Document 2J4Jbk3vrGw69jpDjZdmEZV9L

GLP10-01-02; Interim Report 28 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) located in Decatur, AL, 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 h o n e :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 GLP10-01-02-28 Total Number of Pages 108 The testing reported herein meet the requirements of ISO/IEC 17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052.01. Testing that complies with this International Standard also operate in accordance with ISO 9001:2000. Testing Cert #2052.01 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 This page has been reserved for specific country requirements. Page 2 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 GLP Compliance Statement Report Title: GLP10-01-02; Interim Report 28 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) in Decatur, AL, 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 Date Page 3 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Quality Assurance Statement Report Title: GLP10-01-02; Interim Report 28 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) in Decatur, AL, 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 4/23/12 - 4/24/12 Phase Data / Report Date Re ported to Testing Facility Management Study Director 4/26/12 4/26/12 Page 4 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table of Contents GLP Compliance Statement.......................................................................................................................3 Quality Assurance Statement.....................................................................................................................4 Table of Contents........................................................................................................................................5 List of T ables...............................................................................................................................................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..............................................................................................................................13 7.1 M ethods.............................................................................................................................13 7.2 Sample Collection..............................................................................................................13 7.3 Sample Preparation...........................................................................................................13 7.4 Analysis..............................................................................................................................14 8 Analytical Results............................................................................................................................... 15 8.1 Calibration ..........................................................................................................................15 8.2 System Suitability ..............................................................................................................15 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..........................................................................................18 8.8 Field Matrix Spikes (FMS).................................................................................................19 Page 5 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 9 Data Summary and Discussion........................................................................................................19 10 Conclusion..........................................................................................................................................33 11 Data/Sample Retention..................................................................................................................... 33 12 Attachm ents.......................................................................................................................................33 13 Signatures..........................................................................................................................................34 List of Tables Table 1. Summarized PFBS, PFHS, and PFOS Results (FSIA GW, March/April 2012).......................10 Table 2. Sample Description Key Code.....................................................................................................13 Table 3. Instrument Parameters.................................................................................................................14 Table 4. Liquid Chromatography Conditions.............................................................................................14 Table 5. Mass Transitions...........................................................................................................................15 Table 6. Limit of Quantitation (LOQ).......................................................................................................... 16 Table 7. Laboratory Control Spike Recovery............................................................................................ 17 Table 8. Analytical Uncertainty................................................................................................................... 18 Table 9. Field Matrix Spike Levels............................................................................................................. 19 Table 10. DAL GW 130R 120329.............................................................................................................20 Table 11. DAL GW 130S 120329..............................................................................................................20 Table 12. DAL GW 130L 120329..............................................................................................................21 Table 13. DAL GW 131R 120328.............................................................................................................21 Table 14. DAL GW 131S 120328..............................................................................................................22 Table 15. DAL GW 131L 120328..............................................................................................................22 Table 16. DAL GW 133R 120328.............................................................................................................22 Table 17. DAL GW 133S 120328..............................................................................................................23 Table 18. DAL GW 133L 120328..............................................................................................................23 Table 19. DAL GW 134R 120328.............................................................................................................24 Table 20. DALGW 134S 120327..............................................................................................................24 Page 6 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 21. DAL GW 134L 120327..............................................................................................................25 Table 22. DAL GW 135R 120329.............................................................................................................25 Table 23. DAL GW 135S 120329..............................................................................................................25 Table 24. DAL GW 135L 120329..............................................................................................................26 Table 25. DAL GW 136S 120328..............................................................................................................26 Table 26. DAL GW 136L 120328..............................................................................................................27 Table 27. DAL GW 137S 120328..............................................................................................................27 Table 28. DAL GW 137L 120328..............................................................................................................28 Table 29. DAL GW 138S 120329..............................................................................................................28 Table 30. DAL GW 138L 120330..............................................................................................................29 Table 31. DAL GW 140R 120329.............................................................................................................29 Table 32. DAL GW 141R 120403.............................................................................................................. 30 Table 33. DAL GW 142R 120328.............................................................................................................. 30 Table 34. DAL GW 143R 120329.............................................................................................................. 31 Table 35. DAL GW 144R 120328.............................................................................................................. 31 Table 36. DAL GW 145R 120328.............................................................................................................. 31 Table 37. Trip Blank 1 ................................................................................................................................32 Table 38. Rinseate Blanks ........................................................................................................................ 32 Page 7 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 Kelly Ukes, Analyst Study Dates Study Initiation: March 8, 2010 Interim 28 Experimental Termination: April 18, 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 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 2 Summary The 3M Environmental Laboratory received groundwater samples from wells located at the Former Sludge Incorporation Area (FSIA) in Decatur, AL, for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS), and perfluorooctane sulfonate (PFOS) analysis under 3M project GLP10-01 -02-28. A total of seventy-seven sample bottles were prepared for thirty-two different sampling locations. Samples were not collected at five of the specified sampling locations; DAL GW 136R, DAL GW 137R, DAL GW 138R, DAL GW CW26C, and DAL GW CW26L. Samples were collected March 27 - April 3, 2012 and received from Weston personnel on April 4, 2012. Based on previous sampling of the FSIA (GLP10-01-02-07, GLP10-01-02-11, GLP10-01-02-18, and GLP10-01-02-24), the 3M Environmental Laboratory has demonstrated through the use of field matrix spikes, that 3M Environmental Laboratory Method ETS-8-044.1 used for the analysis of the samples is appropriate for the sample matrix. Therefore, for this sampling event, field matrix spike (FMS) samples were prepared for six of the twenty-seven sampling locations collected. In addition, a trip blank set containing Milli-QTM water and appropriate trip blank spikes were prepared, as well as two equipment rinseate blanks. The equipment rinseate blanks did not have FMS samples prepared for determination of PFBS, PFHS, or PFOS recovery. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.1. Many of the groundwater samples required dilution to attain PFBS, PFHS, and/or PFOS concentrations within the range of the curve, in some instances up to 100-fold dilution were required. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The equipment rinseate blanks and the trip blank sample were below the lower limit of quantitation (LLOQ) for PFBS, PFHS, and PFOS, indicating adequate control of sample contamination during shipping and sample collections. The PFBS concentration results for all groundwater samples ranged from <0.0250 ng/mL to 67.3 ng/mL. The PFHS concentration results for all groundwater samples ranged from 0.0649 ng/mL to 765 ng/mL. The PFOS concentration results for all groundwater samples ranged from 0.355 ng/mL to 1120 ng/mL. The analytical method uncertainties associated with the reported results using external calibration are: PFBS 21%, PFHS 17%, and PFOS 34%. For sample DAL GW 133L, the method uncertainty was expanded for PFOS to 35%. Samples analyzed using internal calibration for PFOS have an analytical method uncertainty of 1 1 %. Page 9 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 1. Summarized PFBS, PFHS, and PFOS Results (FSIA GW, March/April 2012). (1) Sampling Location DAL GW 130R 120329 DAL GW 130S 120329 DAL GW 130L 120329 DAL GW 131R 120328 DAL GW 131S 120328 DAL GW 131L 120328 DAL GW 133R 120328 DAL GW 133S 120328 DAL GW 133L 120328 DAL GW 134R 120328 DAL GW 134S 120327 DAL GW 134L 120327 DAL GW 135R 120329 DAL GW 135S 120329 DAL GW 135L 120329 DAL GW 136S 120328 DAL GW 136L 120328 DAL GW 137S 120328 DAL GW 137L 120328 DAL GW 138S 120329 DAL GW 138L 120330 DAL GW 140R 120329 DAL GW 141R 120403 DAL GW 142R 120328 DAL GW 143R 120329 DAL GW 144R 120328 DAL GW 145R 120328 Trip Blank (Mlilli-Q Water) DAL GW 130R RB 120329 DAL GW 135R RB 120329 PFBS Avg. Conc. (ng/mL) RPD 14.6 2.1% 3.54 3.1% 1.53 0.0% 40.2 3.0% 0.860 6.3% 3.13 0.64% 3.04 4.6% 8.57 5.7% 5.87 0.51% 55.9 2.0% 0.428 0.93% 9.80 6.2% 67.3 2.4% 2.17 1.8% 10.9 0.92% 2.58 0.39% 2.32 0.43% 0.109 1.8% 0.0679 0.74% 5.38 9.3% <0.0250 1.59 2.5% 0.0369 2.7% 2.08 4.8% 1.56 0.64% 1.99 3.0% 1.50 1.3% <0.0250 <0.0250 <0.0250 PFHS Avg. Conc. (ng/mL) RPD 119 0.84% 31.0 0.65% 12.7 0.79% 234 4.7% 4.75 2.9% 20.6 3.4% 19.6 0.51% 61.6 1.8% 39.1 3.3% 556 4.9% 4.77 0.42% 103 0.98% 765 4.2% 21.2 2.4% 79.4 3.2% 17.7 3.4% 16.0 1.3% 0.0922 6.1% 0.0876 3.5% 26.4 1.9% 0.0649 5.2% 17.7 1.1% 0.303 6.3% 11.2 2.7% 5.69 3.0% 9.03 3.0% 7.55 0.79% <0.0250 <0.0250 <0.0250 PFOS Avg. Conc. (ng/mL) RPD 405 8.7% 81.0 1.7% 50.7 3.2% 1120 6.3% 5.80 6.4% (2) 27.3 5.9% 21.2 2.8% 160 6.9% 70.1 0.57% (3) 1030 16% 13.7 6.6% 328 5.2% 974 7.4% 13.5 5.2% 59.0 19% 66.1 24% (4) 60.9 2.0% 0.355 6.2% (2) 1.27 3.1% (2) 2 0 0 15% 0.396 12% (2) 106 16% 5.59 11% (2) 55.4 28% (4) 13.7 9.5% 13.4 7.5% 49.1 4.3% <0.0232 <0.0232 <0.0232 (1) All samples reported using external standard calibration unless noted otherwise. The analytical method uncertainties associated with the reported results using external calibration are: PFBS 21%, PFHS 17%, and PFOS 34%. (2) Sam ple results reported using internal standard calibration. The analytical method uncertainty associated with the reported results using internal calibration is 11% for PFOS. (3) The FMS recovery did not meet acceptance criteria. The analytical uncertainty has been adjusted for PFOS to 35%. (4) The RPD did not meet method acceptance criteria of <20%. Page 10 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 groundwater samples collected from various wells located at the Former Sludge Incorporation Area (FSIA) in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on site groundwater conditions. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample bottle sets for each groundwater sampling location included a field sample and field sample duplicate. A field matrix spike samples was prepared for six of the twenty-seven sampling locations collected. Each empty container for groundwater samplings was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear), PFHS (linear), and PFOS (linear and branched) prior to being sent to the field for sample collection. See section 8.8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Sampling locations with PFOS results <10 ng/mL were reanlyzed with the addition of internal standard 13C8-PFOS to used to aid in the data quality objectives. Sampling locations reported for PFOS using internal standard calibraton included: DAL GW 131S, DAL GW 137S, DAL GW 137L, DAL GW 138L, and DAL G W 141R. Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, the trip blank, and the aqueous equipment rinseate blank samples. Tables 10-38 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 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 5 Reference Substances R eferen ce S ubstance Chemical Name Chemical Formula Identifier Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (p red o m in an tly lin e a r isom er) Perfluorobutane sulfonate C 4F gS O 3-K+ NA Target Analyte Reference Standard 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 W hite Powder 96.7% PFHS (lin e a r isom er) Perfluorohexane sulfonate C aF 13S O 3N a L-PFHXS Target Analyte Reference Standard W elling to n 3/25/2018 Frozen LPFHxSAM08 TCR08-0018 Crystalline 100% PFOS (b ran ch ed and lin e a r isom ers) Perfluorooctane sulfonate C 8F 17S O 3" K+ Br-PFOSK Target Analyte Reference Standard W elling to n 3/17/2014; 12/01/2014 Frozen brPFOSK0708; brP F O S K 1111 TCR11-0010; TCR11-0041 Liquid gg.g% R eferen ce S ubstance Chemical Name Chemical Formula Identifier Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOS (b ran ch ed and lin e a r isom ers) Perfluorooctane sulfonate C 8 F 17S O 3- K+ CAS # 2795-39-3 FMS Reference Standard Aldrich 2/4/2014 Room Temperature 1424328V TCR11-0028 W hite Powder 99.7% 13c 8-p f o s Sodium Perfluorooctanesulfonate 13C8F17SO3-N a + MPFC-C-0511 Internal Standard W elling to n 05/25/2014 Frozen 052411 TCR11-0016 Liquid NA (1) 13c 8-p f o s Sodium Perfluorooctanesulfonate 13C8F17SO3-Na+ MPFC-C-0112 Internal Standard W elling to n 01/24/2015 Frozen 012312 TCR12-0004 Liquid NA (1) (1) Custom mixture of seven mass-labeled (13C) perfluoroalkylcarboxylic acids, two mass labeled (13C) perfluoroalkylsulfonates and one mass-labeled (13C) perfluoro-1-octanesulfonamide at a nominal concentration of 5 pg/mL Page 12 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 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 131R 0 120328 Sampling Location Well ID Sampling Point Well Level Sampling Date Sample Type Example DAL = Decatur, Alabama GW = Groundwater Example: 131 R = Residuum shallow water-bearing zone L = Bedrock water-bearing zone S = Epikarst middle water-bearing zone 120328 - March 28,2012 0=primary sample DB=duplicate sample FMS = Held Matrix Spike 7 Method Summary 7.1 Methods 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 GLP10-01-02-28 were returned to the laboratory at ambient conditions on April 4, 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. Samples that required dilution were prepared by diluting 1 mL sample with 9 mLs of Milli-Q water (dilution 1:10). Samples requiring a 1:100 dilution were prepared by diluting 0.1 mL of sample with 9.9 mLs of MilliQ water Sampling locations with PFOS results <10 ng/mL were reported using internal standard calibraton. Sampling locations DAL GW 131S, DAL GW 137S, DAL GW 137L, DAL GW 138L, and DAL GW 141R were prepared by adding an aliquot of a separate internal standard spiking solution to 10 mLs of sample (nominal concentration of 1 ng/mL). Laboratory control samples were prepared in a similar manner. Page 13 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 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 Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS Buster ETS-8-044.1 4/11/12 - PFBS, PFHS, and PFOS External standard calibration Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5u Betasil C18 (4.6 mm X 100 mm), 5u 10 uL Applied Biosystems API 4000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 ETS Buster ETS-8-044.1 4/17/12 - PFOS Internal standard calibration Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5u Betasil C18 (4.6 mm X 100 mm), 5u 50 uL Applied Biosystems API 4000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Table 4. Liquid Chromatography Conditions. Step Number Total Time (min) 00 1 2.0 2 14.5 3 15.5 4 16.5 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 Page 14 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, anmd PFOS in Groundwater Former Sludge Incorporation Area - March/April 012 Table 5. Mass Transitions. Analyte Mass Transition Q1/Q3 Reference M a te ria l Structure Internal Standard Mass Transition Q1/Q3 PFBS 299/80 299/99 Linear NA NA PFHS 399/80 399/99 Linear NA NA PFOS 499/80 499/99 499/130 Branched and Linear [ 13C a]P FO S (1) 507/80 Dwell tim e was 50 or 75 m sec for each transition. The individual transitions were sum m ed to produce a "total ion chrom atogram " (TIC), which was used for quantitation. (1) Internal standard was only used for PFOS for sampling locations DAL G W 131S, DAL G W 137S, DAL G W 137L, DAL G W 138L, and DAL G W 141R. 8 Analytical Results 8.1 Calibration Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into prepared in Milli Q water. A total of fifteen spiked standards ranging from 0.025 ng/mL to 100 ng/mL (nominal) were analyzed. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area confirmed accuracy of each curve point. For sampling locations DAL GW 131S, DAL GW 137S, DAL GW 137L, DAL GW 138L, and DAL GW 141R for PFOS: 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 a 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 at a nominal concentration of 1 ng/mL. A calibration curve ranging from 0.025 ng/mL to 100 ng/mL (nominal) was analyzed. A quadratic, 1/x weighted, calibration curve of the peak area ratio was used to fit the data for PFOS. 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. For both external and internal 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 all analytes. 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 or peak area ratio and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, and PFOS. Page 15 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 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 4/11/12 Analysis external standard calibration 4/17/12 Analysis internal standard calibration NA = Not Applicable Dilution 1 10 100 1 PFBS LOQ, ng/mL 0.0250 0.250 2.50 NA PFHS LOQ, ng/mL 0.0250 0.250 2.50 NA PFOS LOQ, ng/mL 0.0232 0.232 2.32 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 PFBS, PFHS, and PFOS. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: solvent blanks, trip blanks, and equipment rinseate blanks. Solvent blank results were reviewed and used to evaluate method performance to determine the LOQ for PFBS, PFHS, and PFOS. Trip blanks reflect the shipping and sample collection conditons the sample bottles and samples experience. Equipment rinseate blanks are aqueous samples that reflect the efficiency of equipment cleaning in the field between different sample collections and are proof of no cross contamination of samples from the equipment. 8.6 Lab Control Spikes (LCSs) Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate with each preparation set. LCSs analyzed with the sample dilutions by exteranl standard calibration were prepared by spiking known amounts of PFBS, PFHS, and PFOS into Milli Q water to produce the desired concentration. LCSs analyzed by internal standard calibration were prepared by spiking known amounts of PFOS into synthetic groundwater and adding an aliquot of a separate internal standard spiking solution at a nominal concentration of 1 ng/mL. The method acceptance criteria, average of LCS at each level should be within 100% 20% with an RSD <20%, were met for all LCS samples. 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 M 0 0 % average LCS recovery Page 16 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 7. Laboratory Control Spike Recovery. ETS-8-044.1 Analyzed 4/11/12 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-120405-1 LCS-120405-2 LCS-120405-3 Average %RSD 0.498 0.498 0.498 0.494 0.471 0.475 96.4 2.6% 99.2 94.6 95.3 0.497 0.497 0.497 0.476 0.478 0.498 97.3% 2.4% LCS-120405-4 LCS-120405-5 LCS-120405-6 Average %RSD 4.98 4.98 4.98 5.00 4.99 4.98 100% 0.0% 100 100 100 4.97 4.97 4.97 5.00 4.92 4.88 99.4% 1.5% LCS-120405-7 LCS-120405-8 LCS-120405-9 Average %RSD 29.9 29.9 29.9 29.7 29.2 29.7 98.7% 1.0% 99.4 97.6 99.2 29.9 29.9 29.9 28.4 27.6 28.9 94.6% 2.4% %Recovery 95.7 96.2 100 101 98.9 98.2 94.8 92.2 96.7 ETS-8-044.1 Analyzed 4/11/12 External standard calibration Lab ID PFOS B ranched and Linear) Spiked Calculated Concentration Concentration (n g /m L ) (n g /m L ) %Recovery LCS-120405-1 LCS-120405-2 LCS-120405-3 Average %RSD 0.462 0.462 0.462 0.386 0.390 0.367 82.5% 3.1% 83.6 84.3 79.5 LCS-120405-4 LCS-120405-5 LCS-120405-6 Average %RSD 4.62 4.62 4.62 4.55 4.48 4.49 97.5% 0.80% 98.4 97.0 97.1 LCS-120405-7 LCS-120405-8 LCS-120405-9 Average %RSD 27.8 27.8 27.8 26.0 26.4 27.0 95.2% 1.8% 93.6 95.0 97.0 Page 17 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.1 Analyzed 4/17/12 Internal standard calibration Lab ID PFO S (Branched and Linear) Spiked Concentration (n g /m L ) Calculated Concentration (n g /m L ) %Recovery LCS-120416-1 LCS-120416-2 LCS-120416-3 Average %RSD 0.184 0.184 0.184 0.177 0.186 0.196 101 4.8% 96.3 101 106 LCS-120416-4 LCS-120416-5 LCS-120416-6 Average %RSD 1.84 1.84 1.84 1.83 1.84 1.90 101% 1.9% 99.5 100 103 LCS-120416-7 LCS-120416-8 LCS-120416-9 Average %RSD 9.22 9.22 9.22 9.24 8.60 9.06 97.2% 3.6% 100 93.3 98.3 8.7 Analytical Method Uncertainty Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The method uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The most recent 50 data points were used to generate the method uncertainty values listed in Table 8. Table 8. Analytical Uncertainty. Analyte PFBS PFHS PFOS PFOS Calibration External External External Internal Standard Deviation 10.7 8.69 17.2 5.49 Method Uncertainty 21% 17% 34% 11% Page 18 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 8.8 Field Matrix Spikes (FMS) A field matrix spike (FMS) was collected at six sampling locations 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 and 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 137S and 138L 141R 134S 130L 133L Trip Blank Spike Level FMS FMS FMS FMS FMS Low Mid Mid-High High PFBS, ng/mL 1.00 5.00 10.0 50.0 200 1.00 10.0 50.0 200 PFHS, ng/mL 0.998 4.99 9.98 49.9 200 0.998 9.98 49.9 200 PFOS, ng/mL 0.998 4.99 9.98 49.9 200 0.998 9.98 49.9 200 FMS R (Sample Concentration of FMS - Average Concentration :Field Sample & Field Sample Dup.) Spike Concentraton 9 Data Summary and Discussion The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks and rinseate blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of 30%, demonstrate that the method was appropriate for the given matrix and their respective quantitative ranges. DAL GW 133L - The recovery of the FMS sample for PFOS was 65.5%. Based on the recovery of the FMS sample, the analytical uncertainty has been expanded for PFOS to 35%. DAL GW 136S - The sample/sample duplicate RPD was 24% for PFOS. DAL GW 142R - The sample/sample duplicate RPD was 28% for PFOS. DAL GW TRIP01 - The recovery of the MHS FMS sample for PFOS was 67.1%. Page 19 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 10. DAL GW 130R 120329 3M LIMS ID Description GLP10-01 -02-28-001 GLP10-01-02-28-002 D A L-G W -130R -0-120329 D A L-G W -130R -D B -120329 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 14.4 14.7 14.6 ng/m L 2.1% Samples diluted 1:100 and reported by external standard calibration. PFHS Concentration (n g /m L ) 119 118 119 ng/m L 0.84% PFOS Concentration (n g /m L ) 387 422 405 ng/m L 8.7% Table 11. DAL GW 130S 120329 3M LIMS ID Description GLP10-01 -02-28-003 DAL-GW-130S-0-120329 GLP10-01-02-28-004 DAL-GW-130S-DB-120329 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 3.48 3.59 3.54 ng/m L 3.1% PFHS Concentration (n g /m L ) 30.9 31.1 31.0 ng/m L 0.65% PFOS Concentration (n g /m L ) 80.3 81.7 81.0 ng/m L 1.7% Samples diluted 1:10 and reported by external standard calibration. Page 20 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 12. DAL GW 130L 120329 3M LIMS ID Description GLP10-01 -02-28-005 DAL-GW-130L-0-120329 GLP10-01-02-28-006 DAL-GW-130L-DB-120329 GLP10-01 -02-28-007 DAL-GW-130L-FMS-120329 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 1.53 1.53 48.4 NA NA 93.7 1.53 ng/m L 0.0% Concentration (n g /m L ) %Recovery 12.7 12.6 60.5 NA NA 95.9 1 2 .7 ng/m L 0.79% Concentration (n g /m L ) %Recovery 51.5 49.9 85.5 NA NA 69.7 5 0 .7 ng/m L 3.2% NA = Not Applicable Samples diluted 1:10 and reported by external standard calibration. Table 13. DAL GW 131R 120328 3M LIMS ID Description GLP10-01 -02-28-008 GLP10-01 -02-28-009 D A L-G W -131R -0-120328 D A L-G W -131R -D B -120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 39.6 40.8 40.2 ng/m L 3.0% Samples diluted 1:100 and reported by external standard calibration. PFHS Concentration (n g /m L ) 228 239 234 ng/m L 4.7% PFOS Concentration (n g /m L ) 1080 1150 1120 ng/m L 6.3% Page 21 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 14. DAL GW 131S 120328 3M LIMS ID Description GLP10-01 -02-28-010 GLP10-01 -02-28-011 D A L-G W -131S -0-120328 D AL-G W -131S-D B-120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 0.833 0.887 0.860 ng/m L 6.3% PFHS Concentration (n g /m L ) 4.82 4.68 4.75 ng/m L 2.9% PFOS Concentration (n g /m L ) 5.98 5.61 5.80 ng/m L 6.4% Results for PFBS and PFHS are reported by external standard calibration. Results for PFOS are reported by internal standard calibration. Table 15. DAL GW 131L 120328 3M LIMS ID Description GLP10-01 -02-28-012 DAL-GW-131L-0-120328 GLP10-01 -02-28-013 DAL-GW-131L-DB-120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 3.14 3.12 3.13 ng/m L 0.64% PFHS Concentration (n g /m L ) 20.9 20.2 20.6 ng/m L 3.4% Samples diluted 1:10 and reported by external standard calibration. PFOS Concentration (n g /m L ) 28.1 26.5 27.3 ng/m L 5.9% Table 16. DAL GW 133R 120328 3M LIMS ID Description GLP10-01 -02-28-014 GLP10-01 -02-28-015 D A L-G W -133R -0-120328 D A L-G W -133R -D B -120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 3.11 2.97 3.04 ng/m L 4.6% Samples diluted 1:10 and reported by external standard calibration. PFHS Concentration (n g /m L ) 19.5 19.6 19.6 ng/m L 0.51% PFOS Concentration (n g /m L ) 20.9 21.5 21.2 ng/mL 2.8% Page 22 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 17. DAL GW 133S 120328 3M LIMS ID Description GLP10-01 -02-28-016 DAL-GW-133S-0-120328 GLP10-01 -02-28-017 DAL-GW-133S-DB-120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 8.32 8.81 8 .5 7 ng/m L 5.7% Samples diluted 1:10 and reported by external standard calibration. Table 18. DAL GW 133L 120328 PFHS Concentration (n g /m L ) 61.0 62.1 61.6 ng/m L 1.8% PFOS Concentration (n g /m L ) 154 165 160 ng/m L 6.9% 3M LIMS ID Description GLP10-01 -02-28-018 DAL-GW-133L-0-120328 GLP10-01 -02-28-019 GLP10-01-02-28-020 D A L-G W -133L-D B-120328 D A L-G W -133L-FM S-120328 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 5.85 NA 5.88 NA 189 91.6 5.87 ng/m L 0.51% Concentration (n g /m L ) %Recovery 38.4 NA 39.7 NA 213 87.0 39.1 ng/m L 3.3% Concentration (n g /m L ) %Recovery 70.3 NA 69.9 NA 201 65.5 (1) 70.1 ng/m L 0 .5 7 % (2) NA = Not Applicable Sample and sample duplicate diluted 1:10. FMS diluted 1:100. All samples reported by external standard calibration. (1) FMS did not meet method acceptance criteria of 100 30%. (2) Method uncertainty is expanded to 35% for PFOS. Page 23 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 19. DAL GW 134R 120328 3M LIMS ID Description GLP10-01 -02-28-021 GLP10-01-02-28-022 D A L-G W -134R -0-120328 D A L-G W -134R -D B -120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 55.3 56.4 55.9 ng/m L 2.0% Samples diluted 1:100 and reported by external standard calibration. Table 20. DALGW 134S 120327 PFHS Concentration (n g /m L ) 569 542 556 ng/m L 4.9% PFOS Concentration (n g /m L ) 1110 947 1030 ng/mL 16% 3M LIMS ID Description GLP10-01-02-28-023 DAL-GW-134S-0-120327 GLP10-01-02-28-024 DAL-GW-134S-DB-120327 GLP10-01-02-28-025 DAL-GW-134S-FMS-120327 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) % R ecovery 0.426 NA 0.430 NA 9.99 95.6 0.428 ng/m L 0.93% PFHS PFOS Concentration (n g /m L ) Concentration %Recovery (n g /m L ) %Recovery 4.78 NA 4.76 NA 14.4 96.5 4 .7 7 ng/m L 0.42% 14.1 NA 13.2 NA 20.9 72.6 1 3 .7 ng/m L 6.6% NA = Not Applicable Samples reported by external standard calibration. Page 24 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 21. DAL GW 134L 120327 3M LIMS ID Description GLP10-01-02-28-026 GLP10-01-02-28-027 D A L-G W -134L-0-120327 D A L-G W -134L-D B-120327 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 10.1 9.49 9.80 ng/m L 6.2% Samples diluted 1:100 and reported by external standard calibration. Table 22. DAL GW 135R 120329 PFHS Concentration (n g /m L ) 103 102 103 ng/m L 0.98% PFOS Concentration (n g /m L ) 336 319 328 ng/m L 5.2% 3M LIMS ID Description GLP10-01-02-28-028 DAL-GW-135R-0-120329 GLP10-01-02-28-029 DAL-GW-135R-DB-120329 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 66.5 68.1 67.3 ng/m L 2.4% Samples diluted 1:100 and reported by external standard calibration. Table 23. DAL GW 135S 120329 PFHS Concentration (n g /m L ) 781 749 765 ng/m L 4.2% PFOS Concentration (n g /m L ) 1010 938 974 ng/m L 7.4% 3M LIMS ID Description GLP10-01 -02-28-030 DAL-GW-135S-0-120329 GLP10-01 -02-28-031 DAL-GW -135S-DB-120329 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 2.19 2.15 2.17 ng/m L 1.8% PFHS Concentration (n g /m L ) 21.4 20.9 21.2 ng/m L 2.4% PFOS Concentration (n g /m L ) 13.1 13.8 13.5 ng/m L 5.2% Results reported by external standard calibration. Page 25 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 24. DAL GW 135L 120329 3M LIMS ID Description GLP10-01-02-28-032 GLP10-01 -02-28-033 D A L-G W -135L-0-120329 D A L-G W -135L-D B-120329 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 10.8 10.9 10.9 ng/m L 0.92% Samples diluted 1:10 and reported by external standard calibration. PFHS Concentration (n g /m L ) 80.6 78.1 79.4 ng/m L 3.2% Table 25. DAL GW 136S 120328 PFOS Concentration (n g /m L ) 64.6 53.4 59.0 ng/mL 19% 3M LIMS ID Description GLP10-01-02-28-036 GLP10-01 -02-28-037 D A L-G W -136S -0-120328 D AL-G W -136S-D B-120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 2.58 2.57 2.58 ng/m L 0.39% Samples diluted 1:10 and reported by external standard calibration. (1) Sample/sample duplicate RPD did not meet acceptance criteria of <20%. PFHS Concentration (n g /m L ) 18.0 17.4 17.7 ng/m L 3.4% PFOS Concentration (n g /m L ) 73.9 58.2 66.1 ng/m L 2 4 % (1) Page 26 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 26. DAL GW 136L 120328 3M LIMS ID Description GLP10-01 -02-28-038 GLP10-01 -02-28-039 D A L-G W -136L-0-120328 D A L-G W -136L-D B-120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 2.32 2.31 2.32 ng/m L 0.43% Samples diluted 1:10 and reported by external standard calibration. Table 27. DAL GW 137S 120328 PFHS Concentration (n g /m L ) 16.1 15.9 16.0 ng/m L 1.3% PFOS Concentration (n g /m L ) 60.3 61.5 60.9 ng/m L 2.0% 3M LIMS ID Description GLP10-01-02-28-042 DAL-GW-137S-0-120328 GLP10-01-02-28-043 DAL-GW-137S-DB-120328 GLP10-01-02-28-044 DAL-GW-137S-F MS-120328 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration Concentration (n g /m L ) % R ecovery (n g /m L ) %Recovery 0.108 NA 0.110 NA 1.10 99.1 0.109 ng/m L 1.8% 0.0950 NA 0.0894 NA 0.975 88.5 0.0922 ng/m L 6.1% Concentration (n g /m L ) %Recovery 0.366 NA 0.344 NA 1.25 89.7 0.355 ng/m L 6.2% NA = Not Applicable Results for PFBS and PFHS are reported by external standard calibration. Results for PFOS are reported by internal standard calibration. Page 27 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 28. DAL GW 137L 120328 3M LIMS ID Description GLP10-01-02-28-045 GLP10-01-02-28-046 D A L-G W -137L-0-120328 D A L-G W -137L-D B-120328 Average Concentration (ng/mL) %RPD PFBS PFHS Concentration (n g /m L ) 0.0681 0.0676 0.0679 ng/m L 0.74% Concentration (n g /m L ) 0.0860 0.0891 0.0876 ng/m L 3.5% PFOS Concentration (n g /m L ) 1.25 1.29 1.27 ng/m L 3.1% Results for PFBS and PFHS are reported by external standard calibration. Results for PFOS are reported by internal standard calibration. Table 29. DAL GW 138S 120329 3M LIMS ID Description GLP10-01-02-28-049 GLP10-01 -02-28-050 D A L-G W -138S -0-120329 D AL-G W -138S-D B-120329 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 5.63 5.13 5.38 ng/m L 9.3% Samples diluted 1:10 and reported by external standard calibration. PFHS Concentration (n g /m L ) 26.6 26.1 26.4 ng/m L 1.9% PFOS Concentration (n g /m L ) 214 185 200 ng/mL 15% Page 28 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 30. DAL GW 138L 120330 3M LIMS ID Description GLP10-01 -02-28-051 DAL-GW-138L-0-120330 GLP10-01-02-28-052 DAL-GW-138L-DB-120330 GLP10-01 -02-28-053 DAL-GW-138L-FMS-120330 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (n g /m L ) % R ecovery <0.0250 <0.0250 0.962 NA NA 96.2 <0.0250 ng/mL Concentration (n g /m L ) %Recovery 0.0666 0.0632 0.931 NA NA 86.8 0.0649 ng/m L 5.2% Concentration (n g /m L ) %Recovery 0.419 0.373 1.32 NA NA 92.6 0.396 ng/mL 12% NA = Not Applicable Results for PFBS and PFHS are reported by external standard calibration. Results for PFOS are reported by internal standard calibration. Table 31. DAL GW 140R 120329 3M LIMS ID Description GLP10-01 -02-28-058 GLP10-01 -02-28-059 D A L-G W -140R -0-120329 D A L-G W -140R -D B -120329 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 1.57 1.61 1.59 ng/m L 2.5% Samples diluted 1:10 and reported by external standard calibration. PFHS Concentration (n g /m L ) 17.6 17.8 17.7 ng/m L 1.1% PFOS Concentration (n g /m L ) 115 97.8 106 ng/mL 16% Page 29 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 32. DAL GW 141R 120403 3M LIMS ID Description GLP10-01-02-28-060 GLP10-01 -02-28-061 GLP10-01-02-28-062 D A L-G W -141R -0-120403 D A L-G W -141R -D B -120403 DAL-GW-141 R-F MS-120403 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (n g /m L ) %Recovery 0.0364 0.0374 4.70 NA NA 93.3 0.0369 ng/m L 2.7% Concentration (n g /m L ) %Recovery 0.312 0.293 4.51 NA NA 84.3 0.303 ng/m L 6.3% Concentration (n g /m L ) %Recovery 5.89 5.28 9.70 NA NA 82.5 5.59 ng/mL 11% NA = Not Applicable Results for PFBS and PFHS are reported by external standard calibration. Results for PFOS are reported by internal standard calibration. Table 33. DAL GW 142R 120328 3M LIMS ID Description GLP10-01-02-28-063 DAL-GW-142R-0-120328 GLP10-01-02-28-064 DAL-GW-142R-DB-120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 2.03 2.13 2.08 ng/m L 4.8% Samples diluted 1:10 and reported by external standard calibration. (1) Sample/sample duplicate RPD did not meet acceptance criteria of <20%. PFHS Concentration (n g /m L ) 11.3 11.0 11.2 ng/m L 2.7% PFOS Concentration (n g /m L ) 63.2 47.6 55.4 ng/m L 2 8 % (1) Page 30 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 34. DAL GW 143R 120329 3M LIMS ID Description GLP10-01-02-28-065 DAL-GW-143R-0-120329 GLP10-01-02-28-066 DAL-GW-143R-DB-120329 Average Concentration (ng/mL) %RPD Results reported by external standard calibration. Table 35. DAL GW 144R 120328 PFBS Concentration (n g /m L ) 1.55 1.56 1.56 ng/m L 0.64% PFHS Concentration (n g /m L ) 5.77 5.60 5.69 ng/m L 3.0% PFOS Concentration (n g /m L ) 14.3 13.0 13.7 ng/m L 9.5% 3M LIMS ID Description GLP10-01-02-28-067 GLP10-01-02-28-068 D A L-G W -144R -0-120328 D A L-G W -144R -D B -120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 1.96 2.02 1.99 ng/m L 3.0% Samples diluted 1:10 and reported by external standard calibration. Table 36. DAL GW 145R 120328 PFHS Concentration (n g /m L ) 9.16 8.89 9.03 ng/m L 3.0% PFOS Concentration (n g /m L ) 13.9 12.9 13.4 ng/m L 7.5% 3M LIMS ID Description GLP10-01-02-28-069 GLP10-01 -02-28-070 D A L-G W -145R -0-120328 D A L-G W -145R -D B -120328 Average Concentration (ng/mL) %RPD PFBS Concentration (n g /m L ) 1.49 1.51 1.50 ng/m L 1.3% Samples diluted 1:10 and reported by external standard calibration. PFHS Concentration (n g /m L ) 7.52 7.58 7.55 ng/m L 0.79% PFOS Concentration (n g /m L ) 50.1 48.0 49.1 ng/m L 4.3% Page 31 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 37. Trip Blank 1 3M LIMS ID GLP10-01 -02-28-073 GLP10-01 -02-28-074 GLP10-01 -02-28-075 GLP10-01 -02-28-076 GLP10-01 -02-28-077 Description D A L-G W -T R IP 01-0 DA L-G W -TR IP 01-LS DAL-GW-TRIP01 -MS DAL-GW-TR IP01-MHS DAL-GW-TRIP01 -HS PFBS PFHS PFOS Concentration (n g /m L ) <0.0250 0.910 9.67 48.6 197 %Recovery NA 91.0 96.7 97.2 98.5 Concentration (n g /m L ) <0.0250 0.880 9.47 46.3 192 %Recovery NA 8 8 .2 94.9 92.8 96.2 Concentration (n g /m L ) <0.0232 0.695 8.91 33.5 140 %Recovery NA 69.6 89.3 67.1 (1) 70.1 NA = Not Applicable Results reported by external standard calibration. The MHS sample was diluted 1:10 and the HS sample was diluted 1:100. (1) FMS did not meet acceptance criteria of 100 30%. Table 38. Rinseate Blanks 3M LIMS ID GLP10-01 -02-28-071 GLP10-01 -02-28-072 Description D A L-G W -130R -R B -120329 D A L-G W -135R -R B -120329 Results reported by external standard calibration. PFBS Concentration (n g /m L ) <0.0250 <0.0250 PFHS Concentration (n g /m L ) <0.0250 <0.0250 PFOS Concentration (n g /m L ) <0.0232 <0.0232 Page 32 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 28 (G eneral P roject O utline) A tta chm e nt B: R epresentative C h rom ato gram s and C alibration C urves A tta chm e nt C: A nalytical M ethod - ETS-8-044.1 A tta ch m e n t D: M ethod D eviation Page 33 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 13 Signatures Cleston Lange, Ph.D., 3M Principal Analytical Investigator Date William K. Reagen, Ph.D., 3M Environmental Laboratory Department Manager Date Page 34 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Attachment A: Protocol A mendm ent Page 35 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Analytical Protocol: GLP10-01-02 Amendment 28 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. 28 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 Former Sludge Incorporation Area (FSIA) Groundwater Page 1 of 6 Page 36 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former ff iW - Amendment 28 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 from Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Program for PFOS, PFHS and PFBS (GLP10-01-02). The anticipated sample collection will occur around the timeframe during the week of March 19, 2012. The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-02-28 and reported as interim report GLP10-01-0228, (reflecting study GLP10-01-02 and amendment -28). Reason: The reason for this am endm ent is to document the General Project Outline (GPO) which describes the anticipate groundwater sample collection event to be conducted for the 3M Decatur, AL facility. The GPO is three pages in length and included as attached to this amendment form. Page 2 of 6 Page 37 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Analytical Protocol: GLPl-01-02 Amendment 28 Amendment Approval mil nfmjM Gary Hcffienstein, Sponsor Representative l/l Cleston C. Lang, Principal Analytical Investigator William"Fragen JE(-/sOpns Environmental Lab Management ilhbhl ___ Jaisimha Kesari P.E., DEE, Study Director Date Date 1 Date Page 3 of 6 Page 38 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former S lu^ ei^corpQr^ io n A rB a-.M arch/Apri);2012 Amendment 28 3M Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: Gary Hohenstein, 3M EHS&Opns From: Susan Wolf, 3M EHS&Opns; Environmental Lab cc: William Reagen, 3M EHS&Opns; Environmental Lab Cleston Lange, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions Date: March 16, 2012 Subject: 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 28 - Former Sludge Incorporation Area (FSIA) Groundwater - March 2012 Sampling 1 General Project Information C o n ta cts Lab Request Number S ix D igit 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 aahohensteinOmmm.com 3M Environm ental Laboratory M anagem ent William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaaenOmmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cclanaeOmmm.com Sam pling Coordinator Timothy Frinak Weston Solutions Timothv.frinakOwestonsolutions.com Phone: (334)-332-9123 G LP10-01-02-28 Dept #530711, Project #0022674449 Sampling scheduled for the week of March 19, 2012 All verbal and written correspondence will be directed to Gary Hohenstein. Page 4 of 6 Page 39 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Analytical Protocol: GLP10-01-02 Amendment 28 2 Background Information and Project Objective(s) _ _ _ _ _ , The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze groundwater samples collected from twenty-seven groundwater wells for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) from the Former Sludge Incorporation Area (FSIA). Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples from Decatur, AL will be collected by Weston Solutions personnel the week of March 19, 2012. The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP10-01-02-28. 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 to 3M Decatur for arrival by 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. A total of thirty-two sampling locations have been specified. Based on previous sampling of the FSIA (GLP1001-02-07, GLP10-01-02-011, GLP10-01-02-18, and GLP10-01-02-24), more than half of the sampling locations are expected to have PFBS, PFHS, or PFOS levels greater than 100 ng/mL. The 3M Environmental Laboratory has analyzed these locations multiple times and has demonstrated that the method used for the analysis of the samples is appropriate for the sample matrix (field matrix spike recoveries have demonstrated that the method is accurate for PFBS, PFHS, and PFOS in the given sample matrix). Therefore, for this sampling event, field matrix spikes will only be prepared on select sampling locations. If need be, laboratory matrix spikes may be prepared. For each sampling location, a sample and sample duplicate will be collected. Table 1 indicates the sampling locations included in this sampling event. Table 2 indicates the sampling locations for which a field matrix spike will be included. The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. One sets of trip blanks consisting of reagent-grade water, a low-level trip blank spike, mid-level field spike, mid-high level field matrix spike, and a high-level trip blank spike will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. Two additional bottles will be included to be used for the preparation of the equipment rinseate blanks. A 1-L bottle of laboratory reagent water will be provided to be used to collect the rinseate blanks. Page 5 of 6 Page 40 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Analytical Protocol: GLP10-01-02 Amendment 28 Table 1. Sampling Locations for this Sampling Event. 130R 130S 130L 131R 131S 131L 133R 133S 134R 134S 134L 135R 135S 135L 136R 136S FSIA 137R 137S 137L 138R 138S 138L CW 26C CW 26L 141R 142R 143R 144R 145R Table 2. Sampling Locations with Field Matrix Spike Sample Well No. 130L and 138L 141R 134S 130L 133L Trip Bank Spike Cone. (ng/mL) 1.0 5.0 10 50 200 1 10 50 200 5 Test Methods Samples may be analyzed by ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds In Water by LC/MS/MS; Direct Injection Analysis". This method is a direct injection method where samples would be analyzed as neat aqueous sample or as diluted aqueous samples. Laboratory control samples prepared with the samples must have an average recovery within 10020% and a RSD <20%. The data quality objective for this study is 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. 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 spikes will be reported for the sampling event as will any equipment/rinseate blanks prepared in the field. Laboratory control spikes of reagent water prepared at the time of sample preparation 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 preparation will be used to determine the method detection limit. For those sampling locations where the field matrix spike level was not appropriate, due to higher than expected analyte concentrations, a laboratory matrix spike may be prepared and included in the final report. Page 6 of 6 Page 41 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Attachment B: Representative Sa m ple Chrom atograms and Calibration Curve(s) Page 42 of 108 Workstation: ETSBUSTER GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Printing Time: 10:01:44 AM P r i nting Date: Tuesday, A p r i l 17, 2012 Page 43 of 108 Workstation: ETSBUSTER GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Printing Time: 9:59:28 AM P r i nting Date: Tuesday, A p r i l 17, 2012 Page 44 of 108 Workstation: ETSBUSTER GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Printing Time: 10:01:26 AM P r i nting Date: Tuesday, A p r i l 17, 2012 Page 45 of 108 *** B u ster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:46 AM P r i nting Date: Thu rsday, M a y 03, 2012 Page 1 of 30 Page 46 of 108 *** B u ster J2930203 I Sample Name: "b120411a035" Sample ID: "LCS-120405-7" File: "b120411a.wiff' Peak Name: "PFBS" Mass(es): "299.0/99.0 amu,299.0/80.0 amu' Comment: "30ppb LCS" Annotation: "" Sample Type Sample Index: Concentration QC Calculated Co: 29.9 ng/mL 29.7 ng/mL 35 3.0e6 4/12/2012 12:45:10 AM 2.8e6 Modified: No Proc. Algorithm: IntelliQuan - MQII 2.6e6 Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 1 2.4e6 Report Largest Peak: Yes Min. Peak Height: Min. Peak Width: 0.00 cps 0.00 sec 2.2e6 Smoothing Width: 3 points RT Window: Expected RT: 30.0 sec 13.6 min 2.0e6 Use Relative RT: No Int. Type: Valley Retention Time: 13.6 min Area: 11807788 counts Height: 3.02e+006 cps Start Time: 13.5 min End Time: 14.0 min > 1.4e6 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab I Sample Name: "b120411a042" Sample ID: "GLP10-01-02-28-071" I Peak Name: "PFBS" Mass(es): "299.0/99.0 amu ,299.0/80.0 amu" J Comment: "DAL-GW-130R-RB-" Annotation: "" Sample Index: 42 Sample Type: Unknown Concentration: Calculated Coni 4/12/2012 3:12:56 A File: "b120411a.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 mi Use Relative RT: No Int. Type: Retention Time: Area: Valley 13.6 mi 1144 count :. 19e + 002 13.5 13.6 8.0e5 6.0e5 4.0e5 2.0e5 0.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 Time, min ISample Name: "b120411a045" Sample ID: "GLP10-01-02-28-0731 Peak Name: "PFBS" Mass(es): "299.0/99.0 amu,299.0/80.0 amu Comment: "DAL-GW-TRIP01-0-" Annotation: "" Sample Name: "b120411a048" Sample ID: "GLP10-01-02-28-076" File: "b120411a.wiff" I Peak Name: "PFBS" Mass(es): "299.0/99.0 amu ,299.0/80.0 amu" J Comment: "DAL-GW-TRIP01-MHS-" Annotation: "" Sample Index: 45 Sample Index: 48 Sample Type: Unknown Sample Type: Unknown Concentration: Calculated Conc: <0 1300 Concentration: Calculated Con N/A 48.6 ng/mL Acq. Date: Acq. Time: 4/12/2012 4:16:09 AM 1250 1200 4/12/2012 5:19:21 AM 6.0e5 Modified: No Proc. Algorithm: IntelliQuan - Noise Percentage: 50 Base. Sub. Window: 1.00 m Peak-Split. Factor: 1 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 3 points RT Window: 30.0 sec Expected RT: 13.6 min Use Relative RT: No Int. Type: Retention Time: Area: Height: Start Time: End Time: Valley 13.5 min 1935 counts i .68e+002 cps 13.5 min 13.7 min 1150 1100 1050 1000 950 900 850 800 750 700 650 600 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 mi Use Relative RT: No Int. Type: Valley Retention Time: 13.6 mi Area: 2317522 count Height: 6.36e+005 cp Start Time: 13.4 mi End Time: 13.7 mi o.5e5 5.0e5 4.5e5 4.0e5 3.5e5 3.0e5 lime, mir 13.56 Intensity, cps 550 500 2.5e5 450 400 2.0e5 350 300 1 5e5 250 200 1.0e5 150 100 5.0e4 50 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 Data printed by STW Page 2 of 30 Printing Time: 8:45:46 AM P r i nting Date : Thu rsday, M a y 03, 2012 Page 47 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:46 AM P r i nting Date : Thursday, M a y 03, 2012 Page 3 of 30 Page 48 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:46 AM P r i nting Date: Thursday, M a y 03, 2012 Page 4 of 30 Page 49 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 5 of 30 Page 50 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 6 of 30 Page 51 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 7 of 30 Page 52 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 8 of 30 Page 53 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 9 of 30 Page 54 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 10 of 30 Page 55 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 11 of 30 Page 56 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 12 of 30 Page 57 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 13 of 30 Page 58 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 14 of 30 Page 59 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 15 of 30 Page 60 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 16 of 30 Page 61 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 17 of 30 Page 62 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 18 of 30 Page 63 of 108 *** B u ster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 19 of 30 Page 64 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date: Thursday, M a y 03, 2012 Page 20 of 30 Page 65 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 21 of 30 Page 66 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 22 of 30 Page 67 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 23 of 30 Page 68 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 24 of 30 Page 69 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:47 AM P r i nting Date : Thursday, M a y 03, 2012 Page 25 of 30 Page 70 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:48 AM P r i nting Date : Thursday, M a y 03, 2012 Page 26 of 30 Page 71 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:48 AM P r i nting Date : Thursday, M a y 03, 2012 Page 27 of 30 Page 72 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:48 AM P r i nting Date : Thursday, M a y 03, 2012 Page 28 of 30 Page 73 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:48 AM P r i nting Date : Thursday, M a y 03, 2012 Page 29 of 30 Page 74 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120411a.dab Data printed by STW Printing Time: 8:45:48 AM P r i nting Date : Thursday, M a y 03, 2012 Page 30 of 30 Page 75 of 108 Workstation: ETSBUSTER GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120417a.dab Printing Time: 2:22:04 PM P r i nting Date: W e d n e s d a y , Ap r i l 18, 2012 Page 76 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120417a.dab Printing Time: 8:48:40 AM P r i nting Date : Thursday, M a y 03, 2012 Page 77 of 108 *** B u ster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120417a.dab I Sample Name: "b120417a032" Sample ID: "LCS-120416-7" Peak Name: "M8PFOS(IS)" Mass(es): "507.0/80.0 amu" Comment: "10ppb LCS" Annotation: "" Sample Index: 32 Sample Type: Concentration: QC 0.954 ng/m] 3.2e5 Calculated Conc: N/A Acq. Date: Acq. Time: 4/18/2012 3:37:52 AM 3.0e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII 2.8e5 Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 2.6e5 Report Largest Peak Min. Peak Height: Min. Peak Width: 2.4e5 Smoothing Width: RT Window: : 2.2e5 Expected RT: Use Relative RT: 2.0e5 File: "b120417a.wiff' I Sample Name: "b120417a039" Sample ID: "GLP10-01-02-28-010" I Peak Name: "M8PFOS(IS)" Mass(es): "507.0/80.0 amu" J Comment: "DAL-GW-131S-0-" Annotation: " Sample Index: 39 Sample Type: Unknown Concentration: Calculated Conc: 0.955 N/A ng/mL 3.8e5- Acq. Date: 4/18/2012 Acq. Time: 6:08:10 AM 3.6e5- File: "b120417a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan Noise Percentage: 50 Base. Sub. Window: 1. 00 Peak-Split. Factor: 2 Report Largest Pe Min. Peak Height: 0 .00 Min. Peak Width: 0.00 Smoothing Width: 0 RT Window: 30.0 s Expected RT: 16.1 m Use Relative RT: No cps points 3.4e53.2e53.0e52.8e52.6e52.4e5- 16.05 Intensity, cps Retention : 16. 0 953240 co 3.24e+005 16.0 16.2 Retention Time: 16. 1 m Area: 1134185 coun Height: .88e+005 cps 16.0 m End Time: 16.3 m 2.2e52.0e51 8e5- 1 6e5- 1 4e5- 1 2e5- 8.0e4 6.0e4 4.0e4 2.0e4 1 0e58.0e46.0e44.0e42.0e4- 0.0 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 0.014.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 Time, min Time, min I Sample Name: "b120417a041" Sample ID: "GLP10-01-02-28-042" File: "b120417a.wiff Peak Name: "M8PFOS(IS)" Mass(es): "507.0/80.0 Comment: "DAL-GW-137S-0-" Annotation: "" Sample Name: "b120417a043" Sample ID: "GLP10-01-02-28-044" File: "b120417a.wiff" I Peak Name: "M8PFOS(IS)" Mass(es): "507.0/80.0 amu" Comment: "DAL-GW-137S-FMS-" Annotation: "" Sample Index: 41 Sample Index: 43 Sample Type: Unknown Concentration: 0.955 ng/mL Sample Type: Concentration: Unknown 0.955 ng/mL 16.05 Calculated Conc: N/A Acq. Date: 4/18/2012 3.4e5- Calculated Conc: N/A Acq. Date: 4/18/2012 1 8e5 Acq. Time: 6:51:04 AM 3.2e5- Acq. Time: 7:34:03 AM 1 7e5 Modified: Yes Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 3.0e5- Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 1 6e5 Base. Sub. Window: Peak-Split. Factor: 1.00 min 2 2.8e5- Base. Sub. Window: Peak-Split. Factor: 1.00 2 min 1 5e5 Report Largest Peak: No Report Largest Peak: No Min. Peak Height: Min. Peak Width: 0.00 cps 0.00 sec 2.6e5- Min. Peak Width: 0.00 0.00 1 4e5 Smoothing Width: 0 points RT Window: 30.0 sec 2.4e5- Smoothing Width: RT Window: 0 points 30.0 s 1 3e5 Expected RT: Use Relative RT: 16.1 min No 2.2e5- Expected RT: Use Relative RT: 16.1 m 1 2e5 Int. Type: Base To Base Retention Time: 16.1 min Area: 1035149 counts Height: 3 .52e+005 cps Start Time: 15.9 min End Time: 16.2 min Intensity, cps 2.0e51.8e51.6e51.4e51.2e5- Int. Type: Base To Bas Retention Time: 16.1 m Area: 564920 coun Height: L. 88e+005 cps 16.0 m EndrTimeme: 16.3 m Intensity, cps 1.1e5 1 0e5 9.0e4 8.0e4 7.0e4 6.0e4 1.0e5- 5.0e4 8.0e4- 4.0e4 6.0e4- 3.0e4 4.0e4- 2.0e4 2.0e4- 1 0e4 0.0- Data printed by STW Printing Time: 8:48:40 AM 14.0 14.5 15.0 15.5 16.0 16.5 Time, min 17.0 17.5 18.0 18.5 P r i nting Date: Thu rsday, M a y 03, 2012 0.0 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 Time, min Page 2 of 7 Page 78 of 108 *** B u ster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120417a.dab Data printed by STW Printing Time: 8:48:40 AM P r i nting Date: Thu rsday, M a y 03, 2012 Page 3 of 7 Page 79 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120417a.dab Data printed by STW Printing Time: 8:48:41 AM P r i nting Date: Thursday, M a y 03, 2012 Page 4 of 7 Page 80 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120417a.dab Data printed by STW Printing Time: 8:48:41 AM P r i nting Date : Thursday, M a y 03, 2012 Page 5 of 7 Page 81 of 108 Buster J2930203 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120417a.dab Data printed by STW Printing Time: 8:48:41 AM P r i nting Date : Thursday, M a y 03, 2012 Page 6 of 7 Page 82 of 108 Buster J2930203 ISample Name: "b120417a052" Sample ID: "GLP10-01-02-28-060" File: "b120417a.wiff" Peak Name: "PFOS" Mass(es): "499.0/130.0 amu,499.0/99.0 amu,499.0/80.0 amu" Comment: "DAL-GW-141R-0-" Annotation: "" ample Index: 52 ple Typ 4/18/2012 10:47:32 30.0 16.1 : 16.0 6887313 15.6 16.2 1.3e6 1.3e6 1.2e6 1.2e6 1.1e6 1.1e6 1.0e6 9.5e5 9.0e5 8.5e5 8.0e5 7.5e5 7.0e5 6.5e5 6.0e5 5.5e5 5.0e5 4.5e5 4.0e5 3.5e5 3.0e5 2.5e5 2.0e5 1.5e5 1.0e5 5.0e4 14.0 14.5 15.0 15.89 15.73 15.5 16 16.5 I ime, min 17.0 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Batch Name: b120417a.dab ISample Name: "b120417a054" Sample ID: "GLP10-01-02-28-062" File: "b120417a.wiff" Peak Name: "PFOS" Mass(es): "499.0/130.0 amu,499.0/99.0 amu,499.0/80.0 amu" Comment: "DAL-GW-141R-FMS-" Annotation: "" :ample Index: 54 :ample Type: Unknown :anculared Oonc: 9.70 ng/mL ucq. Date: 4/18/2012 ucq. Time: 11:30:34 7M 1' 1 ' Iodified: Yes 1. 16.0 .0484305 c 1. 92e+006 15.6 16.2 9.0e5 8.0e5 7.0e5 6.0e5 5.0e5 4.0e5 3.0e5 2.0e5 15.73-_ 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 Time, min Data printed by STW Printing Time: 8:48:41 AM P r i nting Date : Thu rsday, M a y 03, 2012 Page 7 of 7 Page 83 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Attachment C: A nalytical Meth o d (s) Page 84 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 A pproved By: W illiam K. R eagen, T echnical D irector, E nvironm ental Laboratory J/J Q i/ // D a te * 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 85 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 (C8 Acid) 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 E 11-0667. 2 Guidance for establishing method QC Criteria based on a.) FDA May 2 0 0 1 , "Guidance for Industry, Bioanalytical Method Validation", b.) EPA Method 5 37, 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 86 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 87 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 88 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 89 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 90 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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, (C4 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 6 P 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 8 P erfluorinated A cid) P FN A, H e ptad eca fluoro no nan oic A cid, (C 9 P 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 91 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation T he follow ing standard preparation procedure serves as an exam ple. W eighed am ounts and final volum e s m a y be changed to suit the needs o f a particular study. F or exam ple, pL vo lu m e s m a y be spiked into v o lu m e tric flasks w h en diluting sto c k solutio ns to ap pro pria te le v e ls . 100 pg/mL target analyte SSSs-- W e ig h o u t 10 m g o f a n a ly tic a l s ta n d a rd (c o r r e c te d fo r p e rc e n t salt, a c id [E T S -4 -0 3 1 ] a n d p urity) and dilute to 100 m L w ith m ethanol o r other s u ita b le so lv e n t, in a 100 m L v o lu m e tric flask. T ra n s fe r to a 125 m L L D P E bottle o r o th e r suitable container. P repare a sep ara te solution fo r each analyte. Expiration da tes and s to ra g e c o n d itio n s o f s to c k s o lu tio n s sh o u ld be a s s ig n e d in a c c o rd a n c e w ith la b o ra to ry s ta n d a rd op e ra tin g p ro ced ure. A n e x a m p le o f pu rity and sa lt co rre ctio n is g iven b e lo w fo r PFOS. lx x. , x m o le c u la r w e ig h t o f anion s a lt c o rre c tio n fa c to r = ------------------------- - ------------------- m o cle cu la r w e ig h t o f salt 499 P F O S (K + )s a lt corre ction fa c to r = -- = 0.9 275 538 10 m g C 8F 17S 0 3"K+ w ith p u rity 9 0 % = 8 .3 5 m g C 8F 17S 0 3- (1 0 m g * 0 .9 0 *0 .9 2 7 5 = 8 .3 5 m g ) 10 pg/mL (10,000 ng/mL) mixed working standard-- A d d 5.0 m L e a ch o f th e 100 p g /m L S S S s to a 50 m L volum etric flask and bring up to volum e w ith solvent. 1 pg/mL (1,000 ng/mL) mixed working standard-- A d d 0 .5 m L o f th e 100 p g /m L S S S s to a 50 m L volum e tric flask and bring up to volum e w ith solvent. 0.1 pg/mL (100 ng/mL) mixed standard-- A d d 0 .0 5 m L o f th e 100 p g /m L S S S s to a 50 m L volum e tric flask and bring up to volum e w ith solvent. Storage Conditions-- S to re all S S S s a n d w o rk in g s ta n d a rd s in a c c o rd a n c e w ith la b o ra to ry s ta n d a rd o p e ra tin g p ro c e d u re o r in a re frig e ra to r a t 4 2 C fo r a m a x im u m pe rio d o f 6 m o n th s from the date o f preparation. 7.5 Calibration Standards C alibration can be perform ed by IS o r external calibration. U sing the w orking standards d e s c rib e d ab o ve , p re p a re ca lib ra tio n s o lu tio n s in A S T M T y p e I w a te r, H P L C w a te r, o th e r s u ita b le w a te r, o r a m ix tu re o f s o lv e n t and w a te r using th e in fo rm a tio n in T a b le 2 as a guideline. N ote: V olum e s o f w a te r o r w ate r/so lve nt m ixtures and w orking stan dard s m a y be a d ju s te d to m e e t th e d a ta q u a lity o b je c tiv e s a d d re s s e d in th e g e n e ra l p ro je c t outline. C alibration levels o th e r tha n th o se listed be lo w can be prepared as needed. F or the quantitation o f P F O A and P FO S , reference m aterials o f certified m ixed linear and branched iso m er are preferred. A lternately, reference m aterials o f prim arily linear isom ers o f P F O A an d/or P F O S m ay be used, how ever, w hen quantitating w ith predom inantly linear reference standards, additional LC S sam p le s containing both linear and branched isom ers o f P F O A and P F O S a re re q u ire d 3. 7.5.1 Internal Standard (IS) and Surrogate Recovery Standard (SRS) F o r IS calibration, stab le isotope internal sta n d a rd s o f each ta rg e t a n alyte o r a p pro pria te s u rro g a te ISs sh o u ld be s p ik e d a t th e s a m e level in all ca lib ra tio n s ta n d a rd s . O n c e th e ca lib ra tio n s ta n d a rd s ha ve be e n p re p a re d as sta te d a b o v e in S e ctio n 7.5, all ca lib ra tio n standards are spiked w ith a sep ara te internal standard spiking solution. T ypica lly the 3 A report summarizing an assessment of the use of reference 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 92 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 93 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 1. Stable Isotope PFCAs and PFSAs used for ISs and SRSs Coim pound Name Synonym or Acronym 13C4 -Perfluorobutanoic acid [1,2,3,4-13C4]PFBA 13C4-Perfluoropentanoic acid [1,2,3,4,5-13C5]PFPeA 13C2-Perfluorohexanoic acid [1,2 -13C2]PFHxA 13C4-Perfluoroheptanoic acid [1,2,3,4-13C4]PFHpA 13C8-Perfluorooctanoic acid [1,2,3,4,5,6,7,8-13C8]PFOA 13C9-Perfluorononanoic acid [1,2,3,4,5,6,7,8,9-13C9]PFNA 13C6-Perfluorodecanoic acid [1,2,3,4,5,6 -13C6]PFDA 13C7-Perfluoroundecanoic acid [1,2,3,4,5,6,7 -13C7]PFUnA 13C2 -Perfluorododecanoic acid [1,2 -13C2]PFDoA 18O2-Ammonium Perfluorobutane sulfonate [18O2]PFBS 13C3 -Ammonium Perfluorohexane sulfonate [1,2,3-13C3]PFHS 13C8-Sodium Perfluorooctane sulfonate [1,2,3,4,5,6,7,8-13C8]PFOS 13C8-Perfluorooctanesulfonamide 13C4-Perfluorooctanoic acid [1,2,3,4,5,6,7,8-13C8]FOSA [1,2,3,4-13C4]PFOA Analytical Purpose IS for PFBA IS for PFPeA IS for PFHxA IS for PFHpA IS for PFOA and [1,2,3,4 13C4]PFOA IS for PFNA IS for PFDA IS for PFUnA IS for PFDoA, *PFTA IS for PFBS IS for PFHS IS for PFOS and PFOS[1,2,3,4 13C4], IS for FOSA SRS for all PFCAs: C4-C8 Reference Standard Source Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) RTI International (Individual) Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Labs (mix) RTI International (Individual) Wellington 13C2 -Perfluoroundecanoic acid 13C8-Perfluorooctane sulfonate [1,2 -13C2]PFUnA [1,2,3,4-13C4]PFOS SRS for all PFCAs C9-C13 Wellington SRS for all PFSAs: C4, C6, and C8 Wellington 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 94 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 95 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 96 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 < 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 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 97 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 the average reco very o f a spiking level falls outside m ethod acce ptan ce, but at least 67 % (6 out o f 9) o f LC 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 om inal value), the average 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 -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 -12012, 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 98 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 99 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 100 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards Analyte 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 2 lP 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 7 lP F U n A [1,2 - 13C 2 lP 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 2 lP F U n A Analyte Description 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 (am u) 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 101 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 incorporated w ithin Q C acceptance criteria.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. 4 3M Environmental Laboratory study E08-0096 evaluated the effect on these results as a function of the number of MRMs 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 102 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 12 Data Analysis and Calculations T h e c h ro m a to g ra p h y a n a lysis so ftw a re w ill ty p ic a lly ca lc u la te th e a m o u n t o f ta rg e t a n a lyte in th e s a m p le extracts using the established calibration curve. C alculate the percent recovery o f the LC S using the follow ing equation: LC S C oncentration (-5^-) L C S % re co ve ry = ----------------------------------- m L * 100% ng Spike C oncentration (--^-) mL C alculate the percent recovery o f the LM S using the follow ing equation: LMS % recovery LMS Concentration (--ng--) - Concentration of Sample (n--g--) mL mL ng Spike Concentration (----) mL 100% F or sam p le s fortified w ith know n am o un ts o f analyte prior to extraction, use the follow ing equation to calculate the percent recovery. R e c o v e ry = T o ta l a n a ly te fo u n d (n g /m L ) - A v e ra g e a n a ly te fo u n d in s a m p le (n g /m L ) ^ 1 0 0 A n a lyte added (ng/m L) 13 Analysis Batch Method Performance Criteria A n y m e th o d p e rfo rm a n c e p a ra m e te rs th a t a re no t a c h ie v e d m u s t be c o n s id e re d in th e e va lu a tio n o f th e data. N o n c o n fo rm a n c e to a n y s p e c ifie d p a ra m e te rs m u s t be d e s c rib e d and d is c u s s e d in th e fina l re p o rt if th e T echnical M an ag er (non-G LP study) o r S tudy D irector (G LP study) chooses to report the data. If c rite ria liste d in th is m e th o d p e rfo rm a n c e s e c tio n a re n o t m e t, m a in te n a n c e m a y be p e rfo rm e d on th e s y s te m and s a m p le s re a n a lyze d , o r o th e r a c tio n s ta k e n as ap p ro p ria te . D o c u m e n t all a c tio n s in th e ra w da ta. If data are to be reported w h en perform ance criteria have not been m et, the data m ust be footnoted on tables and d is c u s s e d in th e te x t o f th e report. 13.1 System Suitability - Analysis Batch A m inim um o f three system suitability sam p le s should be injected at the beginning o f each analytical run. T h e s e s a m p le s a re run p rio r to th e c a lib ra tio n c u rv e . It is s u g g e s te d th a t th e s y s te m s u ita b ility in je c tio n s h a v e are a co u n ts w ith a ta rg e t R S D o f < 5% and a ta rg e t rete n tio n tim e R S D o f < 2% . T h e re is no de fine d a cce ptab ility lim it on th e se results as the % R S D s are d e p e n d e n t on the n u m b e r o f M R M transition s being m o n ito re d in th e L C /M S /M S run o r tim e period. A n y e ffe c t o f s y s te m s u ita b ility is in c o rp o ra te d in th e Q C acce ptan ce criteria. 13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch Calibration Curve: T h e c o e ffic ie n 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 c o rre s p o n d in g to a co rre la tio n c o e ffic ie n t (r) = 0 .9 95. E ach p o in t in th e c u rv e m u s t be w ith in 25% o f the theoretical concentration w ith the exception o f the LLO Q , w hich m ay be w ithin 30% . CCV Performance: T h e c a lib ra tio n s ta n d a rd s th a t a re in te rs p e rs e d th ro u g h o u t th e a n a ly tic a l s e q u e n c e are e v a lu a te d a s c o n tin u in g c a lib ra tio n v e rific a tio n s in a d d itio n to b e in g p a rt o f th e c a lib ra tio n c u rv e . T h e a c c u ra c y 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 103 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 equal to 20% . If the ave rag e reco very o f a spiking level falls outside m ethod acceptance, but at least 67 % (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 the sa m e concentration, m a y be outside 20% o f nom inal value), the ave rag e recovery 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 percent relative standard deviation o f the recoveries m ust be less than 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 analysis batch LC S data fo r the m ethod and reported w ith each analysis batch.5 U ncertainty determ inations 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 104 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 2 002. 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 105 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 106 of 108 Attachment D: Deviation(s) GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - March/April 2012 Page 107 of 108 GLP10-01-02; Interim Report 28 Analysis of PFBS, PFHS, and PFOS in Groundwater Former Sludge Incorporation Area - 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 10-01-02-28 4 /1 1 /1 2 E TS -8-044.1 D e viatio n type SOP E q u ip m e n tP 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. FM S reco very w ith in 3 0% (sectio n 13.4). 2. RPD values <20% (section 13.4). Actual procedure/process: 1. T he sam p lin g location D AL G W 133L had a P FO S FMS reco very o f 65.5% . T rip B la n k M HS FMS recovery was 67.1%. 2. The sam pling location DAL G W 136S had a sam ple/sam ple duplicate RPD o f 24% fo r PFOS and DAL G W 142R had a RPD of 28% 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 sam p lin g location and trip b la n k w ith a FMS reco very o u tside m ethod a cce p ta n ce criteria w ill be fla g g e d in th e rep ort and th e a n a lytica l u n ce rta in ty fo r sam p lin g location D AL G W 133L w ill be expanded to 35% for PFOS. 2. The n o n -co m p lia n t R PD 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): Sponsor Approval (for GLP protocol deviations): NA Technical Reviewer (optional): NA Date: 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.______________ (assigned by Study Director or Team Leader at the end of study or project) 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 108 of 108