o9w4n5 Calculated Conc: N/A Acq. Date: 4/25/2012 Acq. Time: ng/mL Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 4.0e53.8e5- 13.58 Sample Index: 110 Sample Type: Unknown Concentration: 0.815 ng/mL Calculated Conc: N/A Acq. Date: 4/25/2012 Acq. Time: 4:55:49 AM Modified: Yes Proc. Algorithm: IntelliQuan Noise Percentage: 50 4.0e53.8e53.6e53.4e5- 13.57 Base. Sub. Window: Peak-Split. Factor: Report Largest Peak: Min. Peak Height: 1.00 2 Yes 0.00 min cps 3.4e5- Base. Sub. Window: Peak-Split. Factor: Report Largest Peak: Min. Peak Height: 1.00 2 Yes 0.00 3.2e53.0e5- Min. Peak Width: 0.00 sec Min. Peak Width: 0.00 Smoothing Width: 3 points Smoothing Width: 3 2.8e5- RT Window: 30.0 sec RT Window: 30.0 se Expected RT: Use Relative RT: 13.6 min No Expected RT: Use Relative RT: 13.6 mi No 2.6e5- Valley Retention Time: 13.6 min Area: 1746973 counts Height: .33e+005 cps Start Time: 13.4 min End Time: 14.1 min 2.6e5- Intensity, cps Int. Type: Valley Retention Time: 13.6 mi Area: 1602735 count :.01e+005 cps 2.4e52.2e52.0e51 8e5- 1.8e5- 1 6e5- 1.6e51.4e51.2e51.0e5- 1 4e51 2e51 0e5- 8.0e4- 8.0e4- 6.0e4- 6.0e4- 4.0e4- 4.0e4- 2.0e4- 2.0e4- 0.011.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Data printed by STW Printing Time: 1:19:15 PM 0.0-11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Page 33 of 62 P r i nting Date: Tuesday, M a y 08, 2012 Page 83 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a113" Sample ID: "GLP10-01-02-29-064" Peak Name: "18O2PFBS-IS(IS)' Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-MW13S-0- Annotation: "" Sample Index: Sample Type: Unknown Concentration: 0 .945 Calculated Coi N/A 4/25/2012 File: "b120423a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.0i Min. Peak Width: 0.0i Smoothing Width: 3 RT Window: 30.0 Expected RT: 13.6 Use Relative RT: No Int. Type: Valley Retention Time: 13.6 Area: 1714299 coi Height: 4.27e+005 Start Time: 13.4 End Time: 13.8 13.57 Sample Name: "b120423a118" Sample ID: "GLP10-01-02-29-069 Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu Comment: "DAL-GW-MW13I-FMS-" Annotation: "" Sample Index: 118 Sample Type: Concentration: Unknown 0.945 ng/mL 4.2e5 Calculated Conc: N/A Acq. Date: 4/25/2012 4.0e5 Acq. Time: 7:47:42 AM 3.8e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 3.6e5 Base. Sub. Window: Peak-Split. Factor: 1.00 min 2 3.4e5 Report Largest Peak: Yes Min. Peak Height: 0.00 cps 3.2e5 Min. Peak Width: Smoothing Width: 0.00 sec 3 points 3.0e5 RT Window: Expected RT: 30.0 sec 2.8e5 Use Relative RT: No 2.6e5 Int. Type: Valley Retention Time: 13.6 min Area: 1716964 counts Height: 1.20e+005 cps 13.4 min End Time: 14.0 min 2.4e5 2.2e5 2.0e5 Intensity, cps 1.8e5 l ime, mir I Sample Name: "b120423a116" Sample ID: "GLP10-01-02-29-067" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" J Comment: "DAL-GW-MW13I-0-" Annotation: "" Sample Index: 116 Sample Type: Unknown Concentration: Calculated Coni 0.945 N/A ng/mL 4.6e5- 4/25/2012 7:04:44 AM 4.4e5 Modified: Yes Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mi Use Relative RT: No 4.2e54.0e5 3.8e5 3.6e53.4e53.2e5 3.0e5 Int. Type: Valley Retention Time: 13.6 mi Area: 1864573 count 4.71e+005 2.8e52.6e5 2.4e5- File: "b120423a.wiff" 1357 2.2e5 2.0e5- 1 8e5 1 6e5 1 4e5- 1 2e5 1 0e5- 8.0e4 6.0e4- 4.0e4 2.0e4- 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Sample Name: "b120423a122" Sample ID: "GLP10-01-02-29-070" File: "b120423a.wiff" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-MW13B-0-" Annotation: "" Sample Index: 122 Sample Type: Concentration: Unknown 0.945 ng/mL 13.56 Calculated Con N/A 4/25/2012 9:13:39 AM Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 Expected RT: 13.6 1 Use Relative RT: No Int. Type: Valley Retention Time: 13.6 Area: 1707309 cou Height: 09e+005 cps 13.4 min 13.9 min 1.6e5 1.4e5 1.2e5 1.0e5 8.0e4 6.0e4 4.0e4 2.0e4 0.0 Data printed by STW Printing Time: 1:19:15 PM 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Page 34 of 62 Time, mir P r i nting Date: Tuesday, M a y 08, 2012 Page 84 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab ISample Name: "b120423a125" Sample ID: "GLP10-01-02-29-073" Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu' Comment: "DAL-GW-604L-RB-" Annotation: "" Sample Index: 125 Sample Type: Unknown Concentration: 0.945 ng/mL Calculated Conc: N/A Acq. Date: 4/25/2012 4.0e5 Acq. Time: 10:18:06 AM 3.8e5 Modified: No Proc. Algorithm: IntelliQuan - MQII 3.6e5 Noise Percentage: Base. Sub. Window: 50 1.00 min 3.4e5 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps 3.2e5 Min. Peak Width: Smoothing Width: 0.00 sec 3 points 3.0e5 RT Window: Expected RT: 30.0 sec 13.6 min 2.8e5 Use Relative RT: No 2.6e5 File: "b120423a.wiff' Intensity, cps Int. Type: Valley Retention Time: 13.6 min Area: 1699211 counts Height: 1.17e+005 cps 13.4 min EndrTimeme: 2.4e5 2.2e5 2.0e5 1.8e5 1.6e5 1.4e5 1.2e5 1.0e5 8.0e4 6.0e4 I Sample Name: "b120423a126" Sample ID: "GLP10-01-02-29-074" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" J Comment: "DAL-GW-607R-RB-" Annotation: "" Sample Index: 126 Sample Type: Unknown Concentration: Calculated Conc: 0.945 N/A ng/mL 4.0e5 Acq. Date: Acq. Time: 4/25/2012 10:39:37 AM 3.8e5 File: "b120423a.wiff" Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Pe Min. Peak Height: 0 .00 cps Min. Peak Width: 0.00 Smoothing Width: 3 points RT Window: 30.0 s Expected RT: 13.6 m Use Relative RT: No Int. Type: Valley Retention Time: 13.6 m Area: 1633440 coun Height: I. 07e+005 cps Start Time: 13.4 m End Time: 13.9 m Intensity, cps 3.6e5 3.4e5 3.2e5 3.0e5 2.8e5 2.6e5 2.4e5 2.2e5 2.0e5 1 8e5 1 6e5 1 4e5 1 2e5 1 0e5 8.0e4 6.0e4 13.56 4.0e4 4.0e4 2.0e4 2.0e4 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Time, min ISample Name: "b120423a127" Sample ID: "GLP10-01-02-29-0751 Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu Comment: "DAL-GW-TRIP01-0-" Annotation: "" Sample Name: "b120423a128" Sample ID: "GLP10-01-02-29-076" File: "b120423a.wiff" I Peak Name: "18O2PFBS-IS(IS)" Mass(es): "303.0/84.0 amu" Comment: "DAL-GW-TRIP01-FMS-" Annotation: "" Sample Index: 12 7 Sample Index: 128 Sample Type: Unknown Concentration: 0.945 Calculated Coni N/A n< 4.4e5 Sample Type: Unknown Concentration: 0.945 Calculated Conc: N/A ng/mL 4.0e5 13.55 Acq. Date: Acq. Time: 4/25/2012 11:01:06 AM 4.2e5 Acq. Date: Acq. Time: 4/25/2012 11:22:33 AM 3.8e5 Modified: No 4.0e5 Modified: No 3.6e5 Proc. Algorithm: IntelliQuan - MQII 3.8e5 Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Noise Percentage: 50 3.4e5 Base. Sub. Window: 1.00 min 3.6e5 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes 3.4e5 Peak-Split. Factor: 2 Report Largest Peak: Yes 3.2e5 Min. Peak Height: Min. Peak Width: 0.( 0.( 3.2e5 Min. Peak Width: 0.00 0.00 3.0e5 Smoothing Width: 3 RT Window: 30.0 3.0e5 Smoothing Width: RT Window: 3 points 30.0 s 2.8e5 Expected RT: 13.6 Use Relative RT: No 2.8e5 Expected RT: Use Relative RT: 13.6 m 2.6e5 Retention Valley 13.5 1847859 counts 4.43e+005 cps 13.4 min 14.0 min 2.6e5 2.4e5 2.2e5 2.0e5 Int. Type: Valley Retention Time: 13.5 m Area: 1686637 coun I. 07e+005 cps Start Time: 13.4 m End Time: 13.7 m Intensity, cps 2.4e5 2.2e5 2.0e5 1 8e5 1 6e5 1 4e5 1 2e5 1 0e5 8.0e4 6.0e4 4.0e4 2.0e4 0.0 Data printed by STW Printing Time: 1:19:15 PM P r i nting Date: Tuesday, M a y 08, 2012 8.0e4 6.0e4 4.0e4 2.0e4 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min Page 35 of 62 Page 85 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 36 of 62 Page 86 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 37 of 62 Page 87 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 38 of 62 Page 88 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 39 of 62 Page 89 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 40 of 62 Page 90 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:15 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 41 of 62 Page 91 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 42 of 62 Page 92 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 43 of 62 Page 93 of 148 *** B u ster J2930203 I Sample Name: "b120423a126" Sample ID: "GLP10-01-02-29-074" Peak Name: "PFBS" Mass(es): "299.0/99.0 amu.299.0/80.0 amu" Comment: "DAL-GW-607R-RB-" Annotation: "" Sample Index: 126 Sample Type: Unknown Concentration: N/A Calculated Conc: < 0 Acq. Date: 4/25/2012 Acq. Time: 10:39:37 AM File: "b120423a.wiff" Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 1 Report Largest Peak: Yes MMiinn.. PPeeaakk WHieditghh:t: 0.00 Smoothing Width: RT Window: 30.0 Expected RT: 13.6 Use Relative RT: Retention Valley 13. 6 8038 co 2.22e+003 13.5 13.7 13.56 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab I Sample Name: "b120423a127" Sample ID: "GLP10-01-02-29-075" I Peak Name: "PFBS" Mass(es): "299.0/99.0 amu ,299.0/80.0 amu" Comment: "DAL-GW-TRIP01-0-" Annotation: "" Sample Index: 127 Sample Type: Unknown Concentration: Calculated Coni 4/25/2012 11:01:06 File: "b120423a.wiff" Modified: No Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 1 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 13.6 mil Use Relative RT: Yes Int. Type: Valley Retention Time: 13.5 mi Area: 11124 count 2.32e+003 13.55 ISample Name: "b120423a128" Sample ID: "GLP10-01-02-29-076" Peak Name: "PFBS" Mass(es): "299.0/99.0 amu,299.0/80.0 amu Comment: "DAL-GW-TRIP01-FMS-" Annotation: "" Sample Index: 12 8 Sample Type: Unknown Concentration: Calculated Con Acq. Date: ng/mL 4/25/2012 5.4e5 5.2e5 Acq. Time: 11:22:33 AM 5.0e5 File: "b120423a.wiff' Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 1 Report Largest Peak: Yes Min. Peak Height: Min. Peak Width: 0.00 Smoothing Width: RT Window: 30.0 Expected RT: 13.6 Use Relative RT: Yes 4.8e5 4.6e5 4.4e5 4.2e5 4.0e5 3.8e5 3.6e5 3.4e5 Retention Valley 13.5 2276718 co 5.44e+005 13.4 13.8 3.2e5 3.0e5 2.8e5 2.6e5 2.4e5 2.2e5 2.0e5 I ime, mir I Sample Name: "b120423a017" Sample ID: "11012-62-8" Peak Name: "PFHS" Mass(es): "399.0/99.0 Comment: "1.0 ng/mL FC std in Synth. Water Sample Index: 17 Sample Type: Standard Concentration: 0.998 ng/mL Calculated Con ng/mL 4/23/2012 7:37:05 P 6.0e5 Modified: No Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 1 Report Largest Peak: No Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 RT Window: 30.0 se Expected RT: 15.1 mil Use Relative RT: Yes Int. Type: Valley Retention Time: 15.1 mi Area: 2201803 count 6.49e+005 15.0 15.3 5.5e5 5.0e5 4.5e5 4.0e5 3.5e5 3.0e5 2.5e5 2.0e5 lime, mir 1 5e5 8.0e4 6.0e4 4.0e4 2.0e4 0.0 Data printed by STW Printing Time: 1:19:16 PM 14.15 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min P r i nting Date : Tuesday, M a y 08, 2012 1.0e5 5.0e4 0.0 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 Time, min Page 44 of 62 Page 94 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 45 of 62 Page 95 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 46 of 62 Page 96 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 47 of 62 Page 97 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 48 of 62 Page 98 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 49 of 62 Page 99 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 50 of 62 Page 100 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 51 of 62 Page 101 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 52 of 62 Page 102 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 53 of 62 Page 103 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 54 of 62 Page 104 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 55 of 62 Page 105 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 56 of 62 Page 106 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 57 of 62 Page 107 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:16 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 58 of 62 Page 108 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:17 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 59 of 62 Page 109 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:17 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 60 of 62 Page 110 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:17 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 61 of 62 Page 111 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:19:17 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 62 of 62 Page 112 of 148 Workstation: ETSBUSTER GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 2:09:22 PM P r i nting Date: Thu rsday, Ap r i l 26, 2012 Page 113 of 148 Workstation: ETSBUSTER GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 2:09:09 PM P r i nting Date: Thu rsday, Ap r i l 26, 2012 Page 114 of 148 Workstation: ETSBUSTER GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 2:08:38 PM P r i nting Date: Thu rsday, Ap r i l 26, 2012 Page 115 of 148 Workstation: ETSBUSTER GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Printing Time: 2:08:49 PM P r i nting Date: Thu rsday, Ap r i l 26, 2012 Page 116 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:23:31 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 1 of 7 Page 117 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:23:31 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 2 of 7 Page 118 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:23:31 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 3 of 7 Page 119 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:23:32 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 4 of 7 Page 120 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:23:32 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 5 of 7 Page 121 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:23:32 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 6 of 7 Page 122 of 148 *** B u ster J2930203 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Batch Name: b120423a.dab Data printed by STW Printing Time: 1:23:32 PM P r i nting Date : Tuesday, M a y 08, 2012 Page 7 of 7 Page 123 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Attachment C: A nalytical Meth o d (s) Page 124 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 3M Environmental Laboratory Method Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.1 Adoption Date: 4/12/07 Effective Date: I j 7/ K Approved By: William K. Reagen, Technical Director, Environmental Laboratory J/J Q i/ // Date * ETS-8-044.1 Page 1 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 125 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 1 Scope and Application T his m ethod d e scrib es the direct injection analysis o f perfluorinated c o m p o u n d s (P F C s) from w a te r m atrice s using high -perform a nce liquid c h ro m a to g ra p h y ta n d e m m ass spe ctro m e try (H P L C /M S /M S ). T h e m e th o d is g e n e ra lly a p p lica b le but not lim ited to th e m e a s u re m e n t o f perfluoroalkyl sulfonam ides and perfluorinated alkyl acids (P FA A s) such as perfluorosulfonic acids (P F S A s) and p e rflu o ro ca rb o xylic acids (P F C A s) (T able 1). W a te r sa m p le s containing heavy particulate m ay require preparation by an alternate m ethod such as E T S -8-154 " D e te rm in a tio n o f P e rflu o rin a te d A c id s , A lc o h o ls , A m id e s , a n d S u lfo n a te s In W a te r B y S o lid P hase E xtraction and H igh P erfo rm a nce Liquid C h rom ato grap hy/M ass S pe ctrom etry" . T he m e th o d is a p p lic a b le to b o th e x te rn a l s ta n d a rd a n d in te rn a l s ta n d a rd c a lib ra tio n 1. Table 1. Representative Target Analytes Acronym PFBA (C4 Acid) PFPeA (C5 Acid) PFHxA (C6 Acid) PFHpA (C7 Acid) PFOA (C8Acid) PFNA (C9 Acid) PFDA (C10 Acid) PFUnA (C11 Acid) PFDoA (C12 Acid) PFTrDA (C13 Acid) PFBS (C4 Sulfonate) PFHS (C6 Sulfonate) PFOS (C8 Sulfonate) FBSA (C4 Sulfonamide FOSA (C8 Sulfonamide) Analyte Perfluorobutanoic acid Perfluoropentanoic acid Perfluorohexanoic acid Perfluoroheptanoic acid Perfluorooctanoic acid Perfluorononanoic acid Perfluorodecanoic acid Perfluoroundecanoic acid Perfluorododecanoic acid Perfluorotridecanoic acid Perfluorobutanesulfonic acid Perfluorohexanesulfonic acid Perfluorooctanesulfonic acid Perfluorobutanesulfonamide Pefluorooctanesulfonamide Chemical Abstract Services Registry Number (CASRN) 375-22-4 2706-90-3 307-24-4 375-85-9 335-67-1 375-95-1 335-76-2 2058-94-8 307-55-1 72629-94-8 375-73-5 355-46-4 1763-23-1 30334-69-1 754-91-6 T h e M in im u m R e po rting Le vel (M R L ) is th e Lim it o f Q ua ntita tio n (LO Q ) th a t m e e ts D ata Q uality O bjectives (D Q O s) that are developed based on the intended use o f this m ethod. M etho d F lexibility - T h is is a p e rfo rm a n c e -b a s e d m e th o d and m a y be g e n e ra lly a p plied to th e d e te rm in a tio n o f p e rflu o rin a te d c o m p o u n d s in w a te r m a tric e s w h e n a n a ly s is b a tc h q u a lity co n tro l (Q C ) criteria a re m e t2. E ach s e t o f s a m p le s a re p re p a re d in an a n a ly s is ba tch w ith calibration standards, LC Ss, blanks, and continuing calibration che ck standards analyzed on the sa m e instrum ent during a tim e period tha t begins and ends w ith the analysis o f the a p p ro p ria te c o n tin u in g calib ra tio n c h e c k s ta n d a rd s . T h e la b o ra to ry is pe rm itte d to m o d ify th e LC colum n, m obile phase com position, LC conditions, and M S /M S conditions. M ethod m odifications should be considered to im prove m ethod perform ance o r to m eet data quality o b je ctive s fo r th e stud y. In all ca s e s w h e re m e th o d m o d ifica tio n s a re im p le m e n te d , th e batch 1The method is supported by validation with internal standard calibration for C4-C13 PFCAs, C4, C6, and C8 PFSAs, and C8 perfluoroalkane sulfonamide in laboratory control samples under 3M method validation E11-0667. 2Guidance for establishing method QC Criteria based on a.) FDA May 2001, "Guidance for Industry, Bioanalytical Method Validation", b.) EPA Method 537, and c.) European Commission: Guidance for Generating and Reporting Methods of Analysis in Support of Pre-registration Data Requirements for Annex II (Part A, section 4) and Annex III (Part A,section 5) of Directive 91/414, SANCO/3029/99 rev. 4 (11/07/00). ETS-8-044.1 Page 2 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 126 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 analytical Q C s (section 9) m ust be com pleted and pass Q C acce ptan ce criteria (section 13) if the data from the analytical batch are to be reported. 2 Method Summary W a te r sam ples are analyzed as neat aqueous sam p le o r as solven t diluted aq ue ou s sam p le s by direct injection using LC /M S /M S . S am p le s containing heavy particulate m a y not be suitable fo r analysis by this m ethod. S am ples containing suspended particulate should be centrifuged o r filtered prior to rem oving a sa m p le aliquot o r diluting w ith solvent. T he w a te r s a m p le is m ixe d w e ll p rio r to rem o ving an a liq u o t o r d ilutin g, if n e cessa ry, w ith A S T M T y p e I w ater, H P LC w ater, o th e r suitable w ater, o r solven t (m ethanol). Q u a n tita tio n is b y s ta b le iso to pe in ternal s ta n d a rd calib ra tio n in la b o ra to ry re a g e n t w a te r. A ll perfluorinated com pounds (P FC s) targe t analyte concentrations o f perfluorosulfonic acids (P FS A s) and perfluorocarboxylic acids (P FC A s) are reported as anions and corrected for th e ir salt o r free acid form s. A lternatively, quantitation m ay be perform ed by external standard calibration. T h is is a p e rfo rm a n c e -b a s e d m e th o d . M e th o d u n c e rta in ty fo r e a c h ta rg e t a n a ly te is determ ined fo r each analytical batch using m ultiple laboratory control spikes at m ultiple concentrations. T his m ethod also requires that the precision and accu racy fo r each sam p le be d e te rm in e d using field m a trix s p ik e s to v e rify th a t th e m etho d is a p p lica b le to ea ch s a m p le m atrix. C alibration standards fo r P FU nA , P FD oA , P FTrD A , and F O S A have been found to be u n s ta b le fo r m o re th a n 2 d a y s in 10 0% w a te r. S a m p le s req uiring a n a ly s is fo r th e s e c o m p o u n d s b y th is m e th o d s h o u ld be d ilu te d 1:1 w ith m e th a n o l a n d a n a ly z e d a g a in s t a c a lib ra tio n c u rv e p re p a re d in 1:1 s y n th e tic g ro u n d w a te r:M e O H . 3 Definitions 3.1 Analysis Batch A set o f stud y sam p le s tha t are prepared w ith calibration standards, laboratory control sam p le s, and pro ced ural blanks, and analyzed on th e s a m e in stru m en t during a tim e period that begins and ends w ith th e analysis o f the appropriate continuing calibration check standards. 3.2 Analytical Sample A portion o f a laboratory sa m p le prepared fo r analysis. 3.3 Calibration Standard A solution prepared by spiking a know n volum e o f the W orkin g S tandard (W S ) into a p re d e te rm in e d a m o u n t o f A S T M T y p e I, H P L C g ra d e w a te r, o r o th e r s u ita b le w a te r (i.e. m atrix w ater), and analyzed according to this m ethod. C alibration standards are used to calibrate the instrum ent response w ith respect to analyte concentration. 3.4 Laboratory Duplicate Sample (LDS, or Lab Dup) A la b o ra to ry d u p lic a te s a m p le is a s e p a ra te a liq u o t o f a s a m p le ta k e n in th e a n a lytica l la b o ra to ry th a t is a n a ly z e d s e p a ra te ly w ith id en tical p ro ce d u re s. A n a ly s is o f L D S s co m p a re d to tha t o f the first aliquot give a m ea sure o f the precision associated w ith laboratory procedures, but not w ith sam p le collection, preservation, o r storage procedures. ETS-8-044.1 Page 3 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 127 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 3.5 Field Blank (FB)/Trip Blank (TB) A S T M T y p e I, H P L C g ra d e w a te r, o r o th e r s u ita b le w a te r, p la c e d in a s a m p le c o n ta in e r in th e la b o ra to ry and tre a te d as a s a m p le in all re sp e cts, in clu d in g e x p o s u re to s a m p lin g site co n ditions, storag e, pre se rva tio n and all an a lytica l pro ce d u re s. T h e p u rp o se o f th e T B is to d e te rm in e if te s t s u b s ta n c e s o r o th e r in te rfe re n c e s a re p re s e n t in th e field e n v iro n m e n t. T h is s a m p le is also referre d to as a T rip B lank. 3.6 Field Duplicate Sample (FDS, Field Dup) A s a m p le colle cte d in d u p lic a te a t th e s a m e tim e fro m th e s a m e lo catio n as th e s a m p le . T h e F D S is ha nd led u n d e r id en tical c irc u m s ta n c e s and treate d e x a c tly th e s a m e th ro u g h o u t field and laboratory procedures. A nalysis o f the F D S com pared to that o f the first sam ple gives a m easure o f the precision associated w ith sam p le collection, preservation and storage, as w ell as w ith laboratory procedures. 3.7 Field Matrix Spike (FMS) A sam p le to w hich know n quantities o f the ta rg e t analytes, ISs and S R S s are added to the s a m p le bo ttle in th e la b o ra to ry b e fo re th e bo ttle s a re s e n t to th e field fo r co lle ctio n o f a q u e o u s sam ples. A know n, specific volum e o f sam ple m ust be added to the sam ple container w ith o u t rinsing. T h is m a y be a c c o m p lis h e d by m a kin g a "fill to th is le v e l" line on th e o u tside o f th e s a m p le con tain er. T h e F M S is a n a lyze d to a sce rta in if a n y m a trix e ffects, in te rfe ren ces, o r stab ility issues m ay com plicate the interpretation o f the sam p le analysis. 3.8 Trip Blank Matrix Spike (TBMS) A n a liq u o t o f A S T M T y p e I, H P L C g ra d e w a te r, o r o th e r s u ita b le w a te r, to w h ic h k n o w n q u a n titie s o f th e ta rg e t a n a ly te s , IS s and S R S s a re a d d e d in th e la b o ra to ry p rio r to th e s h ip m e n t o f th e collectio n bottles. T h e T B M S is a n a lyze d e x a c tly like a s tu d y s a m p le to help d e te rm in e if th e m e th o d is in co n tro l an d w h e th e r a loss o f a n a ly te o r a n a ly tic a l bias cou ld be attributed to sam p le holding tim e, sam p le storag e a n d /o r s h ip m e n t issues. A low and high T B M S are appropriate w hen expected sam p le concentrations are not know n o r m ay vary. 3.9 Internal Standard (IS) A com pound added to each stud y sam ple, calibration standard, laboratory control sam ples, and procedural blanks at a con sisten t level (typically aro un d 1 ng/m L). T h e internal standard(s) are stable isotope labeled versions o f the ta rg e t analytes. T he area cou nt ratio o f th e ta rg e t a n a lyte to th e in ternal sta n d a rd is used fo r calibra tion . S u rro g a te ISs are a p plied w h e n sta b le iso to pe IS s o f ta rg e t a n a lyte s are un ava ila ble. A su rro g a te IS is not n e c e s s a rily a sta b le isotope labeled version o f th e ta rg e t analyte, but is treate d as an internal sta n d a rd fo r q u a n tita tio n . 3.10 Laboratory Control Sample (LCS) A n aliquot o f control m a trix to w hich know n quantities o f the ta rg e t analytes, ISs and S R S s (w h e n a p p lic a b le ) a re a d d e d in th e la b o ra to ry a t th e tim e w h e n s a m p le s a re a liq u o tte d . A t le a st th re e le vels (tw o le vels fo r S R S s ) in trip lic a te a re in clud ed , o n e g e n e ra lly a t th e lo w end o f the calibration curve and one ne ar the m id range and the up pe r end o f the curve. T he LC S s are analyzed exactly like a laboratory sam p le to determ ine w h e th e r the stability o f the standards. LC S s should be prepared each d a y sam p le s are aliquoted. 3.11 Laboratory Matrix Spike (LMS) A la b o ra to ry m a trix s p ik e is an aliq u o t o f a s a m p le to w h ic h kno w n q u a n titie s o f ta rg e t an alyte s, IS s a n d S R S s (w h e n a p p lic a b le ) a re a d d e d in th e la b o ra to ry. T h e L M S is a n a ly z e d exa ctly like a la bo ratory sa m p le to de te rm in e w h e th e r th e sa m p le m a trix contributes bias to th e a n a ly tic a l results. T h e e n d o g e n o u s c o n c e n tra tio n s o f th e a n a ly te s in th e s a m p le m a trix m u s t be d e te rm in e d in a s e p a ra te a liq u o t a n d th e m e a s u re d v a lu e s in th e L M S c o rre c te d fo r these concentrations. LM S s are optional fo r analysis o f aqueous sam ples. ETS-8-044.1 Page 4 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 128 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 3.12 Laboratory Sample A portion o r aliquot o f a sam p le received from the field fo r testing. 3.13 Limit of Quantitation (LOQ) T h e lo w e r lim it o f qu a n tita tio n (L L O Q ) fo r an an a lytica l batch is th e lo w e s t c o n ce n tra tio n th a t c a n be re lia b ly q u a n tita te d w ith in th e s p e c ifie d lim its o f p re c is io n a n d a c c u ra c y . T h e L L O Q is g e n e ra lly sele cte d as the lo w e st no n-ze ro sta n d a rd in th e calibration cu rve th a t m e e ts m ethod a c c e p ta n c e criteria. T h e L L O Q fo r ea ch ta rg e t an alyte is e sta b lish e d fo r ea ch a n a ly s is batch as the low est calibration stan dard w ith area counts at least tw ice th a t o f the average area counts o f the procedural blanks. T h e u p p e r lim it o f qu a n tita tio n (U L O Q ) fo r an an a lytica l batch is th e h ig h e s t co n c e n tra tio n th a t can be reliably qu an tita te d w ithin th e specified lim its o f precision and accuracy. T he highest s ta n d a rd in th e calibra tion c u rve th a t m e e ts m e th o d a c c e p ta n c e criteria is d e fin e d as th e ULOQ. 3.14 Method/Procedural Blank A n a liq u o t o f co n tro l m a trix th a t is tre a te d e x a c tly like a la b o ra to ry s a m p le in clud in g e xp o su re to all g lassw a re, eq u ip m e n t, solven ts, and reagents th a t are used w ith o th e r la bo ratory s a m p le s. T h e m e th o d b la n k is used to d e te rm in e if te s t s u b s ta n c e s o r o th e r in te rfe re n ce s are p re s e n t in th e la b o ra to ry e n v iro n m e n t, th e re a ge nts, o r th e a p p a ra tu s. 3.15 Sample A s a m p le is an aliq u o t re m o ve d fro m a la rg e r q u a n tity o f m aterial in te nd ed to re p re s e n t the original sou rce m aterial. 3.16 Stock Standard Solution (SSS) A c o n c e n tra te d s o lu tio n o f a s in g le -a n a ly te p re p a re d in th e la b o ra to ry w ith a n a s s a y e d reference com pound. 3.17 Surrogate Internal Standard A n IS th a t is not n e ce ssa rily a stab le iso to p ica lly la be led ta rg e t an alyte , b u t is tre a te d a s an internal stan dard fo r quantitation. S u rro g a te IS s are used w h e n iso to pically labeled counterparts o f the targe t analyte are not co m m e rcially o r readily available. 3.18 Surrogate Recovery Standard (SRS) A n iso to p ica lly labeled stan dard , not used as an in te rna l stan dard , th a t is a d de d to each sam ple and appropriate Q C sam ple as a m eans to evaluate the m ethod perform ance fo r a chem ical class o f com p ou nds (e.g., PFS A s, PFC A s). 3.19 Working Standard (WS) A s o lu tio n o f s e v e ra l a n a ly te s p re p a re d in th e la b o ra to ry fro m S S S s a n d d ilu te d a s n e e d e d to prepare calibration standards and oth er required analyte solutions. 4 Warnings and Cautions 4.1 Health and Safety T he acute and chronic toxicity o f the standards fo r this m ethod have not been precisely determ ined; how ever, each should be treated as a potential health hazard. T he analyst should w e a r gloves, a lab coat, and s a fe ty g la sse s to pre ven t exp osu re to che m ica ls that m ight be present. ETS-8-044.1 Page 5 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 129 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 T h e la b o ra to ry is re sp o n sib le fo r m aintainin g a s a fe w o rk e n v iro n m e n t and a c u rre n t a w a re n e s s o f local re g u la tio n s re g a rd in g th e ha n d lin g o f th e c h e m ic a ls use d in th is m etho d. A reference file o f m aterial s a fe ty da ta she ets (M S D S ) sho uld be available to all personnel in v o lv e d in th e s e a n a ly s e s . 4.2 Cautions T h e analyst m ust be fa m ilia r w ith th e la bo ratory e q u ip m e n t and potential hazards including, but not lim ited to, th e use o f solvents, pre ssurize d ga s and so lv e n t lines, high voltage, and vacuum system s. R e fe r to the appropriate eq uipm en t procedure o r operator m anual fo r additional inform ation and cautions. 5 Interferences D uring sa m p le preparation and analysis, m a jo r potential con tam in ant sou rces are reagents and g la s s w a re . A ll m a te ria ls use d in th e a n a ly s e s sh a ll be d e m o n s tra te d to be fre e fro m interferences under conditions o f analysis by running m ethod blanks. P arts and sup plies th a t contain T e flo n should be avoided o r m inim ized due to the possibility o f interference an d /o r contam ination. T hese m a y include, but are not lim ited to: w a sh bottles, Teflon lined caps, autovial caps, H P LC parts, etc. T h e use o f d is p o s a b le m ic ro p ip e tte s o r pipe ttes to a liq u o t s ta n d a rd so lu tio n s is re c o m m e n d e d to m ake calibration stan dard s and m a trix spikes. 6 Instrumentation, Supplies, and Materials 6.1 Instrumentation A nalytical balance capable o f reading to 0.0001g H P L C /M S /M S o r H P L C /M S s y s te m , as d e s c rib e d in S e c tio n 10. 6.2 Supplies and Materials S am ple collection bottles-- H D P E (e.g., N algeneTM ) w ide-m o uth bottles w ith scre w cap. Note: D o n o t u se flu o rin a te d o r T e flo n b o ttle s o r lin e d c a p s . C oolers o r boxes fo r sam ple shipm ent. 15-m L and 50-m L disposable polypropylene centrifuge tubes. C lass A pipettes and volum etric flasks, various. 2 m L H P LC autovials D isposable pipettes, polypropylene o r glass as appropriate C entrifuge capable o f spinning 15-m L and 50 -m L polypropylene tubes at 3000 rpm . 7 Reagents and Standards Note: S u p p lie rs a n d c a ta lo g n u m b e rs a re fo r illu s tra tiv e p u rp o s e s o n ly. E q u iv a le n t perform ance m ay be achieved using chem icals obtained from other suppliers. Do not use a le sse r gra de o f che m ica l tha n th o se listed. 7.1 Chemicals W a te r - M illi-Q , H P L C grade, o r o th e r su ita b ly ap pro pria te sou rces C alcium A cetate - A .C .S . R eagent G rade ETS-8-044.1 Page 6 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 130 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 M agnesium A cetate - A .C .S . R eagent G rade M ethanol - H PLC grade A m m onium A cetate - A .C .S . R eagent G rade 7.2 Representative Target Analytes, ISs, and SRSs PFBA, H eptafluorobutyric A cid, (C 4 P erfluorinated A cid) P FP eA , N onafluoropentanoic A cid (C5 P erfluorinated Acid) P FH xA , P erflu oro hexa no ic A cid (C 6P erfluorinated A cid) P FH pA , T ridecafluoroheptanoic A cid, (C7 P erfluorinated Acid) P FO A , A m m o n iu m perfluorooctanoate, (C 8P erfluorinated A cid) P FN A, H e ptad eca fluoro no nan oic A cid, (C 9P erfluorinated A cid) P F D A , N o n a d e c a flu o ro d e c a n o ic A c id (C 10 P e rflu o rin a te d A c id ) P F U nA , P erflu oro und eca no ic A cid, (C ^ P erfluorinated A cid) P F D o A , P e rflu o ro d o d e c a n o ic A c id , (C 12 P e rflu o rin a te d A c id ) P F T rD A , P e rflu o ro trid e c a n o ic A c id , (C 13 P e rflu o rin a te d A c id ) FBSA, P erfluorobutanesulfonam ide FO S A , P erfluorooctanesulfonylam ide PFBS, P otassium P erfluorobutanesulfonate PFHS, P erfluorohexanesulfonate PFO S , P otassium perfluorooctanesulfonate P F O A [1,2, 3, 4 - 13C ], 13C 4-is o to p ic a lly la b e le d p e rflu o ro o c ta n o ic a cid (S R S ) P F O S [1,2, 3, 4 - 13C ], 13C 4-is o to p ic a lly la b e le d P e rflu o ro o c ta n e s u lfo n a te (S R S ) P F U n A [1 ,2 -13C ], 13C 2-is o to p ic a lly la b e le d P e rflu o ro u n d e c a n o ic a c id (S R S ) A c u s to m m ix o f IS s in a m e th a n o lic s o lu tio n c o n ta in in g ([1 ,2 ,3 ,4 - C 4]P F B A , [1 ,2 13C 2]P F H x A , [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8 ]P F O A , [1 ,2 ,3 ,4,5 ,6,7 ,8,9- 13C 9]P F N A , [1 ,2 - 13C 2]P F D A , [1 ,2 ,3 ,4 ,5 ,6 ,7 - 13C 7]P F U n A , [1 ,2 - 13C 2]P F D o A , [1 ,2 ,3 - 13C 3]P F H S , [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8]P F O S , a n d [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8]P F O S A (W e llin g to n L a b o ra to rie s , G u e lp h , O N ) in c o m b in a tio n w ith a d d e d ([1 ,2 ,3 ,4,5- 13C 5]P F P e A , ([1 ,2 ,3 ,4- C 4]P F H p A , a n d [18O 2]P F B S c a n be u s e d to p re p a re a sto ck IS solution. A lternatively, individual stable isotope ISs can be used to prepare a stock IS m ixture. O th e r ISs can be applied. 7.3 Reagent Preparation 2 m M A m m on iu m acetate solution (A nalysis)-- W eigh 0.3 g o f A m m on iu m acetate and d is s o lv e in 2 .0 L o f re a g e n t w a te r. S yn th e tic G ro u n d w a te r (containing 25 pp m C a and M g) - W e ig h 0.61 g o f C a lciu m A ce ta te and 0 .9 2 g o f M a g n e s iu m A c e ta te and d is s o lv e in 6 .0 L o f re a g e n t w a te r. Note: A lte rn a tive volu m e s m ay be prepared as long as th e ratios o f the solve n t to solute ratios are m aintained. ETS-8-044.1 Page 7 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 131 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/mL target analyte SSSs--Weigh out 10 mg of analytical standard (c o rre c te d fo r p e rc e n t sa lt, a c id [E T S -4-031] a n d p u rity ) and dilute to 100 mL with methanol or other suitable solvent, in a 100 mL volumetric flask. T ransfer to a 125 mL 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. lx x. , x molecular weight of anion salt correction factor = ---------------------- ---------------- moclecular weight of salt 499 PFOS (K +)salt correction factor = -- = 0.9275 538 10 mg C8F17S03"K+with purity 90% = 8.35 mg C8F17S03- (10 mg*0.90*0.9275=8.35 mg) 10 pg/mL (10,000 ng/mL) mixed working standard--Add 5.0 mL each of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent. 1 pg/mL (1,000 ng/mL) mixed working standard--Add 0.5 mL of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent. 0.1 pg/mL (100 ng/mL) mixed standard--Add 0.05 mL of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent. Storage Conditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. 7.5 Calibration Standards Calibration can be performed by IS or external calibration. Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, other suitable water, or a mixture of solvent and water using the information in Table 2 as a guideline. Note: Volumes of water or water/solvent mixtures 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. For the quantitation of PFOA and PFOS, reference materials of certified mixed linear and branched isomer are preferred. Alternately, reference materials of primarily linear isomers of PFOA and/or PFOS may be used, however, when quantitating with predominantly linear reference standards, additional LCS samples containing both linear and branched isomers of PFOA and PFOS are required3. 7.5.1 Internal Standard (IS) and Surrogate Recovery Standard (SRS) For IS calibration, stable isotope internal standards of each target analyte or appropriate surrogate ISs should be spiked at the same level in all calibration standards. Once the calibration standards have been prepared as stated above in Section 7.5, all calibration standards are spiked with a separate internal standard spiking solution. Typically the 3A report summarizing an assessment of the use ofreference standards containing certified linear and branched isomers of PFOA/PFOS can be found in 3M report E11-0560. ETS-8-044.1 Page 8 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 132 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 c o n ce n tra tio n o f th e in ternal sta n d a rd is co n s is te n t w ith th e in ternal sta n d a rd con ce n tra tio n e x p e c te d in th e s a m p le s being p re p a re d , u s u a lly 1 n g /m L . T h e c o n c e n tra tio n o f th e in te rna l s ta n d a rd s p ik in g s o lu tio n is ty p ic a lly 2 p g /m L . A s e p a ra te z e ro p o in t o r m e th o d b la n k is typica lly prepared at the sam e tim e as the calibration standards, using the sa m e solution used to prepare the standards (A S TM Type I water, H P LC w ater, other suitable w ater, o r a s o lv e n t/w a te r m ixture ), and is sp ike d w ith th e in ternal sta n d a rd at th e s a m e c o n ce n tra tio n as the calibration curve, typica lly at 1 ng/m L. If th e s a m p le s b e in g a n a lz y e d w e re p re -s p ik e d w ith S R S s , th e c a lib ra tio n c u rv e p re p a re d in S ectio n 7.5 is sp ike d w ith a s e p a ra te S R S s p ik in g solu tio n . T yp ica lly, th e s a m p le bo ttles are s p ike d w ith a S R S a t 0.1 ng /m L . T h e fina l ca lib ra tio n c u rve m u s t c o n s is t o f a t le a st s ix calibration points after analysis. T he follow ing table provides an exa m ple o f spike concentrations and volum e s used to achieve a m ulti-point extracted calibration curve w ith internal standard and surrogate standard. T able 1 lists reco m m en ded stable isotope internal stan dard s fo r several P F S A and P F C A ta rg e t c o m p o u n d s . A c u s to m m ix o f is o to p ic a lly la b e le d ta rg e t a n a ly te s in a m e th a n o lic s o lu tio n c o n ta in in g ([1 ,2 ,3 ,4 -13C 4]P F B A , [1 ,2 - 13C 2]P F H x A , [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8]P F O A , [ 1 , 2 , 3 , 4 , 5 , 6 ,7 ,8 ,9 - C q]P F N A , [1 ,2 ,3 ,4 ,5 ,6 - 13C 6 ]P F D A , [1 ,2 ,3 ,4 ,5 ,6 ,7 - 13C 7 ]P F U n A , [1 ,2 - 13C 2]P F D o A , [ 1 ,2 ,3- 13C 3 ]P F H S , [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8 ]P F O S , a n d [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8 ]F O S A (W e llin g to n L a b o ra to rie s , G u e lp h , O N ) in c o m b in a tio n w ith a d d e d ([1 ,2 ,3 ,4 ,5 -13C 5]P F P e A , ([1 ,2 ,3 ,4 -13C 4]P F H p A , a n d [18O 2]P F B S c a n be u s e d to p re p a re a s to c k IS s o lu tio n . A lternative sources o f certified stable isotope labeled ta rg e t analytes are applicable. A lternatively, individual stable isotope ISs can be used to prepare a sto ck IS m ixture. T he ta b le b e lo w lists th e re c o m m e n d e d s ta b le iso to p e IS s an d S R S s a p p lie d in th e m e th o d . O th e r s ta b le iso to p e ISs and S R S s o f ta rg e t a n a ly te s n o t listed in th e ta b le m a y be use d if supported by validation an d /o r analysis batch Q C s m eeting m ethod acceptance criteria (e.g., [13C 2]-P F O A ). T h e s a m e in te rn a l s ta n d a rd s h o u ld be u s e d fo r a g iv e n a n a ly te th ro u g h o u t th e entire project/study. N ote: so m e o f the co m p o u n d s listed below are ap pro pria te to use as su rro g a te ISs w h e n a sta b le isotope IS o f a ta rg e t a n alyte is not available. G enerally, surro ga te isotopically labeled P F C A s are used fo r P F C A s, and surro g a te isotopically labeled PFSAs are used fo r PFSAs. T able 2 provides exam ples o f spike concentrations and volum es used to achieve a m ulti-point calibration curve w ith ISs and SR Ss. ETS-8-044.1 Page 9 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 133 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 1. Stable Isotope PFCAs and PFSAs used for ISs and SRSs Coimpound N am e Synonym or Acronym 13C 4 -P e rflu o ro b u ta n o ic acid [1 ,2 ,3 ,4 -13C 4]P F B A 13C 4-P e rflu o ro p e n ta n o ic acid [1 ,2 ,3 ,4 ,5 -13C 5]P F P eA 13C 2-P e rflu o ro h e x an o ic acid [1,2 - 13C 2]P F H x A 13C 4-P e rflu o ro h e p ta n o ic acid [1 ,2 ,3 ,4 -13C 4]P F H p A 13C 8-P e rflu o ro o c ta n o ic acid [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8]P F O A 13C 9-P e rflu o ro n o n a n o ic acid [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 ,9 -13C 9]P F N A 13C 6-P e rflu o ro d e can o ic acid [1,2,3,4,5,6 - 13C 6]P F D A 13C 7-P erflu o ro u n d e can o ic acid [1 ,2 ,3 ,4 ,5 ,6 ,7 -13C 7]P F U n A 13C 2-P e rflu o ro d o d e c a n o ic acid [1,2 - 13C 2]P F D o A 18O 2-A m m o n iu m P erflu o ro b u tan e sulfo n ate [18O 2]PF B S 13C 3-A m m o n iu m P erflu o ro h ex an e sulfo n ate [1 ,2 ,3 -13C 3]PF H S 13C 8-S o d iu m P erflu o ro o ctan e sulfonate [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8]PF O S 13C 8-P erflu o ro o c ta n esu lfo n am id e 13C 4-P e rflu o ro o c ta n o ic acid [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8]F O S A [1 ,2 ,3 ,4 -13C 4]P F O A Analytical Purpose IS for PFB A IS for PFPeA IS for PFHxA IS for PFH pA IS for PFO A and [1,2,3,4 13C 4]P F O A IS for PFN A IS for PFD A IS for PFUnA IS for PFDoA, *PFTA IS for PFBS IS for PFHS IS for PFOS and P F O S [1 ,2 ,3 ,4 13C 4], IS for FO SA SRS for all PFCAs: C4-C8 Reference Standard Source W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) RTI International (Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix or Individual) W ellington Labs (m ix) RTI International (Individual) W ellington 13C 2-P e rflu o ro u n d e c a n o ic acid [1,2 - 13C 2]P F U n A SRS for all PFCA s C9-C13 W ellington 13C 8-P e rflu o ro o c ta n e sulfonate [1 ,2 ,3 ,4 -13C 4]PFO S SRS for all PFSAs: C4, C6, and C8 W ellington ETS-8-044.1 Page 10 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 134 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 2. Example Preparation of Calibration Curve with ISs and SRSs Sample Description 0.025 ng/mL curve point 0.030 ng/mL curve point 0.04 ng/mL curve point 0.05 ng/mL curve point 0.1 ng/mL curve point 0.25 ng/mL curve point 0.5 ng/mL curve point 1 ng/mL curve point 2.5 ng/mL curve point 5.0 ng/mL curve point 10.0 ng/mL curve point 25.0 ng/mL curve point 50.0 ng/mL curve point 75.0 ng/mL curve point 100 ng/mL curve point Concentration of WS, pg/mL 0.10 0.10 0.10 0.10 0.10 0.10 1.0 1.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Volume of WS, pL 25 30 40 50 100 250 50 100 25 50 100 250 500 750 1000 Volume o f IS (2 pg/mL), pL 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Concentration of Surrogate, pg/mL 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Volume of Surrogate, pL 12.5 15 20 25 50 125 250 500 25 50 100 NA NA NA NA Volume o f ASTM Type I Water, or other suitable solvent(1>, mL 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 N/A - Not Applicable (1) Samples requiring analysis for PFUnA, PFDoA, PFTrDA, and FOSA should be analyzed against a calibration curve prepared in 1:1 synthetic groundwater:MeOH. E TS -8-044.1 P a g e 11 o f 2 2 M e th o d o f A n a ly s is fo r th e D e te rm in a tio n o f P e rflu o rin a te d C o m p o u n d s in W a te r b y L C /M S /M S ; D ire c t In je c tio n A n a ly s is Page 135 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 8 Sample Collection and Bottle Preparation S am ple collection bottles are prepared by 3M E nvironm ental Laboratory (or sub con tra ct supplier) personnel fo r shipm e nt at am bient tem perature to the collection site. T ypically, fo u r separate collection bottles are associated w ith a single collection site: sam p le , field duplicate sam p le , low field m atrix spike, and hig h field m a trix sp ike . A lte rn a tiv e ly , th e s a m p le and field d u p lic a te s a m p le m a y c o n ta in S R S s in lieu o f a d d itio n a l ta rg e t analyte low field m atrix spike and targe t analyte high field m atrix spike sam ples. D epending on the scop e o f th e pro je ct, a d d itio n a l rep lic a te s o f th e field s a m p le and field m a trix s p ik e s m a y be a d d e d . A ls o , it is not uncom m on fo r additional m id-level field m a trix spikes to be collected if the expected sa m p le concentrations are tru ly unknow n o r could span a large concentration range. H igh-density polyethylene (H D P E ) w ide-m outh N algene bottles are used fo r the sam p le collection containers. (V o lu m e s o f th e bottles m a y v a ry d e p e n d in g on h o w m uch s a m p le is req uire d to m e e t da ta q u a lity ob je ctives.) S am ple collection volum es are project spe cific and based on data quality objectives. T he N algene bottles do n o t re q u ire a n y p re tre a tm e n t p rio r to use . T y p ic a lly , p la c e m e n t o f a s a m p le b o ttle v o lu m e tric "fill to h e re " line is done by using a sa m p le bottle m a rke r tem plate. A lternatively, bottles m a y be w e igh ed prior to bottle preparation and w e igh ed again a fter sam p le s have been collected. A ll bottles sh o u ld be cle a rly labeled to indicate its in te nd ed use as a sa m p le , field sa m p le du plicate, lo w field m atrix spike, high field m a trix spike, sam p le /S R S field m a trix spike, field duplicate sam p le /S R S field m atrix spike, trip blank, o r trip blan k m a trix spike. If each location has diffe re nt de sig nate d spike levels, th e label should also clearly indicate the sa m p le location designation. G enerally, a se t o f bottles fo r a given collection site are p re p a re d th e n g ro u p e d to g e th e r in p la stic ba gs fo r o rg a n iza tio n a l pu rpo ses. F o r ea ch s a m p le collection event, at least one set o f trip blank and trip blank m atrix spikes are prepared. B ottle p re p a ra tio n s h o u ld be d o c u m e n te d in a N o te to F ile o r on a s a m p le p re p a ra tio n w o rk s h e e t and sh o u ld include the follow ing inform ation: date prepared, total n u m b e r o f bottles prepared, n u m b e r o f sam ple sites, the stan dard id en tification n u m b e rs and sp ike vo lu m e s used to pre pa re sp ike d bottles, the "fill to h e re" vo lu m e , and a n y o th e r p e rtin e n t in fo rm a tio n n e e d e d fo r re c o n s tru c tib ility o f th e d a ta. T h e N o te to F ile w ill be in clu d e d in th e final data package fo r the project. S a m p le s a re co lle cte d in th e field and s h ip p e d to th e la b o ra to ry a t a m b ie n t te m p e ra tu re . 8.1 Field Matrix Spike Sample (FMS) Field m a trix s p ik e s a m p le s are a re q u ire m e n t o f th e m etho d. A F M S s a m p le is d e fin e d as a Q C s a m p le to w h ic h k n o w n q u a n titie s o f a p p ro p ria te ta rg e t a n a ly te s a re a d d e d to th e s a m p le bottle in th e field o r in th e la bo ratory before th e bottles are s e n t to th e field. T h e sa m p le and field d u plicate sam p le m a y contain a p p ro p ria te S R S s in lieu o f ta rg e t a n a lyte F M S s a m p le s . S a m p le q u a n titie s a re d e te rm in e d v o lu m e tric a lly o r gra vim e trica lly. A kno w n , s p e c ific v o lu m e o r w e ig h t o f s a m p le is ad de d to th e s a m p le co n ta in e r w ith o u t rinsing. V o lu m e tric s a m p le m e a s u re m e n ts m a y be a cq uired by a la bo ratory applied "fill to th is level" line on the outside o f the sam p le container. T arge t analyte FM S sam p le s should be spiked at approxim ately 0.5-10 tim e s th e e x p e c te d a n a ly te c o n c e n tra tio n in th e s a m p le . If th e e x p e c te d ra n g e o f a n a ly te c o n c e n tra tio n s is u n k n o w n , m ultiple spikes at varying levels m ay be prepared to in crea se th e likelihood th a t a spike at an ap pro pria te level is m ad e. T y p ic a lly a lo w and a high ta rg e t a n a lyte sp ik e a re p re p a re d fo r e a ch sa m p lin g lo catio n. In th o se in s ta n c e s w h e re S R S s a re to be use d in lieu o f ta rg e t a n a ly te F M S s a m p le s , th e s a m p le an d field d u p lic a te s a m p le are sp ike d at a p p ro x im a te ly 2 -5 tim e s th e ta rg e t LO Q . T h e F M S is a n a lyze d to a sce rta in if m a trix effects or sam ple holding tim e contributes bias to the analytical results. F o r the sa m p le bottles designated fo r m a trix spikes, an a p p ro p ria te v o lu m e o f m a trix spikin g solutio n is ad de d to th e e m p ty bottle p rio r to s a m p lin g . T he volum e o f spike solution added should produce the desired final concentration o f ta rg e t analytes once the bottle is filled w ith s a m p le to th e "fill to he re lin e " . T h e m a trix s p ik in g s o lu tio n (s ) sh o u ld be p re p a re d in a suitable solve n t and contain all o f th e ap pro pria te ta rg e t analytes, ISs, and S R S s. T h e ta rg e t analyte m a trix s p ik in g solu tio n is often th e s a m e as th e w o rk in g s ta n d a rd s used to cre a te th e calib ra tio n sta n d a rd s. A n e x a m p le o f a bottle s p ik e is g iven below . "Fill to h e re " v o lu m e = 2 0 0 m L (A 2 5 0 m L N a lg e n e bottle is used) D esired Field S pike C o nce ntration = 0.25 ng /m L ETS-8-044.1 Page 12 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 136 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 5 0 0 pL o f a 0.1 p g /m L sp ikin g so lu tio n (co n ta in in g th e ta rg e t a n a lyte s) is a d d e d to th e bottle an d th e bo ttle c a p prom ptly sealed. 8.2 Internal Standard and Surrogate Recovery Standard If a n a lysis o f a su rro g a te re c o v e ry s ta n d a rd (S R S ) is in clud ed in th e p ro je ct ob je ctives, an a p p ro p ria te v o lu m e o f a su rro g a te s ta n d a rd solutio n is a d d e d to all th e bo ttles p rio r to sa m p lin g and S P E . T y p ic a lly s a m p le bottles are sp ike d w ith su rro g a te re c o v e ry s ta n d a rd s at a fina l d e sire d sp ike co n ce n tra tio n o f 0.1 ng/m L. If q u a n tita tio n b y in te rn a l s ta n d a rd (IS ) is in c lu d e d in th e p ro je c t o b je c tiv e , a n a p p ro p ria te v o lu m e o f in te rn a l s ta n d a rd solu tio n is a d d e d to all th e bottles p rio r to sa m p lin g and S P E . T y p ic a lly s a m p le bottles are spiked w ith internal standard at a final desired spike concentration o f 1 ng/m L. F o r th e trip blank, th e S R S sp ik e and IS sp ik e is a d d e d to th e bottle and th e n A S T M T y p e I w a te r (H P L C g ra d e re a g e n t w a te r o r o th e r s u ita b le w a te r m a y used) is a d de d to th e "fill to h e re " line. T h e bottle is cap pe d and sealing tape m ay be placed around the ou ter edge o f the cap. T rip blank m atrix spikes are prepared by adding the a p pro pria te vo lu m e o f ta rg e t a n alyte spiking solution, IS, and S R S spiking so lu tio n s and filling th e bottle to the desired volum e w ith the appropriate w a te r and capping and sealing the cap. 9 Quality Control and Data Quality Objectives 9.1 Data Quality Objectives T h is m e th o d and req uire d q u a lity co n tro l s a m p le s is d e s ig n e d to g e n e ra te d a ta a c c u ra te to 3 0 % w ith a targeted LO Q o f 0.025 ng/m L. A n y d evia tions from the quality control m ea sure s spelled out below w ill be d o c u m e n te d in th e ra w d a ta an d fo o tn o te d in th e fina l report. 9.2 Method/Procedural Blanks T h e m e th o d /p ro c e d u ra l b la n k is ze ro po in t ca lib ra tio n s ta n d a rd (w h ich in clu d e s ISs) a n a ly z e d in a re g u la r basis w ith each analysis batch. A t a m inim um , m ethod blanks are analyzed prior to instrum ent calibration, prior to the analysis o f C C V sam ples, a fte r e ve ry 10 sam p le injections, and at the end o f the an alytical run. T h e m e a n a re a c o u n t o r a re a ratios w h e n using in te rna l s ta n d a rd ca lib ra tio n , fo r e a ch a n a ly te in th e m e th o d blanks m ust be less than 50% o f the area cou nt counts o r area ratios w h en using internal standard calibration, o f the LO Q standard. T he standard deviation o f the area counts, o r area ratios w h en using internal standard calibra tion , o f th e s e m e th o d b la n ks sh o u ld be ca lcu la te d . A s p e c ific % R S D a c c e p ta n c e criteria is not spe cifie d but is a s se sse d on an a n a lytica l batch basis. If th e m ea n are a co u n ts o r are a ratios w h e n using internal standard calibration, o f the m ethod blanks exceed 50% o f the LO Q standard, then the LO Q m ust be raised to th e firs t s ta n d a rd level in th e c u rv e th a t m e e ts criteria. M e th o d b la n k s m a y be e lim in a te d if te c h n ic a l ju stificatio n can be provided (e.g. the procedural blan k w a s analyzed a fte r an un e xp e cte d ly high level sam ple). If a n y p ro c e d u ra l b la n k s a re re m o v e d fro m th e L O Q d e te rm in a tio n , d o c u m e n t in th e ra w d a ta a n d re p o rt as appropriate. L a bo ratory S am p le R eplicates / Field D u plicate S am p le T y p ic a lly , s a m p le s a re c o lle c te d in d u p lic a te s in th e fie ld . T h e re la tiv e p e rc e n t d iffe re n c e (R P D ) o f d u p lic a te s a m p le s s h o u ld be < 20% fo r th e pre cisio n o f s a m p le p re p a ra tio n and a n a ly s is to be c o n s id e re d in con tro l. R eplicate sam p le s not m eeting the <20% R P D criteria are flagged and reported as outside o f Q C acceptance criteria. 9.3 Laboratory Matrix Spikes (LMSs) L M S s m a y b e p e rfo rm e d in lieu o f F M S s if F M S s h a v e p re v io u s ly b e e n p e rfo rm e d fo r th e s a m p le m a trix. A d d itio n a lly , L M S s m a y be p e rfo rm e d in lieu o f F M S s fo r a s a m p le m a trix if th e F M S le vels w e re not ap propriate fo r determ ining spike recoveries relative to endo ge nou s levels o f targe t analytes and ap propriate S R S s. G enerally, each sam p le location represents a diffe re nt sa m p le and sam p le m atrix. LM S s are prepared fo r each sam ple and analyzed to determ ine the m atrix effect on spike recovery efficiency o f each targe t analyte and a p p ro p ria te S R S s. L M S s sh o u ld be p re pa red at a m in im u m o f on e level an d in du plicate. LM S concentrations should be prepared at approxim ately 0.5-10 tim es the endogenous concentration or approxim ately 4-10 tim e s the LO Q concentration o f each target analyte. ETS-8-044.1 Page 13 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 137 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Lab m a trix spike recoveries should fall w ithin 30% o f expected values. S am ple data w ith LM S recovery outside o f 30% but w ithin 50% o f the expected value are flagged and reported as outside o f Q C acceptance crite ria . D a ta w ith L M S re c o v e ry o u ts id e o f 5 0 % o f th e e x p e c te d v a lu e a re re p o rte d a s N R , w h e re N R is defined as "N ot R e po rta ble" da ta outside o f Q C a cce ptan ce criteria. 9.4 Lab Control Sample Lab control spikes are prepared fo r each analysis batch to determ in e m ethod accu racy and precision. LC S s s h o u ld b e p re p a re d a t th re e le v e ls in trip lic a te fo r e a c h ta rg e t a n a ly te a n d a t a m in im u m o f tw o le v e ls in trip lic a te fo r a p p ro p ria te S R S s . L o w la b co n tro l s p ik e s s h o u ld be p re p a re d a t a c o n c e n tra tio n in th e ra n g e o f ap p ro xim a te ly fo u r to ten tim e s high er tha n th e targe ted lo w e r LO Q , th e m id lab control spikes should be prepared at a concentration near the m id-point of the calibration curve and the high lab control spikes at appro xim ately 80% o f the up p e r LO Q . F or each targe t analyte and S R S s, the percent relative standard deviation (m ethod precision) fo r each control spike level m ust be less tha n o r e qual to 20% and th e average reco very (m ethod accuracy) fo r each control sp ike level m ust be 80-120% . S am p le da ta fo r ta rg e t analytes outside o f the la boratory control spike acce ptan ce criteria w ill be handled as follow s: If th e a v e ra g e re c o v e ry o f a s p ik in g le ve l fa lls o u ts id e m e th o d a c c e p ta n c e , b u t a t le a s t 6 7 % (6 o u t o f 9) o f L C S sa m p le s are w ithin 20 % o f th e ir respective nom inal value (33% o f the Q C sam p le s, not all replicates at the sa m e concentration, m a y be outside 20% o f n o m inal value), the ave rag e reco ve ry w ill be flagged as outside m ethod acce ptan ce criteria. A ll LC S sam p le s w ill be control charted as pe r E T S -4-026. If the average recovery o f one o f the spiking levels exceeded the an alytical m ethod uncertainty as determ ined by E T S -12- 0 12, th a t analytical batch uncertainty w ill be expanded fo r th a t particular study. If m ore than 67% o f the LC S sam p le s fail to m eet m ethod acce ptan ce criteria, the data w ill not be reported. C alibration standards consisting o f m ixed branched and linea r iso m e r P F O S /P F O A are preferred. H ow ever, fo r P F O S /P F O A ta rg e t analytes, if the calibration stan dard s are com prised o f predom inantly linea r isom ers only, at least on e level o f triplicate LC S s should be prepared using P F O S /P F O A w hich con tain s a m ix o f linear and branched isom ers. T hese LC S s w ill be used to dem on stra te quantitative e q uivale ncy (or quantitative bias) o f the iso m eric m ix w h en using a pre do m ina ntly linear standard fo r calibration. T he m ixed linea r and branched is o m e r P F O S /P F O A LC S s reco ve rie s sh o u ld fall w ith in 30 % o f e xp e c te d value s. A lte rn a tive ly, in lieu o f m ixed branched and linea r iso m e r P F O S /P F O A LC S s, m ixed branched and linea r iso m e r P F O S /P F O A T B M S s m a y be applied to d e m on stra te m ethod accu ra cy and precision. 9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs) F M S s are prepared fo r each sam pling location and analyzed to determ in e the m atrix e ffect and sa m p le holding tim e on the spike recovery o f each ta rg e t analyte a n d /o r a p propriate S R S . G enerally, each sa m p le location represents a diffe re nt sam p le and sa m p le m atrix. F M S s are Q C sa m p le s to w hich know n quantities o f appropriate ta rg e t analytes are added to the sam p le bottle in th e la b o ra to ry b e fo re th e b o ttle s a re s e n t to th e fie ld . T y p ic a lly a lo w a n d a h ig h ta rg e t a n a ly te F M S a re p re p a re d fo r e a c h s a m p lin g lo c a tio n . T h e s a m p le a n d fie ld d u p lic a te s a m p le m a y c o n ta in a p p ro p ria te S R S s in lieu o f ta rg e t analyte low field m a trix spike and ta rg e t analyte high field m a trix spike sam ples. Field m a trix sp ike m ethod acce ptan ce criteria are reco verie s w ithin 30% o f the exp ected value. If F M S re c o v e ry (ta rg e t a n a lyte o r S R S sp ik e ) is o u tside o f 3 0 % o f th e e xp e cte d v a lu e o r cou ld not be a s se sse d b e ca u se th e F M S (targe t an alyte ) w a s sp ik e d at an in a p p ro p ria te level, th e s a m p le resu lt is rep orted as follow s: 1. ) If ta rg e t analyte F M S reco ve ry could not be asse ssed be cau se the F M S 's w e re at an inappropriate level, then Laboratory M atrix S pikes (LM S) m ay be substituted. If LM S recoveries are w ithin 30% the data are reportable and flagged to indicate th a t the F M S spikes levels w e re inappropriate. 2. ) If m ultiple ta rg e t analyte F M S 's w e re prepared on a sa m p le and th e clo sest F M S level to th e reported sa m p le m ee ts the 30% acce ptan ce criteria but ad ditiona l F M S 's are outside th e 3 0% acce ptan ce range, the d a ta a re re p o rta b le a n d fla g g e d to in d ic a te th a t w h ile th e re w e re fa ilin g F M S 's, th e u n c e rta in ty w ill n o t be exp an de d sin ce the m ost appropriate sp ike level passed. ETS-8-044.1 Page 14 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 138 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 3. ) If the ta rg e t analyte F M S recoveries are outside o f the 30% acceptance range but at least 30 acceptable historical reportable F M S sa m p le results are available, the data m a y be reported but flagged w ith an expanded uncertainty and as not m eeting F M S criteria. 4. ) S am ple data w ith F M S recovery outside o f 30% but w ithin 50% o f the expected value are flagged and reported as outside o f Q C acce ptan ce criteria w ith an expanded uncertainty. 5. ) If F M S re c o v e ry is o u ts id e o f 5 0% , th e s a m p le resu lt is rep orted as N R , w h e re N R is de fin e d as "N ot R e po rta ble" due to no nco m plian t Q C results. T h e targe ted fortification levels should be at least 50% o f the en do g e n o u s level and less tha n 10 tim e s the e n d o ge nou s level to be used w ith o u t ju stificatio n to de te rm in e the s ta te m e n t o f a ccu racy fo r analytical results. N o te : It is p o s s ib le fo r b o ttle s u tilize d fo r F ie ld M a trix S p ik e s a m p le s to be u n d e r-fille d o r o v e r-fille d d u rin g sam p le collection. S ince this scenario w ill effect the actual concentration o f the F M S sa m p le (surrogate and in te rna l s ta n d a rd c o n c e n tra tio n s w ill also be e ffe cte d , if u se d), it is im p o rta n t th a t a n y o b v io u s un de r-filling o r o v e r-fillin g o f s a m p le b o ttle s be d o c u m e n te d in th e d a ta p a c k a g e a n d ta k e n in to a c c o u n t in th e F M S , ISs, o r S R S s reco very calculations. S am p le s over-filled o r under-filled by m ore than 10% w ill be require recalculation o f th e FM S , ISs, and S R S tru e values. T he average o f the sam p le and the field duplicate should be used to calculate the recovery. 10 Procedures 10.1 Water Sample Preparation T h is m e th o d is ap p lica b le to w a te r s a m p le s. S a m p le s con ta in in g h e a v y pa rticu la te m a y n o t be s u ita b le fo r analysis by this m ethod. S am ples containing suspended particulate should be centrifuge prior to rem oving a sam p le aliquot, o r filtered. T h o ro u g h ly m ix s a m p le b e fo re re m o v in g an a liq u o t an d pla cin g in a la b e le d autovia l. D ilute sam ple, if necessary, w ith A S T M T ype I w ater, H P LC w ater, o th e r suitable w ater, o r solvent (m ethanol). Lab control spikes are prepared fo r each analysis batch to determ in e m ethod accu racy and precision. L C S s sh o u ld be p re p a re d a t th re e le ve ls in trip lic a te fo r e a ch ta rg e t a n a ly te a n d a t a m in im u m o f tw o le vels in trip lic a te fo r a p p ro p ria te S R S s . L o w lab co n tro l s p ik e s sh o u ld be p re p a re d a t a co n c e n tra tio n in th e ra n g e o f a p p ro x im a te ly fo u r to te n tim e s h ig h e r th a n th e ta rg e te d lo w e r L O Q , th e m id lab co n tro l spikes should be prepared at a concentration ne ar the m id-point o f the calibration curve and the high lab control spikes at a p p ro xim a te ly 80% o f th e u p p e r LO Q . F o r IS quantitation, stable isotope internal stan dard s o f each ta rg e t analyte o r a p pro pria te surro g a te ISs should be spiked at the s a m e level as the s a m p le s being a n a ly z e d , in all LC S s. If LC S s are being prepared using synth etic groundw ater, allow the LC S s sam p le s to equilibrate fo r a m in im um o f 4 hours before aliquoting fo r analysis o r diluting w ith solven t (m ethanol). 11 Sample Analysis - LC/MS/MS 11.1 Instrument Setup Note: In th is e x a m p le , an A p p lie d B io s y s te m s S c ie x A P I 4 0 0 0 (A P I 5 0 0 0 o r A P I 5 5 0 0 ) T a n d e m M a s s S p e c tro m e te r (L C /M S /M S ) is used. O th e r b ra n d s /m o d e ls o f L C /M S /M S in s tru m e n ts as w e ll as sin g le q u a d ru p o le m ass s p e ctro m e te rs (LC /M S ) m a y be used as long as th e m etho d a c ce p ta n ce criteria are m et. B rand nam es, suppliers, part num bers, and m od els are fo r illustrative pu rpo ses only. E qu iva len t pe rfo rm an ce m ay be achieved using apparatus and m aterials oth er than those specified here, but dem onstration o f e q u iv a le n t p e rfo rm a n c e th a t m e e ts th e re q u ire m e n ts o f th is m e th o d is th e re s p o n s ib ility o f th e la bo ratory. T h e operator m ust optim ize and do cum e nt the eq uipm ent and settings used. ETS-8-044.1 Page 15 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 139 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 E stablish the LC /M S /M S syste m and operating conditions equivalent to the follow ing: M ass Spec: A pplied B iosystem s A P I 4000, A P I 5000, o r AP I 5500 Ion S ou rce: T u rb o Ion S p ra y (A B S ) M ode: E lectrospray N egative S can Type: M R M (M ultiple R eaction M onitoring) C o m pu te r: D ell D H M S oftw are: W in d o w s 2 0 00 o r W in d o w s X P , A na lyst 1.4.2 o r higher versions H PLC: A gilent S eries 1100,1200, o r 1290 A gilent Q uaternary P um p A gilent V acuum D egasser A gilent A uto sam pler A gilent C olum n O ven Note: O n e o r m o re C 1 8 H P L C a n a ly tic a l c o lu m n s (2.1 m m x 1 0 0 m m , 5p.m o r 2.1 m m x 5 0 m m , 5p.m) m a y be attached on-line after the purge valve and before the sam p le injection port to retard and sep ara te an y residue c o n ta m in a n ts th a t m a y be in th e m o b ile p h a s e a n d /o r H P L C sy s te m . H P L C C o lu m n : B etasil C 18, 4 .6 m m x 10 0m m , 5p.m (T h e rm o E le ctro n C o rp o ra tio n ) C olum n Tem perature: 35C Injection V olum e: 5pL M o b ile P h a se (A): 2 m M A m m o n iu m A c e ta te in A S T M T y p e I w a te r (S e e 7.3) M obile P hase (B): M ethanol Table 3. Liquid Chromatography Gradient Program. Step Number 0 1 2 3 4 5 Total Time (min) 0 2.0 14.5 15.5 16.5 20.0 Flow Rate (pL/min) 750 750 750 750 750 750 Percent A (2 m M ammonium acetate) 97.0 97.0 5.0 5.0 97.0 97.0 Percent B (Methanol) 3.0 3.0 95.0 95.0 3.0 3.0 Note: O th e r H P L C gra d ie n ts m a y be used as long as the m etho d criteria and p ro je ct da ta q u a lity o b je ctives are m et. It m a y be n e c e s s a ry to a d ju s t th e H P L C g ra d ie n t in o rd e r to o p tim iz e in s tru m e n t p e rfo rm a n c e . C o lu m n s w ith d iffe re n t d im e n s io n s (e.g. 2.1 m m x 3 0 m m ) and co lu m n s fro m d iffe re n t m a n u fa c tu re rs (K e ysto n e B e ta sil C 1 8 etc.) m ay be used. ETS-8-044.1 Page 16 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 140 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards A n a lyte PFB A (C4 Acid) PFPeA (C5 Acid) PFH xA (C6 Acid) PFH pA (C7 Acid) PFO A (C8 Acid) PFN A (C9 Acid) PFD A (C10 Acid) PFU nA (C11 Acid) PFD oA (C 12 Acid) PFTA (C13 Acid) FBSA (C4 Sulfonamide) FO SA (C8 Sulfonam ide) PFBS (C 4 Sulfonate) PFH S (C6 Sulfonate) PFO S (C8 Sulfonate) [1 ,2 ,3 ,4 -13C 4]P F B A [1,2,3,4,5 - 13C 5]P F P e A H ,2 - 13C 2lP F H x A [1 ,2,3,4- 13C 4lP F H p A [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8lP F O A H ,2 ,3 ,4 ,5 ,6 ,7 ,8 ,9 -13C 9lP F N A r 1,2,3,4,5,6 - 13C 6lP F D A r 1 ,2 ,3,4,5,6,7 - 13C 7lP F U n A [1,2 - 13C 2lP F D o A [18O 2lP F B S [1 ,2 ,3 -13C 3lP F H S [1 ,2,3,4- 13C 4lP F O S [ 1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8lF O S A [1 ,2 ,3 ,4 -13C 4lP F O A [1,2,3,4- ^ l P F O S [1,2 - 13C 2lP F U n A A nalyte D escription T arg et T arg et T arg et T arg et T arg et T arg et T arg et T arg et T arg et T arg et T arg et T arg et T arg et T arg et T arg et IS for PFBA IS for PFPeA IS for PFHxA IS for PFH pA IS for PFO A IS for PFN A IS for PFD A IS for PFU nA IS for PFD oA and PFTA IS for PFBS IS for PFHS IS for PFOS IS for FO SA Surrogate (C4-C8 Acids) Surrogate(Sulfonates, FOSA) Surrogate (C9-C13 Acids) M ass Transition Q1 (amu) 213 263 313 363 413 463 513 563 613 663 298 498 299 399 499 217 268 315 367 421 472 519 570 615 303 402 503 507 417 503 565 M ass Transition Q3 (amu) 169 219 269, 119 319, 169 369, 219, 169 419, 169, 219 469, 269, 219 519, 269, 219 569, 169, 319 619, 369, 319 78 78 99, 80 99, 80 80, 99, 130 172 223 270 322 376 427 474 525 570 84 80 80 80 372 80 520 M ultiple tra n s itio n s fo r m on itorin g th e a n a lyte s is an option. T h e use o f o n e d a u g h te r ion is a c c e p ta b le if da ta s e n s itiv ity and s e le c tiv ity is a ch ie ve d and pro vid ed th a t reten tion tim e criteria are m e t to a s s u re a d e q u a te s p e c ific ity . W h ile th e d a u g h te r io n s m a y be c h o s e n a t th e d is c re tio n o f th e a n a ly s t, m a s s tra n s itio n 9 9 is sug g e ste d fo r P F O S . Q u a n tita tio n m a y be p e rfo rm ed using the total ion ch ro m a to g ra m (T IC , o r su m m e d M R M s) fo r a given analyte. F o r exam ple, the P F O A T IC w o uld su m all three o f the m onitored transitions. U se o f th e s u g g e s te d p rim a ry ion is re c o m m e n d e d . R e te ntio n tim e s m a y v a ry slightly, on a d a y -to -d a y basis, d e p e n d in g on th e b a tc h o f m o b ile p h a s e a n d th e g ra d ie n t, c o lu m n , g u a rd c o lu m n (s ) u s e d e tc. D rift in re te n tio n tim e s is a cce p ta b le w ith in an an a lytica l run, as long as th e d rift c o n tin u e s th ro u g h th e en tire a n a lysis and the standards are interspersed throu gh ou t the analytical run. 11.2 Calibration Curve Q u a n tita tio n is by in te rn a l s ta n d a rd o r e x te rn a l s ta n d a rd ca lib ra tio n . C a lib ra tio n s ta n d a rd s m a y be p re p a re d in A S T M T ype I, H P L C w ater, o th e r suita ble w ater, o r a so lve n t/w a te r m ixture. If internal stan dard calibration does not m eet calibration acce ptan ce criteria, external calibration can be applied. S ee T able 1 fo r ETS-8-044.1 Page 17 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 141 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 re c o m m e n d e d a p plicatio n o f a va ila ble in ternal s ta n d a rd s. Q u a n tita tio n o f P F O A and P F O S is b y s u m m e d analyte-specific m ass transitions. A na lyze the standard curve prior to each set o f sam ples. If internal stan dard s w e re added to the calibration standards area ratios are used to ge ne rate the calibration curve. T he standard curve m a y be plotted using a linea r reg ressio n (y = m x + b), w e ig h te d 1/x o r un w e igh te d, o r by q u a d ra tic fit (y = ax2 + b x + c), w e ig h te d 1/x o r unw eighted, using suitable so ftw a re . T he m athem atical m ethod used to calculate the calibration curve should be ap plied c o n s is te n tly th ro u g h o u t a stud y. A n y ch a n g e sh o u ld be th o ro u g h ly d o c u m e n te d in th e ra w data. High a n d/or low points m a y be excluded from the calibration curves to provide a be tte r fit o ve r the range ap propriate to the data o r because th e y did not m eet the pre-determ ined acce ptan ce criteria. Low -level curve points sh o u ld also be exclud ed if th e ir are a co u n ts (o r area ratio if q u an tita ting by IS) are not at least tw ice th a t o f th e ave ra g e are a co u n ts (o r are a ratio if qu an tita ting by IS) o f m etho d a n d /o r so lve n t blanks. T h e coefficien t o f d e te rm in a tio n (r2) v a lu e fo r th e c a lib ra tio n c u rv e m u s t be g re a te r th a n o r e q u a l to 0 .9 9 0 (o r a c o rre la tio n c o e ffic ie n t (r) o f 0 .9 95). E ach po in t in th e c u rv e m u s t be w ith in 2 5 % o f th e th e o re tic a l c o n c e n tra tio n w ith th e exception o f the LLO Q , w hich m a y be w ithin 30% . Justification fo r exclusion o f calibration curve points w ill be noted in th e ra w d a ta. A m in im u m o f 6 po in ts w ill be use d to c o n s tru c t th e ca lib ra tio n curve. If the calibration curve does not m eet acce ptan ce criteria, perform routine m ainten ance o r prepare a new standard curve (if necessary) and reanalyze. 11.3 Continuing Calibration Verification (CCV) C ontinuing calibration verifications (C C V) are analyzed to verify the accu racy o f the calibration curve. A na lyze a m id-range calibration standard, one o f the sam e standards used to construct the calibration curve, at a m in im um a fte r eve ry ten th sam p le , not including s o lve n t blanks, w ith a m in im u m o f one p e r sa m p le set. C alibration verification injections m ust be w ithin 2 5% to be considered acceptable. T he calibration curve and the last passing C C V w ill the n b ra cket acce ptab le sam p le s. M ultiple C C V levels m a y be used. S am p le s m ust be bracketed by passing C C V s o r the calibration curve and a passing C C V to be reportable. 11.4 System Suitability A m inim um o f three system suitability sam p le s should be injected at the beginning o f each analytical run, prior to the analysis o f the calibration curve. T ypica lly the se sam p le s are at a concentration n e ar the m id-level o f the calibra tion c u rve and are re p ea te d in jectio ns fro m on e a u to s a m p le r vial. It is su g g e s te d th a t th e sy s te m suitability injections have area counts o r area ratios w h en using internal standard calibration, w ith a ta rg e t R S D o f < 5% and a ta rg e t reten tion tim e R S D o f < 2% . T h e re is no d e fin e d a c c e p ta b ility lim it on th e s e resu lts as th e % R S D v a lu e is d e p e n d e n t on th e n u m b e r o f M R M tra n s itio n s b e in g m o n ito re d in th e L C /M S /M S run o r tim e period. U ltim ately, an y effects on the se param eters fo r the S ystem S uitability sam p le s w ill also be evident on all s ta n d a rd s a n d Q C s a m p le s a n a ly z e d a s p a r t o f th e a n a ly s is b a tch . A n y e ffe c t o f s y s te m s u ita b ility is in co rp o ra te d w ith in Q C a c c e p ta n c e c rite ria .4 11.5 Sample Analysis and QCs F or each analysis batch, th e in stru m en t analysis run seq u e n ce should include an initial calibration curve, sam p le s, F D S s, in te rspe rsed blanks, inte rspe rsed C C V s, a p pro pria te Q C s (i.e., LC S s, LM S s, F M S s, T B M S s, and T B s), and a final C C V o r calibration curve bracketing sam p le s and appropriate Q C s Inject the sa m e volum e (betw een 5 - 100pL) o f each standard, analytical sa m p le and blank into the instrum ent (unless an o n -in s tru m e n t sa m p le dilution is desired). S a m p le s con ta in in g a n a lyte s th a t are q u a n tita te d a b o ve th e c o n ce n tra tio n o f th e h ig h e s t sta n d a rd in th e curve should be fu rth e r diluted and reanalyzed. 43M Environmental Laboratory study E08-0096 evaluated the effect on these results as a function ofthe number ofMRMs being monitored. ETS-8-044.1 Page 18 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 142 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 12 Data Analysis and Calculations The chromatography analysis software will typically calculate the amount of target analyte in the sample extracts using the established calibration curve. Calculate the percent recovery of the LCS using the following equation: LCS Concentration (-5^-) LCS% recovery = ----------------------------- mL * 100% ng Spike Concentration (--^-) mL Calculate the percent recovery of the LMS using the following equation: LMS % recovery ng ng LMS Concentration (----) - Concentration of Sample (----) mL mL ng Spike Concentration (----) mL 100% For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. Recovery = Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) ^ 1 0 0 Analyte added (ng/mL) 13 Analysis Batch Method Performance Criteria 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 in the final report if the Technical Manager (non-GLP 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. 13.1 System Suitability - Analysis Batch A minimum of three system suitability samples should be injected at the beginning of each analytical run. These samples are run prior to the calibration curve. It is suggested that the system suitability injections have area counts with a target RSD of <5% and a target retention time RSD of <2%. There is no defined acceptability limit on these results as the %RSDs are dependent on the number of MRM transitions being monitored in the LC/MS/MS run or time period. Any effect of system suitability is incorporated in the QC acceptance criteria. 13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch Calibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990 corresponding to a correlation coefficient (r) = 0.995. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Performance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy ETS-8-044.1 Page 19 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 143 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 o f each curve point m ust be w ithin 25% o f the theoretical value (within 30% fo r low est curve point). S am ples tha t are bracketed by C C V s not m eeting the se criteria m ust be reanalyzed. Limits of Quantitation (LOQ): T h e lo w e r L O Q (L L O Q ) is th e lo w e s t n o n -z e ro a c tiv e s ta n d a rd in th e calibra tion curve; th e p e a k are a o f th e LL O Q m u s t be at le a st 2 X th a t o f th e a ve ra g e are a co u n ts fo r all prepared procedural blank(s). B y definition, the m easured value o f the LL O Q m ust be w ithin 30% o f the theoretical value. Demonstration of Specificity: S p e c ific ity is d e m o n s tra te d b y c h ro m a to g ra p h ic re te n tio n tim e (w ith in 4 % o f stan dard ) and th e m ass sp e ctra l resp on se o f unique ions. 13.3 Blanks - Method/Procedural Blanks and Trip Method/Procedural Blanks: M u ltip le p ro c e d u ra l b la n k s s h o u ld be in te rs p e rs e d th ro u g h o u t th e a n a ly s is b a tch and the analytical sequence. A t a m inim um , m ethod blanks are analyzed prior to in stru m en t calibration, prior to the analysis o f C C V sam ples, after eve ry 10 sam p le injections, and at the end o f the analytical run. T h e m ean area cou nts (o r area ratios w h e n using IS calibration) fo r each analyte m ust be less tha n 50% o f the area count o f the LO Q standard. If the area counts o f the procedural blanks exceed 50% o f the LO Q standard, then the LO Q m ust be raised to the first standard level th a t m eets criteria. Trip Blank: A trip b la n k o f A S T M T y p e I w a te r (o r la b e q u iv a le n t) is p re p a re d in a s a m p le c o n ta in e r in th e laboratory and treated as a sam ple, including exposure to shipping, sam p lin g site conditions, storage, preservation and all analytical procedures. T h e trip blanks results fo r each analyte are included w ith the reported sam p le results. 13.4 Data Accuracy and Precision - Analysis Batch Lab Control Spikes: T h e a v e ra g e re c o v e ry a t e a c h L C S le ve l fo r e a c h ta rg e t a n a ly te a n d a p p ro p ria te S R S should be w ithin 80-120% and the percent relative standard deviation o f the recoveries m ust be less than or e q u a l to 2 0 % . If th e a v e ra g e re c o v e ry o f a s p ik in g le v e l fa lls o u ts id e m e th o d a c c e p ta n c e , b u t a t le a s t 6 7 % (6 o u t o f 9) o f L C S s a m p le s are w ith in 2 0 % o f th e ir re sp e ctive n o m in a l va lu e (33 % o f th e Q C sa m p le s, not all replicates at th e sa m e concentration, m a y be outside 20% o f nom inal value), th e a ve rag e reco very w ill be flagged as outside m ethod acce ptan ce criteria. A ll LC S sam p le s w ill be control charted as pe r E T S -12-012. If the average reco very o f one o f the spiking levels exceeded the analytical m ethod uncertainty as determ ined by E T S -12-012, tha t analytical batch uncertainty w ill be expanded fo r th a t particular study. T he average recovery at each LC S level fo r m ixed bra nch ed/line ar iso m e r P F O A and P F O S should be w ithin 70-130% and the pe rcen t relative stan dard deviation o f the recoveries m u st be less tha n o r equal to 20%. Field Duplicates: T h e re la tiv e p e rc e n t d iffe re n c e (R P D ) o f d u p lic a te s a m p le s s h o u ld be le ss th a n 2 0 % fo r th e pre cisio n o f s a m p le p re p a ra tio n and a n a ly s is to be c o n s id e re d in co n tro l. R e p lic a te s a m p le s no t m e e tin g th e 20% R P D criteria are flagged and reported as outside o f Q C acce ptan ce criteria. Field Matrix Spikes: F M S a c c e p ta n c e c rite ria a re re c o v e rie s w ith in 3 0 % o f th e e x p e c te d v a lu e fo r e a c h target analyte and appropriate SR S. S am ple data w ith F M S recovery outside o f 30% but w ithin 50% o f the expected value are flagged and reported as outside o f Q C acce ptan ce criteria. D ata w ith F M S recovery o u tside o f 5 0 % o f th e e x p e c te d va lu e are rep orted as N R , w h e re N R is d e fin e d as "N o t R e p o rta b le " da ta outside o f Q C acce ptan ce criteria. If F M S recovery could not be assessed because F M S s w ere at an inappropriate level, the n Labo ratory M a trix S pikes (LM S s) m a y be substituted. If LM S recoveries are w ithin 30% fo r each targe t analyte and S R S s the data are reportable but flagged as not m eeting the F M S m ethod acce ptan ce criteria. 13.5 Analytical Method Uncertainty A n a ly tic a l m e th o d u n c e rta in ty fo r e a ch ta rg e t a n a lyte an d S R S is d e te rm in e d w ith co n tro l ch a rte d historical a n a ly s is b a tch L C S d a ta fo r th e m e th o d a n d re p o rte d w ith e a c h a n a ly s is b a tc h .5 U n c e rta in ty d e te rm in a tio n s 5 Method uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of Uncertainty in Measurement). Method application demonstrated in ETS-12-012, citing references: a.) EURACHEM/CITAC Guide, "Quantifying Uncertainty in Analytical Measurement," Second Edition; Editors: S.L.R. Ellison, M. Rosslein, and A. Williams. b.)Georgian, Thomas, "Estimation of Laboratory Analytical Uncertainty Using Laboratory Control Samples," Environmental Testing & ETS-8-044.1 Page 20 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 144 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 are based on IN T E R N A T IO N A L A N S /IS O /IE D S T A N D A R D 17025 reference (G U M , G uide to the E xpression o f U n c e rta in ty in M e a s u re m e n t) and d e s c rib e d in E T S -1 2 -0 1 2 . A t le a s t th irty d a ta po in ts a re req uire d fo r d e te rm in in g an alytica l m e th o d un certainty. T h e m e th o d u n c e rta in ty is de fin e d as 2 x th e s ta n d a rd d e via tio n o f the pe rcen t recoveries o f the pooled lab control spikes. W hile all LC S da ta points are control charted, o n ly the m ost recent fifty data points are used fo r determ ining the m ethod uncertainty. W hen less than thirty LC S data points have been gene rated fo r a given analyte, the analysis batch LC S s are used to d e te rm in e th e da ta uncertainty. If F M S s m ee t th e 30% reco very criteria at a level ap pro pria te to the e n d o g e n o u s level, an d th e L C S m e e t th e 2 0 % re c o v e ry criteria, th e n th e u n c e rta in ty o f th e da ta is d e te rm in e d as w ithin 10020%. A nalysis batch sam ple data w ith F M S recovery outside o f 30% but w ithin 50% o f the expected value are flagged and reported as outside o f Q C acce ptan ce criteria w ith expanded uncertainties. D ata w ith FM S re c o v e ry o u tsid e o f 5 0 % o f th e e xp e c te d v a lu e are rep orted as N R , w h e re N R is d e fin e d as "N o t R e p o rta b le " data outside o f Q C acce ptan ce criteria. If F M S recovery could not be assessed because F M S s w ere at an inappropriate level, the n Labo ratory M a trix S pikes (LM S s) m a y be substituted. If LM S recoveries are w ithin 30% fo r each target analyte and appropriate S R S s the data are reportable but flagged as not m eeting the F M S m ethod a cce ptan ce criteria w ith un certainties o f 30% . If F M S do not m e e t the 30% reco very criteria, and histo rica l F M S d a ta d o e s not exist, th e an a lytica l u n c e rta in ty is e va lu a te d on a s a m p le -b y -s a m p le basis, the data m ay be reported w ith expanded uncertainty and are flagged. 13.6 Quantitation of PFOA/PFOS - Analysis Batch C alibration standards consisting o f m ixed branched and linear iso m e r P F O S /P F O A are preferred. Q ua ntita tio n is p e rfo rm e d b y in tegrating the lin e a r and bra n ch e d is o m e rs tog ether. A lte rn a te ly, the lin e a r a nd branched isom ers can be integrated separately, applying the appropriate true value to each calibration curve point fo r each isom er. T he LC S and sam p le s are then quantitated by integrating the linea r and branched isom ers sep ara te ly (requires separate analytical results files) and quantitating the resulting peak against the linear o r branched calibration curve. T he results from both integrations are then sum m e d to produce the final result. Integrating the linea r and bra nch ed iso m ers sep a ra te ly m a y be helpful fo r th o se sa m p le s w h e re the linear/branched ratios do not clo sely m atch those o f the reference standards. H ow ever, fo r P F O S /P F O A targe t analytes, if the calibration standards are com prised o f predom inantly linear isom ers on ly the m ethod requires the addition o f LC S s o f m ixed bra nch ed/line ar iso m er P F O S /P F O A . T he p u rp o se o f including th e s e L C S s is to d e m o n s tra te q u a n tita tiv e e q u iv a le n c y (o r q u a n tita tive bias) o f th e is o m e ric m ix w h e n using a p re d o m in a n tly lin e a r P F O S o r P F O A s ta n d a rd fo r ca lib ra tio n . A lte rn a tiv e ly , in lieu o f m ixed branched and linea r iso m e r P F O S /P F O A LC S s, m ixed branched and linear iso m er P F O S /P F O A T B M S s m a y be applied to d e m on stra te m ethod accu ra cy and precision. A n a lte rn a te m e th o d o f q u a n tita tio n c a n be p e rfo rm e d w h e re b y o n ly th e lin e a r is o m e r o f P F O S /P F O A is integrated and used fo r g ene rating th e calibration curve. T h e LC S and sa m p le s are the n qu an tita te d by integrating the linea r and branched isom ers sep ara te ly (requires sep ara te analytical results files) and quantitating the resulting p e ak against the linear calibration curve. T he results from both integrations are then su m m e d to produce the final result. Integrating the linea r and branched iso m ers se p a ra te ly reduces the oncolum n concentration fo r those sam ples tha t contain both linear and branched isom ers o f P F O A /P F O S . This e n s u re s th a t th e co n c e n tra tio n d e te cte d is w ith in th e a ra n g e o f th e calibra tion curve th a t is c o m p a ra b le regardless o f w h e th e r the calibration curve w a s generated using predom inantly linear isom ers o f P F O S /P F O A o r linear plus branched isom ers o f P F O S /P F O A . 14 Pollution Prevention and Waste Management W a ste generated w h en perform ing this m ethod w ill be dispo sed o f appropriately. T he original sam p le s w ill be arch ive d at th e 3M E n v iro n m e n ta l L a b o ra to ry in a c c o rd a n c e w ith in te rna l p ro ced ures. Analysis, November/December 2000. c.)Taylor, B.N. and CE. Kuyatt, NIST Technical Note 1297, 1994 Edition: "Guidelines for Evaluating and Expressing the Uncertainty of NIST Measurement Results."d.)Adams, T.M., "A2LA Guide for the Estimation of Measurement Uncertainty in Testing", July 2002. ETS-8-044.1 Page 21 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 145 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 15 Records E ach da ta pa ckag e ge ne ra te d fo r a s tu d y m ust include all sup po rting inform ation fo r reconstruction o f the data. In fo rm a tio n fo r th e da ta p a cka g e m u s t in clud e, b u t is not lim ited to th e fo llo w in g ite m s: s tu d y o r pro je ct num ber, sa m p le and sta n d a rd pre p sh e e ts/re co rd s, in stru m e n t run log (in stru m e n t batch records, in stru m en t acquisition m ethod, s u m m a ry pages), in stru m en t results files, chro m atog ram s, calibration curves, and data c a lc u la tio n s . 16 Affected Documents None. 17 Revisions R e visio n N um ber 1 S um m ary of C hanges Section 1. Included the use of internal standard calibration by this method. Section 2. Included the use of internal standard calibration by this method. Included the use of a solvent/water mixture when analyzing for PFUnA, PFDoA, PFTrDA, and FOSA. Section 3. Added definitions for internal standard, surrogate internal standard, and surrogate recovery standard. Section 6.Removed the details regarding the instrument parameters to section 10 of the method. Section 7. Updated reference standards to include internal standards and surrogates. Changed concentration levels for working standards and included the use of internal standards and surrogates. Section 8. Inserted a new section on sample bottle preparation. Section 9 Quality Control. This section was previously section 10 in ETS-8-044.0. Updated QC criteria to be consistent with method ETS-8-154.4. Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8044.0. Added detail regarding the preparation of LCSs. Included the use of methanol as a dilution solvent. Section 11 Sample Analysis. This section was previously section 10 in ETS-8-044.0. Included the details regarding the instrument parameters. Section 12 Data Analysis and Calculations. This section was previously section 11 in ETS8-044.0. Removed the equation for calculating the analytes concentration, indicating that this is done by the instrument software. Section 13 Method Performance. This section was previously section 12 in ETS-8-044.0. Updated QC criteria to be consistent with ETS-8-154.4. Added information on the determination of analytical method uncertainty and quantitation of PFOA/PFOS. Section 14 Pollution Prevention. This section was previously section 13 in ETS-8-044.0. Section 15 Records. This section was previously section 14 in ETS-8-044.0. Section 16 Affected Documents. This section was previously section 15 in ETS-8-044.0. Section 17 Revisions. This section was previously section 16 in ETS-8-044.0. ETS-8-044.1 Page 22 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 146 of 148 Attachment D: Deviation(s) GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 Page 147 of 148 GLP10-01-02; Interim Report 29 Analysis of PFBS, PFHS, and PFOS in Groundwater Off-Site Wells in Decatur, AL - March/April 2012 __________ Re c o r d o f De v ia t io n /No n c o n f o r m a n c e _________ ____________________________ I. Identification__________________________ S tudy / P roject No. D ate(s) o f O ccu rre n ce : D ocum ent N um ber: G LP 10-01-02-29 4 /2 3 /1 2 E TS -8-044.1 D e viatio n type SOP E q u ip m e n t P roce du re 0 M ethod (C heck one) P ro to c o l_________ G P O ____________________ O th e r:__________________________ __________________II. Description (attach ex tra p a g e s a s n e e d e d )_________________________ Method Requirements: 1. C C V reco very w ith in 2 5 % (section 13.4). 2. LCS recovery w ithin 20% (section 13.4). 3. R P D va lu e s <20% (sectio n 13.4). Actual procedure/process: 1. T he 0.5 ng /m L C C V (sam p le b1 2 0 4 2 3 a 0 3 6 ) had a reco very o f 71 .8% fo r PFO S su rro g a te (b1 20 423 a external). 2. The 2ppb LCSs had an overall average recovery o f 122% for PFOS and PFOS surrogate (b120423a external). 3. T he sam p lin g location D AL G W 60 5R had a sa m p le /sa m p le d u plicate RPD o f 2 9 % fo r PFO S; D AL G W 609L had a RPD of 33% for PFHS; DAL G W M W 13B had a sam ple/sam ple duplicate RPD of 49% for PFOS. III. Actions Taken ___________________________ (such as amendment issued, SOP revision, etc.)__________________________ Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1. T he n o n -co m p lia n t C C V fo r P FO S su rro g a te w ill be flag ge d in the final report. 2. T he n o n -co m p lia n t LC Ss w ill be flag ge d in the final report. S ince the overall m ethod u n certainty fo r PFO S using external calibration was calculated to be 38% follow ing ETS-12-012.2, the m ethod uncertainty will not be expanded further. 3. T he n o n -co m p lia n t R P D s w ill be flag ge d in the final report. A ctio n s: H alting o f W o rk C lie n t N o tificatio n W o rk R e call 0 O th e r: D e viatio ns w ill be noted in final report. W ith h o ld in g o f R eport Project Lead/PAI Approval: Date: Study Director (if GLP): Date: Sponsor Approval (for GLP protocol deviations): NA Technical Reviewer (optional): NA Date: NA Date: NA Laboratory Department Manager Approval: Date: 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 No.______________ (assignedby StudyDirector or TeamLeader at the endofstudy orproject) E T S -4-008.7 Page 1 of 1 D o cum e ntation o f D e viatio ns and C o ntrol o f N o n co n fo rm in g T esting Page 148 of 148
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