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3M GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 GLP10-01-02: Interim Report 09 - Analysis of PFBS, PFHS. and PFOS in Ground Water Samples Collected from Decatur. AL in September 2010 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 Author Susan Wolf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP10-01-02-09 Total Number of Pages 83 lA C C R The testing reported herein meet the requirements of ISO/IEC 17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052.01. Testing that complies with this International Standard also operate in accordance with ISO 9001:2000. Certificate #2052.01 Page 1 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 This page has been reserved for specific country requirements. GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 GLP C o m p l ia n c e S t a t e m e n t Report Title: Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Ground W ater Samples Collected from Decatur, AL in September, 2010 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below: These are environmental samples where there is no specific test substance, no specific test system and no dosing of a test system. The reference substances have not been characterized under the GLPs and the stability under storage conditions at the test site have not been determined under GLPs. Page 3 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Q u a lity A s s u r a n c e S tatem ent Report Title: Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Ground Water Samples Collected from Decatur, AL in September 2010 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 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 3/2/11 -3/4/11 Phase Data / Report Date Reported to Testing Facility Management Study Director 3/21/11 3/21/11 Date Page 4 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table of C ontents GLP Compliance Statem ent................................................................................................................. 3 Quality Assurance Statement................................................................................................................ 4 Table of C ontents.................................................................................................................................. 5 List of Tables.......................................................................................................................................... 6 1 Study Information............................................................................................................................ 8 2 Summary......................................................................................................................................... 9 3 Introduction................................................................................................................................... 10 4 Test & Control Substances.......................................................................................................... 11 5 Reference Substances................................................................................................................. 12 6 Test System ...................................................................................................................................13 7 Method Summary..........................................................................................................................13 7.1 M ethods........................................................................................................................ 13 7.2 Sample Collection..........................................................................................................13 7.3 Sample Preparation.......................................................................................................13 7.4 Analysis......................................................................................................................... 14 8 Analytical R esults......................................................................................................................... 15 8.1 Calibration..................................................................................................................... 15 8.2 System Suitability..........................................................................................................15 8.3 Limit of Quantitation (LO Q )........................................................................................... 15 8.4 Continuing Calibration...................................................................................................16 8.5 Blanks............................................................................................................................ 16 8.6 Lab Control Spikes (LC Ss)........................................................................................... 16 8.7 Analytical Method Uncertainty...................................................................................... 20 8.9 Field Matrix Spikes (FMS)..............................................................................................21 9 Data Summary and Discussion.................................................................................................... 22 Page 5 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 10 Conclusion.................................................................................................................................... 33 11 Data/Sample Retention................................................................................................................ 33 12 Attachm ents.................................................................................................................................. 33 13 Signatures..................................................................................................................................... 34 L ist of Ta b le s Table 1. Summarized PFBS, PFHS, and PFOS Results (Decatur Groundwater, September 2010). .10 Sample Description Key Code..............................................................................................................13 Table 2. Instrument Parameters...........................................................................................................14 Table 3. Liquid Chromatography Conditions....................................................................................... 14 Table 4. Mass Transitions.................................................................................................................... 15 Table 5. Limit of Quantitation (LOQ).................................................................................................... 16 Table 6. Laboratory Control Spike Recovery....................................................................................... 18 Table 6 continued. Laboratory Control Spike Recovery......................................................................19 Table 6 continued. Laboratory Control Spike Recovery......................................................................20 Table 7. Analytical Uncertainty............................................................................................................ 21 Table 8. Field Matrix Spikes.................................................................................................................21 Table 9. DAL GW 203L 100929..........................................................................................................23 Table 10. DAL GW 220R 100930....................................................................................................... 23 Table 11. DAL GW 220L 100930........................................................................................................ 24 Table 12. DAL GW 222R 100929....................................................................................................... 24 Table 13. DAL GW 227R 100924....................................................................................................... 25 Table 14. DAL GW 227L 100924........................................................................................................ 25 Table 15. DAL GW GRS04 100930.....................................................................................................26 Table 16. DAL GW 31 OR 100924....................................................................................................... 26 Table 17. DAL GW 312R 100930....................................................................................................... 27 Table 18. DAL GW 317L 100924........................................................................................................ 27 Page 6 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 19. DAL GW 324L 100929......................................................................................................... 28 Table 20. DAL GW 327R 100930........................................................................................................ 28 Table 21. DAL GW 328R 100928........................................................................................................ 29 Table 22. DAL GW 328L 100928......................................................................................................... 29 Table 23. DAL GW 330R 100923........................................................................................................ 30 Table 24. DAL GW 330L 100923......................................................................................................... 30 Table 25. DAL GW 331S 100930......................................................................................................... 31 Table 26. Trip Blank 1 ...........................................................................................................................31 Table 26. Trip Blank 2 ...........................................................................................................................32 Table 27. Rinseate Blank......................................................................................................................32 Page 7 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 1 Study Information Sponsor 3M Company Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j.kesari@ westonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106 Study Personnel W illiam K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, tclanae@mmm.com): phone (651)-733-9860 Susan Wolf, 3M Analyst Chelsie Grochow; analyst Jonathan Steege; analyst Study Dates Study Initiation: March 8, 2010 Interim 09 Sample Collection: September 23 - 30,2010 Interim 09 Experimental Termination: March 16,2011 Interim Report Completion: Date of Interim Report Signing Location of Archives All original raw data and the analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792 Page 8 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 2 Summary The 3M Environmental Laboratory received groundwater samples from wells located in Decatur, AL, representing 17 different sampling locations. A total of seventy-seven sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate groundwater samples from each sampling location. Samples also included field matrix spike (FMS) samples for each location, two trip blanks containing Milli-QTM water and appropriate trip blank spikes, and one equipment rinseate blank. The equipment rinseate blanks did not have FMS samples prepared for determination of PFBS, PFHS or PFOS recovery. All groundwater samples for this project were logged under GLP10-01 -02-09. The groundwater samples, trip and equipment rinseate blanks were received from Weston personnel on October 1, 2010. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project GLP-1001-02-09. Many of the groundwater samples required dilution to attain PFBS, PFHS, and PFOS concentrations within the range of the curve, in some instances up to a 200-fold dilution were required. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. Equipment rinseate and the trip blanks were below the lower limit of quantitation (LLOQ), indicating adequate control of sample contamination during shipping and sample collections. The PFBS concentration results for all groundwaters ranged over four orders of magnitude from 0.324 ng/mL to 2780 ng/mL. The PFHS concentration results for all groundwaters ranged over four orders of magnitude from 0.237 ng/mL to 7630 ng/mL. The PFOS concentration results for all groundwaters ranged over four orders of magnitude from <0.500 ng/mL to 5060 ng/mL. Page 9 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 1. Summarized PFBS, PFHS, and PFOS Results (Decatur Groundwater, September 2010). Sampling Location DAL GW203L 100929 DAL GW220R 100930 DAL GW220L 100930 DAL GW222R 100929 DAL GW227R 100924 DAL GW227L 100924 DAL GWGRS04 100930 DAL GW 310R 100924 DAL GW312R 100930 DAL GW317L 100924 DAL GW324L 100929 DAL GW 327R 100930 DAL GW328R 100928 DAL GW328L 100928 DAL GW330R 100923 DAL GW330L 100923 DAL GW 331S 100930 Trip Blank (Milli-QTM Water) DAL GW220R RB 100930 (rinseate blank) PFBS (nAg/vmg.LC) onReP. D 70.6 1.4 10.0 1.8 7.85 3.6 126 2.4 16.7 4.2 376 0.53 2410 3.7 451 1.3 1420 0.71 0.324 (2) 89.3 0.45 126 1.6 31.8 0.31 63.1 3.0 2780 2.2 636 5.2 925 0.54 <0.250 <0.250 PFHS Avg. Cone. (ng/mL) RPD 481 6.2 48.7 0.62 41.9 5.7 872 0.0 97.5 11 255 0.39 7630 4.1 453 3.1 842 1.8 0.237 0.42 110 8.2 229 1.7 68.0 5.0 23.6 8.9 330 0.61 476 9.2 (3) 611 0.0 <0.100 <0.100 PFOS Avg. Cone. (ng/mL) RPD 836 2.8 70.2 10 64.6 4.3 1230 4.9 852 4.5 5060 10 (1) 1370 8.8 895 15 1510 5.3 <0.500 257 5.8 675 0.74 168 3.6 0.686 11 802 0.25 1 7 2 2 4 <4) 1180 1.7 <0.999 <0.999 The analytical method uncertainties associated with the reported results are as follows: PFBS 100% 19%, PFHS 100% 26%, and PFOS 100% 33%. (1) Sampling location did not have an appropriate FMS spike level to sufficiently evaluate analyte recovery. (2) A sample/sample duplicate RPD could not be calculated since one sample replicate had a result of BLOQ. (3) The analytical uncertainty for PFHS has been expanded to 35% based on FMS recovery. (4) The RPD did not meet method acceptance criteria of 20%. 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 Page 10 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 conducted to analyze ground water samples collected from various wells located in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on-site groundwater conditions. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and field spike samples. Each empty container was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear), PFHS (linear), and PFOS (linear) prior to being sent to the field for sample collection. All sample bottles included the addition of 180 2-PFBS, 180 2-PFHS, and 13C8PFOS (internal standards) at a nominal concentration of 1 ng/mL. All sample bottles also included the addition of 13C4-PFOS (surrogate spike) at a nominal concentration of 0.1 ng/mL. See section 8.8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, trip blanks and equipment rinseate samples. Tables 9-27 summarize the individual sample results and the associated FMS recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report 4 Test & Control Substances There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. Page 11 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 5 Reference Substances Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predominantly linear) Perfluorobutane sulfonate C 4F 9SO 3 Potassium Salt 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOS (linear) Perfluorooctane sulfonate C 8F1 7 S O 3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% PFHS (linear) Perfluorohexane sulfonate C F 13SO 3 Sodium Salt Wellington 4/2/2013 Frozen LPFHXSAM08 TCR08-0018 Crystalline 98% PFOS (linear + branched) Perfluorooctane sulfonate C 8F 1 7 S O 3 Potassium Salt CAS # 2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% Page 12 of 83 GLP10-01 -02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 6 Test System The test system for this study are ground water samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. Sample Description Key Code. String Number Exam ple 1 2 3 4 5 String Descriptor DAL GW 203L 0100929 Sam ple Location Sam ple Type W ell ID W ell Level S am pling Date S am ple Type Example D A L = Decatur, A L GW = G round W ater Exam ple: 203 R = R esidum shallow w ater-bearing zone L = B edrock w ater-bearing zone S = E pikarst m iddle w ater-bearing zone 100929 = Septem ber 29,2010 0=prim ary sam ple 1=dupllcate sam ple LS = lo w spike M S = m id spike H S = high spike RB = rinseate blank ,7 Method Summary 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on October 1, 2010. Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with the sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. Samples that required dilution were prepared as follows: 1:10 dilutions were prepared by diluting 1mL sample with 9 mL of laboratory reagent water, 1:20 dilutions were prepared by diluting 0.5mL sample with 9.5mL of laboratory reagent water, 1:50 dilutions were prepared by diluting 0.2mL sample with 9.8mL of laboratory reagent water, 1:100 dilutions were prepared by diluting 0.1 mL sample with 9.9mL of laboratory reagent water, and 1:500 dilutions were prepared by removing 2mL of the 1:100 dilutions and further diluting it with 8mL of laboratory reagent water. Page 13 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Samples may also have been diluted furhter by varying the injection volume during analysis. 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below. Table 2. Instrument Parameters. Instrument Name Analytical Method Followed Analysis Date Liquid Chromatograph Guard column Analytical column Infection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS Buster ETS-8-044.0 10/25/10,11/8/10, and 3/15/11 Agilent 1100 10/25/10; Betasil C18 (2.1 mm X 100 mm), 5 g 11/8/10; Prism RP (2.1 mm X 50 mm), 5 g Betasil C18 (2.1 mm X 100 mm), 5g 5 ,2 , or 1 pL Applied Biosystems API 4000 Turbo Spray Turbo ion electrode Neqative Analyst 1.4.2 ETS Ginger ETS-8-044.0 2/11/11 Agilent 1100 Prism RP (2.1 mm X 50 mm), 5 g Betasil C18 (2.1 mm X 100 mm), 5g 2 or 10 gL Applied Biosystems API 5000 Turbo Spray Turbo ion electrode Neqative Analyst 1.4.2 Table 3. Liquid Chromatography Conditions. Step Num ber 0 1 2 3 4 5 0 1 2 3 4 5 Total Tim e (m in) 0 2.0 14.5 15.5 16.5 20.0 0 2.0 11.0 14.0 14.5 17.0 Flow Rate (pL/m in) Percent A (2 m M am m onium acetate) ETS -8-044.0 A nalysis 10/25/10 a n d 11/8/10 300 97.0 300 97.0 300 5.0 300 5.0 300 97.0 300 97.0 E TS -8-044.0 A nalysis 2/11/11 a n d 3/15/11 300 97.0 300 97.0 300 5.0 300 5.0 300 97.0 300 97.0 Percent B (M ethanol) 3.0 3.0 95.0 95.0 3.0 3.0 3.0 3.0 95.0 95.0 3.0 3.0 Page 14 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 4. Mass Transitions. A n a ly te R eference M aterial S tru c tu re M ass Transition Q 1/Q 3 293/80 PFBS Linear 299/99 299/130 399/80 PFHS L in e a r 399/99 399/130 4 9 9 /8 0 PFOS Linear 4 9 9 /9 9 4 9 9 /1 3 0 Dwell time was 50 msec (2/11/11 and 3/15/11 analysis) or 75 msec (10/25/10and 11/8/10 analysis) for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation. 8 Analytical Results 8.1 Calibration Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into prepared in Milli Q water. A total of fifteen spiked standards ranging from 0.025 ng/mL to 100 ng/mL (nominal) were prepared, however, not all analytical runs included all fifteen standards. Low curve points were disabled to meet accuracy or method blank criteria. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS for each analytical batch. Due to the concentration of PFBS, PFHS, and PFOS detected in the samples, isotopically-labeled PFBS, PFHS, and PFOS were not used during instrument calibration. In addition, due to the number of samples requiring dilution, the 13C4-PFOS surrogate was not analyzed. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, and PFOS for each analytical batch. 8.3 Limit of Quantitation (LOQ) The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The LOQs associated with the sample analysis are listed in the table below. Page 15 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 5. Limit of Quantitation (LOQ). A nalysis Date D ilu tio n PFBS PFHS PFOS LO Q, nq/m L LOQ, nq/m L LO Q, nq/m L 10/25/10 1 0.250 0.100 0.999 10 2.50 1.00 9.99 20 5.00 2.00 20.0 50 12.5 5.00 50.0 100 25.0 10.0 99.9 11/8/10 1 0.250 0.100 0.500 50 NA NA 25.0 2/11/11 100 2.50 NA NA 500 12.5 12.5 15.0 3/15/11 1 NA NA 0.0500 NA = Not Applicable; analytical results at the specified dilution were not reported from the run. 8.4 Continuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All CCVs met method criteria of 100% 25% with the following exceptions: 10/25/10 Analysis: Founrteen CCVs were anayzed during the course of the run. Two CCVs for PFBS were outside method acceptance crteria. One CCV for PFBS had a recovery of 137% and bracketed samples DAL GW 310R, DAL GW 312R, DAL GW 317L, and DAL GW 324L. A second CCV for PFBS had a recovery 130% and bracketed samples DAL GW 330L, DAI GW 331S, and the Trip Blank samples. Two CCVs for PFOS had recoveries of 128% and 127% and bracketed samples DAL GW 222R, DAL GW 227L, and DAL GW GRS04. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: method blanks, field/trip blanks, and equipment blanks. Method blank results were reviewed and used to evaluate method performance and to determine the LOQ for each analyte 8.6 Lab Control Spikes (LCSs) A minuimum of two lab control spike levels were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into 10 mL of Midi Q water to produce the desired concentration. The spiked water samples were then analyzed in the same manner as the samples. The method acceptance criteria, average of LCS at each level should be within 100% 20% with an RSD <20%. 10/25/10 Analysis: Two levels of LCS were prepared and met method acceptance criteria for PFBS, PFHS, and linear PFOS. 11/8/10 Analysis: Two levels of LCS were prepared and met method acceptance criteria for PFBS, PFHS, and linear PFOS. 2/11/11 Analysis: Three levels of LCS were prepared and met method acceptance crtieria for PFBS, PFHS, and PFOS. 3/15/11 Analysis: Two levels of LCS were prepared and met method acceptance criteria for PFOS. Page 16 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 As the reference materials used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of both linear and branched isomers, additional LCS samples of PFOS (linear + branched) were prepared to evaluate the potential for analytical bias. 10/25/10 Analysis: Two levels of linear and branched PFOS LCS were prepared and met method acceptance criteria. 11/8/10 Analysis: Two levels of linear and branched PFOS LCS were prepared with the high set of LCS having an average recovery of 129%. 2/11/11 Analysis: Three levels of linear and branched PFOS LCS were prepared with the high set of LCS having an average recovery of 133%. 3/15/11 Analysis: Two levels of linear and branched PFOS LCS were prepared and met method acceptance criteria. The average recovery of the high set of linear and branched PFOS LCS at 129% and 133% suggests a slight bias when quantitating branched isomers of PFOS against a calibration curve of linear PFOS. Therefore, the method uncertainty for this study has been set of 33%, based on the highest average recovery of the linear and branched LCS samples. A method deviation is filed with the raw data for PFOS (linear + branched) LCS that did not meet method acceptance criteria. The following calculations were used to generate data in Table 6 for laboratory control spikes. , __ ,, . Calculated Concentration * . LCS Percent Recovery ------------------------------------------ * 100% Spike Concentration LCS% R S D = standard deviation LCS replicates . 1QQ% average LCS recovery Page 17 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 6. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 10/25/10 Lab ID LCS-101020-1 LCS-101020-2 LCS-101020-3 Average %RSD LCS-101020-4 LCS-101020-5 LCS-101020-6 Average %RSD S p ik e d C o n c e n tra tio n (ng/m L) 2.00 2.00 2.00 20.0 20.0 20.0 PFBS C alculated C o n c e n tra tio n (ng/m L) 1.86 1.98 1.98 97.1% 3.5% 17.4 19.6 19.1 93.4% 6.2% % Recoverv 93.2 98.9 99.1 86.8 97.8 95.5 S p ik e d C o n c e n tra tio n (ng/m L) 2.00 2.00 2.00 20.0 20.0 20.0 PFHS C alculated C o n c e n tra tio n (ng/m L) 1.89 1.98 1.97 97.4% 2.5% 17.3 19.5 18.7 92.5% 6.1% "/R e c o v e r y 94.6 99.2 98.4 86.4 97.6 93.5 ETS-8-044.0 Analyzed 10/25/10 Lab ID S p ik e d C o n c e n tra tio n (ng/m L) LCS-101020-1 LCS-101020-2 LCS-101020-3 Average %RSD 2.00 2.00 2.00 LCS-101020-4 LCS-101020-5 LCS-101020-6 Average %RSD 20.0 20.0 20.0 P FO S (linear) C alculated C o n c e n tra tio n (ng/m L) 1.70 1.79 1.79 88.1% 2.9% 17.0 19.3 18.6 91.4% 6.5% "/R e c o v e r y Lab ID 85.2 89.7 89.5 LCS-101020-7 LCS-101020-8 LCS-101020-9 Average %RSD 84.9 96.5 92.8 LCS-101020-10 LCS-101020-11 LCS-101020-12 Average %RSD PFO S (lin ear+ branched) S p ik e d C o n c e n tra tio n (ng/m L) C a lc u la te d C o n c e n tra tio n (ng/m L) "/R e c o v e r y 1.98 1.91 96.7 1.98 1.98 1.89 1.91 95.6 96.4 96.2% 0.59% 19.8 19.8 19.8 21.5 21.5 21.6 108% 0.53% 108 108 109 ETS-8-044.0 Analyzed 11/8/10 Lab ID L C S -1 0 1 105-1 LCS-101105-2 LCS-101105-3 Average %RSD L C S -1 0 1 105-4 L C S -1 0 1 105-5 LCS-101105-6 Average %RSD S p ik e d C o n c e n tra tio n (ng/m L) 2.00 2.00 2.00 20.0 20.0 20.0 PFBS C a lc u la te d C o n c e n tra tio n (ng/m L) 2.44 2.36 2.29 118% 3.0% 24.3 23.8 22.5 118% 3.5% % R eco very 122 118 115 121 119 113 S p ik e d C o n c e n tra tio n (ng/m L) 2.00 2.00 2.00 20.0 20.0 20.0 PFHS C alculated C o n c e n tra tio n (ng/m L) 2.47 2.37 2.28 119% 4.2% 24.00 24.00 23.00 118% 2.4% (1) The average recovery did not meet method acceptance criteria of 100% 20%. % Recovery 124 118 114 120 120 115 Page 18 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 6 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 11/8/10 Lab ID S piked C o n c e n tra tio n (ng/m L) L C S -1 0 1 105-1 2.00 LCS-101105-2 LCS-101105-3 Average %RSD 2.00 2.00 LCS-101105-4 LCS-101105-5 LCS-101105-6 Average %RSD 20.0 20.0 20.0 P FO S (lineali C alculated C o n c e n tra tio n (ng/m L) 2.30 2.23 2.17 111% 3.2% 23.7 24.6 23.1 119% 3.4% % Recovery Lab ID 115 LCS-101105-7 111 L C S -1 01105-8 108 LCS-101105-9 Average %RSD 119 LCS-101105-10 123 LCS-101105-11 115 LCS-101105-12 Average %RSD PFO S (linear+ branched) S p ik e d C o n c e n tra tio n (ng/m L) C alculated C o n c e n tra tio n (ng/m L) % Recovery 1.98 2.14 108 1.98 1.98 2.58 2.18 130 110 116% 10% 19.8 24.3 123 19.8 19.8 27.2 24.9 138 126 129% 6.2% (" ETS-8-044.0 Analyzed 2/11/11 Lab ID L C S -1 10210-1 L C S -1 10210-2 LCS-110210-3 Average %RSD L C S -1 10210-4 L C S -1 10210-5 L C S -1 10210-6 Average %RSD L C S -1 10210-7 L C S -1 10210-8 L C S -1 10210-9 Average %RSD S piked C o n c e n tra tio n (ng/m L) 0.498 0.498 0.498 4.98 4.98 4.98 29.9 29.9 29.9 PFBS C a lc u la te d C o n c e n tra tio n (ng/m L) 0.563 0.542 0.581 113% 3.5% 5.37 5.52 5.58 110% 1.9% 29.8 31.1 32.0 104% 3.6% %Recovery 113 109 117 108 111 112 99.5 104 107 S p ik e d C o n c e n tra tio n (ng/m L) 0.498 0.498 0.498 4.98 4.98 4.98 29.9 29.9 29.9 PFHS C alculated C o n c e n tra tio n (ng/m L) 0.603 0.594 0.599 120% 0.83% 5.61 5.36 5.96 114% 5.3% 30.7 30.8 32.7 105% 3.3% (1) The average recovery did not meet method acceptance criteria of 100% 20%. "/R e c o v e r y 121 119 120 113 108 120 103 103 109 Page 19 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 6 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 2/11/11 Lab ID L C S -1 10210-1 LCS-110210-2 L C S -1 10210-3 Average %RSD L C S -110210-4 L C S -1 10210-5 L C S -1 10210-6 Average % R S D L C S -1 10210-7 L C S -11 0210 -8 L C S -1 10210-9 Average %RSD S p ik e d C o n c e n tra tio n (ng/m L) 0.498 0.498 0.498 4.98 4.98 4.98 29.9 29.9 29.9 P FO S (linear) C alculated C o n c e n tra tio n (ng/m L) 0.650 0.587 0.540 119% 9.3% 5.43 4.93 5.86 109% 8.7% 30.8 30.7 32.4 105% 2.8% % R eco very Lab ID 130 LCS-110210-10 118 LCS-110210-11 108 LCS-110210-12 Average %RSD 109 99.1 L C S -1 10 210-13 L C S -1 1021 0-1 4 118 LCS-110210-15 Average %RSD 103 LCS-110210-16 103 LCS-110210-17 108 LCS-110210-18 Average %RSD PFO S (lin ear+ branched) S p ik e d C o n c e n tra tio n (ng/m L) C a lc u la te d C o n c e n tra tio n (ng/m L) % Recovery 0.502 0.539 107 0.502 0.502 0.585 0.541 117 108 111% 5.0% 5.04 6.15 122 5.04 5.38 107 5.04 5.44 108 112% 7.5% 30.2 40.7 135 30.2 40.4 134 30.2 39.6 131 133% 1.6% ETS-8-044.0 Analyzed 3/15/11 Lab ID LCS-110315-1 L C S -1 10315-2 LCS-110315-3 Average %RSD LCS-110315-4 LCS-110315-5 LCS-110315-6 Average %RSD S piked C o n c e n tra tio n (ng/m L) 0.498 0.498 0.498 4.98 4.98 4.98 P FO S (linear) C alculated C o n c e n tra tio n (ng/m L) 0.456 0.497 0.463 94.8% 4.7% 4.35 5.05 5.04 96.4% 8.2% X R eco very Lab ID 91.5 L C S -1 10315-7 99.9 93.0 L C S -1 10315-8 L C S -1 10315-9 Average %RSD 87.3 101 101 LCS-110315-10 L C S -1 10315-11 L C S -1 10 315-12 Average %RSD PFO S (linear+ branched) S p ik e d C o n c e n tra tio n (ng/m L) C alculated C o n c e n tra tio n (ng/m L) % Recovery 0.502 0.427 85.1 0.502 0.502 0.456 0.429 90.9 85.5 87.2% 3.7% 5.04 5.04 5.04 5.02 4.90 5.12 99.6 97.2 102 99.6% 2.4% (1) The average recovery did not meet method acceptance criteria of 100% 20%. 8.7 Analytical Method Uncertainty Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The most recent 50 data points were used to generate the method uncertainty values. The method uncertainty for PFOS by ETS-12-012-2 was found to be 27% however, since one of the high sets of linear and branched LCS for PFOS had an average recovery of 133%, the analytical uncertainty assigned to this study for PFOS will be 33%. Page 20 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 7. Analytical Uncertainty. Analyte Standard Deviation Method Uncertainty PFBS 9.52 19% PFHS 13.2 26% PFOS NA 33% m (1) Analytical uncertainty for PFOS was based on batch QC prepared with the study samples. 8.8 Field Matrix Spikes (FMS) Field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes were generated by adding a measured volume of field sample to a container spiked by the laboratory with PFBS (linear), PFHS (linear), and PFOS (linear) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. Table 8. Field Matrix Spikes. Sampling Location 317L 220R, 220L, 328L(i| 203L, 222R, 227L, 227R, 310R, 324L, 327R, 330L(1), 331S GRS04, 312R, 330R 3 2 8 R 111 Trip Blank Sets 1-4 Spike Level Low FMS High FM S Low FMS High FM S Low FMS High FM S Low FMS High FM S Low FMS High FM S Low FMS Mid FM S High FM S PFBS (ng/mL) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 PFHS (ng/mL) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 PFOS (ng/mL) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 (1) Sample bottles were overfilled by more than 10% for DAL G W 3 2 8 R HS (221 mL), DAL G W 328L LS (224 mL), DAL G W 330L LS (221 mL), and DAL G W 330L HS (224 mL). The FM S spike concentration has been adjusted accordingly. Due to the high concentration of PFBS, PFHS, and PFOS detected in the samples, the surrogate spike of 13C4-PFOS was not analyzed. FMS Recovery - (Sample Concentration o f F M S -A ve ra g e Concentration: Field Sample & Field Sample Dup.) * jQ gy Spike Concentraton 8.9 Lab Matrix Spikes (LMS) Sampling location DAL GW GRS04 100930 high spike at 5000 ng/mL produced recoveries <50% when initially ananyzed on 10/25/10. A laboratory matrix spike at 5000 ng/mL was prepared and analyzed on 2/11/11. The lab matrix spike result is presented in section 9 of this report. Page 21 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 9 Data Summary and Discussion The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks and rinseate blank. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of 30%, demonstrate that the method was appropriate for the given matrix and their respective quantitative ranges. DAL GW 330L100923 - The recovery of the high FMS sample for PFHS was 135%. This was the only appropriate field matrix spike level for PFHS. The method uncertainty has been adjusted for PFHS to 35%. DAL GW GRS04100923 - The recovery of the high FMS sample for PFBS, PFHS, and PFOS were <50%. A LMS at 5000ppb was prepared on the sample with acceptable recoveries for PFBS, PFHS, and PFOS. DAL GW 328L100928 - The recovery of the high FMS sample for PFOS was 69.0%, while the recovery of the low FMS was 102%. Since the low FMS was the more appropriate spike level as compared to the sample concentration, no adjustment was made to the analytical uncertainty. Page 22 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 9. DAL GW 203L 100929 PFBS PFHS PFOS 3M U M S ID GLP10-01-02-09-001 G LP10-01 -02-09-002 G LP10-01 -02-09-003 GLP10-01-02-09-004 Description DAL GW 203L 0 100929 DAL GW203L DB 100929 DAL GW203L LS 100929 DAL GW203L HS 100929 Average Concentration (ng/mL) %RPD Concentration (ng/mL) 70.1 71.1 175 1000 %Recovery NA NA 104 92.9 70.6 ng/mL 1.4% Concentration (ng/mL) 466 496 643 1700 %Recovery NA NA NC 122 481 ng/mL 6.2% Concentration (ng/mL) 824 847 907 1930 %Recovery NA NA NC 109 836 ng/mL 2.8% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 10/25/10 and 11/8/10. Table 10. DAL GW 220R 100930 3M U M S ID G LP10-01 -02-09-005 G LP10-01 -02-09-006 G LP10-01 -02-09-007 G LP10-01 -02-09-008 Description DAL GW220R 0 100930 DAL GW220R DB 100930 DAL GW220R LS 100930 DAL GW220R HS 100930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 9.92 10.1 20.1 112 %Recovery NA NA 101 102 10.0 ng/mL 1.8% Concentration (ng/mL) 48.5 48.8 59.3 150 %Recovery NA NA NC 101 48.7 ng/mL 0.62% Concentration (ng/mL) 73.8 66.5 81.1 152 %Recovery NA NA NC 81.9 70.2 ng/mL 10% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 10x and analyzed 10/25/10. Page 23 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 11. DAL GW 220L 100930 PFBS PFHS PFOS 3M U M S ID GLP10-01-02-09-009 GLP10-01-02-09-010 GLP10-01-02-09-011 GLP10-01-02-09-012 Description DAL GW 220L 0 100930 DALGW 220L DB 100930 DAL GW220L LS 100930 DAL GW 220LHS 100930 Average Concentration (ng/mL) %RPD Concentration (ng/mL) %Recovery 7.99 NA 7.71 NA 20.8 130 112 104 7.85 ng/mL 3.6% Concentration (ng/mL) %Recovery 40.7 NA 43.1 NA 55.4 NC 150 108 41.9 ng/mL 5.7% Concentration (ng/mL) 63.2 66.0 80.8 152 %Recovery NA NA NC 87.4 64.6 ng/mL 4.3% N A = Not Applicable NO = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 10/25/10. Table 12. DAL GW 222R 100929 3M U M S ID GLP10-01-02-09-013 GLP10-01 -02-09-014 GLP10-01-02-09-015 GLP10-01-02-09-016 Description DAL GW222R 0 100929 DAL GW222R DB 100929 DALGW222R LS 100929 DAL GW222R HS 100929 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 124 127 238 1200 %Recovery NA NA 113 107 126 ng/mL 2.4% Concentration (ng/mL) 872 872 996 2010 %Recovery NA NA NC 114 872 ng/mL 0.0% Concentration (ng/mL) 1200 1260 1220 2310 %Recovery NA NA NC 108 1230 ng/mL 4.9% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 10/25/10. Page 24 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 13. DAL GW 227R 100924 3M U M S ID GLP10-01-02-09-017 GLP10-01-02-09-018 GLP10-01-02-09-019 G LP 10-01 -02-09-020 Description DAL GW 227R 0100924 DALGW227R DB 100924 DAL GW227RLS 100924 DALGW227R HS 100924 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 16.3 17.0 117 1030 %Recovery NA NA 100 101 16.7 ng/mL 4.2% Concentration (ng/mL) 103 91.9 185 1190 %Recovery NA NA 87.6 109 97.5 ng/mL 11% Concentration (ng/mL) 871 833 801 2050 %Recovery NA NA NC 120 852 ng/mL 4.5% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 10/25/10. Table 14. DAL GW 227L 100924 3M U M S ID GLP 10-01-02-09-021 G LP 10-01 -02-09-022 GLP 10-01-02-09-023 G LP 10-01 -02-09-024 Description DAL GW227L 0100924 DALGW227L DB 100924 DAL GW227LLS 100924 DALGW227L HS 100924 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 377 375 474 1270 %Recovery NA NA NC 89.4 376 ng/mL 0.53% Concentration (ng/mL) 254 255 364 1260 %Recovery NA NA NC 101 255 ng/mL 0.39% Concentration (ng/mL) 4790 5320 5680 6860 %Recovery NA NA NC NC 5060 ng/mL 10% m NA = Not Applicable N C = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x for PFBS and PFHS, and 100x for PFOS and analyzed on 10/25/10. (1) Sampling location did not have an appropriate field matrix spike level for PFOS. Page 25 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 15. DAL GW GRS04 100930 3M UNIS ID GLP10-01-02-09-025 GLP10-01-02-09-026 GLP10-01-02-09-027 GLP10-01-02-09-028 GLP10-01-02-09-025; 5000ppb LMS Description DAL GW GRS04 0 100930 DAL GW GRS04 DB 100930 DAL GW GRS04 LS 100930 DAL GW GRS04 HS 100930 DAL GWGRS04 0 100930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 2360 2450 NA (1) 4450 7690 %Recovery NA NA N A (1> 4 0 . 9 (2) 106 2410 ng/mL 3.7% Concentration (ng/mL) 7780 7470 N A <1) 9440 13300 %Recovery NA NA NA (1) 36.3 (2) 114 7630 ng/mL 4.1% Concentration (ng/mL) 1310 1430 N A (1) 2410 5740 %Recovery NA NA N A <1) 20.8 (2) 87.4 1370 ng/mL 8.8% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 500x and analyzed on 2/11/11. (1) The LS sample was not diluted as the HS was the more appropriate spike for PFBA and PFHS. (2) Field matrix spike did not meet method acceptance criteria of 100% 30%. Table 16. DAL GW 31OR 100924 3M U M S ID GLP10-01-02-09-029 GLP10-01-02-09-030 GLP10-01-02-09-031 GLP10-01-02-09-032 Description DAL GW 310R 0100924 DAL GW 31OR DB 100924 DAL GW 31OR LS 100924 DAL GW 31OR HS 100924 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 448 454 563 1440 %Recovery NA NA NC 98.9 451 ng/mL 1.3% Concentration (ng/mL) 460 446 563 1460 %Recovery NA NA NC 101 453 ng/mL 3.1% Concentration (ng/mL) 961 829 863 1920 %Recovery NA NA NC 103 895 ng/mL 15% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 100x and analyzed 10/25/10. Page 26 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 17. DAL GW 312R 100930 3M LIM SID G L P 10-01 -02-09-033 GLP10-01-02-09-034 GLP10-01-02-09-035 GLP10-01-02-09-036 Description DAL GW312R 0100930 DAL GW 312R DB 100930 DAL GW312RLS 100930 DALGW312R HS 100930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 1420 1410 2460 6280 %Recovery NA NA 105 97.3 1420ng/mL 0.71% Concentration (ng/mL) 834 849 1920 6170 %Recovery NA NA 108 107 842 ng/mL 1.8% Concentration (ng/mL) 1470 1550 2370 6740 %Recovery NA NA 86.0 105 1510 ng/mL 5.3% NA = Not Applicable Samples diluted 100x and analyzed 10/25/10. Table 18. DAL GW 317L 100924 3M U M SID GLP10-01-02-09-037 GLP10-01-02-09-038 G L P 10-01 -02-09-039 GLP 10-01-02-09-040 Description DAL GW317L 0100924 DAL GW317L DB 100924 DAL GW317LLS 100924 DAL GW 317L HS 100924 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) <0.250 0.324 1.20 9.76 %Recovery NA NA 87.6 94.4 Concentration (ng/mL) 0.236 0.237 1.22 9.93 %Recovery NA NA 98.4 96.9 Concentration (ng/mL) <0.500 <0.500 1.20 8.52 %Recovery NA NA 120 85.2 0.324 ng/mLTM 0.237ng/mL 0.42% <0.500 ng/mL NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples were analyzed 11/8/10. (1) A sample/sample duplicate RPD could not be calculated since one sample replicate had a result of BLOQ. Page 27 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 19. DAL GW 324L 100929 3 M UNIS ID Description GLP10-01 -02-09-041 DAL GW 324L 0100929 GLP10-01 -02-09-042 DALGW324L DB 100929 GLP10-01 -02-09-043 DALGW324LLS 100929 GLP10-01 -02-09-044 DALGW324L HS 100929 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 89.1 89.5 186 978 %Recovery NA NA 96.7 88.9 89.3 ng/mL 0.45% Concentration (ng/mL) 105 114 216 1140 %Recovery NA NA 107 103 110 ng/mL 8.2% Concentration (ng/mL) YoRecovery 249 NA 264 NA 359 NC 1280 102 257 ng/mL 5.8% N A = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 10/25/10. Table 20. DAL GW 327R 100930 3M U M S ID GLP10-01 -02-09-045 GLP10-01-02-09-046 GLP10-01 -02-09-047 GLP10-01 -02-09-048 Description DAL GW327R 0100930 DAL GW327R DB 100930 DAL GW 327RLS 100930 DALGW327R HS 100930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 125 NA 127 NA 235 109 1110 98.4 126 ng/mL 1.6% Concentration (ng/mL) 227 231 337 1340 YoRecovery NA NA NC 111 229 ng/mL 1.7Yo Concentration (ng/mL) 672 677 761 1930 YoRecovery NA NA NC 126 675 ng/mL 0.74Yo NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 10/25/10. Page 28 of 83 N GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 21. DAL GW 328R 100928 3M LIM S ID GLP10-01-02-09-049 GLP10-01 -02-09-050 GLP10-01 -02-09-051 GLP10-01-02-09-052 Description DAL GW 328R 0100928 DALGW328R DB 100928 DAL GW 328RLS 100928 DALGW328R HS 100928 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 31.8 31.7 137 491 %Recovery NA NA 105 101 31.8 ng/mL 0.31% Concentration (ng/mL) 66.3 69.7 183 561 %Recovery NA NA 115 109 68.0 ng/mL 5.0% Concentration (ng/mL) 171 165 261 632 XRecovery NA NA 93.0 102 168 ng/mL 3.6% NA = Not Applicable Samples diluted 20x and analyzed on 10/25/10. Table 22. DAL GW 328L 100928 3M LIM SID GLP10-01-02-09-053 GLP10-01-02-09-054 GLP10-01-02-09-055 GLP10-01-02-09-056 Description DAL GW 328L 0100928 DALGW328L DB 100928 DAL GW 328LLS 100928 DALGW328L HS 100928 Average Concentration (ng/mL) %RPD PFBS m PFHS m PFOSm Concentration (ng/mL) 62.1 64.0 72.6 167 %Recovery NA NA NC 104 63.1 ng/mL 3.0% Concentration (ng/mL) 22.5 24.6 32.3 131 %Recovery NA NA NC 107 23.6 ng/mL 8.9% Concentration (ng/mL) 0.722 0.649 9.83 69.7 XRecovery NA NA 102 69.0 (3) 0.686 ng/mL 11% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) Samples diluted 20x and analyzed on 10/25/10 for PFBS and PFHS. (2) Samples analyzed on 3/15/11 for PFOS. (3) Field matrix spike did not meet method acceptance criteria of 100% 30%. Page 29 of 83 \ >ts G LP10-01-02; Interim Report 09 Analysis of PFBS, P FH S , and P FO S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 23. DAL GW 330R 100923 3M LIM SID GLP10-01-02-09-057 GLP10-01-02-09-058 GLP10-01-02-09-059 GLP10-01-02-09-060 Description DAL GW 330R 0 100923 DALGW330R DB 100923 DALGW330RLS 100923 DALGW330R HS 100923 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 2810 2750 3750 7610 %Recovery NA NA NC 96.6 2780 ng/mL 2.2% Concentration (ng/mL) 331 329 1380 N A (1) %Recovery NA NA 105 N A (1) 330 ng/mL 0.61% Concentration (ng/mL) 803 801 1780 N A (1) %Recovery NA NA 97.8 N A (1) 802 ng/mL 0.25% NA = Not Applicable Samples were diluted 50x for PFHS and PFOS, and 100x for PFBS and analyzed on 10/25/10. (1) Sample concentration exceeded calibration range. A further dilution was not prepared as the LS sample was the more appropriate spike level for PFHS and PFOS. Table 24. DAL GW 330L 100923 3M LIM SID GLP10-01 -02-09-061 GLP10-01-02-09-062 GLP10-01-02-09-063 GLP10-01-02-09-064 Description DAL GW 330L 0100923 DALGW330L DB 100923 DAL GW 330LLS 100923 DALGW330L HS 100923 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) 619 652 677 1510 XRecovery NA NA NC 97.8 636 ng/mL 5.2% Concentration (ng/mL) 498 454 560 1680 %Recovery NA NA NC 135 (1) 476 ng/mL 9 .2 % Concentration (ng/mL) 192 151 248 1270 %Recovery NA NA 84.5 123 172 ng/mL 24% p> NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed on 10/25/10. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for FMS recovery for PFHS to 35%. (3) The R PD did not meet method acceptance criteria of S20%. Page 30 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 25. DAL GW 331S 100930 3M UNIS ID Description GLP10-01 -02-09-065 DAL GW 331S 0100930 GLP10-01 -02-09-066 DAL GW331S DB 100930 GLP10-01 -02-09-067 DAL GW331SLS 100930 GLP10-01 -02-09-068 DAL GW331SHS 100930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 927 NA 922 NA 1070 NC 1990 107 925 ng/mL 0.54% Concentration (ng/mL) 611 611 788 1770 VoRecovery NA NA NC 116 611 ng/mL 0.0% Concentration (ng/mL) 1170 1190 1670 2390 %Recovery NA NA NC 121 1180 ng/mL 1.7% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed on 10/25/10 Table 26. Trip Blank 1 3M LIM SID GLP10-01 -02-09-069 GLP10-01 -02-09-070 GLP10-01 -02-09-071 GLP10-01-02-09-072 Description Trip Blank 1 Sample Trip Blank 1 FMS Low Trip Blank 1 FMS Mid Trip Blank 1 FMS High PFBS PFHS PFOS Concentration (ng/mL) <0.250 10.7 108 1100 VoRecovery NA 107 108 110 Concentration (ng/mL) <0.100 11.4 114 1160 %Recovery NA 114 114 116 Concentration (ng/mL) <0.999 11.4 102 1080 VoRecovery NA 114 102 108 N A = Not Applicable FM S Mid diluted 10x, FMS High diluted 50x, and analyzed on 10/25/10. Page 31 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Table 26. Trip Blank 2 3M LIM SID GLP10-01 -02-09-073 GLP10-01-02-09-074 GLP10-01-02-09-075 GLP10-01-02-09-076 Description Trip Blank 2 Sample Trip Blank 2 FMS Low Trip Blank 2 FMS Mid Trip Blank 2 FMS High PFBS PFHS PFOS Concentration (ng/mL) <0.250 10.8 108 1100 %Recovery NA 108 108 110 Concentration (ng/mL) <0.100 11.4 115 1190 %Recovery NA 114 115 119 Concentration (ng/mL) <0.999 11.0 99.6 1090 %Recovery NA 110 99.6 109 NA = Not Applicable FMS Mid diluted 10x, FMS High diluted 50x, and analyzed on 10/25/10. Table 27. Rinseate Blank 3M UNIS ID GLP10-01-02-09-077 Description DAL GW 220R RB 100930 PFBS PFHS PFOS Concentration (ng/mL) <0.250 %Recovery NA Concentration (ng/mL) <0.100 %Recovery NA Concentration (ng/mL) <0.999 %Recovery NA NA = Not Applicable Sample was analyzed on 10/25/10 Page 32 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS In Groundwater Quarterly Groundwater Sampling - Sept 2010 10 Conclusion Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for PFBS, PFHS, and PFOS. Analysis was successfully completed following 3M Environmental Laboratory method ETS-8-044.0 described herein. 11 Data/Sampie Retention All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 12 Attachments Attachment A: Protocol Amendment 09 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 33 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 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 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Attachment A : Protocol A mendment Page 35 of 83 G LP10-01-02; Interim Report 09 Analysis of P FBS, P FH S , and P FO S in Groundwater QuarterlyAGnroaulnydtiwcaatel rPSraomtoplcinogl:- GSeLpPt 12001-001-02 Amendment 9 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. 9 Amendment Date: September 13, 2010 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP10-01-02 Page 1 of 7 Page 36 of 83 G LP10-01-02; Interim Report 09 Analysis of P FBS, P FH S , and P FO S in Groundwater Quarterly GArnoaunlydtwicaatelrPSaromtpolicnogl:- SGeLptP210Q10-01-02 Amendment 9 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 of September 20, 2010, The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-01-09 and reported as interim report GLP10-01-02-09, (reflecting study GLP10-01-Q2 and amendment -09). Reason: The reason for this amendment is to document the General Project Outline (GPO) which describes the anticipate groundwater sample collection event to be conducted for the 3M Decatur, AL facility. The GPO is four pages in length and included as attached to this amendment form. Page 2 of 7 Page 37 of 83 G LP10-01-02; Interim Report 09 Analysis of PFBS, PFH S, and P FO S In Groundwater Quarterly AGrnoaulnydtwicaatelrPSraomtpolcinogl:- GSeLpPt 21001-001-02 Amendment 9 Amendment Approval Gary Hohenstein, Sponsor Representative Cleston C. Lange, Principal Analytical Investigator ^ ------------------------------- --William Reaoen, EHS Opns Environmental Lab Management i n k A h j j,,. Jaisimha^Cesari P.E., DEE, Study Director ^<ji3U-el* Date Date mm Date Page 3 of 7 Page 38 of 83 G LP10-01-02; Interim Report 09 Analysis of P FBS, P FH S , and P FO S in Groundwater Quarterly AGrnoaunlydtwicaatelrPSraomtpolcinogl:- SGeLpPt 21001-001-02 Amendment 9 3 M Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: From: cc: Date: Subject: Gary Hohenstein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Cliffton Jacoby, 3M EHS&Opns; Environmental Lab Cleston Lange, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions Charles Young, Weston Solutions Tim Frinak, Weston Solutions September 13,2010 Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 09 - Decatur 3rd Quarter Groundwater Sampling 1 General Project Information Contacts Lab Request Number Six Digit Departm ent Num ber Project Schedule/Test Dates 3M Sponsor Representative Gary Hohenstein 3IVI EHS Operations 3M Building 22 4-5W -0 3 Saint Paul, MN 55144-1000 Phone: (651)737-3570 aaboh en stein@ m m m .com 3M Environm ental Laboratory Managem ent William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 w krea aen @ m m m .c o m Principal Analytical investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cclanae@ m m m .com Sam pling Coordinator Timothy Frinak W eston Solutions Timothv.frinak@westonsolutions.com Phone: (334>-332-9123 G L P 1 0 -0 1 -02-09 Dept #530711, Project #0022674449 Sampling scheduled for the week of Septem ber 20, 2010 All verbal and written correspondence will be directed to Gary Hohenstein. Page 4 of 7 Page 39 of 83 G LP10-01-02; Interim Report 09 Analysis of P FBS, P FH S , and P FO S In Groundwater Quarterly GArnouanlydwticataelr PSarmotpolicnog l-: SGepLtP210100-01-02 Amendment 9 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) w ill receive and analyze groundwater samples collected from seventeen groundwater wells for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS). Analyses w ill be conducted under the GLP requirem ents o f EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater sam ples from Decatur, AL w ill be collected by W eston Solutions personnel the week of September 20, 2010. The 3M Environmental Laboratory w ill prepare the sample bottles with all required spikes to ensure that results for PFBS, PFHS, and PFOS are o f a known precision and accuracy. The final report w ill be subm itted to Gary Hohenstein and Jai Kesari upon com pletion under interim report GLP1001-02-09. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of September 20.2010. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival by Friday, September 17.2010. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ W eston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 4 Test Parameters The targeted limit of quantitation will be 0.025 ng/mL (ppb) for PFBS, PFHS, and PFOS. A total of seventeen sampling locations have been specified. For each sampling location, four sample bottles will be collected (sample, sample duplicate, low field matrix spike, and high field matrix spike). The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. Four sets of trip blank spikes consisting o f reagent-grade water, as well as an additional bottle to be used for the preparation of the equipment rinseate blanks, will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. Results from GLP10-01-02-02 were used to determine the field matrix spike levels for GLP10-01-01-09 listed in Table 1. A total of 85 sample bottles will be prepared. Table 1. Sampling Locations and Field Matrix Spike levels. Well No. Sample Level Spike Cone. (ng/mL) 317L 220R, 220L, 328L 203L, 222R, 227L, 227R, 31OR, 324L, 327R, 330L, 331S GRS04, 312R, 330R 328R Trip Blank Sets 1,2, 3, and 4 Low High Low High Low High Low High Low High Low Mid High 1 10 10 100 100 1000 1000 5000 100 500 10 100 1000 Page 5 of 7 Page 40 of 83 G LP10-01-02; Interim Report 09 Analysis of PFBS, P FH S , and P FO S in Groundwater Quarterly GArnouanldywtiactaerl PSarmoptolincgol-:SGepLtP210100-01-02 Amendment 9 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Due to previous data for these sampling locations (GLP10-01-01-02) samples will most likely require dilution. Samples requiring dilution will be prepared in Milli-Q water prior to analysis by ETS-8-044.0. The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 100+30%. Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Alternately, samples may be analyzed by ETS 8-110.1 "Analysis of Fluorochemicals in Extracts Using HPLCElectrospray-Mass Spectrometry-Mass Spectrometry" as an analytical reference for the sample locations analyzed by direct on-column injection analysis of samples diluted with methanol as opposed to Milli-Q water. Calibration curves used for both ETS-8-044.0 and ETS-8-110.1 will be constructed using the linear isomer of PFOS only, from nominal concentrations of 0.02 ng/mL -1 0 0 ng/mL. Due to the expected concentration of linear + branched PFOS in the samples, there may be the potential for analytical bias due to quantitating linear and branched isomers of PFOS against a predominately linear reference standard for PFOS at the higher end of the calibration curve. Laboratory control samples (LCS) of linear + branched PFOS will be prepared at three concentrations to evaluate the potential for analytical bias. LCS with average recoveries greater than 100%30%may suggest analytical bias. If the recovery of the linear + branched LCS is greater than 100%30% it may be necessary to quantitate PFOS by processing the linear and branched isomers separately and summing the calculated concentrations together to generate the final PFOS concentration. This may be done to help minimize any potential analytical bias due to quantitating linear and branched isomers of PFOS against a predominately linear reference standard for PFOS. 6 Reporting Requirements For each sampling location, the report will contain the results for the sample, sample duplicate, and the field matrix spikes. Trip blank sets will be reported for the sampling event as will any equipment blanks prepared in the field. Laboratory control spikes of reagent water prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks of reagent water prepared at the time of sample extraction will be used to determine the method detection limit. Any laboratory matrix spikes that may be prepared will also be included in the final report. 7 Email Correspondence Attachment A: Sampling Bottle Request Page 6 of 7 Page 41 of 83 G LP10-01-02; Interim Report 09 Analysis of PFBS, P FH S , and P FO S in Groundwater Quarterly GArnoaunlydtwicaatelrPSaromtpolicnogl:- SGeLptP210010-01-02 Amendment 9 LABORATORY REQUEST FOR SAMPLE CONTAINERS SITE PROJECT PROJECT NO. SHIPPING AODRESS SHIPMENT REQUIRED BY PROJECT CONTACT CONTACT NUMBER EMAIL Confidential Client, Decatur, Alabama 3RD QUARTER GROUNDWATER SAMPLING _______________ 02181.129.145.0003__________ Martin Smith - WESTON TRAILER 3M DECATUR P U N T 1400 STATE DOCKS ROAD DECATUR, AL 3S601 __________________ 256-552-6189_____________ ___________________ 20-Sep-10______________ TIM FRINAK OFFICE: 334-466-S653; CELL 334-332-9123 t.frinak(S)westonsolutions.com Samples 17 1 4 Sample Type Groundwater GW Duplicate Field Blanks Rinsate Samples Trip Blanks Parameter FCs FCs FCs Lab H20 Required Yes Containers Preserv. COCs Required USDA Permit 625 and Labels Required MS/MSDs Selected by Lab YES No YES COMMENTS: Please pack to prevent breakage. Please provide the laboratory Project Number for reference on the COC. One trip blank will be used per cooler shipped. Un-used trip blanks will be returned to the laboratory for disposal.___________________________________ ____ 203L 220R 220L 222R 227R 227L GRS04 310R RW312R 317L 324L RW327R WELL LIST 328R 328L 330R 330L RW331S Page 7 of 7 Page 42 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Atta c h m en t B: S a m p le C hr o m a to g ram s a n d C a lib r a tio n C urve Page 43 of 83 *** B u s t e r J2930203 Sample Name: "b101025b021" Sampi ID: "08008-194-10" F ie: "b10102Sb.vwtr Peak Name: *PFBS* Mas*(a): *299.0/99.0 *mu,299.0/80.0 amu" I C om m ent *5.0 ng/mL FC ttd in MiS Q Water" Annotation: ~ Sample Index: 21 Sample Type: Standard Concentration: 5.00 ng/mL Calculated Cone: S.04 ng/mL Acq. Date: 10/25/2010 Acq. Time: 10:54:06 PH Modified: RT Window: Expected RT: yes 30.0 12.6 sec min Retention Time: 12.8 min Area: 1930264 counts Height: 2.73e+005 cps Start Time: 12.4 min End Tima: 12.8 min Sample Name: "61010250045" Sample ID: LCS-101020-10" Fie: Peak Name: "PFBS Masa/es): *299.0/99.0 amu.299.0/80.0 amu" 1 C om m ent "20ppb LCS ECF* Annotation: " Sample Index: 45 Sample Tvpe: OC Concentration: 0.00 ng/mL Calculated Cone: 0.219 ng/mL Acq. Date: Acq. Time: 10/26/2010 7:19:04 AM 2.0e4 Modified: Pcoc. Algorithm: Min. Peak Height Min. Peak Width: Smoothing Width: RT Window: Expected RT: Use Relative RT: No Intel1iQuan - IGA 0.00 cps 0.00 sec 0 points 30.0 sec 12.6 min No Int. Tvpe: Valley Retention Time: 12.6 min 109399 counts Height : 2.14 e0Q4 cps Start Tit 12.5 min End Time 12.8 min 1.9*4 1.8*4 1.7*4 1.6*4 1.5*4 1.4*4 P r i n t i n g T i m e : 1 : 3 2 : 4 2 PM P r i n t i n g D a t e : T u e s d a y , F e b r u a r y 08, 2011 GLP10-01-02; Interim Report 09 B a ?f f f i % 2^ Hc | b a n d PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Sample Name: *b10102Sb034' Sample ID: ' Peak Name: "PFBS* Messfea): "299.0/99.0 Comment "20ppb LCS" Annotation: - Sample Index: 34 Sample Type: QC Concentration: 20.0 ng/mL Calculated Cone: 17.4 ng/mL Acq. Date: 10/26/2010 Acq. Time: 3:27:27 AM 1.15*6 1.10*6 Modified: RT Window: Expected RT: Use Relative RT: Yes 30.0 12.6 No sec min Int. Type: Manual Retention Time: 12.6 min Area: 62IJ5119 counts Height: :I.19e+00S cps Start Time: 12.3 min End Time: 13.0 min 1.05*6 1.00*6 9.50*5 9.00*5 6.50*5 8.00*5 7.50*5 7.00*5 & 6.50*5 Sample Name: "b101025b049p Sample ID: Peak Name: "PFBS" M asses): *299.0/99.0 Comment "Method Blank* Annotation:-- Sample Index: 49 known N/A Proe. Algorithm: In Hin. Peak Height: Min. Peak Width: Smoothing Width: 0 RT Window: Expected RT: Use Relative RT: 4.61a002 cps 12.5 min 12.7 min Page 1 of 6 12 14 16 18 Page 44 of 83 GLP10-01-02; Interim Report 09 Bat^Ka!e?e?f ffiSo-2f5H b and PFO S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Printing Time : 1 : 3 2 : 4 2 PM Printing Date : T u e s d a y , F e b r u a r y 0 8 , 2 0 1 1 Page 2 of 6 Page 45 of 83 *** B u s t e r J2930203 GLP10-01-02; Interim Report 09 B a t R a ( y m ? f EF(B&ft1n?nd PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Page 46 of 83 GLP10-01-02; Interim Report 09 Bat&)a!y m ? f Ffi$2S!1&i?nd PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Page 47 of 83 *** B u s te r J2930203 GLP10-01-02; Interim Report 09 2B atP a ly jm ? f iT fi% - ^ H b and P FO S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Printing Time: 1 : 3 2 : 4 3 PM P rin tin g Tuesday, F e b ru ary 08, 2011 Page 5 of 6 Page 48 of 83 B u ster J2930203 P r in tin g Date: Tuesday, February 08, 2011 GLP10-01-02; Interim Report 09 BatPa!y m ? f PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Page 6 of 6 Page 49 of 83 *** B u s te r J2930203 GLP10-01-02; Interim Report 09 BatRaiy m ? f PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 b 1 0 1 0 2 5 b .rd b (P F B S ): "Q uadratic" R eg ressio n ("1 /x " w eighting): y = -1 .4 3 e + 0 0 3 x A2 + 3 .8 5 e + 0 0 5 x + 2 .5 1 e + 0 0 4 (r = 0 .9 9 9 5 ) A rea, counts 2 .5 e 7 2.4e7 2 .3 e 7 2 .2 e 7 2 .1 e 7 2 .0 e 7 1 .9 e 7 1 .8 e 7 1 .7 e 7 1 .6 e 7 1 .5 e 7 1 .4 e 7 1 .3 e 7 1 .2 e 7 1 .1 e 7 1 .0 e 7 9 .0 e 6 8 .0 e 6 7 .0 e 6 6 .0 e 6 5 .0 e 6 4.0e6 3 .0 e 6 2.0e6 1.0e6 0.0 A 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 ________ C on cen tratio n, ng /m L P r i n t i n g T i m e : 1 : 3 3 : 0 2 PM Page 1 of 1 P r i n t i n g D ate: T uesday, F e b r u a r y 08, 2011 Page 50 of 83 GLP10-01-02; Interim Report 09 Bat ^ a(y^se?f E>Ffi%'2(5 H^ b and PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Page 51 of 83 *** B u s t e r J2930203 GLP10-01-02; Interim Report 09 satRaly m ? f PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Page 52 of 83 *** Buster J2930203 I Sample Name: -b10l108b026- Sample ID: Peak Name: *PF8S* M s te t): *299.0/99.0 s Comment *2.5 n g frnl FC std in M ill Q W ate r Sample Index: 26 Sample Type: Standard .centration: 2.50 ng/mL Calculated Cone: 2.60 ng/mL Act). Date: 11/6/2010 Acq. Time: 10:15:18 PM Modif ie d : No Proc. Algori' Intel1iQi ,. Peak Height:: 0 . 00 Peak Width: 0.00 Smoothing width: RT Window: Expected RT: Use Relative RT: No Height : Start Tir Va 1ley e: 12.6 min 1191038 counts 2.71e+00S cps 12.5 mir, 12.9 min hoe: D1UVUWD.WTTT [ Sample Name: "b101108b036" Sample ID: *LCS-101020-2* File: *b101108b.wir Peak Name: *PFBS* Masses): *299.0/99.0 amu,299.0/BO.O amu` Comment *2ppb LCS* Annotation: ** SSaammppllee TIynpdee:x: 36 Concentration: 2.00 ng/i Calculated Cone: 2.3$ ng/i Acq. Date: 11/9/2010 Acq. Time: 1:45:44 AM Modi tied: No Proc. Algorithm: Intel 1iOuan - i. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: RT Window: Expected RT: i Relative RT: No Int. Type: Valley e: 12.6 1094142 coi 2.S2e*005 12.5 12. 9 Data printed by STW Printing Time: 12:29:11 PM P r in t in g Date: Tuesday, March 22, 2011 GLP10-01-02; Interim Report 09 BatR a ( M se?f ? F M '0 l8 ^ ) # nd P F 0 S in Groundwater Quarterly Groundwater Sampling - Sept 2010 I Peak Name: *PFBS* M asses): *299.0/99.0 ai Comment 'M ethod Blank" Annotation: "* Sample Index: Sample Type: link: Concentration: M/A Acq. Date: Acq. Time: : : Modi tied: Proc. Algorithm: : Min. Peak Haight: Min. Peak Width: Smoothing Width: RT Window: 30.0 Expected RT: 12.6 Use Relative RT: Ho sec min int. Type:^ Valley Height: 13940 counts 3.62e00 3 cps End Time: 12.7 min a 1 1 3600 3400 3200 3000 2800 2600 2400 2200 2000 1600 1600 1400 1200 1000- ( Sample Name: 1)1011086043* Sample ID: 'LCS-101020-7* File: *b101108b.wiT Peak Name: "PFBS* M asses): *299.0/99.0 amu.299.0/80.0 amu* Comment *2ppb LCS ECF* Annotation: ** Sample Index: Sample Type: Concentration: I.0043 ng/mL Calculated Con Acq. Time: Modified: cps 2600 Smoothing Width RT Window: Expected RT: 2400 Height : Start Timi End Time: 12.6 13559 co> 2.S9e-i-003 1200 1000 Page 1 of 4 Page 53 of 83 GLP10-01-02; Interim Report 09 Bat^Ra!y#fe?f ^ o ^ ^ b and PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 P r in t in g Date: Tuesday, March 22, 2011 Page 54 of 83 *** B u s te r J2930203 GLP10-01-02; Interim Report 09 BatRaIy m ? f PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Data printed by STW Printing Time: 12:29:12 PM P r in tin g Date: Tuesday, March 22, 2011 Page 3 of 4 Page 55 of 83 *** B u s t e r J 2 9 30203 GLP10-01-02; Interim Report 09 B a P F O S in Groundwater Quarterly Groundwater Sampling - Sept 2010 P r in t in g Date: Tuesday, March 22, 2011 Page 56 of 83 *** B u ster J 2 930203 GLP10-01-02; Interim Report 09 Bat Ra!yjm ?f f<fftol8 h & # nd PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Data printed by STW Printing Time: 12:26:25 PM P r in tin g Date: Tuesday, March 22, 2011 Page 1 of 1 Page 57 of 83 B uster J2930203 GLP10-01-02; Interim Report 09 Bat^Ra!y m ? f ? f f f i ' 0l8 ^<&band PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 I b 1 0 1 1 0 8 b .rd b (P F H S ): "Q uadratic" R eg ressio n ("1 / x" w eighting): y = -2 .1 2 e + 0 0 3 x A2 + 4 .0 5 e + 0 0 5 x + 8 .3 1 e + 0 0 3 (r = 0 .9 9 9 7 ) 1 .5 e 7 - 1 .4 e 7 - 1 .3 e 7 - 1 .2 e 7 - 1 .1 e 7 - 1 .0 e 7 - 9 .0 e 6 - </> f 8.0 e6oo 2 7.0e6- 6.0 e6- 5.0 e6- 4.0 e6- 3 .0 e 6 - 2.0 e6- 1 .0 e 6 - 0.0 * y / Data printed by STW Printing Time: 12:26:46 PM P r i n t i n g Date: T u e sd a y , March 22, 2011 Page 1 of 1 Page 58 of 83 GLP10-01-02; Interim Report 09 BatRaly m ? f PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 b 1 0 1 1 0 8 b .rd b (P F O S ): "Q uadratic" R eg ressio n ("1 / x " w eighting): y = -1 .8 3 e + 0 0 3 xA2 + 3 .8 4 e + 0 0 5 x + 1 .6 6 e + 0 0 4 (r = 0 .9 9 9 7 ) 1.5e7 1 .4 e 7 - 1.3e7 H 1.2e7 1.1 e 7 1 .0 e 7 -| 9 .0 e 6 c 8 .0 e 6 <coo 7 .0 e 6 6 .0 e 6 5 .0 e 6 4 .0 e 6 3 .0 e 6 2 .0 e 6 1 .0 e 6 - / 0.0- & 0 '2 4 '6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 Data printed by STW Printing Time: 12:27:05 PM _______________________ C o n cen tratio n, ng /m L_________________________________________________________________________________ Page 1 of 1 P r in t in g Date: Tuesday, March 22, 2011 Page 59 of 83 *** G in g e r AG01330509 GLP10-01-02; Interim Report 09 R e s $ P ? !m 8 fFJ M f t s.'m d PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 P r in t in g Date: Tuesday, March 22, 2011 Page 60 of 83 *** G in g e r AG01330509 GLP10-01-02; Interim Report 09 Re ^ PF0S Groundwater Quarterly Groundwater Sampling - Sept 2010 P r i n t i n g D ate: T u e sd a y , March 22, 2011 Page 61 of 83 *** G inger AG01330509 GLP10-01-02; Interim Report 09 P F 0 S in Groundwater Quarterly Groundwater Sampling - Sept 2010 P r in t in g Date: Tuesday, March 22, 2011 Page 62 of 83 *** G in g e r AG01330509 GLP10-01-02; Interim Report 09 Re y# PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 P r i n t i n g D ate: T uesday, M arch 22, 2011 Page 63 of 83 *** G in g er AG01330509 GLP10-01-02; Interim Report 09 P F 0 S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Data printed by STW Printing Time: 12:30:59 PM P r in tin g D ate: Tuesday, M arch 22, 2011 Page 1 of 1 Page 64 of 83 *** G in g e r AG01330509 GLP10-01-02; Interim Report 09 m?R e PFK ^ a S.' PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Data printed by STW Printing Time: 12:31:17 PM P r i n t i n g D ate: T u esd ay , M arch 22, 2011 Page 1 of 1 Page 65 of 83 G inger AG01330509 GLP10-01-02; Interim Report 09 R e s f i P ? t P FJ & < m S/ im d PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 g 1 1 0 2 1 1 a .rd b (P F O S ): "Q uadratic" R eg ressio n ("1 / x" w eighting): y = -1 .2 4 e + 0 0 4 x A2 + 1 .7 6 e + 0 0 6 x + 8 .6 1 e + 0 0 3 (r = 0 .9 9 9 8 ) 5 .9 e 7 5 .5 e 7 - 5 .0 e 7 - 4 .5 e 7 - 4 .0 e 7 - 3 .5 e 7 - u> oo 3 .0 e 7 - C0O) ^ 2.5e7- 2 .0 e 7 1 .5 e 7 1 .0 e 7 - / / 5 .0 e 6 - 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 Concentration, ng/m L Data printed by STW Printing Time: 12:31:34 PM Page 1 of 1 Printing Date: Tuesday, March 22, 2011 Page 66 of 83 GLP10-01-02; Interim Report 09 Ba tRalM se?f PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Data printed by STW Printing Time: 12:36:59 PM P r in t in g D ate: T u esd ay , M arch 22, 2011 Page 1 of 2 Page 67 of 83 * Buster J2930203 Printing Time: 12:36:59 PM Printing Date: Tuesday, March 22, 2011 GLP10-01-02; Interim Report 09 Bat^Paly m ? f PF0S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Page 2 o f 2 Page 68 of 83 Buster J2930203 GLP10-01-02; Interim Report 09 B a ^ R a (yjm ?f H b a n d P F 0 S in Groundwater Quarterly Groundwater Sampling - Sept 2010 b 1 1 0 3 1 5 a .rd b (P F O S ): "Q uadratic" R eg ressio n ("1 / x" w eighting): y = -8 8 5 x A2 + 2 .0 4 e + 0 0 5 x + -1 .4 2 e + 0 0 3 (r = 0 .9 9 9 6 ) 4 .6 e 6 4 .4 e 6 4 .2 e 6 4 .0 e 6 3 .8 e 6 3 .6 e 6 3 .4 e 6 3 .2 e 6 3.0 e62 .8 e 6 2.6 e62.4e6 2 .2 e 6 2 .0 e 6 1 .8 e 6 1 .6 e 6 1 .4 e 6 1 .2 e 6 1 .0 e 6 8.0 e56 .0 e 5 4.0 e52 .0 e 5 0.0 0 -- I-------- >---------- 1 '--------- 1--------- 1--------- 1--------- '------- 1-- 12 3 4 5 6 Data printed by STW Printing Time: 12:35:33 PM P r in t in g D ate: T u esd ay , M arch 22, 2011 i 1 r~ -|----- 1-----j-- --1 1 I 1 0 11 1 2 13 1 4 1 5 1 6 1 7 1 8 1 9 2 0 21 2 2 2 3 2 4 2 5 _________ C on cen tratio n, ng /m L_________________________________________________________________________________ Page 1 of 1 Page 69 of 83 GLP10-01-02; Interim Report 09 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Atta c h m en t C: A nalytical M etho d Page 70 of 83 Document may beGusii0#)-if2asii`rim'TtepJftstffoi4 days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 3M Environm ental Laboratory Method Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing o y /n /o iEffective Date: Approved By: William K. Reagen, Laboratory Manager ' / O > Date ETS-8-044.0 Page 1 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 71 of 83 Document may beaijF3i;o^ti2astirarf!ep%roM days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 1 Scope and Application This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in clean water samples. Water samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method is considered a performance-based method. Data is considered acceptable as long as the defined QC elements are satisfied. Sample collection is not covered under this analytical procedure. 2 Method Summary Clean aqueous samples are analyzed by direct injection using LC/MS/MS. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered. This is a performance-based method. Method accuracy is determined for each sample set using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to each sample matrix. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. Fortification levels for field matrix spikes and for laboratory matrix spikes should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used to determine the statement of accuracy for analytical results. 3 Definitions 3.1 Calibration Standard A solution prepared by spiking a known volume of the Working Standard (WS) into a predetermined amount of ASTM Type I, HPLC grade water, or other suitable water, and analyzed according to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration. 3.2 Laboratory Duplicate Sample (LDS, or Lab Dup) A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures. 3.3 Field Blank (FB)/Trip Blank ASTM Type I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose of the FB is to determine if test substances or other interferences are present in the field environment. This sample is also referred to as a Trip Blank. E T S -8 -0 4 4 .0 P age 2 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W a te r by LC /M S/M S; Direct Injection Analysis Page 72 of 83 Document may beauw-sdj-Efeaatsrafri^ffoW days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 3.4 Field Duplicate Sample (FDS, Field Dup) A sample collected in duplicate at the same time from the same location as the sample. The FDS is handled under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures. 3.5 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to the sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside of the sample container. The FMS should be spiked between approximately 50% and 10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes are added in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a study sample to help determine if the method is in control and whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At least one separate, un-spiked sample must be taken at the same time and place as each FMS. 3.7 Laboratory Control Sample (LCS) An aliquot of control matrix to which known quantities of the target analytes are added in the laboratory at the time of sample extraction. At least two levels are included, one generally at the low end of the calibration curve and one near the mid to upper range of the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared each day samples are extracted. 3.8 Laboratory Matrix Spike (LMS) A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous samples. 3.9 Laboratory Sample A portion or aliquot of a sample received from the field for testing. 3.10 Limit of Quantitation (LOQ) The lower limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix-dependent. The upper limit of quantitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. The highest standard in the calibration curve that meets method criteria is defined as the ULOQ. E T S -8 -0 4 4 .0 P age 3 of 11 Method of Analysis for the Determination of Perfluorinated Com pounds in W a te r by LC /M S/M S; Direct Injection Analysis Page 73 of 83 Document may be3usi8^j-if2otiiii^TrSefii.foM days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 3.11 Method Blank An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus. 3.12 Sample A sample is an aliquot removed from a larger quantity of material intended to represent the original source material. 3.13 Stock Standard Solution (SSS) A concentrated solution of a single-analyte prepared in the laboratory with an assayed reference compound. 3.14 Surrogate A compound similar in chemical composition and behavior to the target analyte(s), but is not normally found in the sample(s). A surrogate compound is typically a target analyte with at least one atom containing an isotopically-labeled substitution. If used, surrogate(s) are added to all samples and quality control samples. Surrogate(s) are added to quantitatively evaluate the entire analytical procedure including sample collection, preparation, and analysis. Inclusion of a surrogate analyte is an optional quality control measure and is NOT required. 3.15 Working Standard (WS) A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions. 4 Warnings and Cautions 4.1 Health and Safety The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that might be present. The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses. 4.2 Cautions The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or operator manual for additional information and cautions. 5 Interferences During sample preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks. E T S -8 -0 4 4 .0 P age 4 of 11 Method of Analysis for the Determination of Perfluorinated Com pounds in W a te r by LC /M S/M S; Direct Injection Analysis Page 74 of 83 Document may besustB^lj-tfeaiSiimrrt^iiw'oi4 days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to two solvents and equipped with a variable volume injector capable of injecting 5-100 pL connected to a tandem Mass Spectrometer (LC/MS/MS). I Analytical balance capable of reading to 0.0001 g A device to collect raw data for peak integration and quantitation 15-mL and 50-mL disposable polypropylene centrifuge tubes. Gas tight syringes, 25pL, 50pL, 100pL, 250pL, 500pL, 1000pL. 1 mL plastic HPLC autovial. Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 6.2 Chromatographic System Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm Analytical Column: Betasil C18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Time (min) 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (mL/min) 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak Area - quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. f The previous information is intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met. E T S -8 -0 4 4 .0 P age 5 of 11 Method of Analysis for the Determination of Perfluorinated Com pounds in W a te r by LC /M S/M S; Direct Injection Analysis Page 75 of 83 Document may days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: Analyte Transition Monitored PFBA 2 1 3 -> 169 PFPeA 263 ->219 PFHA 313 --> 269 and 313 -> 1 1 9 PFHpA 363 - 319, 363 -> 169 and 363 - 119 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 219 PFDA 513 -> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 2 1 9 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 - * 99 PFHS 399 --^ 80 and 399 --> 99 PFOS 499 -> 80, 499 -> 99 and 499 -> 130 Multiple transitions for monitoring the analytes is an option, as summing multiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention time criteria are met to assure adequate specificity. The previous information is intended as a guide, alternate instruments and equipment may be used. 7 Reagents and Standards 7.1 Chemicals Water - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate - A. C.S. Reagent Grade 7.2 Standards Perfluorobutanoic Acid (P F B A -C 4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (P F H A -C 6 acid); Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M Perfluorononanoic Acid (PFNA - C9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (P F D A -C 1 0 acid); Oakwood Products, Inc Perfluoroundecanoic Acid (PFUnA-C11 acid); Oakwood Products, Inc Perfluorododecanoic Acid (PFDoA - C12 acid); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 76 of 83 Document may be3uisi^^2paiSTOfEt9ffc0iroi4 days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 The previous information is intended as a guide. Reagents and standards from alternate sources may be used. 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)--Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/mL target analyte SSSs--Weigh out 10 mg of analytical standard (corrected for percent salt and purity) and dilute to 10OmL with methanol or other suitable solvent, in a 10OmL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. molecular weight of anion salt correction factor moclecular weight of salt PFOS (K +)salt correction factor = ------= 0.9275 538 10 mg C8F17S03'K+with purity 90% = 8.35mg C8F17S03- (10 mg*0.90*0.9275=8.35 mg) 5 pg/mL (5000 ng/mL) mixed w orking standard--Add 0.5mL each of the 10Opg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/mL mixed w orking standard--Add 1.25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/mL mixed standard--Add 625pL of the 5 pg/mL-mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage Conditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. E T S -8 -0 4 4 .0 Page 7 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W a te r by LC /M S/M S; Direct Injection Analysis Page 77 of 83 Document may be3ualj-feabtirafrteffei.iro^4 days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, or other suitable water, using the following table as a guideline. Note: Volumes of water and working standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. C oncentration o f W S, ng/m L 125 125 125 125 250 250 250 250 5000 5000 5000 V olu m e o f W S, pL 10 15 20 30 20 50 100 200 25 50 100 Final V olum e o f C alibration S tan dard (m L o f A S T M Type 1 W ater, o r o th er su itab le water) 50 50 50 50 50 50 50 50 50 50 50 F in al C oncentration o f C alibration S tandard, ng/m L (ppb) in A S T M Type 1 W ater, o r o th er su itab le w ater 0.025 0.0375 0.050 0.075 0.100 0.250 0.500 1.00 2.50 5.00 10.0 8 Sample Handling 8.1 Water Sample Preparation This method is applicable to clean water samples. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered. Thoroughly mix sample before removing an aliquot and placing in a labeled plastic autovial. Plastic is preferred over the use of glass autovials, to prevent the possibly of fluorochemical sticking to the glass. Dilute sample, if necessary, with ASTM Type I, HPLC water, or other suitable water. Prepare method QC samples and multiple method blanks and aliquot into labeled plastic autovials. Prepare at least five method blanks. 9 Sample Analysis - LC/MS/MS Analyze the standard curve prior to each set of samples. The standard curve may be plotted using a linear fit, weighted 1/x or unweighted, or by quadratic fil (y = ax2+ bx + c), weighted 1/x or unweighted, using suitable software. The calibration curves may include but should not be forced through zero. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data. High and/or low points may be excluded from the calibration curves to provide a better fit over the range appropriate to the data or because they did not meet the pre-determined acceptance criteria. Low-level curve points should also be excluded if their area counts are not at least twice that of the method and/or solvent blanks. The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may E T S -8 -0 4 4 .0 Page 8 of 11 Method of Analysis for the Determination of Perfluorinated Com pounds in W a te r by LC /M S /M S ; Direct Injection Analysis Page 78 of 83 Document may besua8!lj-ifea6itsiiTflep%foi4 days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 be within 30%. Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples containing analytes that are quantitated above the concentration of the highest standard in the curve should be further diluted and reanalyzed. 10 Quality Control 10.1 Data Quality Objectives This method and required quality control samples is designed to generate data accurate to 30% with a targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report. 10.2 Method Blanks Method blanks must be prepared with each analysis batch. At least five method blanks must be prepared. Method blanks may be injected multiple times, but no more than 3 injections should be removed from a single method blank. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, and at the end of the analytical run. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts of these method blanks should be calculated and reported. If the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria, or alternatively, the method blanks must be evaluated statistically to determine outliers, or technical justification to eliminate one or more results should be made. 10.3 Sample Replicates Samples duplicates are collected in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks. 10.4 Surrogate Spikes Surrogate spikes are not required but may be used on project specific requirements. 10.5 Lab Control Sample Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each preparation batch. Low lab control spikes should be prepared at concentrations in the range of five to ten times higher than the targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve. The relative standard deviation of the control spikes evaluated independently at each concentration level must be less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire set of samples should be re-injected or re-prepared as appropriate. E T S -8 -0 4 4 .0 P age 9 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC /M S /M S ; Direct Injection Analysis Page 79 of 83 Document may besiB^i-EfeaatsiRSir!ieiiie'o^4 days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: (Peak Area - Intercept) Analyte found (ng/mL) = xDF Slope DF = factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) Recovery = x100 Analyte added (ng/mL) 12 Method Performance Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report. 12.1 System Suitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of <5% and a retention time RSD of 2% to be compliant. 12.2 Quantitation Calibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Performance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. E T S -8 -0 4 4 .0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W a te r by LC /M S /M S ; Direct Injection Analysis Page 80 of 83 Document may be3lJ^^tfeaatawrte^few^o^4 days from 03/22/2011 Analysis of PFBS, PFHS, and PFOS in Groundwater Quarterly Groundwater Sampling - Sept 2010 Demonstration o f Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions Revision Number Summary of Changes E T S -8 -0 4 4 .0 P age 11 of 11 Method of Analysis for the Determination of Perfluorinated Com pounds in W a te r by LC /M S /M S ; Direct Injection Analysis Page 81 of 83 Atta c h m en t D: D evia tio n (s ) G LP10-01-02; Interim Report 09 Analysis of P FBS, P FH S, and P FO S in Groundwater Quarterly Groundwater Sampling - Sept 2010 Page 82 of 83 3M Confidential G LP10-01-02; Interim Report 09 Analysis of P FBS, P FH S , and P FO S in Groundwater __ _ Quarterly Groundwater S am plin g-S ep t 2010 R eco rd of D eviation/N o n c o n fo r m a n c e ______________________________ I. Identification_____________________________ S tu dy / P roject N o. G LP 10-01-02-09 D ate(s) of O ccurrence: Sequence b101108a, g110211a, and b110315a D ocum ent Num ber: E T S -8-044.0 (Check one)D eviatio n typ e S O P Equipm ent Procedure 0 M ethod P ro to c o l________ 0 G P O ______________________ O th e r :___________________________ ___________________ II. Description (attach extra pages as needed)___________________________ Method Requirements: (1) LCS average recovery of 100% 20%. (2) Sample/Sample Duplicate RPD s20%. (3) FMS recovery of 100% 30%. Actual procedure/process: (1) LCS average recovery for the high set of linear and branched PFOS was 129% (b101108a). LCS average recovery for the high set of linear and branched PFOS was 133% (g110211 a). (2) The RPD value for PFOS for DAL GW 330L was 24%. (3) Sampling location DAL GW 227L did not have an appropriate FMS level for PFOS. The recovery of the HS for PFHS for DAL GW 330L was 135%. The recovery of the HS for PFBA, PFHS, and PFOS for ________ DAL GW GRS04 were <50%. The recovery of the HS for PFOS for DAL GW 328L was 69.0%________ III. Actions Taken ___________________________(such as amendment issued, SOP revision, etc.)__________________________ Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconform ing work: 1) The linear and branched LCS had been running 5-15% higher when quantitated against a calibration curve comprised of primarily linear PFOS. All LCS were used in the determination of method uncertainty. 2) The RPD value for PFOS for DAL GW 330L with a value >20% will be footnoted in the data tables. 3) Sampling location DAL GW 227L will be footnoted in the report as not having an appropriate spike level for PFOS. The analytical uncertainty for sampling location DAL GW 330L will be adjusted accordingly. A 5000ppb LMS was prepared on sampling location DAL GW GRS04 and met method acceptance criteria. Sampling location DAL GW 328L LS met method acceptance criteria and was the more appropriate spike level. No adjustment will be made to the analytical uncertainty. Actions: Halting of Work Client Notification Work Recall Withholding of Report 0 Other: Deviations will be noted in final report. Project Lead/PAI Approval: y u lY , Study Director (if GLP): K ]y S ponsor Approval (for GLP protocol deviations): NA Date: , . 3 in / r ii Date: m ill Date: N A y Technical Reviewer (optional): NA Date: NA Laboratory D epartm entM gnager Approval: Date: " IV. Authorization to Resume Work Where halting of work occurred, resumption of work must first be approved by Laboratory Management Laboratory D epartm ent M anager Approval: NA Date: NA \ Deviation N o ._______________ (assigned by Study Director or Team Leader at the end o f study or project) Attachment A ETS-4-008.7 Page 1 of 1 Documentation of Deviations and Control of Nonconforming Testing Page 83 of 83